Partial oxidation power plant with reheating and method thereof

DOEpatents

Newby, Richard A.; Yang, Wen-Ching; Bannister, Ronald L.

1999-01-01

A system and method for generating power having an air compression/partial oxidation system, a turbine, and a primary combustion system. The air compression/partial oxidation system receives a first air stream and a fuel stream and produces a first partially oxidized fuel stream and a first compressed air stream therefrom. The turbine expands the first partially oxidized fuel stream while being cooled by the first compressed air stream to produce a heated air stream. The heated air stream is injected into the expanding first partially oxidized fuel stream, thereby reheating it in the turbine. A second partially oxidized fuel stream is emitted from the turbine. The primary combustion system receives said second partially oxidized fuel stream and a second air stream, combusts said second partially oxidized fuel stream, and produces rotating shaft power and an emission stream therefrom.

Roles of free radicals in NO oxidation by Fenton system and the enhancement on NO oxidation and H2O2 utilization efficiency.

PubMed

Zhao, Haiqian; Dong, Ming; Wang, Zhonghua; Wang, Huaiyuan; Qi, Hanbing

2018-06-20

Low H 2 O 2 utilization efficiency is the main problem when Fenton system was used to oxidize NO in flue gas. To understand the behavior of the free radicals during NO oxidation process in Fenton system is crucial to solving this problem. The oxidation capacity of ·OH and HO 2 · on NO in Fenton system was compared and the useless consumption path of ·OH and HO 2 · that caused the low utilization efficiency of H 2 O 2 were studied. A method to enhance the oxidation ability and H 2 O 2 utilization efficiency by adding reducing additives in Fenton system was proposed. The results showed that both of ·OH and HO 2 · were active substances that oxidize NO. However, the oxidation ability of ·OH radicals was stronger. The vast majority of ·OH and HO 2 · was consumed by rapid reaction ·OH+HO 2 ·→H 2 O+O 2 , which was the primary reason for the low utilization efficiency of H 2 O 2 in Fenton system. Hydroxylamine hydrochloride and ascorbic acid could accelerate the conversion of Fe 3+ to Fe 2+ , thereby increase the generation rate of ·OH and decrease the generation rate of HO 2 ·. As a result, the oxidation ability and H 2 O 2 utilization efficiency were enhanced.

Air feed tube support system for a solid oxide fuel cell generator

DOEpatents

Doshi, Vinod B.; Ruka, Roswell J.; Hager, Charles A.

2002-01-01

A solid oxide fuel cell generator (12), containing tubular fuel cells (36) with interior air electrodes (18), where a supporting member (82) containing a plurality of holes (26) supports oxidant feed tubes (51), which pass from an oxidant plenum (52") into the center of the fuel cells, through the holes (26) in the supporting member (82), where a compliant gasket (86) around the top of the oxidant feed tubes and on top (28) of the supporting member (82) helps support the oxidant feed tubes and center them within the fuel cells, and loosen the tolerance for centering the air feed tubes.

Metal Nanoshells for Plasmonically Enhanced Solar to Fuel Photocatalytic Conversion

DTIC Science & Technology

2016-05-18

interlayer of ~17 nm generated a rate of hydrogen production 2.6 times higher than that of unmodified ZIS. Second thrust: Tin oxide-coated gold-silver...nanoshells were prepared as an alternative plasmonic enhancement system to the silicon oxide system described above. Tin oxide is an attractive...this grant, we developed two synthetic approaches for preparing tin oxide-coated gold-silver nanoshells, as illustrated in Scheme 2. These particles

Supramolecular water oxidation with Ru-bda-based catalysts.

PubMed

Richmond, Craig J; Matheu, Roc; Poater, Albert; Falivene, Laura; Benet-Buchholz, Jordi; Sala, Xavier; Cavallo, Luigi; Llobet, Antoni

2014-12-22

Extremely slow and extremely fast new water oxidation catalysts based on the Ru-bda (bda=2,2'-bipyridine-6,6'-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycles s(-1) , respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system π-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solar-Driven Reduction of Aqueous Protons Coupled to Selective Alcohol Oxidation with a Carbon Nitride-Molecular Ni Catalyst System.

PubMed

Kasap, Hatice; Caputo, Christine A; Martindale, Benjamin C M; Godin, Robert; Lau, Vincent Wing-Hei; Lotsch, Bettina V; Durrant, James R; Reisner, Erwin

2016-07-27

Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride ((NCN)CNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The (NCN)CNx-NiP system showed an activity of 763 μmol (g CNx)(-1) h(-1) toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h(-1), and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of (NCN)CNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited (NCN)CNx in the presence of an organic substrate can accumulate ultralong-lived "trapped electrons", which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel.

Extended Durability Testing of an External Fuel Processor for a Solid Oxide Fuel Cell (SOFC)

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

Mark Perna; Anant Upadhyayula; Mark Scotto

2012-11-05

Durability testing was performed on an external fuel processor (EFP) for a solid oxide fuel cell (SOFC) power plant. The EFP enables the SOFC to reach high system efficiency (electrical efficiency up to 60%) using pipeline natural gas and eliminates the need for large quantities of bottled gases. LG Fuel Cell Systems Inc. (formerly known as Rolls-Royce Fuel Cell Systems (US) Inc.) (LGFCS) is developing natural gas-fired SOFC power plants for stationary power applications. These power plants will greatly benefit the public by reducing the cost of electricity while reducing the amount of gaseous emissions of carbon dioxide, sulfur oxides,more » and nitrogen oxides compared to conventional power plants. The EFP uses pipeline natural gas and air to provide all the gas streams required by the SOFC power plant; specifically those needed for start-up, normal operation, and shutdown. It includes a natural gas desulfurizer, a synthesis-gas generator and a start-gas generator. The research in this project demonstrated that the EFP could meet its performance and durability targets. The data generated helped assess the impact of long-term operation on system performance and system hardware. The research also showed the negative impact of ambient weather (both hot and cold conditions) on system operation and performance.« less

Cigarette smoke exposure inhibits contact hypersensitivity via the generation of platelet activating factor agonists

PubMed Central

Sahu, Ravi P.; Petrache, Irina; Van Demark, Mary J; Rashid, Badri M.; Ocana, Jesus A.; Tang, Yuxuan; Yi, Qiaofang; Turner, Matthew J.; Konger, Raymond L.; Travers, Jeffrey B.

2013-01-01

Previous studies have established that pro-oxidative stressors suppress host immunity due to their ability to generate oxidized lipids with PAF-receptor (PAF-R) agonist activity. Although exposure to the pro-oxidative stressor cigarette smoke (CS) is known to exert immunomodulatory effects, little is known regarding the role of platelet-activating factor (PAF) in these events. The current studies sought to determine the role of PAF-R signaling in CS-mediated immunomodulatory effects. We demonstrate that CS exposure induces the generation of a transient PAF-R agonistic activity in the blood of mice. CS exposure inhibits contact hypersensitivity in a PAF-R-dependent manner as PAF-R-deficient mice were resistant to these effects. Blocking PAF-R agonist production either by systemic antioxidants or treatment with serum PAF-acetyl hydrolase enzyme blocked both the CS-mediated generation of PAF-R-agonists and PAF-R dependent inhibition of CHS reactions, indicating a role for oxidized glycerophosphocholines with PAF-R agonistic activity in this process. In addition, cyclooxygenase-2 (COX-2) inhibition did not block PAF-R agonist production but prevented CS-induced inhibition of CHS. This suggests that COX-2 acts downstream of the PAF-R in mediating CS-induced systemic immunosuppression. Moreover, CS-exposure induced a significant increase in the expression of the regulatory T cell reporter gene in FoxP3EGFP mice but not in FoxP3EGFP mice on a PAF-R-deficient background. Finally, Treg depletion via anti-CD25 antibodies blocked CS-mediated inhibition of CHS, indicating the potential involvement of Tregs in CS-mediated systemic immunosuppression. These studies provide the first evidence that the pro-oxidative stressor CS can modulate cutaneous immunity via the generation of PAF-R agonists produced through lipid oxidation. PMID:23355733

Partial oxidation power plant with reheating and method thereof

DOEpatents

Newby, R.A.; Yang, W.C.; Bannister, R.L.

1999-08-10

A system and method are disclosed for generating power having an air compression/partial oxidation system, a turbine, and a primary combustion system. The air compression/partial oxidation system receives a first air stream and a fuel stream and produces a first partially oxidized fuel stream and a first compressed air stream therefrom. The turbine expands the first partially oxidized fuel stream while being cooled by the first compressed air stream to produce a heated air stream. The heated air stream is injected into the expanding first partially oxidized fuel stream, thereby reheating it in the turbine. A second partially oxidized fuel stream is emitted from the turbine. The primary combustion system receives said second partially oxidized fuel stream and a second air stream, combusts said second partially oxidized fuel stream, and produces rotating shaft power and an emission stream therefrom. 2 figs.

Singlet-Oxygen Generation in Alkaline Periodate Solution.

PubMed

Bokare, Alok D; Choi, Wonyong

2015-12-15

A nonphotochemical generation of singlet oxygen ((1)O2) using potassium periodate (KIO4) in alkaline condition (pH > 8) was investigated for selective oxidation of aqueous organic pollutants. The generation of (1)O2 was initiated by the spontaneous reaction between IO4(-) and hydroxyl ions, along with a stoichiometric conversion of IO4(-) to iodate (IO3(-)). The reactivity of in-situ-generated (1)O2 was monitored by using furfuryl alcohol (FFA) as a model substrate. The formation of (1)O2 in the KIO4/KOH system was experimentally confirmed using electron spin resonance (ESR) measurements in corroboration with quenching studies using azide as a selective (1)O2 scavenger. The reaction in the KIO4/KOH solution in both oxic and anoxic conditions initiated the generation of superoxide ion as a precursor of the singlet oxygen (confirmed by using superoxide scavengers), and the presence of molecular oxygen was not required as a precursor of (1)O2. Although hydrogen peroxide had no direct influence on the FFA oxidation process, the presence of natural organic matter, such as humic and fulvic acids, enhanced the oxidation efficiency. Using the oxidation of simple organic diols as model compounds, the enhanced (1)O2 formation is attributed to periodate-mediated oxidation of vicinal hydroxyl groups present in humic and fulvic constituent moieties. The efficient and simple generation of (1)O2 using the KIO4/KOH system without any light irradiation can be employed for the selective oxidation of aqueous organic compounds under neutral and near-alkaline conditions.

Oxidant Mechanisms in Renal Injury and Disease

PubMed Central

Ratliff, Brian B.; Abdulmahdi, Wasan; Pawar, Rahul

2016-01-01

Abstract Significance: A common link between all forms of acute and chronic kidney injuries, regardless of species, is enhanced generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS) during injury/disease progression. While low levels of ROS and RNS are required for prosurvival signaling, cell proliferation and growth, and vasoreactivity regulation, an imbalance of ROS and RNS generation and elimination leads to inflammation, cell death, tissue damage, and disease/injury progression. Recent Advances: Many aspects of renal oxidative stress still require investigation, including clarification of the mechanisms which prompt ROS/RNS generation and subsequent renal damage. However, we currently have a basic understanding of the major features of oxidative stress pathology and its link to kidney injury/disease, which this review summarizes. Critical Issues: The review summarizes the critical sources of oxidative stress in the kidney during injury/disease, including generation of ROS and RNS from mitochondria, NADPH oxidase, and inducible nitric oxide synthase. The review next summarizes the renal antioxidant systems that protect against oxidative stress, including superoxide dismutase and catalase, the glutathione and thioredoxin systems, and others. Next, we describe how oxidative stress affects kidney function and promotes damage in every nephron segment, including the renal vessels, glomeruli, and tubules. Future Directions: Despite the limited success associated with the application of antioxidants for treatment of kidney injury/disease thus far, preventing the generation and accumulation of ROS and RNS provides an ideal target for potential therapeutic treatments. The review discusses the shortcomings of antioxidant treatments previously used and the potential promise of new ones. Antioxid. Redox Signal. 25, 119–146. PMID:26906267

System and method for regeneration and recirculation of a reducing agent using highly exothermic reactions induced by mixed industrial slags

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

Nakano, Jinichiro; Bennett, James P.; Nakano, Anna

Embodiments relate to systems and methods for regenerating and recirculating a CO, H.sub.2 or combinations thereof utilized for metal oxide reduction in a reduction furnace. The reduction furnace receives the reducing agent, reduces the metal oxide, and generates an exhaust of the oxidized product. The oxidized product is transferred to a mixing vessel, where the oxidized product, a calcium oxide, and a vanadium oxide interact to regenerate the reducing agent from the oxidized product. The regenerated reducing agent is transferred back to the reduction furnace for continued metal oxide reductions.

System for operating solid oxide fuel cell generator on diesel fuel

NASA Technical Reports Server (NTRS)

Singh, Prabhu (Inventor); George, Raymond A. (Inventor)

1997-01-01

A system is provided for operating a solid oxide fuel cell generator on diesel fuel. The system includes a hydrodesulfurizer which reduces the sulfur content of commercial and military grade diesel fuel to an acceptable level. Hydrogen which has been previously separated from the process stream is mixed with diesel fuel at low pressure. The diesel/hydrogen mixture is then pressurized and introduced into the hydrodesulfurizer. The hydrodesulfurizer comprises a metal oxide such as ZnO which reacts with hydrogen sulfide in the presence of a metal catalyst to form a metal sulfide and water. After desulfurization, the diesel fuel is reformed and delivered to a hydrogen separator which removes most of the hydrogen from the reformed fuel prior to introduction into a solid oxide fuel cell generator. The separated hydrogen is then selectively delivered to the diesel/hydrogen mixer or to a hydrogen storage unit. The hydrogen storage unit preferably comprises a metal hydride which stores hydrogen in solid form at low pressure. Hydrogen may be discharged from the metal hydride to the diesel/hydrogen mixture at low pressure upon demand, particularly during start-up and shut-down of the system.

40 CFR 86.332-79 - Oxides of nitrogen analyzer calibration.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Emission Regulations for New Gasoline-Fueled and Diesel-Fueled Heavy-Duty Engines; Gaseous Exhaust Test.... (2) Zero the oxides of nitrogen analyzer. (3) Connect the outlet of the NOX generator (see Figure D79... operating range. (4) Introduce into the NOX generator-analyzer system a span gas with a NO concentration...

40 CFR 86.332-79 - Oxides of nitrogen analyzer calibration.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Emission Regulations for New Gasoline-Fueled and Diesel-Fueled Heavy-Duty Engines; Gaseous Exhaust Test.... (2) Zero the oxides of nitrogen analyzer. (3) Connect the outlet of the NOX generator (see Figure D79... operating range. (4) Introduce into the NOX generator-analyzer system a span gas with a NO concentration...

Cyanide oxidation by singlet oxygen generated via reaction between H2O2 from cathodic reduction and OCl(-) from anodic oxidation.

PubMed

Tian, Shichao; Li, Yibing; Zeng, Huabin; Guan, Wei; Wang, Yan; Zhao, Xu

2016-11-15

Cyanide is widely present in electroplating wastewater or metallurgical effluents. In the present study, the electrochemical destruction of cyanide with various anode and cathode compositions under alkaline conditions was investigated. The results indicated that the electrochemical system using RuO2/Ti as anode and activated carbon fiber (ACF) as cathode in the presence of sodium chloride was efficient for the cyanide removal. In this system, in situ generation of HClO by anodic oxidation of Cl(-) at RuO2/Ti anode occurred with the H2O2 generation by O2 reduction at ACF cathode. As confirmed by the electron spin resonance technique, the reaction between HClO and H2O2 led to the generation of singlet oxygen, which was responsible for the cyanide removal. Further experiment indicated that the cyanide removal efficiency increased with the increase of the current density or the sodium chloride concentration. Cyanate was identified as main product in the system. Besides, the system exhibited good stability for the cyanide removal, which was beneficial to its practical application. Copyright © 2016. Published by Elsevier Inc.

Relationship in between Chemical Oxidation and Browning of Flavanols

NASA Astrophysics Data System (ADS)

Dong, X.; Zhang, Y. L.; Wang, F.; Pang, M. X.; Qi, J. H.

2016-08-01

Catechin, epicatechin and chlorogenic acid are widely distributed in the plant kingdom. At present, influencing factors of phenol chemical oxidation is little research. In order to study non-enzymatic browning factors, this research utilized catechin, epicatechin and chlorogenic acid to establish simulation systems. The browning degree and products of flavanols were investigated by transmittance and high-performance liquid chromatography (HPLC). The main results and conclusions were follows. The brown generation is increased after phenols of chemical oxidation at 50°C and at pH 3.7 phosphate buffered saline, the sequence of influencing factor of browning is pH > kind of phenol > temperature. Oxidation of compounds of catechin and epicatechin results in formation of their Methylene quinone or o -Quinones. In addition, oxidation products of catechin, epicatechin and chlorogenic acid were mixture of different molecular sizes. The research has showed that brown generation correlated well with chemical oxidation of phenols and chemical oxidation reaction generated larger molecular weight polymers.

Removal of Iron Oxide Scale from Feed-water in Thermal Power Plant by Using Magnetic Separation

NASA Astrophysics Data System (ADS)

Nakanishi, Motohiro; Shibatani, Saori; Mishima, Fumihito; Akiyama, Yoko; Nishijima, Shigehiro

2017-09-01

One of the factors of deterioration in thermal power generation efficiency is adhesion of the scale to inner wall in feed-water system. Though thermal power plants have employed All Volatile Treatment (AVT) or Oxygen Treatment (OT) to prevent scale formation, these treatments cannot prevent it completely. In order to remove iron oxide scale, we proposed magnetic separation system using solenoidal superconducting magnet. Magnetic separation efficiency is influenced by component and morphology of scale which changes their property depending on the type of water treatment and temperature. In this study, we estimated component and morphology of iron oxide scale at each equipment in the feed-water system by analyzing simulated scale generated in the pressure vessel at 320 K to 550 K. Based on the results, we considered installation sites of the magnetic separation system.

Solid Oxide Fuel Cell Hybrid System for Distributed Power Generation

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

Nguyen Minh

2002-03-31

This report summarizes the work performed by Honeywell during the January 2002 to March 2002 reporting period under Cooperative Agreement DE-FC26-01NT40779 for the U. S. Department of Energy, National Energy Technology Laboratory (DOE/NETL) entitled ''Solid Oxide Fuel Cell Hybrid System for Distributed Power Generation''. The main objective of this project is to develop and demonstrate the feasibility of a highly efficient hybrid system integrating a planar Solid Oxide Fuel Cell (SOFC) and a turbogenerator. For this reporting period the following activities have been carried out: {lg_bullet} Conceptual system design trade studies were performed {lg_bullet} System-level performance model was created {lg_bullet}more » Dynamic control models are being developed {lg_bullet} Mechanical properties of candidate heat exchanger materials were investigated {lg_bullet} SOFC performance mapping as a function of flow rate and pressure was completed« less

Anode protection system for shutdown of solid oxide fuel cell system

DOEpatents

Li, Bob X; Grieves, Malcolm J; Kelly, Sean M

2014-12-30

An Anode Protection Systems for a SOFC system, having a Reductant Supply and safety subsystem, a SOFC anode protection subsystem, and a Post Combustion and slip stream control subsystem. The Reductant Supply and safety subsystem includes means for generating a reducing gas or vapor to prevent re-oxidation of the Ni in the anode layer during the course of shut down of the SOFC stack. The underlying ammonia or hydrogen based material used to generate a reducing gas or vapor to prevent the re-oxidation of the Ni can be in either a solid or liquid stored inside a portable container. The SOFC anode protection subsystem provides an internal pressure of 0.2 to 10 kPa to prevent air from entering into the SOFC system. The Post Combustion and slip stream control subsystem provides a catalyst converter configured to treat any residual reducing gas in the slip stream gas exiting from SOFC stack.

Exploring oxidative ageing behaviour of hydrocarbons using ab initio molecular dynamics analysis

NASA Astrophysics Data System (ADS)

Pan, Tongyan; Cheng, Cheng

2016-06-01

With a proper approximate solution to the Schrödinger Equation of a multi-electron system, the method of ab initio molecular dynamics (AIMD) performs first-principles molecular dynamics analysis without pre-defining interatomic potentials as are mandatory in traditional molecular dynamics analyses. The objective of this study is to determine the oxidative-ageing pathway of petroleum asphalt as a typical hydrocarbon system, using the AIMD method. This objective was accomplished in three steps, including (1) identifying a group of representative asphalt molecules to model, (2) determining an atomistic modelling method that can effectively simulate the production of critical functional groups in oxidative ageing of hydrocarbons and (3) evaluating the oxidative-ageing pathway of a hydrocarbon system. The determination of oxidative-ageing pathway of hydrocarbons was done by tracking the generations of critical functional groups in the course of oxidative ageing. The chemical elements of carbon, nitrogen and sulphur all experience oxidative reactions, producing polarised functional groups such as ketones, aldehydes or carboxylic acids, pyrrolic groups and sulphoxides. The electrostatic forces of the polarised groups generated in oxidation are responsible for the behaviour of aged hydrocarbons. The developed AIMD model can be used for modelling the ageing of generic hydrocarbon polymers and developing antioxidants without running expensive experiments.

Nox control for high nitric oxide concentration flows through combustion-driven reduction

DOEpatents

Yeh, James T.; Ekmann, James M.; Pennline, Henry W.; Drummond, Charles J.

1989-01-01

An improved method for removing nitrogen oxides from concentrated waste gas streams, in which nitrogen oxides are ignited with a carbonaceous material in the presence of substoichiometric quantities of a primary oxidant, such as air. Additionally, reductants may be ignited along with the nitrogen oxides, carbonaceous material and primary oxidant to achieve greater reduction of nitrogen oxides. A scrubber and regeneration system may also be included to generate a concentrated stream of nitrogen oxides from flue gases for reduction using this method.

Antioxidant effects of statins in the management of cardiometabolic disorders.

PubMed

Lim, Soo; Barter, Philip

2014-01-01

Redox systems are key players in vascular health. A shift in redox homeostasis-that results in an imbalance between reactive oxygen species (ROS) generation and endogenous antioxidant defenses has the potential to create a state of oxidative stress that subsequently plays a role in the pathogenesis of a number of diseases, including those of the cardiovascular and metabolic system. Statins, which are primarily used to reduce the concentration of low-density lipoprotein cholesterol, have also been shown to reduce oxidative stress by modulating redox systems. Studies conducted both in vitro and in vivo support the role of oxidative stress in the development of atherosclerosis and cardiovascular diseases. Oxidative stress may also be responsible for various diabetic complications and the development of fatty liver. Statins reduce oxidative stress by blocking the generation of ROS and reducing the NAD+/NADH ratio. These drugs also have effects on nitric oxide synthase, lipid peroxidation and the adiponectin levels. It is possible that the antioxidant properties of statins contribute to their protective cardiovascular effects, independent of the lipid-lowering actions of these agents. However, possible adverse effects of statins on glucose homeostasis may be related to the redox system. Therefore, studies investigating the modulation of redox signaling by statins are warranted.

Single module pressurized fuel cell turbine generator system

DOEpatents

George, Raymond A.; Veyo, Stephen E.; Dederer, Jeffrey T.

2001-01-01

A pressurized fuel cell system (10), operates within a common pressure vessel (12) where the system contains fuel cells (22), a turbine (26) and a generator (98) where preferably, associated oxidant inlet valve (52), fuel inlet valve (56) and fuel cell exhaust valve (42) are outside the pressure vessel.

Self-Assembled Nano-energetic Gas Generators based on Bi2O3

NASA Astrophysics Data System (ADS)

Hobosyan, Mkhitar; Trevino, Tyler; Martirosyan, Karen

2012-10-01

Nanoenergetic Gas-Generators are formulations that rapidly release a large amount of gaseous products and generate a fast moving thermal wave. They are mainly based on thermite systems, which are pyrotechnic mixtures of metal powders (fuel- Al, Mg, etc.) and metal oxides (oxidizer, Bi2O3, Fe2O3, WO3, MoO3 etc.) that can generate an exothermic oxidation-reduction reaction referred to as a thermite reaction. A thermite reaction releases a large amount of energy and can generate rapidly extremely high temperatures. The intimate contact between the fuel and oxidizer can be enhanced by use of nano instead of micro particles. The contact area between oxidizer and metal particles depends from method of mixture preparation. In this work we utilize the self-assembly processes, which use the electrostatic forces to produce ordered and self-organized binary systems. In this process the intimate contact significantly enhances and gives the ability to build an energetic material in molecular level, which is crucial for thepressure discharge efficiency of nano-thermites. The DTA-TGA, Zeta-size analysis and FTIR technique were performed to characterize the Bi2O3 particles. The self-assembly of Aluminum and Bi2O3 was conducted in sonic bath with appropriate solvents and linkers. The resultant thermite pressure discharge values were tested in modified Parr reactor. In general, the self-assembled thermites give much higher-pressure discharge values than the thermites prepared with conventional roll-mixing technique.

Antioxidant properties of nicergoline; inhibition of brain auto-oxidation and superoxide production of neutrophils in rats.

PubMed

Tanaka, M; Yoshida, T; Okamoto, K; Hirai, S

1998-05-22

Oxidative stress has been suggested to adversely influence cerebrovascular disorders and some neurodegenerative disorders. We examined whether nicergoline, an agent widely used for treating cerebrovascular disorders and senile mental impairment, possesses antioxidant activities and some beneficial effect on neutrophils generating free radicals. Although nicergoline did not scavenge superoxide produced from a superoxide-generating system, it significantly inhibited superoxide secretion from stimulated neutrophils. Auto-oxidation of brain homogenate of rats, monitored by formation of thiobarbituric acid-reactive substances, was suppressed by nicergoline in a dose-dependent manner. The oxidation of the homogenate was accelerated by activated neutrophils and was significantly suppressed by nicergoline. These observations suggest that nicergoine is an antioxidant that inhibits not only lipid peroxidation but also free radical generation from neutrophils. These properties of nicergoline should be beneficial in some pathological conditions including cerebrovascular and neurodegenerative disorders in which oxidative stress may have a pathoetiological role.

Environmental factors and unhealthy lifestyle influence oxidative stress in humans--an overview.

PubMed

Aseervatham, G Smilin Bell; Sivasudha, T; Jeyadevi, R; Arul Ananth, D

2013-07-01

Oxygen is the most essential molecule for life; since it is a strong oxidizing agent, it can aggravate the damage within the cell by a series of oxidative events including the generation of free radicals. Antioxidative agents are the only defense mechanism to neutralize these free radicals. Free radicals are not only generated internally in our body system but also trough external sources like environmental pollution, toxic metals, cigarette smoke, pesticides, etc., which add damage to our body system. Inhaling these toxic chemicals in the environment has become unavoidable in modern civilization. Antioxidants of plant origin with free radical scavenging properties could have great importance as therapeutic agents in several diseases caused by environmental pollution. This review summarizes the generation of reactive oxygen species and damage to cells by exposure to external factors, unhealthy lifestyle, and role of herbal plants in scavenging these reactive oxygen species.

Advanced Polymer Systems for Defence Applications: Power Generation, Protection and Sensing

DTIC Science & Technology

2014-05-01

oxide nanoparticles synthesized via non-sol-gel methods, e.g., via a flame process; and, (d) Amine sensors based on silver nanoparticle- doped ...Hongmin Chen, Guodong Chen, Xiaohong Gu, James L. Lee, E. E. Abdel-Hady, Y. C. Jean. Free Volumes, Glass Transitions, and Cross-Links in Zinc Oxide ...properties in a system of zinc oxide (ZnO) nanoparticles (20 nm) dispersed in waterborne polyurethane (WBPU) were measured using positron annihilation

Inflammation, Oxidative Stress, and Obesity

PubMed Central

Fernández-Sánchez, Alba; Madrigal-Santillán, Eduardo; Bautista, Mirandeli; Esquivel-Soto, Jaime; Morales-González, Ángel; Esquivel-Chirino, Cesar; Durante-Montiel, Irene; Sánchez-Rivera, Graciela; Valadez-Vega, Carmen; Morales-González, José A.

2011-01-01

Obesity is a chronic disease of multifactorial origin and can be defined as an increase in the accumulation of body fat. Adipose tissue is not only a triglyceride storage organ, but studies have shown the role of white adipose tissue as a producer of certain bioactive substances called adipokines. Among adipokines, we find some inflammatory functions, such as Interleukin-6 (IL-6); other adipokines entail the functions of regulating food intake, therefore exerting a direct effect on weight control. This is the case of leptin, which acts on the limbic system by stimulating dopamine uptake, creating a feeling of fullness. However, these adipokines induce the production of reactive oxygen species (ROS), generating a process known as oxidative stress (OS). Because adipose tissue is the organ that secretes adipokines and these in turn generate ROS, adipose tissue is considered an independent factor for the generation of systemic OS. There are several mechanisms by which obesity produces OS. The first of these is the mitochondrial and peroxisomal oxidation of fatty acids, which can produce ROS in oxidation reactions, while another mechanism is over-consumption of oxygen, which generates free radicals in the mitochondrial respiratory chain that is found coupled with oxidative phosphorylation in mitochondria. Lipid-rich diets are also capable of generating ROS because they can alter oxygen metabolism. Upon the increase of adipose tissue, the activity of antioxidant enzymes such as superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx), was found to be significantly diminished. Finally, high ROS production and the decrease in antioxidant capacity leads to various abnormalities, among which we find endothelial dysfunction, which is characterized by a reduction in the bioavailability of vasodilators, particularly nitric oxide (NO), and an increase in endothelium-derived contractile factors, favoring atherosclerotic disease. PMID:21686173

Nitroaryl-1,4-dihydropyridines as antioxidants against rat liver microsomes oxidation induced by iron/ascorbate, nitrofurantoin and naphthalene.

PubMed

Letelier, María Eugenia; Entrala, Paz; López-Alarcón, Camilo; González-Lira, Víctor; Molina-Berríos, Alfredo; Cortés-Troncoso, Juan; Jara-Sandoval, José; Santander, Paola; Núñez-Vergara, Luis

2007-12-01

1,4-Dihydropyridines (DHPs) used in the treatment of cardiovascular diseases, are calcium channel antagonists and also antioxidant agents. These drugs are metabolized through cytochrome P(450) oxidative system, majority localized in the hepatic endoplasmic reticulum. Several lipophilic drugs generate oxidative stress to be metabolized by this cellular system. Thus, DHP antioxidant properties may prevent the oxidative stress associated with hepatic biotransformation of drugs. In this work, we tested the antioxidant capacity of several synthetic nitro-phenyl-DHPs. These compounds (I-IV) inhibited the microsomal lipid peroxidation, UDPGT oxidative activation and microsomal thiols oxidation; all phenomena induced by Fe(3+)/ascorbate, a generator system of oxygen free radicals. As the same manner, these compounds inhibited the oxygen consumption induced by Cu(2+)/ascorbate in the absence of microsomes. Furthermore, compound III (2,6-dimethyl-4-(4-nitrophenyl)-1,4-dihydropyridin-3,5-ethyl-dicarboxylate) and compound V (N-ethyl-2,6-dimethyl-4-(4-nitrophenyl)-1,4-dihydropyridin-3,5-methyl-dicarboxylate) inhibited the microsomal lipid peroxidation induced by Nitrofurantoin and naphthalene in the presence of NADPH. Oxidative stress induced on endoplasmic reticulum may alter the biotransformation of drugs, so, modifying their plasmatic concentrations and therapeutic effects. When drugs which are activated by biotransformation are administered together with antioxidant drugs, such as DHPs, oxidative stress induced in situ may be prevented.

Lipid oxidation in baked products: impact of formula and process on the generation of volatile compounds.

PubMed

Maire, Murielle; Rega, Barbara; Cuvelier, Marie-Elisabeth; Soto, Paola; Giampaoli, Pierre

2013-12-15

This paper investigates the effect of ingredients on the reactions occurring during the making of sponge cake and leading to the generation of volatile compounds related to flavour quality. To obtain systems sensitive to lipid oxidation (LO), a formulation design was applied varying the composition of fatty matter and eggs. Oxidation of polyunsaturated fatty acids (PUFA) and formation of related volatile compounds were followed at the different steps of cake-making. Optimised dynamic Solid Phase Micro Extraction was applied to selectively extract either volatile or semi-volatile compounds directly from the baking vapours. We show for the first time that in the case of alveolar baked products, lipid oxidation occurs very early during the step of dough preparation and to a minor extent during the baking process. The generation of lipid oxidation compounds depends on PUFA content and on the presence of endogenous antioxidants in the raw matter. Egg yolk seemed to play a double role on reactivity: protecting unsaturated lipids from oxidation and being necessary to generate a broad class of compounds of the Maillard reaction during baking and linked to the typical flavour of sponge cake. Copyright © 2013 Elsevier Ltd. All rights reserved.

Development of Residential SOFC Cogeneration System

NASA Astrophysics Data System (ADS)

Ono, Takashi; Miyachi, Itaru; Suzuki, Minoru; Higaki, Katsuki

2011-06-01

Since 2001 Kyocera has been developing 1kW class Solid Oxide Fuel Cell (SOFC) for power generation system. We have developed a cell, stack, module and system. Since 2004, Kyocera and Osaka Gas Co., Ltd. have been developed SOFC residential co-generation system. From 2007, we took part in the "Demonstrative Research on Solid Oxide Fuel Cells" Project conducted by New Energy Foundation (NEF). Total 57 units of 0.7kW class SOFC cogeneration systems had been installed at residential houses. In spite of residential small power demand, the actual electric efficiency was about 40%(netAC,LHV), and high CO2 reduction performance was achieved by these systems. Hereafter, new joint development, Osaka Gas, Toyota Motors, Kyocera and Aisin Seiki, aims early commercialization of residential SOFC CHP system.

Activation of Oxygen and Hydrogen Peroxide by Copper(II) Coupled with Hydroxylamine for Oxidation of Organic Contaminants.

PubMed

Lee, Hongshin; Lee, Hye-Jin; Seo, Jiwon; Kim, Hyung-Eun; Shin, Yun Kyung; Kim, Jae-Hong; Lee, Changha

2016-08-02

This study reports that the combination of Cu(II) with hydroxylamine (HA) (referred to herein as Cu(II)/HA system) in situ generates H2O2 by reducing dissolved oxygen, subsequently producing reactive oxidants through the reaction of Cu(I) with H2O2. The external supply of H2O2 to the Cu(II)/HA system (i.e., the Cu(II)/H2O2/HA system) was found to further enhance the production of reactive oxidants. Both the Cu(II)/HA and Cu(II)/H2O2/HA systems effectively oxidized benzoate (BA) at pH between 4 and 8, yielding a hydroxylated product, p-hydroxybenzoate (pHBA). The addition of a radical scavenger, tert-butyl alcohol, inhibited the BA oxidation in both systems. However, electron paramagnetic resonance (EPR) spectroscopy analysis indicated that (•)OH was not produced under either acidic or neutral pH conditions, suggesting that the alternative oxidant, cupryl ion (Cu(III)), is likely a dominant oxidant.

Ethanol generation, oxidation and energy production in a cooperative bioelectrochemical system.

PubMed

Pagnoncelli, Kamila C; Pereira, Andressa R; Sedenho, Graziela C; Bertaglia, Thiago; Crespilho, Frank N

2018-08-01

Integrating in situ biofuel production and energy conversion into a single system ensures the production of more robust networks as well as more renewable technologies. For this purpose, identifying and developing new biocatalysts is crucial. Herein, is reported a bioelectrochemical system consisting of alcohol dehydrogenase (ADH) and Saccharomyces cerevisiae, wherein both function cooperatively for ethanol production and its bioelectrochemical oxidation. Here, it is shown that it is possible to produce ethanol and use it as a biofuel in a tandem manner. The strategy is to employ flexible carbon fibres (FCF) electrode that could adsorb both the enzyme and the yeast cells. Glucose is used as a substrate for the yeast for the production of ethanol, while the enzyme is used to catalyse the oxidation of ethanol to acetaldehyde. Regarding the generation of reliable electricity based on electrochemical systems, the biosystem proposed in this study operates at a low temperature and ethanol production is proportional to the generated current. With further optimisation of electrode design, we envision the use of the cooperative biofuel cell for energy conversion and management of organic compounds. Copyright © 2018 Elsevier B.V. All rights reserved.

Hybrid propulsion technology program

NASA Technical Reports Server (NTRS)

1990-01-01

Technology was identified which will enable application of hybrid propulsion to manned and unmanned space launch vehicles. Two design concepts are proposed. The first is a hybrid propulsion system using the classical method of regression (classical hybrid) resulting from the flow of oxidizer across a fuel grain surface. The second system uses a self-sustaining gas generator (gas generator hybrid) to produce a fuel rich exhaust that was mixed with oxidizer in a separate combustor. Both systems offer cost and reliability improvement over the existing solid rocket booster and proposed liquid boosters. The designs were evaluated using life cycle cost and reliability. The program consisted of: (1) identification and evaluation of candidate oxidizers and fuels; (2) preliminary evaluation of booster design concepts; (3) preparation of a detailed point design including life cycle costs and reliability analyses; (4) identification of those hybrid specific technologies needing improvement; and (5) preperation of a technology acquisition plan and large scale demonstration plan.

Neutrophil-generated oxidative stress and protein damage in Staphylococcus aureus

PubMed Central

Beavers, William N.; Skaar, Eric P.

2016-01-01

Staphylococcus aureus is a ubiquitous, versatile and dangerous pathogen. It colonizes over 30% of the human population, and is one of the leading causes of death by an infectious agent. During S. aureus colonization and invasion, leukocytes are recruited to the site of infection. To combat S. aureus, leukocytes generate an arsenal of reactive species including superoxide, hydrogen peroxide, nitric oxide and hypohalous acids that modify and inactivate cellular macromolecules, resulting in growth defects or death. When S. aureus colonization cannot be cleared by the immune system, antibiotic treatment is necessary and can be effective. Yet, this organism quickly gains resistance to each new antibiotic it encounters. Therefore, it is in the interest of human health to acquire a deeper understanding of how S. aureus evades killing by the immune system. Advances in this field will have implications for the design of future S. aureus treatments that complement and assist the host immune response. In that regard, this review focuses on how S. aureus avoids host-generated oxidative stress, and discusses the mechanisms used by S. aureus to survive oxidative damage including antioxidants, direct repair of damaged proteins, sensing oxidant stress and transcriptional changes. This review will elucidate areas for studies to identify and validate future antimicrobial targets. PMID:27354296

Jet fuel based high pressure solid oxide fuel cell system

NASA Technical Reports Server (NTRS)

Gummalla, Mallika (Inventor); Yamanis, Jean (Inventor); Olsommer, Benoit (Inventor); Dardas, Zissis (Inventor); Bayt, Robert (Inventor); Srinivasan, Hari (Inventor); Dasgupta, Arindam (Inventor); Hardin, Larry (Inventor)

2013-01-01

A power system for an aircraft includes a solid oxide fuel cell system which generates electric power for the aircraft and an exhaust stream; and a heat exchanger for transferring heat from the exhaust stream of the solid oxide fuel cell to a heat requiring system or component of the aircraft. The heat can be transferred to fuel for the primary engine of the aircraft. Further, the same fuel can be used to power both the primary engine and the SOFC. A heat exchanger is positioned to cool reformate before feeding to the fuel cell. SOFC exhaust is treated and used as inerting gas. Finally, oxidant to the SOFC can be obtained from the aircraft cabin, or exterior, or both.

Jet Fuel Based High Pressure Solid Oxide Fuel Cell System

NASA Technical Reports Server (NTRS)

Srinivasan, Hari (Inventor); Hardin, Larry (Inventor); Gummalla, Mallika (Inventor); Yamanis, Jean (Inventor); Olsommer, Benoit (Inventor); Dardas, Zissis (Inventor); Dasgupta, Arindam (Inventor); Bayt, Robert (Inventor)

2015-01-01

A power system for an aircraft includes a solid oxide fuel cell system which generates electric power for the aircraft and an exhaust stream; and a heat exchanger for transferring heat from the exhaust stream of the solid oxide fuel cell to a heat requiring system or component of the aircraft. The heat can be transferred to fuel for the primary engine of the aircraft. Further, the same fuel can be used to power both the primary engine and the SOFC. A heat exchanger is positioned to cool reformate before feeding to the fuel cell. SOFC exhaust is treated and used as inerting gas. Finally, oxidant to the SOFC can be obtained from the aircraft cabin, or exterior, or both.

Glyphosate-induced oxidative stress in Arabidopsis thaliana affecting peroxisomal metabolism and triggers activity in the oxidative phase of the pentose phosphate pathway (OxPPP) involved in NADPH generation.

PubMed

de Freitas-Silva, Larisse; Rodríguez-Ruiz, Marta; Houmani, Hayet; da Silva, Luzimar Campos; Palma, José M; Corpas, Francisco J

2017-11-01

Glyphosate is a broad-spectrum systemic herbicide used worldwide. In susceptible plants, glyphosate affects the shikimate pathway and reduces aromatic amino acid synthesis. Using Arabidopsis seedlings grown in the presence of 20μM glyphosate, we analyzed H 2 O 2 , ascorbate, glutathione (GSH) and protein oxidation content as well as antioxidant catalase, superoxide dismutase (SOD) and ascorbate-glutathione cycle enzyme activity. We also examined the principal NADPH-generating system components, including glucose-6-phosphate dehydrogenase (G6PDH), 6-phosphogluconate dehydrogenase (6PGDH), NADP-malic enzyme (NADP-ME) and NADP-isocitrate dehydrogenase (NADP-ICDH). Glyphosate caused a drastic reduction in growth parameters and an increase in protein oxidation. The herbicide also resulted in an overall increase in GSH content, antioxidant enzyme activity (catalase and all enzymatic components of the ascorbate-glutathione cycle) in addition to the two oxidative phase enzymes, G6PDH and 6PGDH, in the pentose phosphate pathway involved in NADPH generation. In this study, we provide new evidence on the participation of G6PDH and 6PGDH in the response to oxidative stress induced by glyphosate in Arabidopsis, in which peroxisomal enzymes, such as catalase and glycolate oxidase, are positively affected. We suggest that the NADPH provided by the oxidative phase of the pentose phosphate pathway (OxPPP) should serve to maintain glutathione reductase (GR) activity, thus preserving and regenerating the intracellular GSH pool under glyphosate-induced stress. It is particularly remarkable that the 6PGDH activity was unaffected by pro-oxidant and nitrating molecules such as H 2 0 2 , nitric oxide or peroxynitrite. Copyright © 2017 Elsevier GmbH. All rights reserved.

DB Riley-low emission boiler system (LEBS): Superior power for the 21st century

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

Beittel, R.; Ruth, L.A.

1997-12-31

In conjunction with the US Department of Energy, DB Riley, Inc., is developing a highly advanced coal-fired power-generation plant called the Low Emission Boiler Systems (LEBS). By the year 2000, LEBS will provide the US electric power industry with a reliable, efficient, cost-effective, environmentally superior alternative to current technologies. LEBS incorporates significant advances in coal combustion, supercritical steam boiler design, environmental control, and materials development. The system will include a state-of-the-art steam cycle operating at supercritical steam conditions; a slagging combustor that produces vitrified ash by-products; low nitrogen oxide (NOx) burners; a new, dry, regenerable flue gas cleanup system (coppermore » oxide process) for simultaneously capturing sulfur dioxide (SO{sub 2}) and nitrogen oxides (NOx); a pulse-jet fabric filter for particulate capture; and a low-temperature heat-recovery system. The copper oxide flue gas cleanup system, which has been under development at DOE`s Pittsburgh field center, removes over 98% of SO{sub 2} and 95% of NOx from flue gas. A new moving-bed design provides efficient sorbent utilization that lowers the cleanup process cost. The captured SO{sub 2} can be converted to valuable by-products such as sulfuric acid and/or element sulfur, and the process generates no waste.« less

Analysis and performance assessment of a new solar-based multigeneration system integrated with ammonia fuel cell and solid oxide fuel cell-gas turbine combined cycle

NASA Astrophysics Data System (ADS)

Siddiqui, Osamah; Dincer, Ibrahim

2017-12-01

In the present study, a new solar-based multigeneration system integrated with an ammonia fuel cell and solid oxide fuel cell-gas turbine combined cycle to produce electricity, hydrogen, cooling and hot water is developed for analysis and performance assessment. In this regard, thermodynamic analyses and modeling through both energy and exergy approaches are employed to assess and evaluate the overall system performance. Various parametric studies are conducted to study the effects of varying system parameters and operating conditions on the energy and exergy efficiencies. The results of this study show that the overall multigeneration system energy efficiency is obtained as 39.1% while the overall system exergy efficiency is calculated as 38.7%, respectively. The performance of this multigeneration system results in an increase of 19.3% in energy efficiency as compared to single generation system. Furthermore, the exergy efficiency of the multigeneration system is 17.8% higher than the single generation system. Moreover, both energy and exergy efficiencies of the solid oxide fuel cell-gas turbine combined cycle are determined as 68.5% and 55.9% respectively.

Effects of reactive oxygen species and interplay of antioxidants during physical exercise in skeletal muscles.

PubMed

Thirupathi, Anand; Pinho, Ricardo A

2018-05-01

A large number of researches have led to a substantial growth of knowledge about exercise and oxidative stress. Initial investigations reported that physical exercise generates free radical-mediated damages to cells; however, in recent years, studies have shown that regular exercise can upregulate endogenous antioxidants and reduce oxidative damage. Yet, strenuous exercise perturbs the antioxidant system by increasing the reactive oxygen species (ROS) content. These alterations in the cellular environment seem to occur in an exercise type-dependent manner. The source of ROS generation during exercise is debatable, but now it is well established that both contracting and relaxing skeletal muscles generate reactive oxygen species and reactive nitrogen species. In particular, exercises of higher intensity and longer duration can cause oxidative damage to lipids, proteins, and nucleotides in myocytes. In this review, we summarize the ROS effects and interplay of antioxidants in skeletal muscle during physical exercise. Additionally, we discuss how ROS-mediated signaling influences physical exercise in antioxidant system.

Development of a Catalytic Wet Air Oxidation Method to Produce Feedstock Gases from Waste Polymers

NASA Technical Reports Server (NTRS)

Kulis, Michael J.; Guerrero-Medina, Karen J.; Hepp, Aloysius F.

2012-01-01

Given the high cost of space launch, the repurposing of biological and plastic wastes to reduce the need for logistical support during long distance and long duration space missions has long been recognized as a high priority. Described in this paper are the preliminary efforts to develop a wet air oxidation system in order to produce fuels from waste polymers. Preliminary results of partial oxidation in near supercritical water conditions are presented. Inherent corrosion and salt precipitation are discussed as system design issues for a thorough assessment of a second generation wet air oxidation system. This work is currently being supported by the In-Situ Resource Utilization Project.

A strategy for the prevention of protein oxidation by drug product in polymer-based syringes.

PubMed

Nakamura, Koji; Abe, Yoshihiko; Kiminami, Hideaki; Yamashita, Arisa; Iwasaki, Kazuhiro; Suzuki, Shigeru; Yoshino, Keisuke; Dierick, William; Constable, Kevin

2015-01-01

Recently, new and advanced ideas have been presented on the value of polymer-based syringes for improved safety, better strength, reduced aggregation, and the prevention of drug degradation. In this report, our findings on drug degradation from protein oxidation will be presented and discussed. Commonly, dissolved oxygen is one of the factors for causing protein degradation. Due to the nature of higher gas permeability in polymer-based syringes, it was thought to be difficult to control the oxygen level during storage. However, this report demonstrates the appropriateness of combining the use of an oxygen absorber within the secondary packaging as a deoxygenated packaging system. In addition, this report suggests that another factor to enhance protein oxidization is related to radicals on the syringe barrel from sterilization by irradiation. We demonstrate that steam sterilization can minimize protein oxidization, as the protein filled in steam sterilized syringe is much more stable. In conclusion, the main oxidation pathway of a protein has been identified as dissolved oxygen and radical generation within a polymer container. Possible solutions are herewith presented for controlling oxidation by means of applying a deoxygenated packaging system as well as utilizing steam sterilization as a method of sterilization for prefillable polymer syringes. There have been many presentations and discussions about the risks associated with glass prefilled syringes. Advanced ideas are being presented on the value of polymer-based syringes for improved safety, better strength, reduced protein aggregation, and the prevention of drug degradation. Drug degradation based on protein oxidation is discussed in this report. Identification of the main factors causing this degradation and possible solutions available by using polymer-based syringes will be presented. The causes of protein oxidation have been identified as dissolved oxygen and radicals generated by the applied method of sterilization. The oxidation reaction created by dissolved oxygen within the drug product can be effectively inhibited by controlling the removal of the oxygen through the use of a deoxygenated packaging system. This packaging system can control the level or complete removal of oxygen from the primary container and the secondary packaging system. Protein oxidation induced by the formation of radicals from sterilization by irradiation is another critical aspect where it was thought that various sterilization methods were acceptable without loosing drug product quality. However, this report is first to demonstrate that gamma sterilized polymer-based syringes accelerated protein oxidation by radical generation; this effect can be prevented by means of steam sterilization. © PDA, Inc. 2015.

Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide.

PubMed

Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

2015-12-18

Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants.

Process for light-driven hydrocarbon oxidation at ambient temperatures

DOEpatents

Shelnutt, John A.

1990-01-01

A photochemical reaction for the oxidation of hydrocarbons uses molecular oxygen as the oxidant. A reductive photoredox cycle that uses a tin(IV)- or antimony(V)-porphyrin photosensitizer generates the reducing equivalents required to activate oxygen. This artificial photosynthesis system drives a catalytic cycle, which mimics the cytochrome P.sub.450 reaction, to oxidize hydrocarbons. An iron(III)- or manganese(III)-porphyrin is used as the hydrocarbon-oxidation catalyst. Methylviologen can be used as a redox relay molecule to provide for electron-transfer from the reduced photosensitizer to the Fe or Mn porphyrin. The system is long-lived and may be used in photo-initiated spectroscopic studies of the reaction to determine reaction rates and intermediates.

A self-improved water-oxidation catalyst: is one site really enough?

PubMed

López, Isidoro; Ertem, Mehmed Z; Maji, Somnath; Benet-Buchholz, Jordi; Keidel, Anke; Kuhlmann, Uwe; Hildebrandt, Peter; Cramer, Christopher J; Batista, Victor S; Llobet, Antoni

2014-01-03

The homogeneous catalysis of water oxidation by transition-metal complexes has experienced spectacular development over the last five years. Practical energy-conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water-oxidation catalyst that is generated by self-assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water-oxidation catalyst that does not decompose over extended periods of time. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perovskite electrodes and method of making the same

DOEpatents

Seabaugh, Matthew M [Columbus, OH; Swartz, Scott L [Columbus, OH

2009-09-22

The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

Perovskite electrodes and method of making the same

DOEpatents

Seabaugh, Matthew M.; Swartz, Scott L.

2005-09-20

The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

Major design issues of molten carbonate fuel cell power generation unit

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

Chen, T.P.

1996-04-01

In addition to the stack, a fuel cell power generation unit requires fuel desulfurization and reforming, fuel and oxidant preheating, process heat removal, waste heat recovery, steam generation, oxidant supply, power conditioning, water supply and treatment, purge gas supply, instrument air supply, and system control. These support facilities add considerable cost and system complexity. Bechtel, as a system integrator of M-C Power`s molten carbonate fuel cell development team, has spent substantial effort to simplify and minimize these supporting facilities to meet cost and reliability goals for commercialization. Similiar to other fuels cells, MCFC faces design challenge of how to complymore » with codes and standards, achieve high efficiency and part load performance, and meanwhile minimize utility requirements, weight, plot area, and cost. However, MCFC has several unique design issues due to its high operating temperature, use of molten electrolyte, and the requirement of CO2 recycle.« less

Engine-integrated solid oxide fuel cells for efficient electrical power generation on aircraft

NASA Astrophysics Data System (ADS)

Waters, Daniel F.; Cadou, Christopher P.

2015-06-01

This work investigates the use of engine-integrated catalytic partial oxidation (CPOx) reactors and solid oxide fuel cells (SOFCs) to reduce fuel burn in vehicles with large electrical loads like sensor-laden unmanned air vehicles. Thermodynamic models of SOFCs, CPOx reactors, and three gas turbine (GT) engine types (turbojet, combined exhaust turbofan, separate exhaust turbofan) are developed and checked against relevant data and source material. Fuel efficiency is increased by 4% and 8% in the 50 kW and 90 kW separate exhaust turbofan systems respectively at only modest cost in specific power (8% and 13% reductions respectively). Similar results are achieved in other engine types. An additional benefit of hybridization is the ability to provide more electric power (factors of 3 or more in some cases) than generator-based systems before encountering turbine inlet temperature limits. A sensitivity analysis shows that the most important parameters affecting the system's performance are operating voltage, percent fuel oxidation, and SOFC assembly air flows. Taken together, this study shows that it is possible to create a GT-SOFC hybrid where the GT mitigates balance of plant losses and the SOFC raises overall system efficiency. The result is a synergistic system with better overall performance than stand-alone components.

Reversible solid oxide fuel cell for natural gas/renewable hybrid power generation systems

NASA Astrophysics Data System (ADS)

Luo, Yu; Shi, Yixiang; Zheng, Yi; Cai, Ningsheng

2017-02-01

Renewable energy (RE) is expected to be the major part of the future energy. Presently, the intermittence and fluctuation of RE lead to the limitation of its penetration. Reversible solid oxide fuel cell (RSOFC) as the energy storage device can effectively store the renewable energy and build a bidirectional connection with natural gas (NG). In this paper, the energy storage strategy was designed to improve the RE penetration and dynamic operation stability in a distributed system coupling wind generators, internal combustion engine, RSOFC and lithium-ion batteries. By compromising the relative deviation of power supply and demand, RE penetration, system efficiency and capacity requirement, the strategy that no more than 36% of the maximum wind power output is directly supplied to users and the other is stored by the combination of battery and reversible solid oxide fuel cell is optimal for the distributed system. In the case, the RE penetration reached 56.9% and the system efficiency reached 55.2%. The maximum relative deviation of power supply and demand is also lower than 4%, which is significantly superior to that in the wind curtailment case.

Effects of fuel processing methods on industrial scale biogas-fuelled solid oxide fuel cell system for operating in wastewater treatment plants

NASA Astrophysics Data System (ADS)

Farhad, Siamak; Yoo, Yeong; Hamdullahpur, Feridun

The performance of three solid oxide fuel cell (SOFC) systems, fuelled by biogas produced through anaerobic digestion (AD) process, for heat and electricity generation in wastewater treatment plants (WWTPs) is studied. Each system has a different fuel processing method to prevent carbon deposition over the anode catalyst under biogas fuelling. Anode gas recirculation (AGR), steam reforming (SR), and partial oxidation (POX) are the methods employed in systems I-III, respectively. A planar SOFC stack used in these systems is based on the anode-supported cells with Ni-YSZ anode, YSZ electrolyte and YSZ-LSM cathode, operated at 800 °C. A computer code has been developed for the simulation of the planar SOFC in cell, stack and system levels and applied for the performance prediction of the SOFC systems. The key operational parameters affecting the performance of the SOFC systems are identified. The effect of these parameters on the electrical and CHP efficiencies, the generated electricity and heat, the total exergy destruction, and the number of cells in SOFC stack of the systems are studied. The results show that among the SOFC systems investigated in this study, the AGR and SR fuel processor-based systems with electrical efficiency of 45.1% and 43%, respectively, are suitable to be applied in WWTPs. If the entire biogas produced in a WWTP is used in the AGR or SR fuel processor-based SOFC system, the electricity and heat required to operate the WWTP can be completely self-supplied and the extra electricity generated can be sold to the electrical grid.

Inhaled Diesel Emissions Generated with Cerium Oxide Nanoparticle Fuel Additive Induce Adverse Pulmonary and Systemic Effects

EPA Science Inventory

Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe res...

NITROUS OXIDE BEHAVIOR IN THE ATMOSPHERE, AND IN COMBUSTION AND INDUSTRIAL SYSTEMS

EPA Science Inventory

Tropospheric measurements show that nitrous oxide (N2O) concentrations are increasing over time. This demonstrates the existence of one or more significant anthropogenic sources, a fact that has generated considerable research interest over the last several years. The debate has ...

Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

NASA Technical Reports Server (NTRS)

Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

1992-01-01

The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

Effect of calcium oxide on the efficiency of ferrous ion oxidation and total iron precipitation during ferrous ion oxidation in simulated acid mine drainage treatment with inoculation of Acidithiobacillus ferrooxidans.

PubMed

Liu, Fenwu; Zhou, Jun; Jin, Tongjun; Zhang, Shasha; Liu, Lanlan

2016-01-01

Calcium oxide was added into ferrous ion oxidation system in the presence of Acidithiobacillus ferrooxidans at concentrations of 0-4.00 g/L. The pH, ferrous ion oxidation efficiency, total iron precipitation efficiency, and phase of the solid minerals harvested from different treatments were investigated during the ferrous ion oxidation process. In control check (CK) system, pH of the solution decreased from 2.81 to 2.25 when ferrous ions achieved complete oxidation after 72 h of Acidithiobacillus ferrooxidans incubation without the addition of calcium oxide, and total iron precipitation efficiency reached 20.2%. Efficiency of ferrous ion oxidation and total iron precipitation was significantly improved when the amount of calcium oxide added was ≤1.33 g/L, and the minerals harvested from systems were mainly a mixture of jarosite and schwertmannite. For example, the ferrous ion oxidation efficiency reached 100% at 60 h and total iron precipitation efficiency was increased to 32.1% at 72 h when 1.33 g/L of calcium oxide was added. However, ferrous ion oxidation and total iron precipitation for jarosite and schwertmannite formation were inhibited if the amount of calcium oxide added was above 2.67 g/L, and large amounts of calcium sulfate dihydrate were generated in systems.

Hydrogen Peroxide Sensing and Signaling by Protein Kinases in the Cardiovascular System

PubMed Central

Burgoyne, Joseph R.; Oka, Shin-ichi; Ale-Agha, Niloofar

2013-01-01

Abstract Significance: Oxidants were once principally considered perpetrators of injury and disease. However, this has become an antiquated view, with cumulative evidence showing that the oxidant hydrogen peroxide serves as a signaling molecule. Hydrogen peroxide carries vital information about the redox state of the cell and is crucial for homeostatic regulation during health and adaptation to stress. Recent Advances: In this review, we examine the contemporary concepts for how hydrogen peroxide is sensed and transduced into a biological response by introducing post-translational oxidative modifications on select proteins. Oxidant sensing and signaling by kinases are of particular importance as they integrate oxidant signals into phospho-regulated pathways. We focus on CAMKII, PKA, and PKG, kinases whose redox regulation has notable impact on cardiovascular function. Critical Issues: In addition, we examine the mechanism for regulating intracellular hydrogen peroxide, considering the net concentrations that may accumulate. The effects of endogenously generated oxidants are often modeled by applying exogenous hydrogen peroxide to cells or tissues. Here we consider whether model systems exposed to exogenous hydrogen peroxide have relevance to systems where the oxidant is generated endogenously, and if so, what concentration can be justified in terms of relevance to health and disease. Future Directions: Improving our understanding of hydrogen peroxide signaling and the sensor proteins that it can modify will help us develop new strategies to regulate intracellular signaling to prevent disease. Antioxid. Redox Signal. 18, 1042–1052. PMID:22867279

Cell-delivered magnetic nanoparticles caused hyperthermia-mediated increased survival in a murine pancreatic cancer model.

PubMed

Basel, Matthew T; Balivada, Sivasai; Wang, Hongwang; Shrestha, Tej B; Seo, Gwi Moon; Pyle, Marla; Abayaweera, Gayani; Dani, Raj; Koper, Olga B; Tamura, Masaaki; Chikan, Viktor; Bossmann, Stefan H; Troyer, Deryl L

2012-01-01

Using magnetic nanoparticles to absorb alternating magnetic field energy as a method of generating localized hyperthermia has been shown to be a potential cancer treatment. This report demonstrates a system that uses tumor homing cells to actively carry iron/iron oxide nanoparticles into tumor tissue for alternating magnetic field treatment. Paramagnetic iron/ iron oxide nanoparticles were synthesized and loaded into RAW264.7 cells (mouse monocyte/ macrophage-like cells), which have been shown to be tumor homing cells. A murine model of disseminated peritoneal pancreatic cancer was then generated by intraperitoneal injection of Pan02 cells. After tumor development, monocyte/macrophage-like cells loaded with iron/ iron oxide nanoparticles were injected intraperitoneally and allowed to migrate into the tumor. Three days after injection, mice were exposed to an alternating magnetic field for 20 minutes to cause the cell-delivered nanoparticles to generate heat. This treatment regimen was repeated three times. A survival study demonstrated that this system can significantly increase survival in a murine pancreatic cancer model, with an average post-tumor insertion life expectancy increase of 31%. This system has the potential to become a useful method for specifically and actively delivering nanoparticles for local hyperthermia treatment of cancer.

Curcumin targeting the thioredoxin system elevates oxidative stress in HeLa cells

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

Cai, Wenqing; Zhang, Baoxin; Duan, Dongzhu

2012-08-01

The thioredoxin system, composed of thioredoxin reductase (TrxR), thioredoxin (Trx), and NADPH, is ubiquitous in all cells and involved in many redox-dependent signaling pathways. Curcumin, a naturally occurring pigment that gives a specific yellow color in curry food, is consumed in normal diet up to 100 mg per day. This molecule has also been used in traditional medicine for the treatment of a variety of diseases. Curcumin has numerous biological functions, and many of these functions are related to induction of oxidative stress. However, how curcumin elicits oxidative stress in cells is unclear. Our previous work has demonstrated the waymore » by which curcumin interacts with recombinant TrxR1 and alters the antioxidant enzyme into a reactive oxygen species (ROS) generator in vitro. Herein we reported that curcumin can target the cytosolic/nuclear thioredoxin system to eventually elevate oxidative stress in HeLa cells. Curcumin-modified TrxR1 dose-dependently and quantitatively transfers electrons from NADPH to oxygen with the production of ROS. Also, curcumin can drastically down-regulate Trx1 protein level as well as its enzyme activity in HeLa cells, which in turn remarkably decreases intracellular free thiols, shifting the intracellular redox balance to a more oxidative state, and subsequently induces DNA oxidative damage. Furthermore, curcumin-pretreated HeLa cells are more sensitive to oxidative stress. Knockdown of TrxR1 sensitizes HeLa cells to curcumin cytotoxicity, highlighting the physiological significance of targeting TrxR1 by curcumin. Taken together, our data disclose a previously unrecognized prooxidant mechanism of curcumin in cells, and provide a deep insight in understanding how curcumin works in vivo. -- Highlights: ► Curcumin induces oxidative stress by targeting the thioredoxin system. ► Curcumin-modified TrxR quantitatively oxidizes NADPH to generate ROS. ► Knockdown of TrxR1 augments curcumin's cytotoxicity in HeLa cells. ► Curcumin sensitizes HeLa cells to oxidative stress.« less

Clinical Perspective of Oxidative Stress in Sporadic ALS

PubMed Central

D’Amico, Emanuele; Factor-Litvak, Pam; Santella, Regina M.; Mitsumoto, Hiroshi

2013-01-01

Sporadic amyotrophic lateral sclerosis (sALS) is one of the most devastating neurological diseases; most patients die within 3 to 4 years after symptom onset. Oxidative stress is a disturbance in the pro-oxidative/anti-oxidative balance favoring the pro-oxidative state. Autopsy and laboratory studies in ALS indicate that oxidative stress plays a major role in motor neuron degeneration and astrocyte dysfunction. Oxidative stress biomarkers in cerebrospinal fluid, plasma, and urine, are elevated, suggesting that abnormal oxidative stress is generated outside of the central nervous system. Our review indicates that agricultural chemicals, heavy metals, military service, professional sports, excessive physical exertion, chronic head trauma, and certain foods might be modestly associated with ALS risk, with a stronger association between risk and smoking. At the cellular level, these factors are all involved in generating oxidative stress. Experimental studies indicate that a combination of insults that induce modest oxidative stress can exert additive deleterious effects on motor neurons, suggesting multiple exposures in real-world environments are important. As the disease progresses, nutritional deficiency, cachexia, psychological stress, and impending respiratory failure may further increase oxidative stress. Moreover, accumulating evidence suggests that ALS is possibly a systemic disease. Laboratory, pathologic, and epidemiologic evidence clearly support the hypothesis that oxidative stress is central in the pathogenic process, particularly in genetically susceptive individuals. If we are to improve ALS treatment, well-designed biochemical and genetic epidemiological studies, combined with a multidisciplinary research approach, are needed and will provide knowledge crucial to our understanding of ALS etiology, pathophysiology, and prognosis. PMID:23797033

Multi-generation chemical aging of α-pinene ozonolysis products by reactions with OH

NASA Astrophysics Data System (ADS)

Wang, Ningxin; Kostenidou, Evangelia; Donahue, Neil M.; Pandis, Spyros N.

2018-03-01

Secondary organic aerosol (SOA) formation from volatile organic compounds (VOCs) in the atmosphere can be thought of as a succession of oxidation steps. The production of later-generation SOA via continued oxidation of the first-generation products is defined as chemical aging. This study investigates aging in the α-pinene ozonolysis system with hydroxyl radicals (OH) through smog chamber experiments. The first-generation α-pinene ozonolysis products were allowed to react further with OH formed via HONO photolysis. After an equivalent of 2-4 days of typical atmospheric oxidation conditions, homogeneous OH oxidation of the α-pinene ozonolysis products resulted in a 20-40 % net increase in the SOA for the experimental conditions used in this work. A more oxygenated product distribution was observed after aging based on the increase in aerosol atomic oxygen-to-carbon ratio (O : C) by up to 0.04. Experiments performed at intermediate relative humidity (RH) of 50 % showed no significant difference in additional SOA formation during aging compared to those performed at a low RH of less than 20 %.

HMGB1 redox during sepsis.

PubMed

Abdulmahdi, Wasan; Patel, Devika; Rabadi, May M; Azar, Tala; Jules, Edson; Lipphardt, Mark; Hashemiyoon, Rameen; Ratliff, Brian B

2017-10-01

During sepsis, the alarmin HMGB1 is released from tissues and promotes systemic inflammation that results in multi-organ damage, with the kidney particularly susceptible to injury. The severity of inflammation and pro-damage signaling mediated by HMGB1 appears to be dependent on the alarmin's redox state. Therefore, we examined HMGB1 redox in kidney cells during sepsis. Using intravital microscopy, CellROX labeling of kidneys in live mice indicated increased ROS generation in the kidney perivascular endothelium and tubules during lipopolysaccharide (LPS)-induced sepsis. Subsequent CellROX and MitoSOX labeling of LPS-stressed endothelial and kidney proximal tubule cells demonstrated increased ROS generation in these cells as sepsis worsens. Consequently, HMGB1 oxidation increased in the cytoplasm of kidney cells during its translocation from the nucleus to the circulation, with the degree of oxidation dependent on the severity of sepsis, as measured in in vivo mouse samples using a thiol assay and mass spectrometry (LC-MS/MS). The greater the oxidation of HMGB1, the greater the ability of the alarmin to stimulate pro-inflammatory cyto-/chemokine release (measured by Luminex Multiplex) and alter mitochondrial ATP generation (Luminescent ATP Detection Assay). Administration of glutathione and thioredoxin inhibitors to cell cultures enhanced HMGB1 oxidation during sepsis in endothelial and proximal tubule cells, respectively. In conclusion, as sepsis worsens, ROS generation and HMGB1 oxidation increases in kidney cells, which enhances HMGB1's pro-inflammatory signaling. Conversely, the glutathione and thioredoxin systems work to maintain the protein in its reduced state. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Environmentally persistent free radicals amplify ultrafine particle mediated cellular oxidative stress and cytotoxicity

PubMed Central

Balakrishna, Shrilatha; Lomnicki, Slawo; McAvey, Kevin M; Cole, Richard B; Dellinger, Barry; Cormier, Stephania A

2009-01-01

Background Combustion generated particulate matter is deposited in the respiratory tract and pose a hazard to the lungs through their potential to cause oxidative stress and inflammation. We have previously shown that combustion of fuels and chlorinated hydrocarbons produce semiquinone-type radicals that are stabilized on particle surfaces (i.e. environmentally persistent free radicals; EPFRs). Because the composition and properties of actual combustion-generated particles are complex, heterogeneous in origin, and vary from day-to-day, we have chosen to use surrogate particle systems. In particular, we have chosen to use the radical of 2-monochlorophenol (MCP230) as the EPFR because we have previously shown that it forms a EPFR on Cu(II)O surfaces and catalyzes formation of PCDD/F. To understand the physicochemical properties responsible for the adverse pulmonary effects of combustion by-products, we have exposed human bronchial epithelial cells (BEAS-2B) to MCP230 or the CuO/silica substrate. Our general hypothesis was that the EPFR-containing particle would have greater toxicity than the substrate species. Results Exposure of BEAS-2B cells to our combustion generated particle systems significantly increased reactive oxygen species (ROS) generation and decreased cellular antioxidants resulting in cell death. Resveratrol treatment reversed the decline in cellular glutathione (GSH), glutathione peroxidase (GPx), and superoxide dismutase (SOD) levels for both types of combustion-generated particle systems. Conclusion The enhanced cytotoxicity upon exposure to MCP230 correlated with its ability to generate more cellular oxidative stress and concurrently reduce the antioxidant defenses of the epithelial cells (i.e. reduced GSH, SOD activity, and GPx). The EPFRs in MCP230 also seem to be of greater biological concern due to their ability to induce lipid peroxidation. These results are consistent with the oxidizing nature of the CuO/silica ultrafine particles and the reducing nature and prolonged environmental and biological lifetimes of the EPFRs in MCP230. PMID:19374750

Oxidation of Levafix CA reactive azo-dyes in industrial wastewater of textile dyeing by electro-generated Fenton's reagent.

PubMed

El-Desoky, Hanaa S; Ghoneim, Mohamed M; El-Sheikh, Ragaa; Zidan, Naglaa M

2010-03-15

The indirect electrochemical removal of pollutants from effluents has become an attractive method in recent years. Removal (decolorization and mineralization) of Levafix Blue CA and Levafix Red CA reactive azo-dyes from aqueous media by electro-generated Fenton's reagent (Fe(2+)/H(2)O(2)) using a reticulated vitreous carbon cathode and a platinum gauze anode was optimized. Progress of oxidation (decolorization and mineralization) of the investigated azo-dyes with time of electro-Fenton's reaction was monitored by UV-visible absorbance measurements, Chemical oxygen demand (COD) removal and HPLC analysis. The results indicated that the electro-Fenton's oxidation system is efficient for treatment of such types of reactive dyes. Oxidation of each of the investigated azo-dyes by electro-generated Fenton's reagent up to complete decolorization and approximately 90-95% mineralization was achieved. Moreover, the optimized electro-Fenton's oxidation was successfully applied for complete decolorization and approximately 85-90% mineralization of both azo-dyes in real industrial wastewater samples collected from textile dyeing house at El-Mahalla El-Kobra, Egypt. (c) 2009 Elsevier B.V. All rights reserved.

Oxygen-producing inert anodes for SOM process

DOEpatents

Pal, Uday B

2014-02-25

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

Antioxidant properties of xanthones from Calophyllum brasiliense: prevention of oxidative damage induced by FeSO₄.

PubMed

Blanco-Ayala, Tonali; Lugo-Huitrón, Rafael; Serrano-López, Elizabeth M; Reyes-Chilpa, Ricardo; Rangel-López, Edgar; Pineda, Benjamín; Medina-Campos, Omar Noel; Sánchez-Chapul, Laura; Pinzón, Enrique; Cristina, Trejo-Solis; Silva-Adaya, Daniela; Pedraza-Chaverrí, José; Ríos, Camilo; de la Cruz, Verónica Pérez; Torres-Ramos, Mónica

2013-10-11

Reactive oxygen species (ROS) are important mediators in a number of degenerative diseases. Oxidative stress refers to the imbalance between the production of ROS and the ability to scavenge these species through endogenous antioxidant systems. Since antioxidants can inhibit oxidative processes, it becomes relevant to describe natural compounds with antioxidant properties which may be designed as therapies to decrease oxidative damage and stimulate endogenous cytoprotective systems. The present study tested the protective effect of two xanthones isolated from the heartwood of Calophyllum brasilienses against FeSO₄-induced toxicity. Through combinatory chemistry assays, we evaluated the superoxide (O₂·⁻), hydroxyl radical (OH·), hydrogen peroxide (H₂O₂) and peroxynitrite (ONO⁻) scavenging capacity of jacareubin (xanthone III) and 2-(3,3-dimethylallyl)-1,3,5,6-tetrahydroxyxanthone (xanthone V). The effect of these xanthones on murine DNA and bovine serum albumin degradation induced by an OH· generator system was also evaluated. Additionally, we investigated the effect of these xanthones on ROS production, lipid peroxidation and glutathione reductase (GR) activity in FeSO₄-exposed brain, liver and lung rat homogenates. Xanthone V exhibited a better scavenging capacity for O₂·⁻, ONOO⁻ and OH· than xanthone III, although both xanthones were unable to trap H₂O₂. Additionally, xanthones III and V prevented the albumin and DNA degradation induced by the OH· generator system. Lipid peroxidation and ROS production evoked by FeSO₄ were decreased by both xanthones in all tissues tested. Xanthones III and V also prevented the GR activity depletion induced by pro-oxidant activity only in the brain. Altogether, the collected evidence suggests that xanthones can play a role as potential agents to attenuate the oxidative damage produced by different pro-oxidants.

TiO2-Based Advanced Oxidation Nanotechnologies For Water Purification And Reuse

EPA Science Inventory

TiO₂ photocatalysis, one of the UV-based advanced oxidation technologies (AOTs) and nanotechnologies (AONs), has attracted great attention for the development of efficient water treatment and purification systems due to the effectiveness of TiO₂ to generate ...

A COMPREHENSIVE APPROACH TO IDENTIFY AND QUANTIFY FUNDAMENTAL PARAMETERS THAT INFLUENCE METAL LEACHING CHEMISTRY IN LANDFILLS SYSTEMS (PRESENTATION)

EPA Science Inventory

Various anthropogenic activities generate hazardous solid wastes that are affluent in heavy metals, which can cause significant damage to the environment and human health. Heavy metals/metalloids can exist in multiple oxidation states, and can undergo oxidation or reduction when ...

A COMPREHENSIVE APPROACH TO IDENTIFY AND QUANTIFY FUNDAMENTAL PARAMETERS THAT INFLUENCE METAL LEACHING CHEMISTRY IN LANDFILLS SYSTEMS (ABSTRACT)

EPA Science Inventory

Various anthropogenic activities generate hazardous solid wastes that are affluent in heavy metals, which can cause significant damage to the environment and human health. Heavy metals/metalloids can exist in multiple oxidation states, and can undergo oxidation or reduction when ...

Chemically Assisted Photocatalytic Oxidation System

NASA Technical Reports Server (NTRS)

Andino, Jean; Wu, Chang-Yu; Mazyck, David; Teixeira, Arthur A.

2009-01-01

The chemically assisted photocatalytic oxidation system (CAPOS) has been proposed for destroying microorganisms and organic chemicals that may be suspended in the air or present on surfaces of an air-handling system that ventilates an indoor environment. The CAPOS would comprise an upstream and a downstream stage that would implement a tandem combination of two partly redundant treatments. In the upstream stage, the air stream and, optionally, surfaces of the air-handling system would be treated with ozone, which would be generated from oxygen in the air by means of an electrical discharge or ultraviolet light. In the second stage, the air laden with ozone and oxidation products from the first stage would be made to flow in contact with a silica-titania photocatalyst exposed to ultraviolet light in the presence of water vapor. Hydroxyl radicals generated by the photocatalytic action would react with both carbon containing chemicals and microorganisms to eventually produce water and carbon dioxide, and ozone from the first stage would be photocatalytically degraded to O2. The net products of the two-stage treatment would be H2O, CO2, and O2.

Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream

DOEpatents

Kromer, Brian R.; Litwin, Michael M.; Kelly, Sean M.

2016-09-27

A method and system for generating electrical power in which a high pressure synthesis gas stream generated in a gasifier is partially oxidized in an oxygen transport membrane based reactor, expanded and thereafter, is combusted in an oxygen transport membrane based boiler. A low pressure synthesis gas slip stream is split off downstream of the expanders and used as the source of fuel in the oxygen transport membrane based partial oxidation reactors to allow the oxygen transport membrane to operate at low fuel pressures with high fuel utilization. The combustion within the boiler generates heat to raise steam to in turn generate electricity by a generator coupled to a steam turbine. The resultant flue gas can be purified to produce a carbon dioxide product.

Enhanced transfection by antioxidative polymeric gene carrier that reduces polyplex-mediated cellular oxidative stress.

PubMed

Lee, Min Sang; Kim, Nak Won; Lee, Kyuri; Kim, Hongtae; Jeong, Ji Hoon

2013-06-01

To test the hypothesis in which polyplex-induced oxidative stress may affect overall transfection efficiency, an antioxidative transfection system minimizing cellular oxidative stress was designed for enhanced transfection. An amphiphilic copolymer (PEI-PLGA) was synthesized and used as a micelle-type gene carrier containing hydrophobic antioxidant, α-tocopherol. Cellular oxidative stress and the change of mitochondrial membrane potential after transfection was measured by using a fluorescent probe (H₂DCFDA) and lipophilic cationic probe (JC-1), respectively. Transfection efficiency was determined by measuring a reporter gene (luciferase) expression level. The initial transfection study with conventional PEI/plasmid DNA polyplex showed significant generation of reactive oxygen species (ROS). The PEI-PLGA copolymer successfully carried out the simultaneous delivery of α-tocopherol and plasmid DNA (PEI-PLGA/Toco/pDNA polyplex) into cells, resulting in a significant reduction in cellular ROS generation after transfection and helped to maintain the mitochondrial membrane potential (ΔΨ). In addition, the transfection efficiency was dramatically increased using the antioxidative transfection system. This work showed that oxidative stress would be one of the important factors that should be considered in designing non-viral gene carriers and suggested a possible way to reduce the carrier-mediated oxidative stress, which consequently leads to enhanced transfection.

Oxidation in Acidic Medium of Lignins from Agricultural Residues

NASA Astrophysics Data System (ADS)

Labat, Gisele Aparecida Amaral; Gonçalves, Adilson Roberto

Agricultural residues as sugarcane straw and bagasse are burned in boilers for generation of energy in sugar and alcohol industries. However, excess of those by-products could be used to obtain products with higher value. Pulping process generates cellulosic pulps and lignin. The lignin could be oxidized and applied in effluent treatments for heavy metal removal. Oxidized lignin presents very strong chelating properties. Lignins from sugarcane straw and bagasse were obtained by ethanol-water pulping. Oxidation of lignins was carried out using acetic acid and Co/Mn/Br catalytical system at 50, 80, and 115 °C for 5 h. Kinetics of the reaction was accomplished by measuring the UV-visible region. Activation energy was calculated for lignins from sugarcane straw and bagasse (34.2 and 23.4 kJ mol-1, respectively). The first value indicates higher cross-linked formation. Fourier-transformed infrared spectroscopy data of samples collected during oxidation are very similar. Principal component analysis applied to spectra shows only slight structure modifications in lignins after oxidation reaction.

Electrochemical treatment of evaporated residue of soak liquor generated from leather industry.

PubMed

Boopathy, R; Sekaran, G

2013-09-15

The organic and suspended solids present in soak liquor, generated from leather industry, demands treatment. The soak liquor is being segregated and evaporated in solar evaporation pans/multiple effect evaporator due to non availability of viable technology for its treatment. The residue left behind in the pans/evaporator does not carry any reuse value and also faces disposal threat due to the presence of high concentration of sodium chloride, organic and bacterial impurities. In the present investigation, the aqueous evaporated residue of soak liquor (ERSL) was treated by electrochemical oxidation. Graphite/graphite and SS304/graphite systems were used in electrochemical oxidation of organics in ERSL. Among these, graphite/graphite system was found to be effective over SS304/graphite system. Hence, the optimised conditions for the electrochemical oxidation of organics in ERSL using graphite/graphite system was evaluated by response surface methodology (RSM). The mass transport coefficient (km) was calculated based on pseudo-first order rate kinetics for both the electrode systems (graphite/graphite and SS304/graphite). The thermodynamic properties illustrated the electrochemical oxidation was exothermic and non-spontaneous in nature. The calculated specific energy consumption at the optimum current density of 50 mA cm(-2) was 0.41 kWh m(-3) for the removal of COD and 2.57 kWh m(-3) for the removal of TKN. Copyright © 2013 Elsevier B.V. All rights reserved.

Inhibition of Cryptococcus neoformans replication by nitrogen oxides supports the role of these molecules as effectors of macrophage-mediated cytostasis

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

Alspaugh, J.A.; Granger, D.L.

Activated macrophages are able to inhibit the replication of intracellular microbes and tumor cells. In the murine system, this cytostatic effect is associated with the oxidation of L-arginine to L-citrulline, nitrite, and nitrate and is thought to be mediated by an intermediate of this reaction, possibly nitric oxide (NO.). By exposing replicating Cryptococcus neoformans cells to conditions under which NO. is chemically generated, we have observed a cytostatic effect similar to that caused by activated murine macrophages. Nitric oxide is formed as a decomposition product of nitrite salts in acidic, aqueous solutions. Although C. neoformans replicates well in the presencemore » of high nitrite concentrations at physiologic pH, its growth in acidic media can be inhibited by the addition of low concentrations of sodium nitrite. The degree of cytostasis is dependent on both the pH and the nitrite concentration of the NO. generating solution. The cytostatic effector molecule appears to be a gas since, in addition to inhibiting C. neoformans replication in solution, it is able to exert its inhibitory effect across a gas-permeable but ion-impermeable membrane. At high nitrite concentrations, a fungicidal effect occurs. We propose that the growth inhibition of C. neoformans upon exposure to chemically generated NO. or some related oxide of nitrogen represents a cell-free system simulating the cytostatic effect of activated murine macrophages.« less

Biomedical implications of information processing in chemical systems: non-classical approach to photochemistry of coordination compounds.

PubMed

Szaciłowski, Konrad

2007-01-01

Analogies between photoactive nitric oxide generators and various electronic devices: logic gates and operational amplifiers are presented. These analogies have important biological consequences: application of control parameters allows for better targeting and control of nitric oxide drugs. The same methodology may be applied in the future for other therapeutic strategies and at the same time helps to understand natural regulatory and signaling processes in biological systems.

Design and assembly of a catalyst bed gas generator for the catalytic decomposition of high concentration hydrogen peroxide propellants and the catalytic combustion of hydrocarbon/air mixtures

NASA Technical Reports Server (NTRS)

Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Sevener, Kathleen M. (Inventor)

2004-01-01

A method for designing and assembling a high performance catalyst bed gas generator for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in target, space, and on-orbit propulsion systems and low-emission terrestrial power and gas generation. The gas generator utilizes a sectioned catalyst bed system, and incorporates a robust, high temperature mixed metal oxide catalyst. The gas generator requires no special preheat apparatus or special sequencing to meet start-up requirements, enabling a fast overall response time. The high performance catalyst bed gas generator system has consistently demonstrated high decomposition efficiency, extremely low decomposition roughness, and long operating life on multiple test articles.

Cell-delivered magnetic nanoparticles caused hyperthermia-mediated increased survival in a murine pancreatic cancer model

PubMed Central

Basel, Matthew T; Balivada, Sivasai; Wang, Hongwang; Shrestha, Tej B; Seo, Gwi Moon; Pyle, Marla; Abayaweera, Gayani; Dani, Raj; Koper, Olga B; Tamura, Masaaki; Chikan, Viktor; Bossmann, Stefan H; Troyer, Deryl L

2012-01-01

Using magnetic nanoparticles to absorb alternating magnetic field energy as a method of generating localized hyperthermia has been shown to be a potential cancer treatment. This report demonstrates a system that uses tumor homing cells to actively carry iron/iron oxide nanoparticles into tumor tissue for alternating magnetic field treatment. Paramagnetic iron/ iron oxide nanoparticles were synthesized and loaded into RAW264.7 cells (mouse monocyte/ macrophage-like cells), which have been shown to be tumor homing cells. A murine model of disseminated peritoneal pancreatic cancer was then generated by intraperitoneal injection of Pan02 cells. After tumor development, monocyte/macrophage-like cells loaded with iron/ iron oxide nanoparticles were injected intraperitoneally and allowed to migrate into the tumor. Three days after injection, mice were exposed to an alternating magnetic field for 20 minutes to cause the cell-delivered nanoparticles to generate heat. This treatment regimen was repeated three times. A survival study demonstrated that this system can significantly increase survival in a murine pancreatic cancer model, with an average post-tumor insertion life expectancy increase of 31%. This system has the potential to become a useful method for specifically and actively delivering nanoparticles for local hyperthermia treatment of cancer. PMID:22287840

Application of the monolithic solid oxide fuel cell to space power systems

NASA Astrophysics Data System (ADS)

Myles, Kevin M.; Bhattacharyya, Samit K.

1991-01-01

The monolithic solid-oxide fuel cell (MSOFC) is a promising electrochemical power generation device that is currently under development at Argonne National Laboratory. The extremely high power density of the MSOFC leads to MSOFC systems that have sufficiently high energy densities that they are excellent candidates for a number of space missions. The fuel cell can also be operated in reverse, if it can be coupled to an external power source, to regenerate the fuel and oxidant from the water product. This feature further enhances the potential mission applications of the MSOFC. In this paper, the current status of the fuel cell development is presented—the focus being on fabrication and currently achievable performance. In addition, a specific example of a space power system, featuring a liquid metal cooled fast spectrum nuclear reactor and a monolithic solid oxide fuel cell, is presented to demonstrate the features of an integrated system.

Loss of macrophage fatty acid oxidation does not potentiate systemic metabolic dysfunction

PubMed Central

Gonzalez-Hurtado, Elsie; Lee, Jieun; Choi, Joseph; Selen Alpergin, Ebru S.; Collins, Samuel L.; Horton, Maureen R.

2017-01-01

Fatty acid oxidation in macrophages has been suggested to play a causative role in high-fat diet-induced metabolic dysfunction, particularly in the etiology of adipose-driven insulin resistance. To understand the contribution of macrophage fatty acid oxidation directly to metabolic dysfunction in high-fat diet-induced obesity, we generated mice with a myeloid-specific knockout of carnitine palmitoyltransferase II (CPT2 Mϕ-KO), an obligate step in mitochondrial long-chain fatty acid oxidation. While fatty acid oxidation was clearly induced upon IL-4 stimulation, fatty acid oxidation-deficient CPT2 Mϕ-KO bone marrow-derived macrophages displayed canonical markers of M2 polarization following IL-4 stimulation in vitro. In addition, loss of macrophage fatty acid oxidation in vivo did not alter the progression of high-fat diet-induced obesity, inflammation, macrophage polarization, oxidative stress, or glucose intolerance. These data suggest that although IL-4-stimulated alternatively activated macrophages upregulate fatty acid oxidation, fatty acid oxidation is dispensable for macrophage polarization and high-fat diet-induced metabolic dysfunction. Macrophage fatty acid oxidation likely plays a correlative, rather than causative, role in systemic metabolic dysfunction. PMID:28223293

Polymer Energy Rechargeable System Battery Being Developed

NASA Technical Reports Server (NTRS)

Manzo, Michelle A.

2003-01-01

Long description. Illustrations of discotic liquid crystals, rod-coil polymers, lithium-ion conducting channel dilithium phthalocyanine (Li2Pc) from top and side, novel star polyethylene oxide structures, composite polyethylene oxide materials (showing polyethylene oxide + lithium salt, carbon atoms and oxygen atoms), homopolyrotaxanes, and diblock copolymers In fiscal year 2000, NASA established a program to develop the next generation, lithium-based, polymer electrolyte batteries for aerospace applications. The goal of this program, known as Polymer Energy Rechargeable Systems (PERS), is to develop a space-qualified, advanced battery system embodying polymer electrolyte and lithium-based electrode technologies and to establish world-class domestic manufacturing capabilities for advanced batteries with improved performance characteristics that address NASA s future aerospace battery requirements.

Oxidation-Resistant Surfaces For Solar Reflectors

NASA Technical Reports Server (NTRS)

Gulino, Daniel A.; Egger, Robert A.; Banholzer, William F.

1988-01-01

Thin films on silver provide highly-reflective, corrosion-resistant mirrors. Study evaluated variety of oxidation-resistant reflective materials for use in solar dynamic power system, one that generates electricity by focusing Sunlight onto reciever of heat engine. Thin films of platinum and rhodium deposited by ion-beam sputtering on various substrate materials. Solar reflectances measured as function of time of exposure to radio-frequency-generated air plasma. Several protective coating materials deposited on silver-coated substrates and exposed to plasma. Analyzed before and after exposure by electon spectroscopy for chemical analysis and by Auger spectroscopy.

PROTEOMIC IDENTIFICATION OF CARBONYLATED PROTEINS AND THEIR OXIDATION SITES

PubMed Central

Madian, Ashraf G.; Regnier, Fred E.

2011-01-01

Excessive oxidative stress leaves a protein carbonylation fingerprint in biological systems. Carbonylation is an irreversible post translational modification (PTM) that often leads to the loss of protein function and can be a component of multiple diseases. Protein carbonyl groups can be generated directly (by amino acids oxidation and the a-amidation pathway) or indirectly by forming adducts with lipid peroxidation products or glycation and advanced glycation end-products. Studies of oxidative stress are complicated by the low concentration of oxidation products and wide array of routes by which proteins are carbonylated. The development of new selection and enrichment techniques coupled with advances in mass spectrometry are allowing identification of hundreds of new carbonylated protein products from a broad range of proteins located at many sites in biological systems. The focus of this review is on the use of proteomics tools and methods to identify oxidized proteins along with specific sites of oxidative damage and the consequences of protein oxidation. PMID:20521848

Oxidation Control with Chromate Pretreatment of MCrAlY Unmelted Particle and Bond Coat in Thermal Barrier Systems

NASA Astrophysics Data System (ADS)

Yamano, Hideaki; Tani, Kazumi; Harada, Yoshio; Teratani, Takema

2008-06-01

MCrAlY alloy bond coat is widely used in thermal barrier coating (TBC) systems to protect substrates from high-temperature oxidizing environments. However, failure of the ceramic topcoat can occur due to a thermally grown oxide (TGO) that grows at the interface between the bond coat and the topcoat. In this study, the effect of chromate treatment was investigated. Prior to topcoat deposition, a thin film of Cr2O3 was formed on the bond coat surface. High-temperature oxidation tests were carried out, and the oxidation rates were determined by inspection of cross sections. Similar oxidation tests were carried out using MCrAlY powder material assumed to be unmelted particles. As a result, the chromate-treated bond coat showed outstanding oxidation resistance. Calculations that take into account the oxidation of particles in the topcoat indicated the generation of internal stress to cause local fracture of the topcoat.

Biocompatible nanocarriers that respond to oxidative environments via interactions between chitosan and multiple metal ions

PubMed Central

Zhang, Shichang; Xia, Liye; Ding, Chenchen; Wen, Lu; Wan, Weihua; Chen, Gang

2016-01-01

Hydrogen peroxide (H2O2) functions as an early damage signal contributing to the oxidative stress response and can act as a trigger in smart oxidation-responsive drug delivery systems that are currently in development. Current H2O2-triggered oxidation-responsive polymeric systems are usually derived from chemical synthesis and rarely include natural polymers. Herein, we report two series of nanoparticle (NP) complexes prepared with the biopolymer chitosan (CS) and four different metal ions (Cu2+, Ca2+, Zn2+, and Fe3+), defined as CSNPs-metal complexes (Series 1) and CS-metal complexes NPs (Series 2), which responded to oxidation by dissolving upon H2O2 exposure. Experiments examining Nile red release and H2O2-triggered degradation confirmed that both series of complexes showed better sensitivity to oxidation than the CSNPs alone. Furthermore, preliminary cytotoxicity and histological observations indicated that the two series exhibited little or no cytotoxicity and generated a mild inflammatory response. Our work provides a novel and promising strategy for developing NPs for use as intelligent oxidation-responsive systems. PMID:27358564

Nitric oxide coupling to generate N2O promoted by a single-heme system as examined by density functional theory.

PubMed

Yi, Jun; Campbell, Adam L O; Richter-Addo, George B

2016-11-30

Bacteria utilize a heme/non-heme enzyme system to detoxify nitric oxide (NO) to N 2 O. In order to probe the capacity of a single-heme system to mediate this NO-to-N 2 O transformation, various scenarios for addition of electrons, protons, and a second NO molecule to a heme nitrosyl to generate N 2 O were explored by density functional theory calculations. We describe, utilizing this single-heme system, several stepwise intermediates along pathways that enable the critical N-N bond formation step yielding the desired Fe-N 2 O product. We also report a hitherto unreported directional second protonation that results in either productive N 2 O formation with loss of water, or formation of a non-productive hyponitrous acid adduct Fe{HONNOH}. Copyright © 2016 Elsevier Inc. All rights reserved.

Molecular interactions and redox effects of carvacrol and thymol on myofibrillar proteins using a non-destructive and solvent-free methodological approach.

PubMed

Lahmar, Aida; Akcan, Tolga; Chekir-Ghedira, Leila; Estévez, Mario

2018-04-01

The present study provides molecular insight into the effect of thymol and carvacrol on the oxidative damage caused to myofibrillar proteins by a hydroxyl-radical generating system (HRGS). An innovative model system was designed, in which gels, prepared with increasing levels of myofibrillar proteins, were oxidized by a HRGS (Fe 3+ /H 2 O 2 , 60 °C and 7 days) in the presence of lipids. The molecular affinity between myofibrillar proteins and both terpenes, as well as their effect on the oxidative stability of the gel systems, were studied using a non-destructive and solvent-free procedure based on fluorescence spectroscopy. Carvacrol displayed more affinity than thymol for establishing chemical interactions with protein residues. Both terpenes exhibited a significant antioxidant potential against the generation of lipid-derived volatile carbonyls and against the formation of protein crosslinking. This procedure may be applied to meat products to assess the effectiveness of a given antioxidant additive without size reduction or sample processing. Copyright © 2018 Elsevier Ltd. All rights reserved.

Design, integration and demonstration of a 50 W JP8/kerosene fueled portable SOFC power generator

NASA Astrophysics Data System (ADS)

Cheekatamarla, Praveen K.; Finnerty, Caine M.; Robinson, Charles R.; Andrews, Stanley M.; Brodie, Jonathan A.; Lu, Y.; DeWald, Paul G.

A man-portable solid oxide fuel cell (SOFC) system integrated with desulfurized JP8 partial oxidation (POX) reformer was demonstrated to supply a continuous power output of 50 W. This paper discusses some of the design paths chosen and challenges faced during the thermal integration of the stack and reformer in aiding the system startup and shutdown along with balance of plant and power management solutions. The package design, system capabilities, and test results of the prototype unit are presented.

Photochromic, electrochromic, photoelectrochromic and photovoltaic devices

DOEpatents

Kostecki, Robert; McLarnon, Frank R.

2000-01-01

A light activated photoelectrochromic device is formed of a two-component system formed of a photoactive charge carrier generating material and electrochromic material (plus an elecrolyte). Light interacts with a semiconductive material to generate hole-electron charge carriers which cause a redox reaction in the electrochromic material. One device is formed of hydrated nickel oxide as the electrochromic layer and polycrystalline titanium dioxide as the charge generating material. The materials may be formed as discrete layers or mixed together. Because of the direct charge transfer between the layers, a circuit to apply a voltage to drive the electrochromic reaction is not required, although one can be used to enhance the reaction. The hydrated nickel oxide-titanium dioxide materials can also be used to form a photovoltaic device for generating electricity.

An Antioxidant Phytotherapy to Rescue Neuronal Oxidative Stress

PubMed Central

Lin, Zhihong; Zhu, Danni; Yan, Yongqing; Yu, Boyang; Wang, Qiujuan; Shen, Pingniang; Ruan, Kefeng

2011-01-01

Oxidative stress is involved in the pathogenesis of ischemic neuronal injury. A Chinese herbal formula composed of Poria cocos (Chinese name: Fu Ling), Atractylodes macrocephala (Chinese name: Bai Zhu) and Angelica sinensis (Chinese names: Danggui, Dong quai, Donggui; Korean name: Danggwi) (FBD), has been proved to be beneficial in the treatment of cerebral ischemia/reperfusion (I/R).This study was carried out to evaluate the protective effect of FBD against neuronal oxidative stress in vivo and in vitro. Rat I/R were established by middle cerebral artery occlusion (MCAO) for 1 h, followed by 24 h reperfusion. MCAO led to significant depletion in superoxide dismutase and glutathione and rise in lipid peroxidation (LPO) and nitric oxide in brain. The neurological deficit and brain infarction were also significantly elevated by MCAO as compared with sham-operated group. All the brain oxidative stress and damage were significantly attenuated by 7 days pretreatment with the aqueous extract of FBD (250 mg kg−1, p.o.). Moreover, cerebrospinal fluid sampled from FBD-pretreated rats protected PC12 cells against oxidative insult induced by 0.2 mM hydrogen peroxide, in a concentration and time-dependent manner (IC50 10.6%, ET50 1.2 h). However, aqueous extract of FBD just slightly scavenged superoxide anion radical generated in xanthine–xanthine oxidase system (IC50 2.4 mg ml−1) and hydroxyl radical generated in Fenton reaction system (IC50 3.6 mg ml−1). In conclusion, FBD was a distinct antioxidant phytotherapy to rescue neuronal oxidative stress, through blocking LPO, restoring endogenous antioxidant system, but not scavenging free radicals. PMID:18955358

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Technical Reports Server (NTRS)

Bents, David J.

1987-01-01

A hydrogen-oxygen regenerative fuel cell energy storage system based on high temperature solid oxide fuel cell technology is discussed which has application to darkside energy storage for solar photovoltaics. The forward and reverse operating cycles are described, and heat flow, mass, and energy balance data are presented to characterize the system's performance and the variation of performance with changing reactant storage pressure. The present system weighs less than nickel hydrogen battery systems after 0.7 darkside operation, and it maintains a specific weight advantage over radioisotope generators for discharge periods up to 72 hours.

High temperature solid oxide regenerative fuel cell for solar photovoltaic energy storage

NASA Astrophysics Data System (ADS)

Bents, David J.

A hydrogen-oxygen regenerative fuel cell energy storage system based on high temperature solid oxide fuel cell technology is discussed which has application to darkside energy storage for solar photovoltaics. The forward and reverse operating cycles are described, and heat flow, mass, and energy balance data are presented to characterize the system's performance and the variation of performance with changing reactant storage pressure. The present system weighs less than nickel hydrogen battery systems after 0.7 darkside operation, and it maintains a specific weight advantage over radioisotope generators for discharge periods up to 72 hours.

The control of iron-induced oxidative damage in isolated rat-liver mitochondria by respiration state and ascorbate.

PubMed

Burkitt, M J; Gilbert, B C

1989-01-01

The reaction of iron (II) with H2O2 is believed to generate highly reactive species (e.g. .OH) capable of initiating biological damage. This study investigates the possibility that the severity of oxidative damage induced by iron in hepatic mitochondria is determined by the level of mitochondrial-H2O2 generation, which is believed to be particularly prominent in state-4 respiration. Iron-induced damage is found to be greater in state-4 than in state-3 respiration. Experiments using uncoupling agents and Ca++ to mimic state-3 conditions indicate that this effect reflects differences in the steady-state oxidation-level of the electron carriers of the respiratory chain (and hence the level of H2O2-generation), rather than changes in redox potential or transportation of the metal-ion. Evidence is also presented for a mechanism in which Fe(II) and H2O2 react inside the mitochondrial matrix. Ascorbate (vitamin C) is shown to be pro-oxidant in this system, except when present at very high concentration when it becomes antioxidant in nature.

Fatty Acid Composition as a Predictor for the Oxidation Stability of Korean Vegetable Oils with or without Induced Oxidative Stress

PubMed Central

Yun, Jung-Mi; Surh, Jeonghee

2012-01-01

This study was designed to investigate whether the fatty acid composition could make a significant contribution to the oxidation stability of vegetable oils marketed in Korea. Ten kinds, 97 items of vegetable oils that were produced in either an industrialized or a traditional way were collected and analyzed for their fatty acid compositions and lipid oxidation products, in the absence or presence of oxidative stress. Peroxidability index (PI) calculations based on the fatty acid composition ranged from 7.10 to 111.87 with the lowest value found in olive oils and the highest in perilla oils. In the absence of induced oxidative stress, malondialdehyde (MDA), the secondary lipid oxidation product, was generated more in the oils with higher PI (r=0.890), while the tendency was not observed when the oils were subjected to an oxidation-accelerating system. In the presence of the oxidative stress, the perilla oils produced in an industrialized manner generated appreciably higher amounts of MDA than those produced in a traditional way, although both types of oils presented similar PIs. The results implicate that the fatty acid compositions could be a predictor for the oxidation stability of the vegetable oils at the early stage of oil oxidation, but not for those at a later stage of oxidation. PMID:24471078

LABORATORY EVALUATION OF A MICROFLUIDIC ELECTROCHEMICAL SENSOR FOR AEROSOL OXIDATIVE LOAD.

PubMed

Koehler, Kirsten; Shapiro, Jeffrey; Sameenoi, Yupaporn; Henry, Charles; Volckens, John

2014-05-01

Human exposure to particulate matter (PM) air pollution is associated with human morbidity and mortality. The mechanisms by which PM impacts human health are unresolved, but evidence suggests that PM intake leads to cellular oxidative stress through the generation of reactive oxygen species (ROS). Therefore, reliable tools are needed for estimating the oxidant generating capacity, or oxidative load, of PM at high temporal resolution (minutes to hours). One of the most widely reported methods for assessing PM oxidative load is the dithiothreitol (DTT) assay. The traditional DTT assay utilizes filter-based PM collection in conjunction with chemical analysis to determine the oxidation rate of reduced DTT in solution with PM. However, the traditional DTT assay suffers from poor time resolution, loss of reactive species during sampling, and high limit of detection. Recently, a new DTT assay was developed that couples a Particle-Into-Liquid-Sampler with microfluidic-electrochemical detection. This 'on-line' system allows high temporal resolution monitoring of PM reactivity with improved detection limits. This study reports on a laboratory comparison of the traditional and on-line DTT approaches. An urban dust sample was aerosolized in a laboratory test chamber at three atmospherically-relevant concentrations. The on-line system gave a stronger correlation between DTT consumption rate and PM mass (R 2 = 0.69) than the traditional method (R 2 = 0.40) and increased precision at high temporal resolution, compared to the traditional method.

Nanostructured Metal Oxides and Sulfides for Lithium-Sulfur Batteries.

PubMed

Liu, Xue; Huang, Jia-Qi; Zhang, Qiang; Mai, Liqiang

2017-05-01

Lithium-sulfur (Li-S) batteries with high energy density and long cycle life are considered to be one of the most promising next-generation energy-storage systems beyond routine lithium-ion batteries. Various approaches have been proposed to break down technical barriers in Li-S battery systems. The use of nanostructured metal oxides and sulfides for high sulfur utilization and long life span of Li-S batteries is reviewed here. The relationships between the intrinsic properties of metal oxide/sulfide hosts and electrochemical performances of Li-S batteries are discussed. Nanostructured metal oxides/sulfides hosts used in solid sulfur cathodes, separators/interlayers, lithium-metal-anode protection, and lithium polysulfides batteries are discussed respectively. Prospects for the future developments of Li-S batteries with nanostructured metal oxides/sulfides are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High throughput photo-oxidations in a packed bed reactor system.

PubMed

Kong, Caleb J; Fisher, Daniel; Desai, Bimbisar K; Yang, Yuan; Ahmad, Saeed; Belecki, Katherine; Gupton, B Frank

2017-12-01

The efficiency gains produced by continuous-flow systems in conducting photochemical transformations have been extensively demonstrated. Recently, these systems have been used in developing safe and efficient methods for photo-oxidations using singlet oxygen generated by photosensitizers. Much of the previous work has focused on the use of homogeneous photocatalysts. The development of a unique, packed-bed photoreactor system using immobilized rose bengal expands these capabilities as this robust photocatalyst allows access to and elaboration from these highly useful building blocks without the need for further purification. With this platform we were able to demonstrate a wide scope of singlet oxygen ene, [4+2] cycloadditions and heteroatom oxidations. Furthermore, we applied this method as a strategic element in the synthesis of the high-volume antimalarial artemisinin. Copyright © 2017. Published by Elsevier Ltd.

Effects of high temperature and exposure to air on mussel (Mytilus galloprovincialis, Lmk 1819) hemocyte phagocytosis: modulation of spreading and oxidative response.

PubMed

Mosca, Francesco; Narcisi, Valeria; Calzetta, Angela; Gioia, Luisa; Finoia, Maria G; Latini, Mario; Tiscar, Pietro G

2013-06-01

Hemocytes are a critical component of the mussel defense system and the present study aims at investigating their spreading and oxidative properties during phagocytosis under in vivo experimental stress conditions. The spreading ability was measured by an automated cell analyzer on the basis of the circularity, a parameter corresponding to the hemocyte roundness. The oxidative activity was investigated by micromethod assay, measuring the respiratory burst as expression of the fluorescence generated by the oxidation of specific probe. Following the application of high temperature and exposure to air, there was evidence of negative modulation of spreading and oxidative response, as revealed by a cell roundness increase and fluorescence generation decrease. Therefore, the fall of respiratory burst appeared as matched with the inhibition of hemocyte morphological activation, suggesting a potential depression of the phagocytosis process and confirming the application of the circularity parameter as potential stress marker, both in experimental and field studies. Copyright © 2012 Elsevier Ltd. All rights reserved.

Detection of oxidative stress in heart by estimating the dinitrophenylhydrazine derivative of malonaldehyde.

PubMed

Cordis, G A; Maulik, N; Das, D K

1995-08-01

Accurate estimation of the oxidative stress in heart is necessary because the pathogenesis of many heart diseases are believed to be mediated at least in part from the development of oxidative stress resulting from the generation of oxygen free radicals and reduced antioxidant defense system. The most widely used method for this purpose has been the estimation of malonaldehyde (MDA), a lipid peroxidation product, by the thiobarbituric acid (TBA) reaction method. However, because of the nonspecificity of this method, the results are often erroneous. The present report describes a method using high-performance liquid chromatography (HPLC) to estimate MDA. To develop the oxidative stress, two different models were used: ischaemic-reperfused heart and perfusing the heart with a hydroxyl radical (OH+) generating system. The coronary effluents obtained from the isolated rat heart before ischaemia and during the reperfusion of ischaemic heart, as well as during the perfusion of the heart with the OH+ generating system were collected, derivatized with 2,4-dinitrophenylhydrazine (DNPH) and extracted with pentane. Aliquots of 25 microliters in acetonitrile were injected onto a Beckman Ultrasphere C18 (3 microns) column. The products were eluted isocratically with a mobile phase containing acetonitrile-water-acetic acid (40:60:0.1, v/v/v), measured at 307 nm using a Waters M-490 multichannel UV detector and collected for gas chromatography-mass spectrometry (GC-MS). The peaks were identified by co-chromatography with DNPH derivatives of authentic standards, peak addition, and by GC-MS. The retention time for MDA-DNPH was 5.3 min.(ABSTRACT TRUNCATED AT 250 WORDS)

Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer).

EPA Science Inventory

This paper describes an automated system for the oxidation state specific speciation of inorganic and methylated arsenicals by selective hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer. The corresponding arsines are ge...

Minimization of nitrous oxide emission in a pilot-scale oxidation ditch: generation, spatial variation and microbial interpretation.

PubMed

Zheng, Maosheng; Tian, Yuhao; Liu, Tang; Ma, Tao; Li, Li; Li, Can; Ahmad, Muhammad; Chen, Qian; Ni, Jinren

2015-03-01

Nitrous oxide (N2O) emission from wastewater treatment plants (WWTPs) has received increasing attention. This paper presented how N2O emission was significantly reduced in a pilot-scale Carrousel oxidation ditch under reasonable nitrification and denitrification. N2O emission from the reactor was found as low as 0.027% of influent nitrogen, which was much less than that from other processes. Further measurements on spatial variation of N2O emission in the alternative aerobic/anoxic zones with help of a series of batch experiments demonstrated that about 90% of the emission was contributed by nitrifier denitrification (ND). Moreover, the taxonomic analysis based on high through-put 16S rRNA gene sequencing revealed that the high abundance of denitrifying bacteria and nitrite-oxidizing bacteria (NOB) was responsible for low nitrite accumulations and consequent low N2O emissions. However, N2O generation would be greatly increased upon the normal operation being shocked by either ammonia overload or aeration failure of the oxidation ditch system. Copyright © 2014 Elsevier Ltd. All rights reserved.

Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.

PubMed

Komaszylo Née Siedlecka, Joanna; Kania, Magdalena; Masnyk, Marek; Cmoch, Piotr; Lozinska, Iwona; Czarnocki, Zbigniew; Skorupinska-Tudek, Karolina; Danikiewicz, Witold; Swiezewska, Ewa

2016-02-01

Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents--reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol-2 and -10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy-, peroxy- and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI-MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI-MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time.

Effective oxidation of benzylic and alkane C-H bonds catalyzed by sodium o-iodobenzenesulfonate with Oxone as a terminal oxidant under phase-transfer conditions.

PubMed

Cui, Li-Qian; Liu, Kai; Zhang, Chi

2011-04-07

Catalytic oxidation of benzylic C-H bonds could be efficiently realized using IBS as a catalyst which was generated in situ from the oxidation of sodium 2-iodobenzenesulfonate (1b) by Oxone in the presence of a phase-transfer catalyst, tetra-n-butylammonium hydrogen sulfate, in anhydrous acetonitrile at 60 °C. Various alkylbenzenes, including toluenes and ethylbenzenes, several oxygen-containing functionalities substituted alkylbenzenes, and a cyclic benzyl ether could be efficiently oxidized. And, the same reagent system of cat. 1b/Oxone/cat. n-Bu(4)NHSO(4) could be applied to the effective oxidation of alkanes as well.

Systemic inflammatory changes and increased oxidative stress in rural Indian women cooking with biomass fuels

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

Dutta, Anindita, E-mail: anidu14@gmail.com; Department of Experimental Hematology, Chittaranjan National Cancer Institute, 37, S.P. Mukherjee Road, Kolkata-700 026; Ray, Manas Ranjan

The study was undertaken to investigate whether regular cooking with biomass aggravates systemic inflammation and oxidative stress that might result in increase in the risk of developing cardiovascular disease (CVD) in rural Indian women compared to cooking with a cleaner fuel like liquefied petroleum gas (LPG). A total of 635 women (median age 36 years) who cooked with biomass and 452 age-matched control women who cooked with LPG were enrolled. Serum interleukin-6 (IL-6), C-reactive protein (CRP), tumor necrosis factor-alpha (TNF-α) and interleukin-8 (IL-8) were measured by ELISA. Generation of reactive oxygen species (ROS) by leukocytes was measured by flow cytometry,more » and erythrocytic superoxide dismutase (SOD) was measured by spectrophotometry. Hypertension was diagnosed following the Seventh Report of the Joint Committee. Tachycardia was determined as pulse rate > 100 beats per minute. Particulate matter of diameter less than 10 and 2.5 μm (PM{sub 10} and PM{sub 2.5}, respectively) in cooking areas was measured using real-time aerosol monitor. Compared with control, biomass users had more particulate pollution in indoor air, their serum contained significantly elevated levels of IL-6, IL-8, TNF-α and CRP, and ROS generation was increased by 37% while SOD was depleted by 41.5%, greater prevalence of hypertension and tachycardia compared to their LPG-using neighbors. PM{sub 10} and PM{sub 2.5} levels were positively associated with markers of inflammation, oxidative stress and hypertension. Inflammatory markers correlated with raised blood pressure. Cooking with biomass exacerbates systemic inflammation, oxidative stress, hypertension and tachycardia in poor women cooking with biomass fuel and hence, predisposes them to increased risk of CVD development compared to the controls. Systemic inflammation and oxidative stress may be the mechanistic factors involved in the development of CVD. -- Highlights: ► Effect of chronic biomass smoke exposure on cardiovascular health was investigated. ► Serum markers of systemic inflammation and oxidative stress were studied. ► Biomass using women had increased systemic inflammation and oxidative stress. ► Indoor air pollution and observed changes were positively associated.« less

Selective oxidation of aliphatic C-H bonds in alkylphenols by a chemomimetic biocatalytic system.

PubMed

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Feng, Yingang; Liu, Shuang-Jiang; Li, Shengying

2017-06-27

Selective oxidation of aliphatic C-H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C-H bonds of p - and m -alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity.

Selective oxidation of aliphatic C–H bonds in alkylphenols by a chemomimetic biocatalytic system

PubMed Central

Du, Lei; Dong, Sheng; Zhang, Xingwang; Jiang, Chengying; Chen, Jingfei; Yao, Lishan; Wang, Xiao; Wan, Xiaobo; Liu, Xi; Wang, Xinquan; Huang, Shaohua; Cui, Qiu; Liu, Shuang-Jiang; Li, Shengying

2017-01-01

Selective oxidation of aliphatic C–H bonds in alkylphenols serves significant roles not only in generation of functionalized intermediates that can be used to synthesize diverse downstream chemical products, but also in biological degradation of these environmentally hazardous compounds. Chemo-, regio-, and stereoselectivity; controllability; and environmental impact represent the major challenges for chemical oxidation of alkylphenols. Here, we report the development of a unique chemomimetic biocatalytic system originated from the Gram-positive bacterium Corynebacterium glutamicum. The system consisting of CreHI (for installation of a phosphate directing/anchoring group), CreJEF/CreG/CreC (for oxidation of alkylphenols), and CreD (for directing/anchoring group offloading) is able to selectively oxidize the aliphatic C–H bonds of p- and m-alkylated phenols in a controllable manner. Moreover, the crystal structures of the central P450 biocatalyst CreJ in complex with two representative substrates provide significant structural insights into its substrate flexibility and reaction selectivity. PMID:28607077

Staged Catalytic Partial Oxidation (SCPO) System - The State of Art Integrated Short Contact Time Hydrogen Generator

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

Ke Liu; Jin Ki Hong; Wei Wei

Research and development on hydrogen and syngas production have great potential in addressing the following challenges in energy arena: (1) produce more clean fuels to meet the increasing demands for clean liquid and gaseous fuels for transportation and electricity generation, (2) increase the efficiency of energy utilization for fuels and electricity production, and (3) eliminate the pollutants and decouple the link between energy utilization and greenhouse gas emissions in end-use systems [Song, 2006, Liu, Song & Subramani 2009]. In this project, GE Global Research (GEGR) collaborated with Argonne National Laboratory (ANL) and the University of Minnesota (UoMn), developed and demonstratedmore » a low cost, compact staged catalytic partial oxidation (SCPO) technology for distributed hydrogen generation. GEGR analyzed different reforming system designs, and developed the SCPO reforming system which is a unique technology staging and integrating 3 different short contact time catalysts in a single, compact reactor: catalytic partial oxidation (CPO), steam methane reforming (SMR) and water-gas shift (WGS). This integration is demonstrated via the fabrication of a prototype scale unit of each key technology. Approaches for key technical challenges of the program includes: · Analyzed different system designs · Designed the SCPO hydrogen production system · Developed highly active and sulfur tolerant CPO catalysts · Designed and built different pilot-scale reactors to demonstrate each key technology · Evaluated different operating conditions · Quantified the efficiency and cost of the system · Developed process design package (PDP) for 1500 kg H2/day distributed H2 production unit. SCPO met the Department of Energy (DOE) and GE’s cost and efficiency targets for distributed hydrogen production.« less

Interaction of Hydrogen Sulfide with Nitric Oxide in the Cardiovascular System

PubMed Central

Nagpure, B. V.; Bian, Jin-Song

2016-01-01

Historically acknowledged as toxic gases, hydrogen sulfide (H2S) and nitric oxide (NO) are now recognized as the predominant members of a new family of signaling molecules, “gasotransmitters” in mammals. While H2S is biosynthesized by three constitutively expressed enzymes (CBS, CSE, and 3-MST) from L-cysteine and homocysteine, NO is generated endogenously from L-arginine by the action of various isoforms of NOS. Both gases have been transpired as the key and independent regulators of many physiological functions in mammalian cardiovascular, nervous, gastrointestinal, respiratory, and immune systems. The analogy between these two gasotransmitters is evident not only from their paracrine mode of signaling, but also from the identical and/or shared signaling transduction pathways. With the plethora of research in the pathophysiological role of gasotransmitters in various systems, the existence of interplay between these gases is being widely accepted. Chemical interaction between NO and H2S may generate nitroxyl (HNO), which plays a specific effective role within the cardiovascular system. In this review article, we have attempted to provide current understanding of the individual and interactive roles of H2S and NO signaling in mammalian cardiovascular system, focusing particularly on heart contractility, cardioprotection, vascular tone, angiogenesis, and oxidative stress. PMID:26640616

Antioxidant properties of xanthones from Calophyllum brasiliense: prevention of oxidative damage induced by FeSO4

PubMed Central

2013-01-01

Background Reactive oxygen species (ROS) are important mediators in a number of degenerative diseases. Oxidative stress refers to the imbalance between the production of ROS and the ability to scavenge these species through endogenous antioxidant systems. Since antioxidants can inhibit oxidative processes, it becomes relevant to describe natural compounds with antioxidant properties which may be designed as therapies to decrease oxidative damage and stimulate endogenous cytoprotective systems. The present study tested the protective effect of two xanthones isolated from the heartwood of Calophyllum brasilienses against FeSO4-induced toxicity. Methods Through combinatory chemistry assays, we evaluated the superoxide (O2●—), hydroxyl radical (OH●), hydrogen peroxide (H2O2) and peroxynitrite (ONOO—) scavenging capacity of jacareubin (xanthone III) and 2-(3,3-dimethylallyl)-1,3,5,6-tetrahydroxyxanthone (xanthone V). The effect of these xanthones on murine DNA and bovine serum albumin degradation induced by an OH• generator system was also evaluated. Additionally, we investigated the effect of these xanthones on ROS production, lipid peroxidation and glutathione reductase (GR) activity in FeSO4-exposed brain, liver and lung rat homogenates. Results Xanthone V exhibited a better scavenging capacity for O2●—, ONOO- and OH● than xanthone III, although both xanthones were unable to trap H2O2. Additionally, xanthones III and V prevented the albumin and DNA degradation induced by the OH● generator system. Lipid peroxidation and ROS production evoked by FeSO4 were decreased by both xanthones in all tissues tested. Xanthones III and V also prevented the GR activity depletion induced by pro-oxidant activity only in the brain. Conclusions Altogether, the collected evidence suggests that xanthones can play a role as potential agents to attenuate the oxidative damage produced by different pro-oxidants. PMID:24119308

Acidithiobacillus caldus Sulfur Oxidation Model Based on Transcriptome Analysis between the Wild Type and Sulfur Oxygenase Reductase Defective Mutant

PubMed Central

Chen, Linxu; Ren, Yilin; Lin, Jianqun; Liu, Xiangmei; Pang, Xin; Lin, Jianqiang

2012-01-01

Background Acidithiobacillus caldus (A. caldus) is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs) for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox) system (omitting SoxCD), non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR). The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system. Results An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor) was created and its growth abilities were measured in media using elemental sulfur (S0) and tetrathionate (K2S4O6) as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR) of the wild type and the Δsor mutant in S0 and K2S4O6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO) and heterodisulfide reductase (HDR), the truncated Sox pathway, and the S4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media. Conclusion An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized. PMID:22984393

Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

PubMed

Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

2014-01-01

The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

Cysteine oxidation impairs systemic glucocorticoid responsiveness in children with difficult-to-treat asthma.

PubMed

Stephenson, Susan T; Brown, Lou Ann S; Helms, My N; Qu, Hongyan; Brown, Sheena D; Brown, Milton R; Fitzpatrick, Anne M

2015-08-01

The mechanisms underlying glucocorticoid responsiveness are largely unknown. Although redox regulation of the glucocorticoid receptor (GR) has been reported, it has not been studied in asthmatic patients. We characterized systemic cysteine oxidation and its association with inflammatory and clinical features in healthy children and children with difficult-to-treat asthma. We hypothesized that cysteine oxidation would be associated with increased markers of oxidative stress and inflammation, increased features of asthma severity, decreased clinically defined glucocorticoid responsiveness, and impaired GR function. PBMCs were collected from healthy children (n = 16) and children with asthma (n = 118) aged 6 to 17 years. Children with difficult-to-treat asthma underwent glucocorticoid responsiveness testing with intramuscular triamcinolone. Cysteine, cystine, and inflammatory chemokines and reactive oxygen species generation were quantified, and expression and activity of the GR were assessed. Cysteine oxidation was present in children with difficult-to-treat asthma and accompanied by increased reactive oxygen species generation and increased CCL3 and CXCL1 mRNA expression. Children with the greatest extent of cysteine oxidation had more features of asthma severity, including poorer symptom control, greater medication use, and less glucocorticoid responsiveness despite inhaled glucocorticoid therapy. Cysteine oxidation also modified the GR protein by decreasing available sulfhydryl groups and decreasing nuclear GR expression and activity. A highly oxidized cysteine redox state promotes a posttranslational modification of the GR that might inhibit its function. Given that cysteine oxidation is prevalent in children with difficult-to-treat asthma, the cysteine redox state might represent a potential therapeutic target for restoration of glucocorticoid responsiveness in this population. Copyright © 2015 American Academy of Allergy, Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

Plant polyphenols mobilize nuclear copper in human peripheral lymphocytes leading to oxidatively generated DNA breakage: implications for an anticancer mechanism.

PubMed

Shamim, Uzma; Hanif, Sarmad; Ullah, M F; Azmi, Asfar S; Bhat, Showket H; Hadi, S M

2008-08-01

It was earlier proposed that an important anti-cancer mechanism of plant polyphenols may involve mobilization of endogenous copper ions, possibly chromatin-bound copper and the consequent pro-oxidant action. This paper shows that plant polyphenols are able to mobilize nuclear copper in human lymphocytes, leading to degradation of cellular DNA. A cellular system of lymphocytes isolated from human peripheral blood and comet assay was used for this purpose. Incubation of lymphocytes with neocuproine (a cell membrane permeable copper chelator) inhibited DNA degradation in intact lymphocytes. Bathocuproine, which is unable to permeate through the cell membrane, did not cause such inhibition. This study has further shown that polyphenols are able to degrade DNA in cell nuclei and that such DNA degradation is inhibited by neocuproine as well as bathocuproine (both of which are able to permeate the nuclear pore complex), suggesting that nuclear copper is mobilized in this reaction. Pre-incubation of lymphocyte nuclei with polyphenols indicates that it is capable of traversing the nuclear membrane. This study has also shown that polyphenols generate oxidative stress in lymphocyte nuclei which is inhibited by scavengers of reactive oxygen species (ROS) and neocuproine. These results indicate that the generation of ROS occurs through mobilization of nuclear copper resulting in oxidatively generated DNA breakage.

Pathophysiology of mitochondrial lipid oxidation: Role of 4-hydroxynonenal (4-HNE) and other bioactive lipids in mitochondria.

PubMed

Xiao, Mengqing; Zhong, Huiqin; Xia, Lin; Tao, Yongzhen; Yin, Huiyong

2017-10-01

Mitochondrial lipids are essential for maintaining the integrity of mitochondrial membranes and the proper functions of mitochondria. As the "powerhouse" of a cell, mitochondria are also the major cellular source of reactive oxygen species (ROS). Oxidative stress occurs when the antioxidant system is overwhelmed by overproduction of ROS. Polyunsaturated fatty acids in mitochondrial membranes are primary targets for ROS attack, which may lead to lipid peroxidation (LPO) and generation of reactive lipids, such as 4-hydroxynonenal. When mitochondrial lipids are oxidized, the integrity and function of mitochondria may be compromised and this may eventually lead to mitochondrial dysfunction, which has been associated with many human diseases including cancer, cardiovascular diseases, diabetes, and neurodegenerative diseases. How mitochondrial lipids are oxidized and the underlying molecular mechanisms and pathophysiological consequences associated with mitochondrial LPO remain poorly defined. Oxidation of the mitochondria-specific phospholipid cardiolipin and generation of bioactive lipids through mitochondrial LPO has been increasingly recognized as an important event orchestrating apoptosis, metabolic reprogramming of energy production, mitophagy, and immune responses. In this review, we focus on the current understanding of how mitochondrial LPO and generation of bioactive lipid mediators in mitochondria are involved in the modulation of mitochondrial functions in the context of relevant human diseases associated with oxidative stress. Copyright © 2017 Elsevier Inc. All rights reserved.

Low-temperature liquid precursors of crystalline metal oxides assisted by heterogeneous photocatalysis.

PubMed

Bretos, Iñigo; Jiménez, Ricardo; Pérez-Mezcua, Dulce; Salazar, Norberto; Ricote, Jesús; Calzada, M Lourdes

2015-04-24

The photocatalytically assisted decomposition of liquid precursors of metal oxides incorporating TiO2 particles enables the preparation of functional layers from the ferroelectric Pb(Zr,Ti)O3 and multiferroic BiFeO3 perovskite systems at temperatures not exceeding 350 ºC. This enables direct deposition on flexible plastic, where the multifunctionality provided by these complex-oxide materials guarantees their potential use in next-generation flexible electronics. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Beyond Graphene: Advanced 2D Electronic and Optoelectronic Crystals and Devices for Next Generation Applications

DTIC Science & Technology

2015-06-25

layered systems including transitional metal dichalcogenides, oxides and nitrides which have an exciting spectrum of electronic, optical, thermal and...disulfide (WS2)islands materials were prepared by using H2S gas and Tungsten oxide thin films at 950C. Both AFM and FEG-SEM showed the triangular...gains defects after few layers growth. They also reported the property of h-BN protecting Ni from oxidation up to 1100C; it is more difficult to grow

Development of a Novel Efficient Solid-Oxide Hybrid for Co-generation of Hydrogen and Electricity Using Nearby Resources for Local Application

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

Tao, Greg, G.; Virkar, Anil, V.; Bandopadhyay, Sukumar

2009-06-30

Developing safe, reliable, cost-effective, and efficient hydrogen-electricity co-generation systems is an important step in the quest for national energy security and minimized reliance on foreign oil. This project aimed to, through materials research, develop a cost-effective advanced technology cogenerating hydrogen and electricity directly from distributed natural gas and/or coal-derived fuels. This advanced technology was built upon a novel hybrid module composed of solid-oxide fuel-assisted electrolysis cells (SOFECs) and solid-oxide fuel cells (SOFCs), both of which were in planar, anode-supported designs. A SOFEC is an electrochemical device, in which an oxidizable fuel and steam are fed to the anode and cathode,more » respectively. Steam on the cathode is split into oxygen ions that are transported through an oxygen ion-conducting electrolyte (i.e. YSZ) to oxidize the anode fuel. The dissociated hydrogen and residual steam are exhausted from the SOFEC cathode and then separated by condensation of the steam to produce pure hydrogen. The rationale was that in such an approach fuel provides a chemical potential replacing the external power conventionally used to drive electrolysis cells (i.e. solid oxide electrolysis cells). A SOFC is similar to the SOFEC by replacing cathode steam with air for power generation. To fulfill the cogeneration objective, a hybrid module comprising reversible SOFEC stacks and SOFC stacks was designed that planar SOFECs and SOFCs were manifolded in such a way that the anodes of both the SOFCs and the SOFECs were fed the same fuel, (i.e. natural gas or coal-derived fuel). Hydrogen was produced by SOFECs and electricity was generated by SOFCs within the same hybrid system. A stand-alone 5 kW system comprising three SOFEC-SOFC hybrid modules and three dedicated SOFC stacks, balance-of-plant components (including a tailgas-fired steam generator and tailgas-fired process heaters), and electronic controls was designed, though an overall integrated system assembly was not completed because of limited resources. An inexpensive metallic interconnects fabrication process was developed in-house. BOP components were fabricated and evaluated under the forecasted operating conditions. Proof-of-concept demonstration of cogenerating hydrogen and electricity was performed, and demonstrated SOFEC operational stability over 360 hours with no significant degradation. Cost analysis was performed for providing an economic assessment of the cost of hydrogen production using the targeted hybrid technology, and for guiding future research and development.« less

Electrophotolysis oxidation system for measurement of organic concentration in water

NASA Technical Reports Server (NTRS)

Winkler, H. E. (Inventor)

1981-01-01

Methods and apparatus for determining organic carbon in aqueous solution are described. The method comprises subjecting the aqueous solution to electrolysis, for generating oxygen from water, and simultaneously to ultraviolet radiation, for oxidation of substantially all organic carbon to carbon dioxide. The carbon dioxide is measured and the value is related to the concentration of organic carbon in the aqueous solution.

OXIDATION OF ALKANES WITH AIR USING IRON AND MANGANESE CATALYSTS. AN OVERALL GREEN CHEMISTRY APPROACH INCLUDING THE USE OF ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II

EPA Science Inventory

The selective oxidation of alkanes is an industrially important process that is often plagued by low conversions and the formation of unwanted by-products. Research being conducted at the USEPA, implements a Green chemistry approach which is utilized to improve these difficult o...

[Efficiency of oxidant gas generator cells powered by electric or solar energy].

PubMed

Brust Carmona, H; Benitez, A; Zarco, J; Sánchez, E; Mascher, I

1998-02-01

Diseases caused by microbial contaminants in drinking water continue to be a serious problem in countries like Mexico. Chlorination, using chlorine gas or chlorine compounds, is one of the best ways to treat drinking water. However, difficulties in handling chlorine gas and the inefficiency of hypochlorite solution dosing systems--due to sociopolitical, economic, and cultural factors--have reduced the utility of these chlorination procedures, especially in far-flung and inaccessible rural communities. These problems led to the development of appropriate technologies for the disinfection of water by means of the on-site generation of mixed oxidant gases (chlorine and ozone). This system, called MOGGOD, operates through the electrolysis of a common salt solution. Simulated system evaluation using a hydraulic model allowed partial and total costs to be calculated. When powered by electrical energy from the community power grid, the system had an efficiency of 90%, and in 10 hours it was able to generate enough gases to disinfect about 200 m3 of water at a cost of approximately N$8 (US $1.30). When the electrolytic cell was run on energy supplied through a photoelectric cell, the investment costs were higher. A system fed by photovoltaic cells could be justified in isolated communities that lack electricity but have a gravity-fed water distribution system.

Continuous-flow synthesis of functionalized phenols by aerobic oxidation of Grignard reagents.

PubMed

He, Zhi; Jamison, Timothy F

2014-03-24

Phenols are important compounds in chemical industry. An economical and green approach to phenol preparation by the direct oxidation of aryl Grignard reagents using compressed air in continuous gas-liquid segmented flow systems is described. The process tolerates a broad range of functional groups, including oxidation-sensitive functionalities such as alkenes, amines, and thioethers. By integrating a benzyne-mediated in-line generation of arylmagnesium intermediates with the aerobic oxidation, a facile three-step, one-flow process, capable of preparing 2-functionalized phenols in a modular fashion, is established. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Subcritical and supercritical water oxidation of organic, wet wastes for carbon cycling in regenerative life support systems

NASA Astrophysics Data System (ADS)

Ronsse, Frederik; Lasseur, Christophe; Rebeyre, Pierre; Clauwaert, Peter; Luther, Amanda; Rabaey, Korneel; Zhang, Dong Dong; López Barreiro, Diego; Prins, Wolter; Brilman, Wim

2016-07-01

For long-term human spaceflight missions, one of the major requirements is the regenerative life support system which has to be capable of recycling carbon, nutrients and water from both solid and liquid wastes generated by the crew and by the local production of food through living organisms (higher plants, fungi, algae, bacteria, …). The European Space Agency's Life Support System, envisioned by the MELiSSA project, consists of a 5 compartment artificial ecosystem, in which the waste receiving compartment (so-called compartment I or briefly 'CI') is based on thermophilic fermentation. However, as the waste generated by the crew compartment and food production compartment contain typical plant fibres (lignin, cellulose and hemicellulose), these recalcitrant fibres end up largely unaffected in the digestate (sludge) generated in the C-I compartment. Therefore, the C-I compartment has to be supplemented with a so-called fibre degradation unit (in short, FDU) for further oxidation or degradation of said plant fibres. A potential solution to degrading these plant fibres and other recalcitrant organics is their oxidation, by means of subcritical or supercritical water, into reusable CO2 while retaining the nutrients in an organic-free liquid effluent. By taking advantage of the altered physicochemical properties of water above or near its critical point (647 K, 22.1 MPa) - including increased solubility of non-polar compounds and oxygen, ion product and diffusivity - process conditions can be created for rapid oxidation of C into CO2. In this research, the oxidizer is provided as a hydrogen peroxide solution which, at elevated temperature, will dissociated into O2. The purpose of this study is to identify ideal process conditions which (a) ensure complete oxidation of carbon, (b) retaining the nutrients other than C in the liquid effluent and (c) require as little oxidizer as possible. Experiments were conducted on a continuous, tubular heated reactor and on batch micro-autoclaves and the experimental variables considered where temperature (and corresponding saturated vapour pressure), residence time and oxidizer-to-feed ratio. The feed material was sludge from the C-I compartment treating MELiSSA model waste (vegetables, toilet paper, feces). The feed was diluted down to 1 wt% DM. Our experimental results show that, given sufficient residence time, complete or near-complete (>90%) oxidation of carbon at supercritical (in case 400°C) conditions can be attained. However, the most influencing parameter is the stoichiometric oxidizer-to-feed ratio. Below ratios of 1.5, incomplete oxidation occurred together with the formation of char or tar-like carbonaceous dispersion in the effluent. Gas phase chromatographic analysis confirmed the presence of significant quantities of O2, formed out of the hydrogen peroxide supplied and not having taking part in the oxidation reaction.

Identification of novel loci for the generation of reporter mice

PubMed Central

Rebecchi, Monica; Levandis, Giovanna

2017-01-01

Abstract Deciphering the etiology of complex pathologies at molecular level requires longitudinal studies encompassing multiple biochemical pathways (apoptosis, proliferation, inflammation, oxidative stress). In vivo imaging of current reporter animals enabled the spatio-temporal analysis of specific molecular events, however, the lack of a multiplicity of loci for the generalized and regulated expression of the integrated transgenes hampers the creation of systems for the simultaneous analysis of more than a biochemical pathways at the time. We here developed and tested an in vivo-based methodology for the identification of multiple insertional loci suitable for the generation of reliable reporter mice. The validity of the methodology was tested with the generation of novel mice useful to report on inflammation and oxidative stress. PMID:27899606

Oxidative Stress, Unfolded Protein Response, and Apoptosis in Developmental Toxicity

PubMed Central

Kupsco, Allison; Schlenk, Daniel

2016-01-01

Physiological development requires precise spatiotemporal regulation of cellular and molecular processes. Disruption of these key events can generate developmental toxicity in the form of teratogenesis or mortality. The mechanism behind many developmental toxicants remains unknown. While recent work has focused on the unfolded protein response (UPR), oxidative stress, and apoptosis in the pathogenesis of disease, few studies have addressed their relationship in developmental toxicity. Redox regulation, UPR, and apoptosis are essential for physiological development and can be disturbed by a variety of endogenous and exogenous toxicants to generate lethality and diverse malformations. This review examines the current knowledge of the role of oxidative stress, UPR, and apoptosis in physiological development as well as in developmental toxicity, focusing on studies and advances in vertebrates model systems. PMID:26008783

Environmentally friendly chemoselective oxidation of primary aliphatic amines by using a biomimetic electrocatalytic system.

PubMed

Largeron, Martine; Chiaroni, Angèle; Fleury, Maurice-Bernard

2008-01-01

Environmentally friendly oxidation of primary aliphatic amines to imines has been successfully achieved, under metal-free conditions, by the use of diverse electrogenerated o-azaquinone mediators. High catalytic performance, together with high chemoselectivity, were observed with electron-poor o-azaquinone catalysts generated from 2-aminoresorcinol derivatives. Similar to copper amine oxidase enzymes, these mediators exhibited lower reactivity toward alpha-branched primary amines and no reactivity toward secondary amines. In the case of 3,4-aminophenol derivatives lacking a 2-hydroxy group, the generated o-azaquinone species failed to catalyze the oxidation of the amine to the corresponding imine. Further mechanistic considerations allowed a rationalization of the crucial role of the 2-hydroxy group in converting a catalytically inert species into a highly effective biomimetic catalyst.

Interaction of butylated hydroxyanisole with mitochondrial oxidative phosphorylation.

PubMed

Fusi, F; Sgaragli, G; Murphy, M P

1992-03-17

The antioxidant, butylated hydroxyanisole (BHA), has a number of effects on mitochondrial oxidative phosphorylation. In this study we apply the novel approach developed by Brand (Brand MD, Biochim Biophys Acta 1018: 128-133, 1990) to investigate the site of action of BHA on oxidative phosphorylation in rat liver mitochondria. Using this approach we show that BHA increases the proton leak through the mitochondrial inner membrane and that it also inhibits the delta p (proton motive force across the mitochondrial inner membrane) generating system, but has no effect on the phosphorylation system. This demonstrates that compounds having pleiotypic effects on mitochondrial oxidative phosphorylation in vitro can be analysed and their many effects distinguished. This approach is of general use in analysing many other compounds of pharmacological interest which interact with mitochondria. The implications of these results for the mechanism of interaction of BHA with mitochondrial oxidative phosphorylation are discussed.

Selective Oxidation of Lignin Model Compounds.

PubMed

Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K; Ralph, John

2018-05-02

Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation and Detoxification of Reactive Oxygen Species

ERIC Educational Resources Information Center

Kuciel, Radoslawa; Mazurkiewicz, Aleksandra

2004-01-01

A model of reactive oxygen species metabolism is proposed as a laboratory exercise for students. The superoxide ion in this model is generated during the reaction of oxidation of xanthine, catalyzed by xanthine oxidase. The effect of catalase, superoxide dismutase, and allopurinol on superoxide ion generation and removal in this system is also…

Highly efficient binuclear ruthenium catalyst for water oxidation.

PubMed

Sander, Anett C; Maji, Somnath; Francàs, Laia; Böhnisch, Torben; Dechert, Sebastian; Llobet, Antoni; Meyer, Franc

2015-05-22

Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generating dioxygen, is a major challenge in the field. Herein, we introduce a new, and rationally designed, pyrazolate-based diruthenium complex with the highest activity in water oxidation catalysis for binuclear systems reported to date. Single-crystal X-ray diffraction showed favorable preorganization of the metal ions, well suited for binding two water molecules at a distance adequate for OO bond formation; redox titrations as well as spectroelectrochemistry allowed characterization of the system in several oxidation states. Low oxidation potentials reflect the trianionic character of the elaborate compartmental pyrazolate ligand furnished with peripheral carboxylate groups. Water oxidation has been mediated both by a chemical oxidant (Ce(IV) )-by means of manometry and a Clark electrode for monitoring the dioxygen production-and electrochemically with impressive activities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enzymes oxidizing the azo dye 1-phenylazo-2-naphthol (Sudan I) and their contribution to its genotoxicity and carcinogenicity.

PubMed

Stiborova, Marie; Schmeiser, Heinz H; Frei, Eva; Hodek, Petr; Martinek, Vaclav

2014-01-01

Sudan I [1-(phenylazo)-2-naphthol, C.I. Solvent Yellow 14] is an industrial dye, which was found as a contaminant in numerous foods in several European countries. Because Sudan I has been assigned by the IARC as a Category 3 carcinogen, the European Union decreed that it cannot be utilized as food colorant in any European country. Sudan I induces the malignancies in liver and urinary bladder of rats and mice. This carcinogen has also been found to be a potent mutagen, contact allergen and sensitizer, and exhibits clastogenic properties. The oxidation of Sudan I increases its toxic effects and leads to covalent adducts in DNA. Identification of enzymatic systems that contribute to Sudan I oxidative metabolism to reactive intermediates generating such covalent DNA adducts on the one hand, and to the detoxification of this carcinogen on the other, is necessary to evaluate susceptibility to this toxicant. This review summarizes the identification of such enzymes and the molecular mechanisms of oxidation reactions elucidated to date. Human and animal cytochrome P450 (CYP) and peroxidases are capable of oxidizing Sudan I. Of the CYP enzymes, CYP1A1 is most important both in Sudan I detoxification and its bio-activation. Ring-hydroxylated metabolites and a dimer of this carcinogen were found as detoxification products of Sudan I generated with CYPs and peroxidases, respectively. Oxidative bio-activation of this azo dye catalyzed by CYPs and peroxidases leads to generation of proximate genotoxic metabolites (the CYP-catalyzed formation of the benzenediazonium cation and the peroxidase-mediated generation of one-electron oxidation products), which covalently modify DNA both in vitro and in vivo. The predominant DNA adduct generated with the benzenediazonium cation was characterized to be 8-(phenylazo)guanine. The Sudan I radical species mediated by peroxidases reacts with the -NH2 group in (deoxy)guanosine, generating the 4-[(deoxy)guanosin-N(2)-yl]Sudan I product. Sudan I was also found to be a strong inducer of CYP1A1 and its enzyme activity mediated by the aryl hydrocarbon receptor, thereby increasing its own genotoxic potential and the cancer risk for humans.

Highly sensitive determination of transient generation of biophotons during hypersensitive response to cucumber mosaic virus in cowpea.

PubMed

Kobayashi, Masaki; Sasaki, Kensuke; Enomoto, Masaru; Ehara, Yoshio

2007-01-01

The hypersensitive response (HR) is one mechanism of the resistance of plants to pathogen infection. It involves the generation of reactive oxygen species (ROS) which have crucial roles in signal transduction or as toxic agents leading to cell death. Often, ROS generation is accompanied by an ultraweak photon emission resulting from radical reactions that are initiated by ROS through the oxidation of living materials such as lipids, proteins, and DNA. This photon emission, referred to as 'biophotons', is extremely weak, but, based on the technique of photon counting imaging, a system has been developed to analyse the spatiotemporal properties of photon emission. Using this system, the dynamics of photon emission which might be associated with the oxidative burst, which promotes the HR, have been determined. Here, the transient generation of biophotons is demonstrated during the HR process in cowpea elicited by cucumber mosaic virus. The distinctive dynamics in spatiotemporal properties of biophoton emission during the HR expression on macroscopic and microscopic levels are also described. This study reveals the involvement of ROS generation in biophoton emission in the process of HR through the determination of the inhibitory effect of an antioxidant (Tiron) on biophoton emission.

From O2 to H2S: a landscape view of gas biology.

PubMed

Kashiba, Misato; Kajimura, Mayumi; Goda, Nobuhito; Suematsu, Makoto

2002-03-01

The majority of molecular oxygen (O2) consumed in the body is used as a substrate of cytochrome c oxidase to maintain oxidative phosphorylation for ATP synthesis. Rest of the O2 is used for oxidative biosynthesis including synthesis of vasoactive substances such as prostaglandins and secondary gaseous mediators such as nitric oxide (NO) and carbon monoxide (CO). Thus, O2 is not only used for maintenance of energy supply but also for regulating blood supply into tissues. Nitrous oxide (N2O), laughing gas for anesthesia, is generated endogenously through NO reductase in bacteria and fungi, and has recently been shown to modulate N-methyl-D-aspartic acid (NMDA) receptor function. A number of other biologically active gases could participate in regulation of cell and tissue functions. Carbon dioxide (CO2) is generated mainly through the Krebs cycle as a result of glucose oxidation and serves as a potent vasodilator, and hydrogen sulfide (H2S) synthesized through degradation of cysteine has recently been postulated to be a neuromodulator, although their receptor proteins for signaling have not been verified as a discernible molecular entity. Easy penetration allow these gases to access the inner space of receptor proteins and to execute their biological actions. These gases are generated and consumed in anaerobic bacteria through varied reactions distinct from those in mammals. This review summarizes recent information on mechanisms for gas generation and reception in biological systems.

Oxidative stress drivers and modulators in obesity and cardiovascular disease: from biomarkers to therapeutic approach.

PubMed

Santilli, F; Guagnano, M T; Vazzana, N; La Barba, S; Davi, G

2015-01-01

This review article is intended to describe how oxidative stress regulates cardiovascular disease development and progression. Epigenetic mechanisms related to oxidative stress, as well as more reliable biomarkers of oxidative stress, are emerging over the last years as potentially useful tools to design therapeutic approaches aimed at modulating enhanced oxidative stress "in vivo", thereby mitigating the consequent atherosclerotic burden. As a paradigm, we describe the case of obesity, in which the intertwining among oxidative stress, due to caloric overload, chronic low-grade inflammation induced by adipose tissue dysfunction, and platelet activation represents a vicious cycle favoring the progression of atherothrombosis. Oxidative stress is a major player in the pathobiology of cardiovascular disease (CVD). Reactive oxygen species (ROS)- dependent signaling pathways prompt transcriptional and epigenetic dysregulation, inducing chronic low-grade inflammation, platelet activation and endothelial dysfunction. In addition, several oxidative biomarkers have been proposed with the potential to improve current understanding of the mechanisms underlying CVD. These include ROS-generating and/or quenching molecules, and ROS-modified compounds, such as F2-isoprostanes. There is also increasing evidence that noncoding micro- RNA (mi-RNA) are critically involved in post- transcriptional regulation of cell functions, including ROS generation, inflammation, regulation of cell proliferation, adipocyte differentiation, angiogenesis and apoptosis. These molecules have promising translational potential as both markers of disease and site of targeted interventions. Finally, oxidative stress is a critical target of several cardioprotective drugs and nutraceuticals, including antidiabetic agents, statins, renin-angiotensin system blockers, polyphenols and other antioxidants. Further understanding of ROS-generating mechanisms, their biological role as well as potential therapeutic implications would translate into consistent benefits for effective CV prevention.

Protein oxidative modifications during electrospray ionization: solution phase electrochemistry or corona discharge-induced radical attack?

PubMed

Boys, Brian L; Kuprowski, Mark C; Noël, James J; Konermann, Lars

2009-05-15

The exposure of solution-phase proteins to reactive oxygen species (ROS) causes oxidative modifications, giving rise to the formation of covalent +16 Da adducts. Electrospray ionization (ESI) mass spectrometry (MS) is the most widely used method for monitoring the extent of these modifications. Unfortunately, protein oxidation can also take place as an experimental artifact during ESI, such that it may be difficult to assess the actual level of oxidation in bulk solution. Previous work has demonstrated that ESI-induced oxidation is highly prevalent when operating at strongly elevated capillary voltage V(0) (e.g., +8 kV) and with oxygen nebulizer gas in the presence of a clearly visible corona discharge. Protein oxidation under these conditions is commonly attributed to OH radicals generated in the plasma of the discharge. On the other hand, charge balancing oxidation reactions are known to take place at the metal/liquid interface of the emitter. Previous studies have not systematically explored whether such electrochemical processes could be responsible for the formation of oxidative +16 Da adducts instead of (or in combination with) plasma-generated ROS. Using hemoglobin as a model system, this work illustrates the occurrence of extensive protein oxidation even under typical operating conditions (e.g., V(0) = 3.5 kV, N(2) nebulizer gas). Surprisingly, measurements of the current flowing in the ESI circuit demonstrate that a weak corona discharge persists for these relatively gentle settings. On the basis of comparative experiments with nebulizer gases of different dielectric strength, it is concluded that ROS generated under discharge conditions are solely responsible for ESI-induced protein oxidation. This result is corroborated through off-line electrolysis experiments designed to mimic the electrochemical processes taking place during ESI. Our findings highlight the necessity of using easily oxidizable internal standards in biophysical or biomedical ESI-MS studies where knowledge of protein oxidation in bulk solution is desired. Strategies for eliminating ESI-induced oxidation artifacts are discussed.

Vacuum distillation: vapor filtered-catalytic oxidation water reclamation system utilizing radioisotopes

NASA Technical Reports Server (NTRS)

Honegger, R. J.; Remus, G. A.; Kurg, E. K.

1971-01-01

The development of a functional model water reclamation system is discussed. The system produces potable water by distillation from the urine and respiration-perspiration condensate at the normal rate generated by four men. Basic processes employed are vacuum distillation, vapor filtration, vapor phase catalytic oxidation, and condensation. The system is designed to use four 75-watt isotope heaters for distillation thermal input, and one 45-watt isotope for the catalytic oxidation unit. The system is capable of collecting and storing urine, and provides for stabilizing the urine by chemical pretreatment. The functional model system is designed for operation in a weightless condition with liquid-vapor phase separators for the evaporator still, and centrifugal separators for urine collection and vapor condensation. The system provides for storing and dispensing reclaimed potable water. The system operates in a batch mode for 40 days, with urine residues accumulating in the evaporator. The evaporator still and residue are removed to storage and replaced with a fresh still for the next 40-day period.

Laccase-catalyzed oxidation of oxybenzone in municipal wastewater primary effluent.

PubMed

Garcia, Hector A; Hoffman, Catherine M; Kinney, Kerry A; Lawler, Desmond F

2011-02-01

Pharmaceuticals and personal care products (PPCPs) are now routinely detected in raw and treated municipal wastewater. Since conventional wastewater treatment processes are not particularly effective for PPCP removal, treated wastewater discharges are the main entry points for PPCPs into the environment, and eventually into our drinking water. This study investigates the use of laccase-catalyzed oxidation for removing low concentrations of PPCPs from municipal wastewater primary effluent. Oxybenzone was selected as a representative PPCP. Like many other PPCPs, it is not recognized directly by the laccase enzyme. Therefore, mediators were used to expand the oxidative range of laccase, and the efficacy of this laccase-mediator system in primary effluent was evaluated. Eight potential mediators were investigated, and 2,2'-Azino-bis(3-ethylbenzthiazoline-6sulphonic acid) diammonium salt (ABTS), a synthetic mediator, and acetosyringone (ACE), a natural mediator, provided the greatest oxybenzone removal efficiencies. An environmentally relevant concentration of oxybenzone (43.8 nM, 10 μg/L) in primary effluent was completely removed (below the detection limit) after two hours of treatment with ABTS, and 95% was removed after two hours of treatment with ACE. Several mediator/oxybenzone molar ratios were investigated at two different initial oxybenzone concentrations. Higher mediator/oxybenzone molar ratios were required at the lower (environmentally relevant) oxybenzone concentration, and ACE required higher molar ratios than ABTS to achieve comparable oxybenzone removal. Oxybenzone oxidation byproducts generated by the laccase-mediator system were characterized and compared to those generated during ozonation. Enzymatic treatment generated byproducts with higher mass to charge (m/z) ratios, likely due to oxidative coupling reactions. The results of this study suggest that, with further development, the laccase-mediator system has the potential to extend the treatment range of laccase to PPCPs not directly recognized by the enzyme, even in a primary effluent matrix. Copyright © 2011 Elsevier Ltd. All rights reserved.

Reactive oxygen species regulated mitochondria-mediated apoptosis in PC12 cells exposed to chlorpyrifos

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

Lee, Jeong Eun; Hanyang Biomedical Research Institute, Seoul; Park, Jae Hyeon

2012-09-01

Reactive oxidative species (ROS) generated by environmental toxicants including pesticides could be one of the factors underlying the neuronal cell damage in neurodegenerative diseases. In this study we found that chlorpyrifos (CPF) induced apoptosis in dopaminergic neuronal components of PC12 cells as demonstrated by the activation of caspases and nuclear condensation. Furthermore, CPF also reduced the tyrosine hydroxylase-positive immunoreactivity in substantia nigra of the rat. In addition, CPF induced inhibition of mitochondrial complex I activity. Importantly, N-acetyl cysteine (NAC) treatment effectively blocked apoptosis via the caspase-9 and caspase-3 pathways while NAC attenuated the inhibition of mitochondrial complex I activity asmore » well as the oxidative metabolism of dopamine (DA). These results demonstrated that CPF-induced apoptosis was involved in mitochondrial dysfunction through the production of ROS. In the response of cellular antioxidant systems to CPF, we found that CPF treatment increased HO-1 expression while the expression of CuZnSOD and MnSOD was reduced. In addition, we found that CPF treatment activated MAPK pathways, including ERK 1/2, the JNK, and the p38 MAP kinase in a time-dependent manner. NAC treatment abolished MAPK phosphorylation caused by CPF, indicating that ROS are upstream signals of MAPK. Interestingly, MAPK inhibitors abolished cytotoxicity and reduced ROS generation by CPF treatment. Our results demonstrate that CPF induced neuronal cell death in part through MAPK activation via ROS generation, suggesting its potential to generate oxidative stress via mitochondrial damage and its involvement in oxidative stress-related neurodegenerative disease. -- Highlights: ► Chlorpyrifos induces apoptosis. ► Chlorpyrifos inhibits mitochondrial complex I activity. ► ROS is involved in chlorpyrifos-induced apoptosis. ► Chlorpyrifos affects cellular antioxidant systems. ► Chlorpyrifos-induced apoptosis mediates activation of MAPK.« less

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

DOE PAGES

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

2017-09-01

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

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

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O-O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O-O radical coupling.

PubMed

Shaffer, David W; Xie, Yan; Concepcion, Javier J

2017-10-16

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O-O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O-O bond formation step as the key step in water oxidation catalysis. The two main pathways to accomplish this step, single-site water nucleophilic attack and O-O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.

Fuel Cell Power Plant Initiative. Volume 1; Solid Oxide Fuel Cell/Logistics Fuel Processor 27 kWe Power System Demonstration for ARPA

NASA Technical Reports Server (NTRS)

Veyo, S.E.

1997-01-01

This report describes the successful testing of a 27 kWe Solid Oxide Fuel Cell (SOFC) generator fueled by natural gas and/or a fuel gas produced by a brassboard logistics fuel preprocessor (LFP). The test period began on May 24, 1995 and ended on February 26, 1996 with the successful completion of all program requirements and objectives. During this time period, this power system produced 118.2 MWh of electric power. No degradation of the generator's performance was measured after 5582 accumulated hours of operation on these fuels: local natural gas - 3261 hours, jet fuel reformate gas - 766 hours, and diesel fuel reformate gas - 1555 hours. This SOFC generator was thermally cycled from full operating temperature to room temperature and back to operating temperature six times, because of failures of support system components and the occasional loss of test site power, without measurable cell degradation. Numerous outages of the LFP did not interrupt the generator's operation because the fuel control system quickly switched to local natural gas when an alarm indicated that the LFP reformate fuel supply had been interrupted. The report presents the measured electrical performance of the generator on all three fuel types and notes the small differences due to fuel type. Operational difficulties due to component failures are well documented even though they did not affect the overall excellent performance of this SOFC power generator. The final two appendices describe in detail the LFP design and the operating history of the tested brassboard LFP.

Ceriodaphnia dubia as a Potential Bio-Indicator for Assessing Acute Aluminum Oxide Nanoparticle Toxicity in Fresh Water Environment

PubMed Central

Pakrashi, Sunandan; Dalai, Swayamprava; Humayun, Ahmed; Chakravarty, Sujay; Chandrasekaran, Natarajan; Mukherjee, Amitava

2013-01-01

Growing nanomaterials based consumer applications have raised concerns about their potential release into the aquatic ecosystems and the consequent toxicological impacts. So environmental monitoring of the nanomaterials in aqueous systems becomes imperative. The current study reveals the potential of Ceriodaphnia dubia (C. dubia) as a bio-indicator for aluminum oxide nanoparticles in a fresh water aquatic ecosystem where it occupies an important ecological niche as a primary consumer. This study aims to investigate the aluminium oxide nanoparticle induced acute toxicity on Ceriodaphnia dubia in a freshwater system. The bioavailability of the aluminum oxide nanoparticles has been studied with respect to their aggregation behavior in the system and correlated with the toxicity endpoints. The oxidative stress generated by the particles contributed greatly toward their toxicity. The crucial role of leached aluminium ion mediated toxicity in the later phases (48 h and 72 h) in conjunction with the effects from the nano-sized particles in the initial phases (24 h) puts forth the dynamics of nanotoxicity in the test system. The internalization of nanoparticles (both gross and systemic uptake) as substantiated through the transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectral (ICP-OES) analysis was another major contributor toward acute toxicity. Concluding the present study, Ceriodaphnia dubia can be a promising candidate for bio-monitoring the aluminium oxide nanoparticles in a fresh water system. PMID:24040143

Ceriodaphnia dubia as a potential bio-indicator for assessing acute aluminum oxide nanoparticle toxicity in fresh water environment.

PubMed

Pakrashi, Sunandan; Dalai, Swayamprava; Humayun, Ahmed; Chakravarty, Sujay; Chandrasekaran, Natarajan; Mukherjee, Amitava

2013-01-01

Growing nanomaterials based consumer applications have raised concerns about their potential release into the aquatic ecosystems and the consequent toxicological impacts. So environmental monitoring of the nanomaterials in aqueous systems becomes imperative. The current study reveals the potential of Ceriodaphnia dubia (C. dubia) as a bio-indicator for aluminum oxide nanoparticles in a fresh water aquatic ecosystem where it occupies an important ecological niche as a primary consumer. This study aims to investigate the aluminium oxide nanoparticle induced acute toxicity on Ceriodaphnia dubia in a freshwater system. The bioavailability of the aluminum oxide nanoparticles has been studied with respect to their aggregation behavior in the system and correlated with the toxicity endpoints. The oxidative stress generated by the particles contributed greatly toward their toxicity. The crucial role of leached aluminium ion mediated toxicity in the later phases (48 h and 72 h) in conjunction with the effects from the nano-sized particles in the initial phases (24 h) puts forth the dynamics of nanotoxicity in the test system. The internalization of nanoparticles (both gross and systemic uptake) as substantiated through the transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectral (ICP-OES) analysis was another major contributor toward acute toxicity. Concluding the present study, Ceriodaphnia dubia can be a promising candidate for bio-monitoring the aluminium oxide nanoparticles in a fresh water system.

Microbial Photoelectrosynthesis for Self-Sustaining Hydrogen Generation

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

Lu, Lu; Williams, Nicholas B.; Turner, John A.

Current artificial photosynthesis (APS) systems are promising for the storage of solar energy via transportable and storable fuels, but the anodic half-reaction of water oxidation is an energy intensive process which in many cases poorly couples with the cathodic half-reaction. Here in this paper, we demonstrate a self-sustaining microbial photoelectrosynthesis (MPES) system that pairs microbial electrochemical oxidation with photoelectrochemical water reduction for energy efficient H 2 generation. MPES reduces the overall energy requirements thereby greatly expanding the range of semiconductors that can be utilized in APS. Due to the recovery of chemical energy from waste organics by the mild microbialmore » process and utilization of cost-effective and stable catalyst/electrode materials, our MPES system produced a stable current of 0.4 mA/cm 2 for 24 h without any external bias and ~10 mA/cm 2 with a modest bias under one sun illumination. Finally, this system also showed other merits, such as creating benefits of wastewater treatment and facile preparation and scalability.« less

Microbial Photoelectrosynthesis for Self-Sustaining Hydrogen Generation.

PubMed

Lu, Lu; Williams, Nicholas B; Turner, John A; Maness, Pin-Ching; Gu, Jing; Ren, Zhiyong Jason

2017-11-21

Current artificial photosynthesis (APS) systems are promising for the storage of solar energy via transportable and storable fuels, but the anodic half-reaction of water oxidation is an energy intensive process which in many cases poorly couples with the cathodic half-reaction. Here we demonstrate a self-sustaining microbial photoelectrosynthesis (MPES) system that pairs microbial electrochemical oxidation with photoelectrochemical water reduction for energy efficient H 2 generation. MPES reduces the overall energy requirements thereby greatly expanding the range of semiconductors that can be utilized in APS. Due to the recovery of chemical energy from waste organics by the mild microbial process and utilization of cost-effective and stable catalyst/electrode materials, our MPES system produced a stable current of 0.4 mA/cm 2 for 24 h without any external bias and ∼10 mA/cm 2 with a modest bias under one sun illumination. This system also showed other merits, such as creating benefits of wastewater treatment and facile preparation and scalability.

Microbial Photoelectrosynthesis for Self-Sustaining Hydrogen Generation

DOE PAGES

Lu, Lu; Williams, Nicholas B.; Turner, John A.; ...

2017-10-17

Current artificial photosynthesis (APS) systems are promising for the storage of solar energy via transportable and storable fuels, but the anodic half-reaction of water oxidation is an energy intensive process which in many cases poorly couples with the cathodic half-reaction. Here in this paper, we demonstrate a self-sustaining microbial photoelectrosynthesis (MPES) system that pairs microbial electrochemical oxidation with photoelectrochemical water reduction for energy efficient H 2 generation. MPES reduces the overall energy requirements thereby greatly expanding the range of semiconductors that can be utilized in APS. Due to the recovery of chemical energy from waste organics by the mild microbialmore » process and utilization of cost-effective and stable catalyst/electrode materials, our MPES system produced a stable current of 0.4 mA/cm 2 for 24 h without any external bias and ~10 mA/cm 2 with a modest bias under one sun illumination. Finally, this system also showed other merits, such as creating benefits of wastewater treatment and facile preparation and scalability.« less

Oxide Based Transistor for Flexible Displays

DTIC Science & Technology

2014-09-15

thin film transistors (TFTs) for next generation display technologies. A detailed and comprehensive study was carried out to ascertain the process...Box 12211 Research Triangle Park, NC 27709-2211 Thin film transistors , flexible electronics, RF sputtering, Transparent amorphous oxide semiconductors...NC A&T and RTI, International investigated In free GaSnZnO (GSZO) material system, as the active channel in thin film transistors (TFTs) for next

Automated system for on-line determination of dimethylarsinic and inorganic arsenic by hydride generation-atomic fluorescence spectrometry.

PubMed

Chaparro, L L; Ferrer, L; Cerdà, V; Leal, L O

2012-09-01

A multisyringe flow-injection approach has been coupled to hydride generation-atomic fluorescence spectrometry (HG-AFS) with UV photo-oxidation for dimethylarsinic (DMA), inorganic As and total As determination, depending on the pre-treatment given to the sample (extraction or digestion). The implementation of a UV lamp allows on-line photo-oxidation of DMA and the following arsenic detection, whereas a bypass leads the flow directly to the HG-AFS system, performing inorganic arsenic determination. DMA concentration is calculated by the difference of total inorganic arsenic and measurement of the photo-oxidation step. The detection limits for DMA and inorganic arsenic were 0.09 and 0.47 μg L(-1), respectively. The repeatability values accomplished were of 2.4 and 1.8%, whereas the injection frequencies were 24 and 28 injections per hour for DMA and inorganic arsenic, respectively. This method was validated by means of a solid reference material BCR-627 (muscle of tuna) with good agreement with the certified values. Satisfactory results for DMA and inorganic arsenic determination were obtained in several water matrices. The proposed method offers several advantages, such as increasing the sampling frequency, low detection limits and decreasing reagents and sample consumption, which leads to lower waste generation.

Exergy & economic analysis of biogas fueled solid oxide fuel cell systems

NASA Astrophysics Data System (ADS)

Siefert, Nicholas S.; Litster, Shawn

2014-12-01

We present an exergy and an economic analysis of a power plant that uses biogas produced from a thermophilic anaerobic digester (AD) to fuel a solid oxide fuel cell (SOFC). We performed a 4-variable parametric analysis of the AD-SOFC system in order to determine the optimal design operation conditions, depending on the objective function of interest. We present results on the exergy efficiency (%), power normalized capital cost ( kW-1), and the internal rate of return on investment, IRR, (% yr-1) as a function of the current density, the stack pressure, the fuel utilization, and the total air stoichiometric ratio. To the authors' knowledge, this is the first AD-SOFC paper to include the cost of the AD when conducting economic optimization of the AD-SOFC plant. Our calculations show that adding a new AD-SOFC system to an existing waste water treatment (WWT) plant could yield positives values of IRR at today's average electricity prices and could significantly out-compete other options for using biogas to generate electricity. AD-SOFC systems could likely convert WWT plants into net generators of electricity rather than net consumers of electricity while generating economically viable rates of return on investment if the costs of SOFC systems are within a factor of two of the DOE/SECA cost targets.

Potential risks from UV/H2O2 oxidation and UV photocatalysis: A review of toxic, assimilable, and sensory-unpleasant transformation products.

PubMed

Wang, Wen-Long; Wu, Qian-Yuan; Huang, Nan; Xu, Zi-Bin; Lee, Min-Yong; Hu, Hong-Ying

2018-05-15

UV based advanced oxidation processes (UV-AOPs) that efficiently eliminate organic pollutants during water treatment have been the subject of numerous investigations. Most organic pollutants are not completely mineralized during UV-AOPs but are partially oxidized into transformation products (TPs), thereby adding complexity to the treated water and posing risks to humans, ecological systems, and the environment. While the degradation kinetics and mechanisms of pollutants have been widely documented, there is little information about the risks associated with TPs. In this review, we have collated recent knowledge about the harmful TPs that are generated in UV/H 2 O 2 and UV photocatalysis, two UV-AOPs that have been studied extensively. Toxic and assimilable TPs were ubiquitously observed in more than 80% of UV-AOPs of organic pollutants, of which the toxicity and assimilability levels changed with variations in the reaction conditions, such as the UV fluence and oxidant dosage. Previous studies and modeling assessments showed that toxic and assimilable TPs may be generated during hydroxylation, dealkylation, decarboxylation, and deamination. Among various reactions, TPs generated from dealkylation and decarboxylation were generally less and more toxic than the parent pollutants, respectively; TPs generated from decarboxylation and deamination were generally less and more assimilable than the parent pollutants, respectively. There is also potential concern about the sensory-unpleasant TPs generated by oxidations and subsequent metabolism of microorganisms. In this overview, we stress the need to include both the concentrations of organic pollutants and the evaluations of the risks from TPs for the quality assessments of the water treated by UV-AOPs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Response of Salmonella Typhi to bile-generated oxidative stress: implication of quorum sensing and persister cell populations.

PubMed

Walawalkar, Yogesh D; Vaidya, Yatindra; Nayak, Vijayashree

2016-11-01

Salmonella Typhi can chronically persist within the gallbladder of patients suffering from gallbladder diseases. This study, intended to improve our understanding of bacterial mechanisms underlying bile adaptation, revealed that bile, which is a bactericidal agent, led to the generation of reactive oxygen species in S Typhi. Salmonella Typhi in response showed a significant increase in the production of anti-oxidative enzymes, namely superoxide dismutase and catalase. The work reports that the quorum-sensing (QS) system of S Typhi regulates the level of these enzymes during oxidative stress. In support of these observations, the quorum-sensing mutant of S Typhi was found to be sensitive to bile with significantly lower levels of anti-oxidant enzymes compared to other clinical isolates. Furthermore the addition of exogenous cell-free extracts (CFEs) of S Typhi containing the quorum-sensing signalling molecule significantly increased the levels of these enzymes within the mutant. Interestingly the CFE addition did not significantly restore the biofilm-forming ability of the mutant strain when compared with the wild-type. In the presence of ciprofloxacin and ampicillin, S Typhi formed persister cells which increased >3-fold in the presence of bile. Thus the QS-system of S Typhi aids in oxidative stress management, and enhanced persister cell populations could assist chronic bacterial persistence within the gallbladder. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

A Novel Inlet System for On-line Chemical Analysis of Semi-Volatile Submicron Particulate Matter

NASA Astrophysics Data System (ADS)

Wisthaler, A.; Eichler, P.; Müller, M.

2015-12-01

Semi-volatile organic molecules bound to particles are difficult to measure, especially if they are reactive in nature. Any technique based on aerosol collection onto a substrate generates sampling artifacts due to surface reactions and ad- and desorption of semi-volatile analytes. On-line sampling without sample pre-collection, as for example implemented in the AMS, has greatly reduced many sampling artifacts. AMS measurements of organics do, however, suffer from the drawback that molecular-level information is, in most cases, lost during hard ionization events. As a consequence, only little speciated and thus mechanistically informative data on organic matter is obtained. PTR-ToF-MS is a well-established on-line measurement technique for gas-phase organics. Soft ionization via gas-phase hydronium ions preserves, to a large extent, molecular-level information and thus allows identifying organic compounds at an elemental composition level. We have recently developed a particle inlet system for PTR-ToF-MS instruments (doi:10.5194/amt-8-1353-2015). The CHARON ("Chemical Analysis of Aerosol On-line") inlet consists of a gas-phase denuder, an aerodynamic lens and a thermodesorption unit. In its latest version, it includes a heatable tube upstream of the denuder to form a thermodenuder. Over the last year, the CHARON PTR-ToF-MS system has been successfully used in a series of measurement campaigns to characterize i) POA emitted from a marine diesel engine, ii) SOA generated from the photo-oxidation of toluene, iii) SOA generated from the photo-oxidation of selected amines, iv) ambient aerosol in two major European cities and v) SOA generated from the photo-oxidation of biogenic VOCs. These measurements have demonstrated that the CHARON PTR-ToF-MS system i) generates on-line and real-time elemental composition information of semi-volatile organics in submicron particles (both POA and SOA), ii) detects 80-100 % of the organic mass as measured by the AMS and iii) generates volatility information of semi-volatile organics at an elemental composition level. Selected application examples will be shown.

Chromium(iii) oxidation by biogenic manganese oxides with varying structural ripening.

PubMed

Tang, Yuanzhi; Webb, Samuel M; Estes, Emily R; Hansel, Colleen M

2014-09-20

Manganese (Mn) oxides, which are generally considered biogenic in origin within natural systems, are the only oxidants of Cr(iii) under typical environmental conditions. Yet the influence of Mn biooxide mineral structural evolution on Cr(iii) oxidation under varying geochemical conditions is unknown. In this study we examined the role of light, organic carbon, pH, and the structure of biogenic Mn oxides on Cr(iii) oxidation. Aging of Mn oxides produced by a marine bacterium within the widespread Roseobacter clade resulted in structural ripening from a colloidal hexagonal to a particulate triclinic birnessite phase. The structurally diverse Mn oxides were then reacted with aqueous Cr(iii) within artificial seawater in the presence or absence of carbon and light. Here we found that Cr(iii) oxidation capacity was highest at near neutral pH and in the combined presence of carbon and light. Mn oxide ripening from a hexagonal to a triclinic birnessite phase led to decreased Cr(iii) oxidation in the presence of carbon and light, whereas no change in reactivity was observed in the absence of carbon and/or in the dark. As only minimal Cr(iii) oxidation was observed in the absence of Mn oxides, these results strongly point to coupled Mn oxide- and photo-induced generation of organic and/or oxygen radicals involved in Cr(iii) oxidation. Based on Mn oxide concentration and structural trends, we postulate that Mn(ii) produced from the oxidation of Cr(iii) by the primary Mn oxide is recycled in the presence of organics and light conditions, (re)generating secondary hexagonal birnessite and thereby allowing for continuous oxidation of Cr(iii). In the absence of this Mn oxide regeneration, Cr(iii) induced structural ripening of the hexagonal birnessite precludes further Cr(iii) oxidation. These results highlight the complexity of reactions involved in Mn oxide mediated Cr(iii) oxidation and suggest that photochemical carbon reactions are requisite for sustained Cr(iii) oxidation and persistence of reactive Mn oxides.

Carbon Dioxide Addition to Microbial Fuel Cell Cathodes Maintains Sustainable Catholyte pH and Improves Anolyte pH, Alkalinity, and Conductivity

USDA-ARS?s Scientific Manuscript database

Bioelectrochemical system (BES) pH imbalances develop due to anodic proton-generating oxidation reactions and cathodic hydroxide-ion-generating reduction reactions. Until now, workers added unsustainable buffers to reduce the pH difference between the anode and cathode because the pH imbalance cont...

Note: Application of CR-39 plastic nuclear track detectors for quality assurance of mixed oxide fuel pellets

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

Kodaira, S., E-mail: koda@nirs.go.jp; Kurano, M.; Hosogane, T.

A CR-39 plastic nuclear track detector was used for quality assurance of mixed oxide fuel pellets for next-generation nuclear power plants. Plutonium (Pu) spot sizes and concentrations in the pellets are significant parameters for safe use in the plants. We developed an automatic Pu detection system based on dense α-radiation tracks in the CR-39 detectors. This system would greatly improve image processing time and measurement accuracy, and will be a powerful tool for rapid pellet quality assurance screening.

Thermal barrier coating experience in the gas turbine engine

NASA Technical Reports Server (NTRS)

Bose, S.; Demasi-Marcin, J.

1995-01-01

Thermal Barrier Coatings (TBC), provide thermal insulation and oxidation resistance in an environment consisting of hot combustion gases. TBC's consist of a two layer system. The outer ceramic layer provides good thermal insulation due to the low thermal conductivity of the ceramic coatings used, while the inner metallic bond coat layer provides needed oxidation resistance to the underlying superalloy. Pratt & Whitney has over a decade of experience with several generations of TBC systems on turbine airfoils. This paper will focus on the latest TBC field experience along with a proposed durability model.

Device for generation of pulsed corona discharge

DOEpatents

Gutsol, Alexander F [San Ramon, CA; Fridman, Alexander [Marlton, NJ; Blank, Kenneth [Philadelphia, PA; Korobtsev, Sergey [Moscow, RU; Shiryaevsky, Valery [Moscow, RU; Medvedev, Dmitry [Moscow, RU

2012-05-08

The invention is a method and system for the generation of high voltage, pulsed, periodic corona discharges capable of being used in the presence of conductive liquid droplets. The method and system can be used, for example, in different devices for cleaning of gaseous or liquid media using pulsed corona discharge. Specially designed electrodes and an inductor increase the efficiency of the system, permit the plasma chemical oxidation of detrimental impurities, and increase the range of stable discharge operations in the presence of droplets of water or other conductive liquids in the discharge chamber.

Field-controllable second harmonic generation at a graphene oxide heterointerface

NASA Astrophysics Data System (ADS)

Fernandes, Gustavo E.; Kim, Jin Ho; Osgood, Richard, III; Xu, Jimmy

2018-03-01

We report on the voltage-dependent SHG signal obtained in a reduced-graphene oxide (rGO)/p-type Si heterointerface. A simple qualitative model considering the interaction between the heterointerface depletion region potential and the naturally occurring surface dipole layer on the rGO is introduced to account for the characteristics of the SHG signal, specifically, a minimum point at ≈ -3 V bias on the rGO side of the interface. This feature-rich system has the potential to provide field-controllable surface-dipole moments and second-order nonlinearities, which may find applications in tunable nonlinear photonic devices for realizing second-harmonic generation and optical-rectification.

Cannabidiol as an Emergent Therapeutic Strategy for Lessening the Impact of Inflammation on Oxidative Stress

PubMed Central

Booz, George W.

2011-01-01

Oxidative stress with reactive oxygen species generation is a key weapon in the arsenal of the immune system for fighting invading pathogens and to initiate tissue repair. If excessive or unresolved, however, immune-related oxidative stress can initiate further increasing levels of oxidative stress that cause organ damage and dysfunction. Targeting oxidative stress in these various diseases therapeutically has proven more problematic than first anticipated given the complexities and perversity of both the underlying disease and the immune response. However, growing evidence suggests that the endocannabinoid system, which includes the CB1 and CB2 G protein-coupled receptors and their endogenous lipid ligands, may be an area that is ripe for therapeutic exploitation. In this context, the related nonpsychotropic cannabinoid cannabidiol, which may interact with the endocannabinoid system, but has actions that are distinct, offers promise as a prototype for anti-inflammatory drug development. This review discusses recent studies suggesting that cannabidiol may have utility in treating a number of human diseases and disorders now known to involve activation of the immune system and associated oxidative stress, as a contributor to their etiology and progression. These include rheumatoid arthritis, types I and II diabetes, atherosclerosis, Alzheimer’s disease, hypertension, the metabolic syndrome, ischemia-reperfusion injury, depression, and neuropathic pain. PMID:21238581

Peroxisomal plant metabolism - an update on nitric oxide, Ca2+ and the NADPH recycling network.

PubMed

Corpas, Francisco J; Barroso, Juan B

2018-01-29

Plant peroxisomes are recognized organelles that - with their capacity to generate greater amounts of H 2 O 2 than other subcellular compartments - have a remarkable oxidative metabolism. However, over the last 15 years, new information has shown that plant peroxisomes contain other important molecules and enzymes, including nitric oxide (NO), peroxynitrite, a NADPH-recycling system, Ca 2+ and lipid-derived signals, such as jasmonic acid (JA) and nitro-fatty acid (NO 2 -FA). This highlights the potential for complex interactions within the peroxisomal nitro-oxidative metabolism, which also affects the status of the cell and consequently its physiological processes. In this review, we provide an update on the peroxisomal interactions between all these molecules. Particular emphasis will be placed on the generation of the free-radical NO, which requires the presence of Ca 2+ , calmodulin and NADPH redox power. Peroxisomes possess several NADPH regeneration mechanisms, such as those mediated by glucose-6-phosphate dehydrogenase (G6PDH) and 6-phosphogluconate dehydrogenase (6PGDH) proteins, which are involved in the oxidative phase of the pentose phosphate pathway, as well as that mediated by NADP-isocitrate dehydrogenase (ICDH). The generated NADPH is also an essential cofactor across other peroxisomal pathways, including the antioxidant ascorbate-glutathione cycle and unsaturated fatty acid β-oxidation, the latter being a source of powerful signaling molecules such as JA and NO 2 -FA. © 2018. Published by The Company of Biologists Ltd.

Electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-01-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-09-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Nonintrusive Flowmeter

NASA Technical Reports Server (NTRS)

Greene, M. W.

1976-01-01

The results of analytical and experimental work performed in the design, fabrication, and test of a prototype nonintrusive gaging system for use in monitoring the consumption of earth-storable fuels and oxidants in either a one-g or a zero-g environment are explained. The design specifications were those applicable to the reaction control system and to the orbital maneuvering system (OMS) fuel and oxidant on the space shuttle while in orbit. The major requirement was for the measurement of flow pulses with sufficient accuracy to provide a continuous knowledge of the fuel and oxidant remaining in the OMS system to within 1% or better. An ultrasonic frequency chirp technique was used having a high inherent rejection for signals traversing stray paths, and for random noise generated by the flowing liquid. A detailed analysis of the frequency chirp approach for two modes of operation (period and phase changes), including an error analysis are reported.

Exergy analysis of a solid oxide fuel cell micropowerplant

NASA Astrophysics Data System (ADS)

Hotz, Nico; Senn, Stephan M.; Poulikakos, Dimos

In this paper, an analytical model of a micro solid oxide fuel cell (SOFC) system fed by butane is introduced and analyzed in order to optimize its exergetic efficiency. The micro SOFC system is equipped with a partial oxidation (POX) reformer, a vaporizer, two pre-heaters, and a post-combustor. A one-dimensional (1D) polarization model of the SOFC is used to examine the effects of concentration overpotentials, activation overpotentials, and ohmic resistances on cell performance. This 1D polarization model is extended in this study to a two-dimensional (2D) fuel cell model considering convective mass and heat transport along the fuel cell channel and from the fuel cell to the environment. The influence of significant operational parameters on the exergetic efficiency of the micro SOFC system is discussed. The present study shows the importance of an exergy analysis of the fuel cell as part of an entire thermodynamic system (transportable micropowerplant) generating electric power.

Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

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

Klobukowski, Erik

2011-01-01

This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallicmore » complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and conditions, it was found that the oxidative dehydrogenation of dibenzylamine to Nbenzylidenebenzylamine, with N-methylmorpholine N-oxide (NMMO), was nearly quantitative (96%) within 24 h. However, the reaction with oxygen was much slower, with only a 52% yield of imine product over the same time period. Moreover, the rate of reaction was found to be influenced by the nature of the amine N-oxide. For example, the use of the weakly basic pyridine N-oxide (PyNO) led to an imine yield of only 6% after 24 h. A comparison of amine N-oxide and O2 was also examined in the oxidation of PhCH{sub 2}OH to PhCHO catalyzed by bulk gold. In this reaction, a 52% yield of the aldehyde was achieved when NMMO was used, while only a 7% product yield was afforded when O{sub 2} was the oxidant after 48 h. The bulk gold-catalyzed oxidative dehydrogenation of cyclic amines generates amidines, which upon treatment with Aerosil and water were found to undergo hydrolysis to produce lactams. Moreover, 5-, 6-, and 7-membered lactams could be prepared through a one-pot reaction of cyclic amines by treatment with oxygen, water, bulk gold, and Aerosil. This method is much more atom economical than industrial processes, does not require corrosive acids, and does not generate undesired byproducts. Additionally, the gold and Aerosil catalysts can be readily separated from the reaction mixture. The second project involved studying iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl, as a homogeneous catalyst for the generation of carbenes from diazo reagents and their reaction with heteroatom compounds. Fe(TPP)Cl, efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols. Fe(TPP)Cl was also found to be an effective catalyst for tandem N-H and O-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents. This approach provides a one-pot process for synthesizing piperazinones and morpholinones and related analogues such as quinoxalinones and benzoxazin-2-ones.« less

Effect of trichloroethylene enhancement on deposition rate of low-temperature silicon oxide films by silicone oil and ozone

NASA Astrophysics Data System (ADS)

Horita, Susumu; Jain, Puneet

2017-08-01

A low-temperature silcon oxide film was deposited at 160 to 220 °C using an atmospheric pressure CVD system with silicone oil vapor and ozone gases. It was found that the deposition rate is markedly increased by adding trichloroethylene (TCE) vapor, which is generated by bubbling TCE solution with N2 gas flow. The increase is more than 3 times that observed without TCE, and any contamination due to TCE is hardly observed in the deposited Si oxide films from Fourier transform infrared spectra.

Role of mitochondrial oxidative stress in hypertension

PubMed Central

Ungvari, Zoltan

2013-01-01

Based on mosaic theory, hypertension is a multifactorial disorder that develops because of genetic, environmental, anatomical, adaptive neural, endocrine, humoral, and hemodynamic factors. It has been recently proposed that oxidative stress may contribute to all of these factors and production of reactive oxygen species (ROS) play an important role in the development of hypertension. Previous studies focusing on the role of vascular NADPH oxidases provided strong support of this concept. Although mitochondria represent one of the most significant sources of cellular ROS generation, the regulation of mitochondrial ROS generation in the cardiovascular system and its pathophysiological role in hypertension are much less understood. In this review, the role of mitochondrial oxidative stress in the pathophysiology of hypertension and cross talk between angiotensin II signaling, pathways involved in mechanotransduction, NADPH oxidases, and mitochondria-derived ROS are considered. The possible benefits of therapeutic strategies that have the potential to attenuate mitochondrial oxidative stress for the prevention/treatment of hypertension are also discussed. PMID:24043248

Oxidative Stress and Neurodegenerative Disorders

PubMed Central

Li, Jie; O, Wuliji; Li, Wei; Jiang, Zhi-Gang; Ghanbari, Hossein A.

2013-01-01

Living cells continually generate reactive oxygen species (ROS) through the respiratory chain during energetic metabolism. ROS at low or moderate concentration can play important physiological roles. However, an excessive amount of ROS under oxidative stress would be extremely deleterious. The central nervous system (CNS) is particularly vulnerable to oxidative stress due to its high oxygen consumption, weakly antioxidative systems and the terminal-differentiation characteristic of neurons. Thus, oxidative stress elicits various neurodegenerative diseases. In addition, chemotherapy could result in severe side effects on the CNS and peripheral nervous system (PNS) of cancer patients, and a growing body of evidence demonstrates the involvement of ROS in drug-induced neurotoxicities as well. Therefore, development of antioxidants as neuroprotective drugs is a potentially beneficial strategy for clinical therapy. In this review, we summarize the source, balance maintenance and physiologic functions of ROS, oxidative stress and its toxic mechanisms underlying a number of neurodegenerative diseases, and the possible involvement of ROS in chemotherapy-induced toxicity to the CNS and PNS. We ultimately assess the value for antioxidants as neuroprotective drugs and provide our comments on the unmet needs. PMID:24351827

Approaches for controlling air pollutants and their environmental impacts generated from coal-based electricity generation in China.

PubMed

Xu, Changqing; Hong, Jinglan; Ren, Yixin; Wang, Qingsong; Yuan, Xueliang

2015-08-01

This study aims at qualifying air pollutants and environmental impacts generated from coal-based power plants and providing useful information for decision makers on the management of coal-based power plants in China. Results showed that approximately 9.03, 54.95, 62.08, and 12.12% of the national carbon dioxide, sulfur dioxide, nitrogen oxides, and particulate matter emissions, respectively, in 2011were generated from coal-based electricity generation. The air pollutants were mainly generated from east China because of the well-developed economy and energy-intensive industries in the region. Coal-washing technology can simply and significantly reduce the environmental burden because of the relativity low content of coal gangue and sulfur in washed coal. Optimizing the efficiency of raw materials and energy consumption is additional key factor to reduce the potential environmental impacts. In addition, improving the efficiency of air pollutants (e.g., dust, mercury, sulfur dioxide, nitrogen oxides) control system and implementing the strict requirements on air pollutants for power plants are important ways for reducing the potential environmental impacts of coal-based electricity generation in China.

Evaluation of Porous Silicon Oxide on Silicon Microcantilevers for Sensitive Detection of Gaseous HF.

PubMed

Wallace, Ryan A; Sepaniak, Michael J; Lavrik, Nickolay V; Datskos, Panos G

2017-06-06

Sensitive detection of harmful chemicals in industrial applications is pertinent to safety. In this work, we demonstrate the use of a sensitive silicon microcantilever (MC) system with a porous silicon oxide layer deposited on the active side of the MCs that have been mechanically manipulated to increase sensitivity. Included is the evaluation of porous silicon oxide present on different geometries of MCs and exposed to varying concentrations of hydrogen fluoride in humid air. Profilometry and the signal generated by the stress-induced porous silicon oxide (PSO) coating and bending of the MC were used as methods of evaluation.

Evaluation of Porous Silicon Oxide on Silicon Microcantilevers for Sensitive Detection of Gaseous HF

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

Wallace, Ryan A.; Sepaniak, Michael J.; Lavrik, Nickolay V.

Sensitive detection of harmful chemicals in industrial applications is pertinent to safety. In this paper, we demonstrate the use of a sensitive silicon microcantilever (MC) system with a porous silicon oxide layer deposited on the active side of the MCs that have been mechanically manipulated to increase sensitivity. Included is the evaluation of porous silicon oxide present on different geometries of MCs and exposed to varying concentrations of hydrogen fluoride in humid air. Finally, profilometry and the signal generated by the stress-induced porous silicon oxide (PSO) coating and bending of the MC were used as methods of evaluation.

Evaluation of Porous Silicon Oxide on Silicon Microcantilevers for Sensitive Detection of Gaseous HF

DOE PAGES

Wallace, Ryan A.; Sepaniak, Michael J.; Lavrik, Nickolay V.; ...

2017-05-10

Sensitive detection of harmful chemicals in industrial applications is pertinent to safety. In this paper, we demonstrate the use of a sensitive silicon microcantilever (MC) system with a porous silicon oxide layer deposited on the active side of the MCs that have been mechanically manipulated to increase sensitivity. Included is the evaluation of porous silicon oxide present on different geometries of MCs and exposed to varying concentrations of hydrogen fluoride in humid air. Finally, profilometry and the signal generated by the stress-induced porous silicon oxide (PSO) coating and bending of the MC were used as methods of evaluation.

The Central Role of Biometals Maintains Oxidative Balance in the Context of Metabolic and Neurodegenerative Disorders

PubMed Central

Pokusa, Michal

2017-01-01

Traditionally, oxidative stress as a biological aspect is defined as an imbalance between the free radical generation and antioxidant capacity of living systems. The intracellular imbalance of ions, disturbance in membrane dynamics, hypoxic conditions, and dysregulation of gene expression are all molecular pathogenic mechanisms closely associated with oxidative stress and underpin systemic changes in the body. These also include aspects such as chronic immune system activation, the impairment of cellular structure renewal, and alterations in the character of the endocrine secretion of diverse tissues. All of these mentioned features are crucial for the correct function of the various tissue types in the body. In the present review, we summarize current knowledge about the common roots of metabolic and neurodegenerative disorders induced by oxidative stress. We discuss these common roots with regard to the way that (1) the respective metal ions are involved in the maintenance of oxidative balance and (2) the metabolic and signaling disturbances of the most important biometals, such as Mg2+, Zn2+, Se2+, Fe2+, or Cu2+, can be considered as the central connection point between the pathogenesis of both types of disorders and oxidative stress. PMID:28751933

Machine-learned and codified synthesis parameters of oxide materials

NASA Astrophysics Data System (ADS)

Kim, Edward; Huang, Kevin; Tomala, Alex; Matthews, Sara; Strubell, Emma; Saunders, Adam; McCallum, Andrew; Olivetti, Elsa

2017-09-01

Predictive materials design has rapidly accelerated in recent years with the advent of large-scale resources, such as materials structure and property databases generated by ab initio computations. In the absence of analogous ab initio frameworks for materials synthesis, high-throughput and machine learning techniques have recently been harnessed to generate synthesis strategies for select materials of interest. Still, a community-accessible, autonomously-compiled synthesis planning resource which spans across materials systems has not yet been developed. In this work, we present a collection of aggregated synthesis parameters computed using the text contained within over 640,000 journal articles using state-of-the-art natural language processing and machine learning techniques. We provide a dataset of synthesis parameters, compiled autonomously across 30 different oxide systems, in a format optimized for planning novel syntheses of materials.

Micro-gas analysis system for measurement of nitric oxide and nitrogen dioxide: respiratory treatment and environmental mobile monitoring.

PubMed

Toda, Kei; Hato, Yuki; Ohira, Shin-ichi; Namihira, Takao

2007-11-05

In this paper, novel microsystems for gas analysis and gas generation are described. The same microchannel devices covered with a gas permeable membrane were used for both the gas collection and the gas generation. For the first time, a dual liquid flow system was utilized in a micro-gas analysis system. Even though micropumps are utilized in the dual line microsystem, a good baseline was obtained in the NO2 measurement with Griess-Saltzman chemistry. The system was developed for on-site measurements in medical treatment; the treatment is of respiratory disease syndrome by NO inhalation and the monitoring is of the product NO and the harmful byproduct NO2. The system was also applied to mobile atmospheric monitoring. Chemical NO generation using the microchannel device was investigated for safe NO inhalation as an alternative to a NO generator based on pulsed arc discharge.

Two Dimensional Polymer That Generates Nitric Oxide.

DOEpatents

McDonald, William F.; Koren, Amy B.

2005-10-04

A polymeric composition that generates nitric oxide and a process for rendering the surface of a substrate nonthrombogenic by applying a coating of the polymeric composition to the substrate are disclosed. The composition comprises: (1) a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, and (ii) a crosslinking agent containing functional groups capable of reacting with the amino groups; and (2) a plurality of nitric oxide generating functional groups associated with the crosslinked chemical combination. Once exposed to a physiological environment, the coating generates nitric oxide thereby inhibiting platelet aggregation. In one embodiment, the nitric oxide generating functional groups are provided by a nitrated compound (e.g., nitrocellulose) imbedded in the polymeric composition. In another embodiment, the nitric oxide generating functional groups comprise N2O2- groups covalently bonded to amino groups on the polymer.

Capacity and recycling of polyoxometalate applied in As(III) oxidation by Fe(II)-Amended zero-valent aluminum.

PubMed

Hsu, Liang-Ching; Cho, Yen-Lin; Liu, Yu-Ting; Tzou, Yu-Min; Teah, Heng Yi

2018-06-01

Arsenic remediation is often initiated by oxidizing As(III) to As(V) to alleviate its toxicity and mobility. Due to the easy availability, zero-valent Al (ZVAl) like Al can was considered as potential alternatives to facilitate As(III) oxidation. This study determined the capability and recycling of polyoxometalate (POM) to catalyze As(III) oxidation in Fe(II)-amended ZVAl systems. POM acquired electrons from ZVAl more effectively at pH 1 than at pH 2. While 76% of the reduced POM [POM(e - )] reacted with O 2(g) to generate H 2 O 2 at pH 1, only 60% of POM(e - ) was used to produce H 2 O 2 at pH 2. The remaining POM(e - ) was oxidized by the generated H 2 O 2 . Such additional consumption of POM(e - ) and H 2 O 2 led to the incomplete As(III) oxidation in the system without residual ZVAl and emphasized the need for a continuous electron supply from ZVAl to compensate the depletion of POM(e - ). After the hydrolyzation at pH 6.0, the XANES data evidenced that not only As(V) but WO 4 released from the POM retained on surfaces of Al/Fe hydroxides. The competition for sorption sites on Al/Fe hydroxides between As(V) and WO 4 led to the incomplete As removal. Despite the loss of WO 4 , the POM re-polymerized at pH 1 still showed the comparable capability to catalyze As(III) oxidation with original POM. This study revealed electron transfer pathways from ZVAl to As(III) as catalyzed by POM and evidenced the effective POM recycling after As removal, which lowers the cost of POM application and turns the ZVAl/Fe(II)/POM/O 2 system into a practical strategy for As remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

The Case for Natural Gas Fueled Solid Oxide Fuel Cell Power Systems for Distributed Generation

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

Chick, Lawrence A.; Weimar, Mark R.; Whyatt, Greg A.

2015-02-01

Natural-gas-fueled solid oxide fuel cell (NGSOFC) power systems yield electrical conversion efficiencies exceeding 60% and may become a viable alternative for distributed generation (DG) if stack life and manufacturing economies of scale can be realized. Currently, stacks last approximately 2 years and few systems are produced each year because of the relatively high cost of electricity from the systems. If mass manufacturing (10,000 units per year) and a stack life of 15 years can be reached, the cost of electricity from an NGSOFC system is estimated to be about 7.7 ¢/kWh, well within the price of commercial and residential retailmore » prices at the national level (9.9-10¢/kWh and 11-12 ¢/kWh, respectively). With an additional 5 ¢/kWh in estimated additional benefits from DG, NGSOFC could be well positioned to replace the forecasted 59-77 gigawatts of capacity loss resulting from coal plant closures due to stricter emissions regulations and low natural gas prices.« less

Possibilities for extremophilic microorganisms in microbial electrochemical systems

PubMed Central

Dopson, Mark; Ni, Gaofeng; Sleutels, Tom HJA

2015-01-01

Microbial electrochemical systems exploit the metabolism of microorganisms to generate electrical energy or a useful product. In the past couple of decades, the application of microbial electrochemical systems has increased from the use of wastewaters to produce electricity to a versatile technology that can use numerous sources for the extraction of electrons on the one hand, while on the other hand these electrons can be used to serve an ever increasing number of functions. Extremophilic microorganisms grow in environments that are hostile to most forms of life and their utilization in microbial electrochemical systems has opened new possibilities to oxidize substrates in the anode and produce novel products in the cathode. For example, extremophiles can be used to oxidize sulfur compounds in acidic pH to remediate wastewaters, generate electrical energy from marine sediment microbial fuel cells at low temperatures, desalinate wastewaters and act as biosensors of low amounts of organic carbon. In this review, we will discuss the recent advances that have been made in using microbial catalysts under extreme conditions and show possible new routes that extremophilic microorganisms open for microbial electrochemical systems. PMID:26474966

The Impact of Oxidative Stress on the Bone System in Response to the Space Special Environment.

PubMed

Tian, Ye; Ma, Xiaoli; Yang, Chaofei; Su, Peihong; Yin, Chong; Qian, Ai-Rong

2017-10-12

The space special environment mainly includes microgravity, radiation, vacuum and extreme temperature, which seriously threatens an astronaut's health. Bone loss is one of the most significant alterations in mammalians after long-duration habitation in space. In this review, we summarize the crucial roles of major factors-namely radiation and microgravity-in space in oxidative stress generation in living organisms, and the inhibitory effect of oxidative stress on bone formation. We discussed the possible mechanisms of oxidative stress-induced skeletal involution, and listed some countermeasures that have therapeutic potentials for bone loss via oxidative stress antagonism. Future research for better understanding the oxidative stress caused by space environment and the development of countermeasures against oxidative damage accordingly may facilitate human beings to live more safely in space and explore deeper into the universe.

The Impact of Oxidative Stress on the Bone System in Response to the Space Special Environment

PubMed Central

Tian, Ye; Ma, Xiaoli; Yang, Chaofei; Su, Peihong; Yin, Chong

2017-01-01

The space special environment mainly includes microgravity, radiation, vacuum and extreme temperature, which seriously threatens an astronaut’s health. Bone loss is one of the most significant alterations in mammalians after long-duration habitation in space. In this review, we summarize the crucial roles of major factors—namely radiation and microgravity—in space in oxidative stress generation in living organisms, and the inhibitory effect of oxidative stress on bone formation. We discussed the possible mechanisms of oxidative stress-induced skeletal involution, and listed some countermeasures that have therapeutic potentials for bone loss via oxidative stress antagonism. Future research for better understanding the oxidative stress caused by space environment and the development of countermeasures against oxidative damage accordingly may facilitate human beings to live more safely in space and explore deeper into the universe. PMID:29023398

DNA damage in lens epithelium of cataract patients in vivo and ex vivo.

PubMed

Øsnes-Ringen, Oyvind; Azqueta, Amaia O; Moe, Morten C; Zetterström, Charlotta; Røger, Magnus; Nicolaissen, Bjørn; Collins, Andrew R

2013-11-01

DNA damage has been described in the human cataractous lens epithelium, and oxidative stress generated by UV radiation and endogenous metabolic processes has been suggested to play a significant role in the pathogenesis of cataract. In this study, the aim was to explore the quality and relative quantity of DNA damage in lens epithelium of cataract patients in vivo and after incubation in a cell culture system. Capsulotomy specimens were analysed, before and after 1 week of ex vivo cultivation, using the comet assay to measure DNA strand breaks, oxidized purine and pyrimidine bases and UV-induced cyclobutane pyrimidine dimers. DNA strand breaks were barely detectable, oxidized pyrimidines and pyrimidine dimers were present at low levels, whereas there was a relatively high level of oxidized purines, which further increased after cultivation. The observed levels of oxidized purines in cataractous lens epithelium may support a theory consistent with light damage and oxidative stress as mediators of molecular damage to the human lens epithelium. Damage commonly associated with UV-B irradiation was relatively low. The levels of oxidized purines increased further in a commonly used culture system. This is of interest considering the importance and versatility of ex vivo systems in studies exploring the pathogenesis of cataract. © 2012 The Authors. Acta Ophthalmologica © 2012 Acta Ophthalmologica Scandinavica Foundation.

Electrochemical, H2O2-Boosted Catalytic Oxidation System

NASA Technical Reports Server (NTRS)

Akse, James R.; Thompson, John O.; Schussel, Leonard J.

2004-01-01

An improved water-sterilizing aqueous-phase catalytic oxidation system (APCOS) is based partly on the electrochemical generation of hydrogen peroxide (H2O2). This H2O2-boosted system offers significant improvements over prior dissolved-oxygen water-sterilizing systems in the way in which it increases oxidation capabilities, supplies H2O2 when needed, reduces the total organic carbon (TOC) content of treated water to a low level, consumes less energy than prior systems do, reduces the risk of contamination, and costs less to operate. This system was developed as a variant of part of an improved waste-management subsystem of the life-support system of a spacecraft. Going beyond its original intended purpose, it offers the advantage of being able to produce H2O2 on demand for surface sterilization and/or decontamination: this is a major advantage inasmuch as the benign byproducts of this H2O2 system, unlike those of systems that utilize other chemical sterilants, place no additional burden of containment control on other spacecraft air- or water-reclamation systems.

Experimental analysis of SiC-based refractory concrete in hybrid rocket nozzles

NASA Astrophysics Data System (ADS)

D'Elia, Raffaele; Bernhart, Gérard; Hijlkema, Jouke; Cutard, Thierry

2016-09-01

Hybrid propulsion represents a good alternative to the more widely used liquid and solid systems. This technology combines some important specifications of the latters, as the possibility of re-ignition, thrust modulation, a higher specific impulse than solid systems, a greater simplicity and a lower cost than liquid systems. Nevertheless the highly oxidizing environment represents a major problem as regards the thermo-oxidation and ablative behavior of nozzle materials. The main goal of this research is to characterize a silicon carbide based micro-concrete with a maximum aggregates size of 800 μm, in a hybrid propulsion environment. The nozzle throat has to resist to a highly oxidizing polyethylene/nitrous oxide hybrid environment, under temperatures up to 2900 K. Three tests were performed on concrete-based nozzles in HERA Hybrid Rocket Motor (HRM) test bench at ONERA. Pressure chamber evolution and observations before and after tests are used to investigate the ablated surface at nozzle throat. Ablation behavior and crack generation are discussed and some improvements are proposed.

Relationship of senescence of pulmonary system to chronic obstructive pulmonary disease in the advanced life.

PubMed

Donma, O; Donma, M M

2002-08-01

Chronic obstructive pulmonary disease (COPD) is a major worldwide health problem. There exists a relationship between COPD and increased oxidative stress, and oxidants may be involved in lung damage during the course of COPD. Polymorphonuclear (PMN) cell recruitment at lung level plays an important role in free radical overproduction, impact inflammatory processes and may alter oxidant-antioxidant balance. Biological aging is thought to be influenced by free radical generation, aging, and the diseases. All the components of the respiratory system are affected by aging. Nutrition, smoking habits and sleep-related disorders also affect the respiratory system. Whether these changes are due to aging or associated with aging is a matter of debate. Since alterations caused by aging and cigarette smoke in lungs of various species were informed to be partly simulated with age-related alterations in human lung, the effects of oxidative agents and antioxidative parameters on both COPD and aging were evaluated.

A photochemical strategy for lignin degradation at room temperature.

PubMed

Nguyen, John D; Matsuura, Bryan S; Stephenson, Corey R J

2014-01-29

The development of a room-temperature lignin degradation strategy consisting of a chemoselective benzylic oxidation with a recyclable oxidant ([4-AcNH-TEMPO]BF4) and a catalytic reductive C-O bond cleavage utilizing the photocatalyst [Ir(ppy)2(dtbbpy)]PF6 is described. This system was tested on relevant lignin model substrates containing β-O-4 linkages to generate fragmentation products in good to excellent yields.

Sequential continuous flow processes for the oxidation of amines and azides by using HOF·MeCN.

PubMed

McPake, Christopher B; Murray, Christopher B; Sandford, Graham

2012-02-13

The generation and use of the highly potent oxidising agent HOF·MeCN in a controlled single continuous flow process is described. Oxidations of amines and azides to corresponding nitrated systems by using fluorine gas, water and acetonitrile by sequential gas-liquid/liquid-liquid continuous flow procedures are reported. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polyamine Metabolism and Oxidative Protein Folding in the ER as ROS-Producing Systems Neglected in Virology

PubMed Central

Smirnova, Olga A.; Bartosch, Birke; Zakirova, Natalia F.; Kochetkov, Sergey N.

2018-01-01

Reactive oxygen species (ROS) are produced in various cell compartments by an array of enzymes and processes. An excess of ROS production can be hazardous for normal cell functioning, whereas at normal levels, ROS act as vital regulators of many signal transduction pathways and transcription factors. ROS production is affected by a wide range of viruses. However, to date, the impact of viral infections has been studied only in respect to selected ROS-generating enzymes. The role of several ROS-generating and -scavenging enzymes or cellular systems in viral infections has never been addressed. In this review, we focus on the roles of biogenic polyamines and oxidative protein folding in the endoplasmic reticulum (ER) and their interplay with viruses. Polyamines act as ROS scavengers, however, their catabolism is accompanied by H2O2 production. Hydrogen peroxide is also produced during oxidative protein folding, with ER oxidoreductin 1 (Ero1) being a major source of oxidative equivalents. In addition, Ero1 controls Ca2+ efflux from the ER in response to e.g., ER stress. Here, we briefly summarize the current knowledge on the physiological roles of biogenic polyamines and the role of Ero1 at the ER, and present available data on their interplay with viral infections. PMID:29673197

Method and apparatus for enhanced heat recovery from steam generators and water heaters

DOEpatents

Knight, Richard A.; Rabovitser, Iosif K.; Wang, Dexin

2006-06-27

A heating system having a steam generator or water heater, at least one economizer, at least one condenser and at least one oxidant heater arranged in a manner so as to reduce the temperature and humidity of the exhaust gas (flue gas) stream and recover a major portion of the associated sensible and latent heat. The recovered heat is returned to the steam generator or water heater so as to increase the quantity of steam generated or water heated per quantity of fuel consumed. In addition, a portion of the water vapor produced by combustion of fuel is reclaimed for use as feed water, thereby reducing the make-up water requirement for the system.

Towards a "free radical theory of graying": melanocyte apoptosis in the aging human hair follicle is an indicator of oxidative stress induced tissue damage.

PubMed

Arck, Petra Clara; Overall, Rupert; Spatz, Katharina; Liezman, Christiane; Handjiski, Bori; Klapp, Burghard F; Birch-Machin, Mark A; Peters, Eva Milena Johanne

2006-07-01

Oxidative stress is generated by a multitude of environmental and endogenous challenges such as radiation, inflammation, or psychoemotional stress. It also speeds the aging process. Graying is a prominent but little understood feature of aging. Intriguingly, the continuous melanin synthesis in the growing (anagen) hair follicle generates high oxidative stress. We therefore hypothesize that hair bulb melanocytes are especially susceptible to free radical-induced aging. To test this hypothesis, we subjected human scalp skin anagen hair follicles from graying individuals to macroscopic and immunohistomorphometric analysis and organ culture. We found evidence of melanocyte apoptosis and increased oxidative stress in the pigmentary unit of graying hair follicles. The "common" deletion, a marker mitochondrial DNA-deletion for accumulating oxidative stress damage, occurred most prominently in graying hair follicles. Cultured unpigmented hair follicles grew better than pigmented follicles of the same donors. Finally, cultured pigmented hair follicles exposed to exogenous oxidative stress (hydroquinone) showed increased melanocyte apoptosis in the hair bulb. We conclude that oxidative stress is high in hair follicle melanocytes and leads to their selective premature aging and apoptosis. The graying hair follicle, therefore, offers a unique model system to study oxidative stress and aging and to test antiaging therapeutics in their ability to slow down or even stop this process.

Intermediates of peroxisomal beta-oxidation. A study of the fatty acyl-CoA esters which accumulate during peroxisomal beta-oxidation of [U-14C]hexadecanoate.

PubMed Central

Bartlett, K; Hovik, R; Eaton, S; Watmough, N J; Osmundsen, H

1990-01-01

1. 14C-labelled fatty acyl-CoA esters resulting from beta-oxidation of [U-14C]hexadecanoate by peroxisomal fractions isolated from rats treated with clofibrate showed the presence of the full range of saturated intermediates down to acetyl-CoA. 2. The pattern of intermediates generated was fairly constant. At low concentrations of [U-14C]hexadecanoate (50 microM), decanoyl-CoA was present in lowest amounts. At higher concentrations of [U-14C]hexadecanoate (greater than 100 microM), all intermediates of chain length shorter than 12 carbon atoms (except acetyl-CoA) were present at similar low concentrations; the process of beta-oxidation now resembling chain-shortening of hexadecanoate by two cycles of beta-oxidation. 3. In the absence of an NAD(+)-regenerating system [pyruvate and lactate dehydrogenase (EC 1.1.1.28)] 2-enoyl- and 3-hydroxyacyl-CoA esters were generated, suggesting that re-oxidation of NADH is essential for optimal rates of peroxisomal beta-oxidation in vitro. 4. At high concentrations of [U-14C]hexadecanoate (greater than 100 microM), 3-oxohexadecanoyl-CoA was produced, suggesting that thiolase (acetyl-CoA acetyltransferase; EC 2.3.1.9) can become rate-limiting for peroxisomal beta-oxidation. Images Fig. 2. Fig. 3. Fig. 4. PMID:2396977

Evaluation of biological hydrogen sulfide oxidation coupled with two-stage upflow filtration for groundwater treatment.

PubMed

Levine, Audrey D; Raymer, Blake J; Jahn, Johna

2004-01-01

Hydrogen sulfide in groundwater can be oxidized by aerobic bacteria to form elemental sulfur and biomass. While this treatment approach is effective for conversion of hydrogen sulfide, it is important to have adequate control of the biomass exiting the biological treatment system to prevent release of elemental sulfur into the distribution system. Pilot scale tests were conducted on a Florida groundwater to evaluate the use of two-stage upflow filtration downstream of biological sulfur oxidation. The combined biological and filtration process was capable of excellent removal of hydrogen sulfide and associated turbidity. Additional benefits of this treatment approach include elimination of odor generation, reduction of chlorine demand, and improved stability of the finished water.

Molecular mechanisms of hypertension: role of Nox family NADPH oxidases.

PubMed

Sedeek, Mona; Hébert, Richard L; Kennedy, Chris R; Burns, Kevin D; Touyz, Rhian M

2009-03-01

Molecular mechanisms contributing to the pathoetiology of hypertension are complex, involving many interacting systems such as signaling through G protein-coupled receptors, the renin-angiotensin system, vascular inflammation and remodeling, vascular senescence and aging and developmental programming, as highlighted in the current issue of the journal. Common to these systems is NADPH oxidase-derived reactive oxygen species (ROS). This editorial highlights current concepts relating to the production of ROS in hypertension and focuses on the Nox family NADPH oxidases, major sources of free radicals in the cardiovascular and renal systems. ROS play a major role as intracellular signaling molecules to regulate normal biological cellular responses. In pathological conditions, loss of redox homeostasis contributes to vascular oxidative damage. Recent evidence indicates that specific enzymes, the Nox family of NADPH oxidases, have the sole function of generating ROS in a highly regulated fashion in physiological conditions, and that in disease states, hyperactivation of Noxes contributes to oxidative stress and consequent cardiovascular and renal injury. The Nox family comprises seven members, Nox1-Nox7. Nox1, Nox2 (gp91phox-containing NADPH oxidase), Nox4 and Nox5 have been identified in the cardiovascular-renal systems and have been implicated in the pathophysiology of cardiovascular and renal disease. Noxes, which are differentially regulated in hypertension, are major sources of cardiovascular and renal oxidative stress. This has evoked considerable interest because of the possibilities that therapies targeted against specific Nox isoforms to decrease ROS generation or to increase nitric oxide availability or both may be useful in minimizing vascular injury and renal dysfunction, and thereby prevent or regress target organ damage associated with hypertension.

Health Effects of Dietary Oxidized Tyrosine and Dityrosine Administration in Mice with Nutrimetabolomic Strategies.

PubMed

Yang, Yuhui; Zhang, Hui; Yan, Biao; Zhang, Tianyu; Gao, Ying; Shi, Yonghui; Le, Guowei

2017-08-16

This study aims to investigate the health effects of long-term dietary oxidized tyrosine (O-Tyr) and its main product (dityrosine) administration on mice metabolism. Mice received daily intragastric administration of either O-Tyr (320 μg/kg body weight), dityrosine (Dityr, 320 μg/kg body weight), or saline for consecutive 6 weeks. Urine and plasma samples were analyzed by NMR-based metabolomics strategies. Body weight, clinical chemistry, oxidative damage indexes, and histopathological data were obtained as complementary information. O-Tyr and Dityr exposure changed many systemic metabolic processes, including reduced choline bioavailability, led to fat accumulation in liver, induced hepatic injury, and renal dysfunction, resulted in changes in gut microbiota functions, elevated risk factor for cardiovascular disease, altered amino acid metabolism, induced oxidative stress responses, and inhibited energy metabolism. These findings implied that it is absolutely essential to reduce the generation of oxidation protein products in food system through improving modern food processing methods.

Combustion Characterization and Model Fuel Development for Micro-tubular Flame-assisted Fuel Cells.

PubMed

Milcarek, Ryan J; Garrett, Michael J; Baskaran, Amrish; Ahn, Jeongmin

2016-10-02

Combustion based power generation has been accomplished for many years through a number of heat engine systems. Recently, a move towards small scale power generation and micro combustion as well as development in fuel cell research has created new means of power generation that combine solid oxide fuel cells with open flames and combustion exhaust. Instead of relying upon the heat of combustion, these solid oxide fuel cell systems rely on reforming of the fuel via combustion to generate syngas for electrochemical power generation. Procedures were developed to assess the combustion by-products under a wide range of conditions. While theoretical and computational procedures have been developed for assessing fuel-rich combustion exhaust in these applications, experimental techniques have also emerged. The experimental procedures often rely upon a gas chromatograph or mass spectrometer analysis of the flame and exhaust to assess the combustion process as a fuel reformer and means of heat generation. The experimental techniques developed in these areas have been applied anew for the development of the micro-tubular flame-assisted fuel cell. The protocol discussed in this work builds on past techniques to specify a procedure for characterizing fuel-rich combustion exhaust and developing a model fuel-rich combustion exhaust for use in flame-assisted fuel cell testing. The development of the procedure and its applications and limitations are discussed.

Impact of short-term acidification on nitrification and nitrifying bacterial community dynamics in soilless cultivation media.

PubMed

Cytryn, Eddie; Levkovitch, Irit; Negreanu, Yael; Dowd, Scot; Frenk, Sammy; Silber, Avner

2012-09-01

Soilless medium-based horticulture systems are highly prevalent due to their capacity to optimize growth of high-cash crops. However, these systems are highly dynamic and more sensitive to physiochemical and pH perturbations than traditional soil-based systems, especially during nitrification associated with ammonia-based fertilization. The objective of this study was to assess the impact of nitrification-generated acidification on ammonia oxidation rates and nitrifying bacterial community dynamics in soilless growth media. To achieve this goal, perlite soilless growth medium from a commercial bell pepper greenhouse was incubated with ammonium in bench-scale microcosm experiments. Initial quantitative real-time PCR analysis indicated that betaproteobacterial ammonia oxidizers were significantly more abundant than ammonia-oxidizing archaea, and therefore, research focused on this group. Ammonia oxidation rates were highest between 0 and 9 days, when pH values dropped from 7.4 to 4.9. Pyrosequencing of betaproteobacterial ammonia-oxidizing amoA gene fragments indicated that r-strategist-like Nitrosomonas was the dominant ammonia-oxidizing bacterial genus during this period, seemingly due to the high ammonium concentration and optimal growth conditions in the soilless media. Reduction of pH to levels below 4.8 resulted in a significant decrease in both ammonia oxidation rates and the diversity of ammonia-oxidizing bacteria, with increased relative abundance of the r-strategist-like Nitrosospira. Nitrite oxidizers (Nitrospira and Nitrobacter) were on the whole more abundant and less sensitive to acidification than ammonia oxidizers. This study demonstrates that nitrification and nitrifying bacterial community dynamics in high-N-load intensive soilless growth media may be significantly different from those in in-terra agricultural systems.

Impact of Short-Term Acidification on Nitrification and Nitrifying Bacterial Community Dynamics in Soilless Cultivation Media

PubMed Central

Levkovitch, Irit; Negreanu, Yael; Dowd, Scot; Frenk, Sammy; Silber, Avner

2012-01-01

Soilless medium-based horticulture systems are highly prevalent due to their capacity to optimize growth of high-cash crops. However, these systems are highly dynamic and more sensitive to physiochemical and pH perturbations than traditional soil-based systems, especially during nitrification associated with ammonia-based fertilization. The objective of this study was to assess the impact of nitrification-generated acidification on ammonia oxidation rates and nitrifying bacterial community dynamics in soilless growth media. To achieve this goal, perlite soilless growth medium from a commercial bell pepper greenhouse was incubated with ammonium in bench-scale microcosm experiments. Initial quantitative real-time PCR analysis indicated that betaproteobacterial ammonia oxidizers were significantly more abundant than ammonia-oxidizing archaea, and therefore, research focused on this group. Ammonia oxidation rates were highest between 0 and 9 days, when pH values dropped from 7.4 to 4.9. Pyrosequencing of betaproteobacterial ammonia-oxidizing amoA gene fragments indicated that r-strategist-like Nitrosomonas was the dominant ammonia-oxidizing bacterial genus during this period, seemingly due to the high ammonium concentration and optimal growth conditions in the soilless media. Reduction of pH to levels below 4.8 resulted in a significant decrease in both ammonia oxidation rates and the diversity of ammonia-oxidizing bacteria, with increased relative abundance of the r-strategist-like Nitrosospira. Nitrite oxidizers (Nitrospira and Nitrobacter) were on the whole more abundant and less sensitive to acidification than ammonia oxidizers. This study demonstrates that nitrification and nitrifying bacterial community dynamics in high-N-load intensive soilless growth media may be significantly different from those in in-terra agricultural systems. PMID:22773643

Maneb and Paraquat-Mediated Neurotoxicity: Involvement of Peroxiredoxin/Thioredoxin System

PubMed Central

Roede, James R.; Hansen, Jason M.; Go, Young-Mi; Jones, Dean P.

2011-01-01

Epidemiological and in vivo studies have demonstrated that exposure to the pesticides paraquat (PQ) and maneb (MB) increase the risk of developing Parkinson’s disease (PD) and cause dopaminergic cell loss, respectively. PQ is a well-recognized cause of oxidative toxicity; therefore, the purpose of this study was to determine if MB potentiates oxidative stress caused by PQ, thus providing a mechanism for enhanced neurotoxicity by the combination. The results show that PQ alone at a moderately toxic dose (20–30% cell death in 24 h) caused increased reactive oxygen species (ROS) generation, oxidation of mitochondrial thioredoxin-2 and peroxiredoxin-3, lesser oxidation of cytoplasmic thioredoxin-1 and peroxiredoxin-1, and no oxidation of cellular GSH/GSSG. In contrast, MB alone at a similar toxic dose resulted in no ROS generation, no oxidation of thioredoxin and peroxiredoxin, and an increase in cellular GSH after 24 h. Together, MB increased GSH and inhibited ROS production and thioredoxin/peroxiredoxin oxidation observed with PQ alone, yet resulted in more extensive (> 50%) cell death. MB treatment resulted in increased abundance of nuclear Nrf2 and mRNA for phase II enzymes under the control of Nrf2, indicating activation of cell protective responses. The results show that MB potentiation of PQ neurotoxicity does not occur by enhancing oxidative stress and suggests that increased toxicity occurs by a combination of divergent mechanisms, perhaps involving alkylation by MB and oxidation by PQ. PMID:21402726

Oxidation- and Creep-Enhanced Fatigue of Haynes 188 Alloy-Oxide Scale System Under Simulated Pulse Detonation Engine Conditions

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Fox, Dennis S.; Miller, Robert A.

2002-01-01

The development of the pulse detonation engine (PDE) requires robust design of the engine components that are capable of enduring harsh detonation environments. In this study, a high cycle thermal fatigue test rig was developed for evaluating candidate PDE combustor materials using a CO2 laser. The high cycle thermal fatigue behavior of Haynes 188 alloy was investigated under an enhanced pulsed laser test condition of 30 Hz cycle frequency (33 ms pulse period, and 10 ms pulse width including 0.2 ms pulse spike). The temperature swings generated by the laser pulses near the specimen surface were characterized by using one-dimensional finite difference modeling combined with experimental measurements. The temperature swings resulted in significant thermal cyclic stresses in the oxide scale/alloy system, and induced extensive surface cracking. Striations of various sizes were observed at the cracked surfaces and oxide/alloy interfaces under the cyclic stresses. The test results indicated that oxidation and creep-enhanced fatigue at the oxide scale/alloy interface was an important mechanism for the surface crack initiation and propagation under the simulated PDE condition.

Inhibition of oxidation of aqueous emulsions of omega-3 fatty acids and fish oil by phloretin and phloridzin.

PubMed

Vasantha Rupasinghe, H P; Yasmin, Afsana

2010-01-11

The antioxidant properties of two apple dihydrochalcones, namely phloretin and phloridzin, were evaluated and compared with those of alpha-tocopherol and butylated hydroxytoluene (BHT). The effects were studied in an oil-in-water emulsion system containing methyl linolenate (ML), methyl eicosapentaenoate (MEPA), and methyl docosahexaenoate (MDHA) in which oxidation was initiated by the peroxyl radical generator 2,2-azobis(2-amidinopropane) dihydrochloride (AAPH) and in fish oil where oxidation was initiated thermally. In the emulsion system, phloretin (1 and 5 mM) completely inhibited the oxidation of ML tested as evidenced by the thiobarbituric acid reactive substances (TBARS) assay. Under the same conditions, phloridzin was less effective than phloretin, but still more effective than alpha-tocopherol. Both phloretin and phloridzin molecules had a marginal inhibitory effect against oxidation of fish oil induced by heating at 70 degrees C for 3 hours, when compared to BHT. These results indicate that phloretin and phloridzin have the potential to suppress lipid oxidation in polyunsaturated fatty acid (PUFA) containing foods.

Light-driven water oxidation for solar fuels

PubMed Central

Young, Karin J.; Martini, Lauren A.; Milot, Rebecca L.; III, Robert C. Snoeberger; Batista, Victor S.; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W.

2014-01-01

Light-driven water oxidation is an essential step for conversion of sunlight into storable chemical fuels. Fujishima and Honda reported the first example of photoelectrochemical water oxidation in 1972. In their system, TiO2 was irradiated with ultraviolet light, producing oxygen at the anode and hydrogen at a platinum cathode. Inspired by this system, more recent work has focused on functionalizing nanoporous TiO2 or other semiconductor surfaces with molecular adsorbates, including chromophores and catalysts that absorb visible light and generate electricity (i.e., dye-sensitized solar cells) or trigger water oxidation at low overpotentials (i.e., photocatalytic cells). The physics involved in harnessing multiple photochemical events for multielectron reactions, as required in the four-electron water oxidation process, has been the subject of much experimental and computational study. In spite of significant advances with regard to individual components, the development of highly efficient photocatalytic cells for solar water splitting remains an outstanding challenge. This article reviews recent progress in the field with emphasis on water-oxidation photoanodes inspired by the design of functionalized thin film semiconductors of typical dye-sensitized solar cells. PMID:25364029

Rhesus monkey lens as an in vitro model for studying oxidative stress

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

Zigler, J.S. Jr.; Lucas, V.A.; Du, X.Y.

1989-10-01

Lenses from young rhesus monkeys were incubated in the presence of H{sub 2}O{sub 2} or oxygen radical generating systems to determine their suitability as a model for investigating lenticular oxidative stress. Additionally, direct comparisons were made between the effects found with the monkey lenses and those observed with cultured rat lenses exposed to the same oxidizing systems. As in earlier studies with rat lenses the monkey lenses exhibited impaired ability to actively accumulate from the medium radioactively labelled rubidium and choline following exposure to oxidative stress. Based on the effects of various scavengers of oxygen radicals it appeared that themore » mechanisms responsible for lens damage were the same for both rat and monkey lenses. However, rat lenses were damaged by lower concentrations of oxidants than were monkey lenses. It was concluded that oxidative stress affects both rat and monkey lenses by similar mechanisms but that lenses from monkeys, and probably other primates, are more resistant to these effects because they have better endogenous antioxidant defenses.« less

Development and Lab-Scale Testing of a Gas Generator Hybrid Fuel in Support of the Hydrogen Peroxide Hybrid Upper Stage Program

NASA Technical Reports Server (NTRS)

Lund, Gary K.; Starrett, William David; Jensen, Kent C.; McNeal, Curtis (Technical Monitor)

2001-01-01

As part of a NASA funded contract to develop and demonstrate a gas generator cycle hybrid rocket motor for upper stage space motor applications, the development and demonstration of a low sensitivity, high performance fuel composition was undertaken. The ultimate goal of the development program was to demonstrate successful hybrid operation (start, stop, throttling) of the fuel with high concentration (90+%) hydrogen peroxide. The formulation development and lab-scale testing of a simple DOT Class 1.4c gas generator propellant is described. Both forward injected center perforated and aft injected end burner hybrid combustion behavior were evaluated with gaseous oxygen and catalytically decomposed 90% hydrogen peroxide. Cross flow and static environments were found to yield profoundly different combustion behaviors, which were further governed by binder type, oxidizer level and, significantly, oxidizer particle size. Primary extinguishment was accomplished via manipulation of PDL behavior and oxidizer turndown, which is enhanced with the hydrogen peroxide system. Laboratory scale combustor results compared very well with 11-inch and 24-inch sub-scale test results with 90% hydrogen peroxide.

Cytotoxicity of aluminum oxide nanoparticles on Allium cepa root tip--effects of oxidative stress generation and biouptake.

PubMed

Rajeshwari, A; Kavitha, S; Alex, Sruthi Ann; Kumar, Deepak; Mukherjee, Anita; Chandrasekaran, Natarajan; Mukherjee, Amitava

2015-07-01

The commercial usage of Al2O3 nanoparticles (Al2O3 NPs) has gone up significantly in the recent times, enhancing the risk of environmental contamination with these agents and their consequent adverse effects on living systems. The current study has been designed to evaluate the cytogenetic potential of Al2O3 NPs in Allium cepa (root tip cells) at a range of exposure concentrations (0.01, 0.1, 1, 10, and 100 μg/mL), their uptake/internalization profile, and the oxidative stress generated. We noted a dose-dependent decrease in the mitotic index (42 to 28 %) and an increase in the number of chromosomal aberrations. Various chromosomal aberrations, e.g. sticky, multipolar and laggard chromosomes, chromosomal breaks, and the formation of binucleate cells, were observed by optical, fluorescence, and confocal laser scanning microscopy. FT-IR analysis demonstrated the surface chemical interaction between the nanoparticles and root tip cells. The biouptake of Al2O3 in particulate form led to reactive oxygen species generation, which in turn probably contributed to the induction of chromosomal aberrations.

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries

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

Ma, Tianyuan; Xu, Gui-Liang; Li, Yan

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated frommore » the electrochemical oxidation are energetically unstable, and readily undergo a deprotonation reaction that generates protons and promote the dissolution of Al3+ from the aluminum foil. This new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.« less

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries

DOE PAGES

Ma, Tianyuan; Xu, Gui -Liang; Li, Yan; ...

2017-02-16

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated frommore » the electrochemical oxidation are energetically unstable, and readily undergo a deprotonation reaction that generates protons and promote the dissolution of Al 3+ from the aluminum foil. Finally, this new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.« less

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries.

PubMed

Ma, Tianyuan; Xu, Gui-Liang; Li, Yan; Wang, Li; He, Xiangming; Zheng, Jianming; Liu, Jun; Engelhard, Mark H; Zapol, Peter; Curtiss, Larry A; Jorne, Jacob; Amine, Khalil; Chen, Zonghai

2017-03-02

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated from the electrochemical oxidation are energetically unstable and readily undergo a deprotonation reaction that generates protons and promotes the dissolution of Al 3+ from the aluminum foil. This new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.

A sterilization system using ultraviolet photochemical reactions based on nitrous oxide and oxygen gases.

PubMed

Ohnishi, Yasutaka; Matsumoto, Hiroyuki; Iwamori, Satoru

2016-03-01

Active oxygen species (AOS) generated under ultraviolet (UV) lamps can be applied for various industrial processes owing to extremely strong oxidative abilities. We have already reported on an application of the AOS for a sterilization process of microorganisms. Here, a sterilization method using active oxygen generated under ultraviolet (UV) lamps introducing nitrous oxide (N2O) and oxygen gases into a vacuum chamber was investigated. Nitrogen dioxide (NO2) gas was readily produced from N2O by UV photochemical reactions under the low-pressure mercury lamp and then used to sterilize medical devices. We compared the ability of the N2O gas to sterilize Geobacillus stearothermophilus spores with those of conventional methods. Successful sterilization of spores on various biological indicators was achieved within 60 min, not only in sterilization bags but also in a lumen device. Copyright © 2016 Elsevier B.V. All rights reserved.

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries

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

Ma, Tianyuan; Xu, Gui -Liang; Li, Yan

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated frommore » the electrochemical oxidation are energetically unstable, and readily undergo a deprotonation reaction that generates protons and promote the dissolution of Al 3+ from the aluminum foil. Finally, this new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.« less

Modulation of ROS levels in fibroblasts by altering mitochondria regulates the process of wound healing.

PubMed

Janda, Jaroslav; Nfonsam, Valentine; Calienes, Fernanda; Sligh, James E; Jandova, Jana

2016-05-01

Mitochondria are the major source of reactive oxygen species (ROS) in fibroblasts which are thought to be crucial regulators of wound healing with a potential to affect the expression of nuclear genes involved in this process. ROS generated by mitochondria are involved in all stages of tissue repair process but the regulation of ROS-generating system in fibroblasts still remains poorly understood. The purpose of this study was to better understand molecular mechanisms of how the regulation of ROS levels generated by mitochondria may influence the process of wound repair. Cybrid model system of mtDNA variations was used to study the functional consequences of altered ROS levels on wound healing responses in a uniform nuclear background of cultured ρ(0) fibroblasts. Mitochondrial ROS in cybrids were modulated by antioxidants that quench ROS to examine their ability to close the wound. Real-time PCR arrays were used to investigate whether ROS generated by specific mtDNA variants have the ability to alter expression of some key nuclear-encoded genes central to the wound healing response and oxidative stress. Our data suggest levels of mitochondrial ROS affect expression of some nuclear encoded genes central to wound healing response and oxidative stress and modulation of mitochondrial ROS by antioxidants positively affects in vitro process of wound closure. Thus, regulation of mitochondrial ROS-generating system in fibroblasts can be used as effective natural redox-based strategy to help treat non-healing wounds.

Light-Induced Acid Generation on a Gatekeeper for Smart Nitric Oxide Delivery.

PubMed

Choi, Hyung Woo; Kim, Jihoon; Kim, Jinhwan; Kim, Yonghwi; Song, Hyun Beom; Kim, Jeong Hun; Kim, Kimoon; Kim, Won Jong

2016-04-26

We report herein the design of a light-responsive gatekeeper for smart nitric oxide (NO) delivery. The gatekeeper is composed of a pH-jump reagent as an intermediary of stimulus and a calcium phosphate (CaP) coating as a shielding layer for NO release. The light irradiation and subsequent acid generation are used as triggers for uncapping the gatekeeper and releasing NO. The acids generated from a light-activated pH-jump agent loaded in the mesoporous nanoparticles accelerated the degradation of the CaP-coating layers on the nanoparticles, facilitating the light-responsive NO release from diazeniumdiolate by exposing a NO donor to physiological conditions. Using the combination of the pH-jump reagent and CaP coating, we successfully developed a light-responsive gatekeeper system for spatiotemporal-controlled NO delivery.

Minimizing nitrous oxide in biological nutrient removal from municipal wastewater by controlling copper ion concentrations.

PubMed

Zhu, Xiaoyu; Chen, Yinguang; Chen, Hong; Li, Xiang; Peng, Yongzhen; Wang, Shuying

2013-02-01

In this study, nitrous oxide (N(2)O) production during biological nutrient removal (BNR) from municipal wastewater was reported to be remarkably reduced by controlling copper ion (Cu(2+)) concentration. Firstly, it was observed that the addition of Cu(2+) (10-100 μg/L) reduced N(2)O generation by 54.5-73.2 % and improved total nitrogen removal when synthetic wastewater was treated in an anaerobic-aerobic (with low dissolved oxygen) BNR process. Then, the roles of Cu(2+) were investigated. The activities of nitrite and nitrous oxide reductases were increased by Cu(2+) addition, which accelerated the bio-reductions of both nitrite to nitric oxide (NO (2) (-)  → NO) and nitrous oxide to nitrogen gas (N(2)O → N(2)). The quantitative real-time polymerase chain reaction assay indicated that Cu(2+) addition increased the number of N(2)O reducing denitrifiers. Further investigation showed that more polyhydoxyalkanoates were utilized in the Cu(2+)-added system for denitrification. Finally, the feasibility of reducing N(2)O generation by controlling Cu(2+) was examined in two other BNR processes treating real municipal wastewater. As the Cu(2+) in municipal wastewater is usually below 10 μg/L, according to this study, the supplement of influent Cu(2+) to a concentration of 10-100 μg/L is beneficial to reduce N(2)O emission and improve nitrogen removal when sludge concentration in the BNR system is around 3,200 mg/L.

Altered Gravity Induces Oxidative Stress in Drosophila Melanogaster

NASA Technical Reports Server (NTRS)

Bhattacharya, Sharmila; Hosamani, Ravikumar

2015-01-01

Altered gravity environments can induce increased oxidative stress in biological systems. Microarray data from our previous spaceflight experiment (FIT experiment on STS-121) indicated significant changes in the expression of oxidative stress genes in adult fruit flies after spaceflight. Currently, our lab is focused on elucidating the role of hypergravity-induced oxidative stress and its impact on the nervous system in Drosophila melanogaster. Biochemical, molecular, and genetic approaches were combined to study this effect on the ground. Adult flies (2-3 days old) exposed to acute hypergravity (3g, for 1 hour and 2 hours) showed significantly elevated levels of Reactive Oxygen Species (ROS) in fly brains compared to control samples. This data was supported by significant changes in mRNA expression of specific oxidative stress and antioxidant defense related genes. As anticipated, a stress-resistant mutant line, Indy302, was less vulnerable to hypergravity-induced oxidative stress compared to wild-type flies. Survival curves were generated to study the combined effect of hypergravity and pro-oxidant treatment. Interestingly, many of the oxidative stress changes that were measured in flies showed sex specific differences. Collectively, our data demonstrate that altered gravity significantly induces oxidative stress in Drosophila, and that one of the organs where this effect is evident is the brain.

Solid oxide fuel cell systems for residential micro-combined heat and power in the UK: Key economic drivers

NASA Astrophysics Data System (ADS)

Hawkes, Adam; Leach, Matthew

The ability of combined heat and power (CHP) to meet residential heat and power demands efficiently offers potentially significant financial and environmental advantages over centralised power generation and heat-provision through natural-gas fired boilers. A solid oxide fuel cell (SOFC) can operate at high overall efficiencies (heat and power) of 80-90%, offering an improvement over centralised generation, which is often unable to utilise waste heat. This paper applies an equivalent annual cost (EAC) minimisation model to a residential solid oxide fuel cell CHP system to determine what the driving factors are behind investment in this technology. We explore the performance of a hypothetical SOFC system—representing expectations of near to medium term technology development—under present UK market conditions. We find that households with small to average energy demands do not benefit from installation of a SOFC micro-CHP system, but larger energy demands do benefit under these conditions. However, this result is sensitive to a number of factors including stack capital cost, energy import and export prices, and plant lifetime. The results for small and average dwellings are shown to reverse under an observed change in energy import prices, an increase in electricity export price, a decrease in stack capital costs, or an improvement in stack lifetime.

Removal of bisphenol derivatives through quinone oxidation by polyphenol oxidase and subsequent quinone adsorption on chitosan in the heterogeneous system.

PubMed

Kimura, Yuji; Takahashi, Ayumi; Kashiwada, Ayumi; Yamada, Kazunori

2015-01-01

In this study, the combined use of a biopolymer chitosan and an oxidoreductase polyphenol oxidase (PPO) was systematically investigated for the removal of bisphenol derivatives from aqueous medium. The process parameters, such as the pH value, temperature, and PPO concentration, were estimated to conduct the enzymatic quinone oxidation of bisphenol derivatives by as little enzyme as possible. Bisphenol derivatives effectively underwent PPO-catalysed quinone oxidation without H2O2 unlike other oxidoreductases, such as peroxidase and tyrosinase, and the optimum conditions were determined to be pH 7.0 and 40°C for bisphenol B, bisphenol E, bisphenol O, and bisphenol Z; pH 7.0 and 30°C for bisphenol C and bisphenol F; and pH 8.0 and 40°C for bisphenol T. They were completely removed through adsorption of enzymatically generated quinone derivatives on chitosan beads or chitosan powders. Quinone adsorption on chitosan beads or chitosan powders in the heterogeneous system was found to be a more effective procedure than generation of aggregates in the homogeneous system with chitosan solution. The removal time was shortened by increasing the amount of chitosan beads or decreasing the size of the chitosan powders.

A Theoretical Solid Oxide Fuel Cell Model for System Controls and Stability Design

NASA Technical Reports Server (NTRS)

Kopasakis, George; Brinson, Thomas; Credle, Sydni; Xu, Ming

2006-01-01

As the aviation industry moves towards higher efficiency electrical power generation, all electric aircraft, or zero emissions and more quiet aircraft, fuel cells are sought as the technology that can deliver on these high expectations. The Hybrid Solid Oxide Fuel Cell system combines the fuel cell with a microturbine to obtain up to 70 percent cycle efficiency, and then distributes the electrical power to the loads via a power distribution system. The challenge is to understand the dynamics of this complex multi-discipline system, and design distributed controls that take the system through its operating conditions in a stable and safe manner while maintaining the system performance. This particular system is a power generation and distribution system and the fuel cell and microturbine model fidelity should be compatible with the dynamics of the power distribution system in order to allow proper stability and distributed controls design. A novel modeling approach is proposed for the fuel cell that will allow the fuel cell and the power system to be integrated and designed for stability, distributed controls, and other interface specifications. This investigation shows that for the fuel cell, the voltage characteristic should be modeled, but in addition, conservation equation dynamics, ion diffusion, charge transfer kinetics, and the electron flow inherent impedance should also be included.

Detection and removal of impurities in nitric oxide generated from air by pulsed electrical discharge.

PubMed

Yu, Binglan; Blaesi, Aron H; Casey, Noel; Raykhtsaum, Grigory; Zazzeron, Luca; Jones, Rosemary; Morrese, Alexander; Dobrynin, Danil; Malhotra, Rajeev; Bloch, Donald B; Goldstein, Lee E; Zapol, Warren M

2016-11-30

Inhalation of nitric oxide (NO) produces selective pulmonary vasodilation without dilating the systemic circulation. However, the current NO/N 2 cylinder delivery system is cumbersome and expensive. We developed a lightweight, portable, and economical device to generate NO from air by pulsed electrical discharge. The objective of this study was to investigate and optimize the purity and safety of NO generated by this device. By using low temperature streamer discharges in the plasma generator, we produced therapeutic levels of NO with very low levels of nitrogen dioxide (NO 2 ) and ozone. Despite the low temperature, spark generation eroded the surface of the electrodes, contaminating the gas stream with metal particles. During prolonged NO generation there was gradual loss of the iridium high-voltage tip (-90 μg/day) and the platinum-nickel ground electrode (-55 μg/day). Metal particles released from the electrodes were trapped by a high-efficiency particulate air (HEPA) filter. Quadrupole mass spectroscopy measurements of effluent gas during plasma NO generation showed that a single HEPA filter removed all of the metal particles. Mice were exposed to breathing 50 parts per million of electrically generated NO in air for 28 days with only a scavenger and no HEPA filter; the mice did not develop pulmonary inflammation or structural changes and iridium and platinum particles were not detected in the lungs of these mice. In conclusion, an electric plasma generator produced therapeutic levels of NO from air; scavenging and filtration effectively eliminated metallic impurities from the effluent gas. Copyright © 2016 Elsevier Inc. All rights reserved.

Detection and Removal of Impurities in Nitric Oxide Generated from Air by Pulsed Electrical Discharge

PubMed Central

Yu, Binglan; Blaesi, Aron H.; Casey, Noel; Raykhtsaum, Grigory; Zazzeron, Luca; Jones, Rosemary; Morrese, Alexander; Dobrynin, Danil; Malhotra, Rajeev; Bloch, Donald B.; Goldstein, Lee E.; Zapol, Warren M.

2016-01-01

Inhalation of nitric oxide (NO) produces selective pulmonary vasodilation without dilating the systemic circulation. However, the current NO/N2 cylinder delivery system is cumbersome and expensive. We developed a lightweight, portable, and economical device to generate NO from air by pulsed electrical discharge. The objective of this study was to investigate and optimize the purity and safety of NO generated by this device. By using low temperature streamer discharges in the plasma generator, we produced therapeutic levels of NO with very low levels of nitrogen dioxide (NO2) and ozone. Despite the low temperature, spark generation eroded the surface of the electrodes, contaminating the gas stream with metal particles. During prolonged NO generation there was gradual loss of the iridium high-voltage tip (−90 µg/day) and the platinum-nickel ground electrode (−55 µg/day). Metal particles released from the electrodes were trapped by a high-efficiency particulate air (HEPA) filter. Quadrupole mass spectroscopy measurements of effluent gas during plasma NO generation showed that a single HEPA filter removed all of the metal particles. Mice were exposed to breathing 50 parts per million of electrically generated NO in air for 28 days with only a scavenger and no HEPA filter; the mice did not develop pulmonary inflammation or structural changes and iridium and platinum particles were not detected in the lungs of these mice. In conclusion, an electric plasma generator produced therapeutic levels of NO from air; scavenging and filtration effectively eliminated metallic impurities from the effluent gas. PMID:27592386

Precision Assembly of Systems on Surfaces (PASS)

DTIC Science & Technology

2015-02-06

As a result, under other funding we are pursuing applications of this method for the detection of biogenic amines that are indicators of meat ...conductive materials are made from indium tin oxide or fluorinated tin oxide. The latter involves the substitution of a F- for an O-2 and leads to n...generated by spoiling meat . Our fully drawn sensors and ability to fabricate materials on many substrates has assisted us in ongoing experiments directed

A novel nitric oxide-based anticancer therapeutics by macrophage-targeted poly(l-arginine)-based nanoparticles.

PubMed

Kudo, Shinpei; Nagasaki, Yukio

2015-11-10

In the immune system, macrophages in tumor tissue generate nitric oxide (NO), producing versatile effects including apoptosis of tumor cells, because inducible NO synthase (iNOS) in the cytoplasm of a macrophage produces NO using l-arginine as a substrate. Here, we propose novel NO-triggered immune therapeutics based on our newly designed nanoparticle system. We designed a poly(ethylene glycol)-block-poly(l-arginine) (i.e., PEG-b-P(l-Arg)) block copolymer and prepared polyion complex micelles (PEG-b-P(l-Arg)/m) composed of PEG-b-P(l-Arg) and chondroitin sulfate for systemic anticancer immunotherapy. iNOS treatment of PEG-b-P(l-Arg) did not generate NO, but NO molecules were detected after trypsin pretreatment, indicating that hydrolysis of P(l-Arg) to monomeric arginine was taking place in vitro. RAW264.7 macrophages abundantly generated NO from the PEG-b-P(l-Arg)/m in comparison with control micelles; this finding is indicative of robustness of the proposed method. It is interesting to note that systemic administration of PEG-b-P(l-Arg)/m had no noticeable adverse effects and suppressed the tumor growth rate in C26 tumor-bearing mice in a dose-dependent manner. Our newly designed nanoparticle-assisted arginine delivery system seems to hold promise as an NO-mediated anticancer immunotherapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Study of the use of Metal-Oxide-Silicon (MOS) devices for particulate detection and monitoring in the earth's atmosphere

NASA Technical Reports Server (NTRS)

Brooks, A. D.; Monteith, L. K.; Wortman, J. J.; Mulligan, J. C.

1974-01-01

A metal-oxide-silicon (MOS) capacitor-type particulate sensor was evaluated for use in atmospheric measurements. An accelerator system was designed and tested for the purpose of providing the necessary energy to trigger the MOS-type sensor. The accelerator system and the MOS sensor were characterized as a function of particle size and velocity. Diamond particles were used as particulate sources in laboratory tests. Preliminary tests were performed in which the detector was mounted on an aircraft and flown in the vicinity of coal-fired electric generating plants.

Cellular defense against singlet oxygen-induced oxidative damage by cytosolic NADP+-dependent isocitrate dehydrogenase.

PubMed

Kim, Sun Yee; Park, Jeen-Woo

2003-03-01

Singlet oxygen (1O2) is a highly reactive form of molecular oxygen that may harm living systems by oxidizing critical cellular macromolecules. Recently, we have shown that NADP+-dependent isocitrate dehydrogenase is involved in the supply of NADPH needed for GSH production against cellular oxidative damage. In this study, we investigated the role of cytosolic form of NADP+-dependent isocitrate dehydrogenase (IDPc) against singlet oxygen-induced cytotoxicity by comparing the relative degree of cellular responses in three different NIH3T3 cells with stable transfection with the cDNA for mouse IDPc in sense and antisense orientations, where IDPc activities were 2.3-fold higher and 39% lower, respectively, than that in the parental cells carrying the vector alone. Upon exposure to singlet oxygen generated from photoactivated dye, the cells with low levels of IDPc became more sensitive to cell killing. Lipid peroxidation, protein oxidation, oxidative DNA damage and intracellular peroxide generation were higher in the cell-line expressing the lower level of IDPc. However, the cells with the highly over-expressed IDPc exhibited enhanced resistance against singlet oxygen, compared to the control cells. The data indicate that IDPc plays an important role in cellular defense against singlet oxygen-induced oxidative injury.

SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

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

Steven Shaffer; Sean Kelly; Subhasish Mukerjee

2003-12-08

The objective of Phase I under this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burnmore » internal combustion engine. This technical progress report covers work performed by Delphi from January 1, 2003 to June 30, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; and Task 9 Stack Testing with Coal-Based Reformate.« less

Mathematical model for the analysis of structure and optimal operational parameters of a solid oxide fuel cell generator

NASA Astrophysics Data System (ADS)

Coralli, Alberto; Villela de Miranda, Hugo; Espiúca Monteiro, Carlos Felipe; Resende da Silva, José Francisco; Valadão de Miranda, Paulo Emílio

2014-12-01

Solid oxide fuel cells are globally recognized as a very promising technology in the area of highly efficient electricity generation with a low environmental impact. This technology can be advantageously implemented in many situations in Brazil and it is well suited to the use of ethanol as a primary energy source, an important feature given the highly developed Brazilian ethanol industry. In this perspective, a simplified mathematical model is developed for a fuel cell and its balance of plant, in order to identify the optimal system structure and the most convenient values for the operational parameters, with the aim of maximizing the global electric efficiency. In this way it is discovered the best operational configuration for the desired application, which is the distributed generation in the concession area of the electricity distribution company Elektro. The data regarding this configuration are required for the continuation of the research project, i.e. the development of a prototype, a cost analysis of the developed system and a detailed perspective of the market opportunities in Brazil.

[Advanced treatment of coking wastewater with a novel heterogeneous electro-Fenton technology].

PubMed

Li, Hai-Tao; Li, Yu-Ping; Zhang, An-Yang; Cao, Hong-Bin; Li, Xin-Gang; Zhang, Yi

2011-01-01

A novel electro-catalytic reactor, with oxygen-reduction cathode (PAQ/GF), dimensionally stable anode (IrO2-RuO2 -TiO2/ Ti) and heterogeneous catalysts, is developed for advanced treatment of coking wastewater after biological process, integrating cathodic and anodic simultaneous oxidation processes. A PAQ/GF electrode was synthesized by the electro-polymerization of 2-ethyl anthraquinone on graphite felt, which was characterized with cyclic voltametry measurements; the results indicated that the PAQ/GF electrode showed high reversibility for oxidation-reduction reaction of anthraquinone and catalytic activity for O2 reduction to H2O2; 13.5 mmol/L H2O2 was obtained after electrolysis for 6 h at -0.7 V (vs. SCE) and pH 6 with a current efficiency of 50% in a membrane reactor. Fe-Cu/Y350 catalysts, prepared by impregnation method, could catalyze the production of hydroxyl radicals (*OH) from H2O2, which was confirmed both by fading reaction of crystal violet and oxidation of *OH-probe compound (p-chlorobenzoic acid); Fe-Cu/Y350 also showed high catalytic-activity for the oxidation of organics by hypochlorous sodium, because COD removal of coking wastewater reached 26% in the catalytic process while only 11% of COD removal was obtained in the absence of Fe-Cu/Y350. COD removal of coking wastewater reached 49.4% (26.0% and 23.4% in cathodic system and anodic system, respectively) in the developed electrolytic-reactor, which was higher than that of conventional cathodic-anodic-oxidation process (29.8%). At optimal reaction condition of initial COD = 192 mg/L, I = 10A x m(-2) and pH 4-5, more than 50% COD were removed after electrolysis for 1 h. The mechanism might be as follows: in cathodic system, H2O2 is generated from reduction of O2 on PAQ/GF cathode, and catalyzed by Fe-Cu/Y350 for production of *OH, which causes mineralization and degradation of organic pollutants; in anodic system, Cl2 and HClO are generated from Cl- oxidation on IrO2-RuO2-TiO2/Ti anode and the organic pollutants are oxidized by Cl2, and HClO with Fe-Cu/Y350 catalysts or by direct anodic oxidation.

Anaerobic ammonia removal in presence of organic matter: a novel route.

PubMed

Sabumon, P C

2007-10-01

This study describes the feasibility of anaerobic ammonia removal process in presence of organic matter. Different sources of biomass collected from diverse eco-systems containing ammonia and organic matter (OM) were screened for potential anaerobic ammonia removal. Sequential batch studies confirmed the possibility of anaerobic ammonia removal in presence of OM, but ammonia was oxidized anoxically to nitrate (at oxidation reduction potential; ORP=-248+/-25 mV) by an unknown mechanism unlike in the reported anammox process. The oxygen required for oxidation of ammonia might have been generated through catalase enzymatic activity of facultative anaerobes in mixed culture. The oxygen generation possibility by catalase enzyme route was demonstrated. Among the inorganic electron acceptors (NO(2)(-), NO(3)(-) and SO(4)(2-)) studied, NO(2)(-) was found to be most effective in total nitrogen removal. Denitrification by the developed culture was much effective and faster compared to ammonia oxidation. The results of this study show that anaerobic ammonia removal is feasible in presence of OM. The novel nitrogen removal route is hypothesized as enzymatic anoxic oxidation of NH(4)(+) to NO(3)(-), followed by denitrification via autotrophic and/or heterotrophic routes. The results of batch study were confirmed in continuous reactor operation.

In vitro Repair of Oxidative DNA Damage by Human Nucleotide Excision Repair System: Possible Explanation for Neurodegeneration in Xeroderma Pigmentosum Patients

NASA Astrophysics Data System (ADS)

Reardon, Joyce T.; Bessho, Tadayoshi; Kung, Hsiang Chuan; Bolton, Philip H.; Sancar, Aziz

1997-08-01

Xeroderma pigmentosum (XP) patients fail to remove pyrimidine dimers caused by sunlight and, as a consequence, develop multiple cancers in areas exposed to light. The second most common sign, present in 20-30% of XP patients, is a set of neurological abnormalities caused by neuronal death in the central and peripheral nervous systems. Neural tissue is shielded from sunlight-induced DNA damage, so the cause of neurodegeneration in XP patients remains unexplained. In this study, we show that two major oxidative DNA lesions, 8-oxoguanine and thymine glycol, are excised from DNA in vitro by the same enzyme system responsible for removing pyrimidine dimers and other bulky DNA adducts. Our results suggest that XP neurological disease may be caused by defective repair of lesions that are produced in nerve cells by reactive oxygen species generated as by-products of an active oxidative metabolism.

Self-Driven Photoelectrochemical Splitting of H2S for S and H2 Recovery and Simultaneous Electricity Generation.

PubMed

Luo, Tao; Bai, Jing; Li, Jinhua; Zeng, Qingyi; Ji, Youzhi; Qiao, Li; Li, Xiaoyan; Zhou, Baoxue

2017-11-07

A novel, facile self-driven photoelectrocatalytic (PEC) system was established for highly selective and efficient recovery of H 2 S and simultaneous electricity production. The key ideas were the self-bias function between a WO 3 photoanode and a Si/PVC photocathode due to their mismatched Fermi levels and the special cyclic redox reaction mechanism of I - /I 3 - . Under solar light, the system facilitated the separation of holes in the photoanode and electrons in the photocathode, which then generated electricity. Cyclic redox reactions were produced in the photoanode region as follows: I - was transformed into I 3 - by photoholes or hydroxyl radicals, H 2 S was oxidized to S by I 3 - , and I 3 - was then reduced to I - . Meanwhile, H + was efficiently converted to H 2 in the photocathode region. In the system, H 2 S was uniquely oxidized to sulfur but not to polysulfide (S x n- ) because of the mild oxidation capacity of I 3 - . High recovery rates for S and H 2 were obtained up to ∼1.04 mg h -1 cm -1 and ∼0.75 mL h -1 cm -1 , respectively, suggesting that H 2 S was completely converted into H 2 and S. In addition, the output power density of the system reached ∼0.11 mW cm -2 . The proposed PEC-H 2 S system provides a self-sustaining, energy-saving method for simultaneous H 2 S treatment and energy recovery.

Stability and characterization of perphenazine aerosols generated using the capillary aerosol generator.

PubMed

Li, Xihao; Blondino, Frank E; Hindle, Michael; Soine, William H; Byron, Peter R

2005-10-13

Perphenazine (a potent antiemetic) was aerosolized using capillary aerosol generator to generate respirable condensation aerosols from drug in propylene glycol (PG) solutions, by pumping the liquids through a heated capillary tube. The study characterized the stability of perphenazine during and following aerosol generation. The stability-indicating HPLC method (C-8 column with a mobile phase of 52% 0.01 M pH 3.0 acetate buffer+48% acetonitrile) also enabled the study of perphenazine stability in solution under acidic, basic, oxidizing and photolysing conditions. An LC-MS (ESI+) method was used to characterize the degradation products. Perphenazine was found to be stable in acidic and basic conditions, while perphenazine sulfoxide was the major product formed in dilute peroxide solutions. Two photo-degradation products were formed in PG that were tentatively identified by LC-MS; one of these was synthesized and confirmed to be 2-[4-(3-phenothiazin-10-yl-propyl)-piperazino]-ethanol. Both photolysis products showed that aromatic dechlorination had occurred and one appeared to also result from interaction with the solvent. Within an aerosolization energy window of 84-95 J, fine particle aerosols were generated from perphenazine PG formulations with no significant degradation. Small amounts of degradation products were produced in all samples during aerosolization at elevated (non-optimal) energies. These were largely consistent with those seen to result from oxidation and photolysis in solution, showing that oxidation and dehalogenation appeared to be the main degradation pathways followed when the CAG system was overheated.

Geothermal Thermoelectric Generation (G-TEG) with Integrated Temperature Driven Membrane Distillation and Novel Manganese Oxide for Lithium Extraction

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

Renew, Jay; Hansen, Tim

Southern Research Institute (Southern) teamed with partners Novus Energy Technologies (Novus), Carus Corporation (Carus), and Applied Membrane Technology, Inc. (AMT) to develop an innovative Geothermal ThermoElectric Generation (G-TEG) system specially designed to both generate electricity and extract high-value lithium (Li) from low-temperature geothermal brines. The process combined five modular technologies including – silica removal, nanofiltration (NF), membrane distillation (MD), Mn-oxide sorbent for Li recovery, and TEG. This project provides a proof of concept for each of these technologies. The first step in the process is silica precipitation through metal addition and pH adjustment to prevent downstream scaling in membrane processes.more » Next, the geothermal brine is concentrated with the first of a two stage MD system. The first stage MD system is made of a high-temperature material to withstand geothermal brine temperatures up to 150C.° The first stage MD is integrated with a G-TEG module for simultaneous energy generation. The release of energy from the MD permeate drives heat transfer across the TE module, producing electricity. The first stage MD concentrate is then treated utilizing an NF system to remove Ca 2+ and Mg 2+. The NF concentrate will be disposed in the well by reinjection. The NF permeate undergoes concentration in a second stage of MD (polymeric material) to further concentrate Li in the NF permeate and enhance the efficiency of the downstream Li recovery process utilizing a Mn-oxide sorbent. Permeate from both the stages of the MD can be beneficially utilized as the permeates will contain less contaminants than the feed water. The concentrated geothermal brines are then contacted with the Mn-oxide sorbent. After Li from the geothermal brine is adsorbed on the sorbent, HCl is then utilized to regenerate the sorbent and recover the Li. The research and development project showed that the Si removal goal (>80%) could be achieved by increasing the pH of the brine and adding Fe 3+ under several scenarios. The NF was also successful in achieving significant Ca 2+ and Mg 2+ removal (~80%) while retaining most Li in the permeate for high strength brines. MD experiments showed that geothermal brines could be significantly concentrated with little fouling due to pre-treatment.« less

An SSME High Pressure Oxidizer Turbopump diagnostic system using G2 real-time expert system

NASA Technical Reports Server (NTRS)

Guo, Ten-Huei

1991-01-01

An expert system which diagnoses various seal leakage faults in the High Pressure Oxidizer Turbopump of the SSME was developed using G2 real-time expert system. Three major functions of the software were implemented: model-based data generation, real-time expert system reasoning, and real-time input/output communication. This system is proposed as one module of a complete diagnostic system for the SSME. Diagnosis of a fault is defined as the determination of its type, severity, and likelihood. Since fault diagnosis is often accomplished through the use of heuristic human knowledge, an expert system based approach has been adopted as a paradigm to develop this diagnostic system. To implement this approach, a software shell which can be easily programmed to emulate the human decision process, the G2 Real-Time Expert System, was selected. Lessons learned from this implementation are discussed.

An SSME high pressure oxidizer turbopump diagnostic system using G2(TM) real-time expert system

NASA Technical Reports Server (NTRS)

Guo, Ten-Huei

1991-01-01

An expert system which diagnoses various seal leakage faults in the High Pressure Oxidizer Turbopump of the SSME was developed using G2(TM) real-time expert system. Three major functions of the software were implemented: model-based data generation, real-time expert system reasoning, and real-time input/output communication. This system is proposed as one module of a complete diagnostic system for Space Shuttle Main Engine. Diagnosis of a fault is defined as the determination of its type, severity, and likelihood. Since fault diagnosis is often accomplished through the use of heuristic human knowledge, an expert system based approach was adopted as a paradigm to develop this diagnostic system. To implement this approach, a software shell which can be easily programmed to emulate the human decision process, the G2 Real-Time Expert System, was selected. Lessons learned from this implementation are discussed.

Kinetics and mechanism of auto- and copper-catalyzed oxidation of 1,4-naphthohydroquinone.

PubMed

Yuan, Xiu; Miller, Christopher J; Pham, A Ninh; Waite, T David

2014-06-01

Although quinones represent a class of organic compounds that may exert toxic effects both in vitro and in vivo, the molecular mechanisms involved in quinone species toxicity are still largely unknown, especially in the presence of transition metals, which may both induce the transformation of the various quinone species and result in generation of harmful reactive oxygen species. In this study, the oxidation of 1,4-naphthohydroquinone (NH2Q) in the absence and presence of nanomolar concentrations of Cu(II) in 10 mM NaCl solution over a pH range of 6.5-7.5 has been investigated, with detailed kinetic models developed to describe the predominant mechanisms operative in these systems. In the absence of copper, the apparent oxidation rate of NH2Q increased with increasing pH and initial NH2Q concentration, with concomitant oxygen consumption and peroxide generation. The doubly dissociated species, NQ(2-), has been shown to be the reactive species with regard to the one-electron oxidation by O2 and comproportionation with the quinone species, both generating the semiquinone radical (NSQ(·-)). The oxidation of NSQ(·-) by O2 is shown to be the most important pathway for superoxide (O2(·-)) generation with a high intrinsic rate constant of 1.0×10(8)M(-1)s(-1). Both NSQ(·-) and O2(·-) served as chain-propagating species in the autoxidation of NH2Q. Cu(II) is capable of catalyzing the oxidation of NH2Q in the presence of O2 with the oxidation also accelerated by increasing the pH. Both the uncharged (NH2Q(0)) and the mono-anionic (NHQ(-)) species were found to be the kinetically active forms, reducing Cu(II) with an intrinsic rate constant of 4.0×10(4) and 1.2×10(7)M(-1)s(-1), respectively. The presence of O2 facilitated the catalytic role of Cu(II) by rapidly regenerating Cu(II) via continuous oxidation of Cu(I) and also by efficient removal of NSQ(·-) resulting in the generation of O2(·-). The half-cell reduction potentials of various redox couples at neutral pH indicated good agreement between thermodynamic and kinetic considerations for various key reactions involved, further validating the proposed mechanisms involved in both the autoxidation and the copper-catalyzed oxidation of NH2Q in circumneutral pH solutions. Copyright © 2014 Elsevier Inc. All rights reserved.

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene

PubMed Central

Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

2017-01-01

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m3 smog chamber. The presence of FeSO4 or Fe2(SO4)3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO4 or (NH4)2SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe2(SO4)3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation. PMID:28059151

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene.

PubMed

Chu, Biwu; Liggio, John; Liu, Yongchun; He, Hong; Takekawa, Hideto; Li, Shao-Meng; Hao, Jiming

2017-01-06

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m 3 smog chamber. The presence of FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO 4 or (NH 4 ) 2 SO 4 . These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO 4 or Fe 2 (SO 4 ) 3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.

Inference of the oxidative stress network in Anopheles stephensi upon Plasmodium infection.

PubMed

Shrinet, Jatin; Nandal, Umesh Kumar; Adak, Tridibes; Bhatnagar, Raj K; Sunil, Sujatha

2014-01-01

Ookinete invasion of Anopheles midgut is a critical step for malaria transmission; the parasite numbers drop drastically and practically reach a minimum during the parasite's whole life cycle. At this stage, the parasite as well as the vector undergoes immense oxidative stress. Thereafter, the vector undergoes oxidative stress at different time points as the parasite invades its tissues during the parasite development. The present study was undertaken to reconstruct the network of differentially expressed genes involved in oxidative stress in Anopheles stephensi during Plasmodium development and maturation in the midgut. Using high throughput next generation sequencing methods, we generated the transcriptome of the An. stephensi midgut during Plasmodium vinckei petteri oocyst invasion of the midgut epithelium. Further, we utilized large datasets available on public domain on Anopheles during Plasmodium ookinete invasion and Drosophila datasets and arrived upon clusters of genes that may play a role in oxidative stress. Finally, we used support vector machines for the functional prediction of the un-annotated genes of An. stephensi. Integrating the results from all the different data analyses, we identified a total of 516 genes that were involved in oxidative stress in An. stephensi during Plasmodium development. The significantly regulated genes were further extracted from this gene cluster and used to infer an oxidative stress network of An. stephensi. Using system biology approaches, we have been able to ascertain the role of several putative genes in An. stephensi with respect to oxidative stress. Further experimental validations of these genes are underway.

Fluorescent proteins such as eGFP lead to catalytic oxidative stress in cells.

PubMed

Ganini, Douglas; Leinisch, Fabian; Kumar, Ashutosh; Jiang, JinJie; Tokar, Erik J; Malone, Christine C; Petrovich, Robert M; Mason, Ronald P

2017-08-01

Fluorescent proteins are an important tool that has become omnipresent in life sciences research. They are frequently used for localization of proteins and monitoring of cells [1,2]. Green fluorescent protein (GFP) was the first and has been the most used fluorescent protein. Enhanced GFP (eGFP) was optimized from wild-type GFP for increased fluorescence yield and improved expression in mammalian systems [3]. Many GFP-like fluorescent proteins have been discovered, optimized or created, such as the red fluorescent protein TagRFP [4]. Fluorescent proteins are expressed colorless and immature and, for eGFP, the conversion to the fluorescent form, mature, is known to produce one equivalent of hydrogen peroxide (H 2 O 2 ) per molecule of chromophore [5,6]. Even though it has been proposed that this process is non-catalytic and generates nontoxic levels of H 2 O 2 [6], this study investigates the role of fluorescent proteins in generating free radicals and inducing oxidative stress in biological systems. Immature eGFP and TagRFP catalytically generate the free radical superoxide anion (O 2 •- ) and H 2 O 2 in the presence of NADH. Generation of the free radical O 2 •- and H 2 O 2 by eGFP in the presence of NADH affects the gene expression of cells. Many biological pathways are altered, such as a decrease in HIF1α stabilization and activity. The biological pathways altered by eGFP are known to be implicated in the pathophysiology of many diseases associated with oxidative stress; therefore, it is critical that such experiments using fluorescent proteins are validated with alternative methodologies and the results are carefully interpreted. Since cells inevitably experience oxidative stress when fluorescent proteins are expressed, the use of this tool for cell labeling and in vivo cell tracing also requires validation using alternative methodologies. Published by Elsevier B.V.

Oxidative Stress Responses in the Human Fungal Pathogen, Candida albicans

PubMed Central

da Silva Dantas, Alessandra; Day, Alison; Ikeh, Mélanie; Kos, Iaroslava; Achan, Beatrice; Quinn, Janet

2015-01-01

Candida albicans is a major fungal pathogen of humans, causing approximately 400,000 life-threatening systemic infections world-wide each year in severely immunocompromised patients. An important fungicidal mechanism employed by innate immune cells involves the generation of toxic reactive oxygen species (ROS), such as superoxide and hydrogen peroxide. Consequently, there is much interest in the strategies employed by C. albicans to evade the oxidative killing by macrophages and neutrophils. Our understanding of how C. albicans senses and responds to ROS has significantly increased in recent years. Key findings include the observations that hydrogen peroxide triggers the filamentation of this polymorphic fungus and that a superoxide dismutase enzyme with a novel mode of action is expressed at the cell surface of C. albicans. Furthermore, recent studies have indicated that combinations of the chemical stresses generated by phagocytes can actively prevent C. albicans oxidative stress responses through a mechanism termed the stress pathway interference. In this review, we present an up-date of our current understanding of the role and regulation of oxidative stress responses in this important human fungal pathogen. PMID:25723552

Reactive oxygen species: players in the cardiovascular effects of testosterone

PubMed Central

Carneiro, Fernando S.; Carvalho, Maria Helena C.; Reckelhoff, Jane F.

2015-01-01

Androgens are essential for the development and maintenance of male reproductive tissues and sexual function and for overall health and well being. Testosterone, the predominant and most important androgen, not only affects the male reproductive system, but also influences the activity of many other organs. In the cardiovascular system, the actions of testosterone are still controversial, its effects ranging from protective to deleterious. While early studies showed that testosterone replacement therapy exerted beneficial effects on cardiovascular disease, some recent safety studies point to a positive association between endogenous and supraphysiological levels of androgens/testosterone and cardiovascular disease risk. Among the possible mechanisms involved in the actions of testosterone on the cardiovascular system, indirect actions (changes in the lipid profile, insulin sensitivity, and hemostatic mechanisms, modulation of the sympathetic nervous system and renin-angiotensin-aldosterone system), as well as direct actions (modulatory effects on proinflammatory enzymes, on the generation of reactive oxygen species, nitric oxide bioavailability, and on vasoconstrictor signaling pathways) have been reported. This mini-review focuses on evidence indicating that testosterone has prooxidative actions that may contribute to its deleterious actions in the cardiovascular system. The controversial effects of testosterone on ROS generation and oxidant status, both prooxidant and antioxidant, in the cardiovascular system and in cells and tissues of other systems are reviewed. PMID:26538238

Adaptive control paradigm for photovoltaic and solid oxide fuel cell in a grid-integrated hybrid renewable energy system.

PubMed

Mumtaz, Sidra; Khan, Laiq

2017-01-01

The hybrid power system (HPS) is an emerging power generation scheme due to the plentiful availability of renewable energy sources. Renewable energy sources are characterized as highly intermittent in nature due to meteorological conditions, while the domestic load also behaves in a quite uncertain manner. In this scenario, to maintain the balance between generation and load, the development of an intelligent and adaptive control algorithm has preoccupied power engineers and researchers. This paper proposes a Hermite wavelet embedded NeuroFuzzy indirect adaptive MPPT (maximum power point tracking) control of photovoltaic (PV) systems to extract maximum power and a Hermite wavelet incorporated NeuroFuzzy indirect adaptive control of Solid Oxide Fuel Cells (SOFC) to obtain a swift response in a grid-connected hybrid power system. A comprehensive simulation testbed for a grid-connected hybrid power system (wind turbine, PV cells, SOFC, electrolyzer, battery storage system, supercapacitor (SC), micro-turbine (MT) and domestic load) is developed in Matlab/Simulink. The robustness and superiority of the proposed indirect adaptive control paradigm are evaluated through simulation results in a grid-connected hybrid power system testbed by comparison with a conventional PI (proportional and integral) control system. The simulation results verify the effectiveness of the proposed control paradigm.

Feasibility study of solid oxide fuel cell engines integrated with sprinter gas turbines: Modeling, design and control

NASA Astrophysics Data System (ADS)

Jia, Zhenzhong; Sun, Jing; Dobbs, Herb; King, Joel

2015-02-01

Conventional recuperating solid oxide fuel cell (SOFC)/gas turbine (GT) system suffers from its poor dynamic capability and load following performance. To meet the fast, safe and efficient load following requirements for mobile applications, a sprinter SOFC/GT system concept is proposed in this paper. In the proposed system, an SOFC stack operating at fairly constant temperature provides the baseline power with high efficiency while the fast dynamic capability of the GT-generator is fully explored for fast dynamic load following. System design and control studies have been conducted by using an SOFC/GT system model consisting of experimentally-verified component models. In particular, through analysis of the steady-state simulation results, an SOFC operation strategy is proposed to maintain fairly constant SOFC power (less than 2% power variation) and temperature (less than 2 K temperature variation) over the entire load range. A system design procedure well-suited to the proposed system has also been developed to help determining component sizes and the reference steady-state operation line. In addition, control analysis has been studied for both steady-state and transient operations. Simulation results suggest that the proposed system holds the promise to achieve fast and safe transient operations by taking full advantage of the fast dynamics of the GT-generator.

Adaptive control paradigm for photovoltaic and solid oxide fuel cell in a grid-integrated hybrid renewable energy system

PubMed Central

Khan, Laiq

2017-01-01

The hybrid power system (HPS) is an emerging power generation scheme due to the plentiful availability of renewable energy sources. Renewable energy sources are characterized as highly intermittent in nature due to meteorological conditions, while the domestic load also behaves in a quite uncertain manner. In this scenario, to maintain the balance between generation and load, the development of an intelligent and adaptive control algorithm has preoccupied power engineers and researchers. This paper proposes a Hermite wavelet embedded NeuroFuzzy indirect adaptive MPPT (maximum power point tracking) control of photovoltaic (PV) systems to extract maximum power and a Hermite wavelet incorporated NeuroFuzzy indirect adaptive control of Solid Oxide Fuel Cells (SOFC) to obtain a swift response in a grid-connected hybrid power system. A comprehensive simulation testbed for a grid-connected hybrid power system (wind turbine, PV cells, SOFC, electrolyzer, battery storage system, supercapacitor (SC), micro-turbine (MT) and domestic load) is developed in Matlab/Simulink. The robustness and superiority of the proposed indirect adaptive control paradigm are evaluated through simulation results in a grid-connected hybrid power system testbed by comparison with a conventional PI (proportional and integral) control system. The simulation results verify the effectiveness of the proposed control paradigm. PMID:28329015

Surface- and tip-enhanced Raman spectroscopy reveals spin-waves in iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Rodriguez, Raul D.; Sheremet, Evgeniya; Deckert-Gaudig, Tanja; Chaneac, Corinne; Hietschold, Michael; Deckert, Volker; Zahn, Dietrich R. T.

2015-05-01

Nanomaterials have the remarkable characteristic of displaying physical properties different from their bulk counterparts. An additional degree of complexity and functionality arises when oxide nanoparticles interact with metallic nanostructures. In this context the Raman spectra due to plasmonic enhancement of iron oxide nanocrystals are here reported showing the activation of spin-waves. Iron oxide nanoparticles on gold and silver tips are found to display a band around 1584 cm-1 attributed to a spin-wave magnon mode. This magnon mode is not observed for nanoparticles deposited on silicon (111) or on glass substrates. Metal-nanoparticle interaction and the strongly localized electromagnetic field contribute to the appearance of this mode. The localized excitation that generates this mode is confirmed by tip-enhanced Raman spectroscopy (TERS). The appearance of the spin-waves only when the TERS tip is in close proximity to a nanocrystal edge suggests that the coupling of a localized plasmon with spin-waves arises due to broken symmetry at the nanoparticle border and the additional electric field confinement. Beyond phonon confinement effects previously reported in similar systems, this work offers significant insights on the plasmon-assisted generation and detection of spin-waves optically induced.Nanomaterials have the remarkable characteristic of displaying physical properties different from their bulk counterparts. An additional degree of complexity and functionality arises when oxide nanoparticles interact with metallic nanostructures. In this context the Raman spectra due to plasmonic enhancement of iron oxide nanocrystals are here reported showing the activation of spin-waves. Iron oxide nanoparticles on gold and silver tips are found to display a band around 1584 cm-1 attributed to a spin-wave magnon mode. This magnon mode is not observed for nanoparticles deposited on silicon (111) or on glass substrates. Metal-nanoparticle interaction and the strongly localized electromagnetic field contribute to the appearance of this mode. The localized excitation that generates this mode is confirmed by tip-enhanced Raman spectroscopy (TERS). The appearance of the spin-waves only when the TERS tip is in close proximity to a nanocrystal edge suggests that the coupling of a localized plasmon with spin-waves arises due to broken symmetry at the nanoparticle border and the additional electric field confinement. Beyond phonon confinement effects previously reported in similar systems, this work offers significant insights on the plasmon-assisted generation and detection of spin-waves optically induced. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01277e

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

NASA Astrophysics Data System (ADS)

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-07-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system.

Systemic inflammatory changes and increased oxidative stress in rural Indian women cooking with biomass fuels.

PubMed

Dutta, Anindita; Ray, Manas Ranjan; Banerjee, Anirban

2012-06-15

The study was undertaken to investigate whether regular cooking with biomass aggravates systemic inflammation and oxidative stress that might result in increase in the risk of developing cardiovascular disease (CVD) in rural Indian women compared to cooking with a cleaner fuel like liquefied petroleum gas (LPG). A total of 635 women (median age 36 years) who cooked with biomass and 452 age-matched control women who cooked with LPG were enrolled. Serum interleukin-6 (IL-6), C-reactive protein (CRP), tumor necrosis factor-alpha (TNF-α) and interleukin-8 (IL-8) were measured by ELISA. Generation of reactive oxygen species (ROS) by leukocytes was measured by flow cytometry, and erythrocytic superoxide dismutase (SOD) was measured by spectrophotometry. Hypertension was diagnosed following the Seventh Report of the Joint Committee. Tachycardia was determined as pulse rate >100 beats per minute. Particulate matter of diameter less than 10 and 2.5 μm (PM₁₀ and PM₂.₅, respectively) in cooking areas was measured using real-time aerosol monitor. Compared with control, biomass users had more particulate pollution in indoor air, their serum contained significantly elevated levels of IL-6, IL-8, TNF-α and CRP, and ROS generation was increased by 37% while SOD was depleted by 41.5%, greater prevalence of hypertension and tachycardia compared to their LPG-using neighbors. PM₁₀ and PM₂.₅ levels were positively associated with markers of inflammation, oxidative stress and hypertension. Inflammatory markers correlated with raised blood pressure. Cooking with biomass exacerbates systemic inflammation, oxidative stress, hypertension and tachycardia in poor women cooking with biomass fuel and hence, predisposes them to increased risk of CVD development compared to the controls. Systemic inflammation and oxidative stress may be the mechanistic factors involved in the development of CVD. Copyright © 2012 Elsevier Inc. All rights reserved.

OXIDANT FORMATION IN THE GENERATION OF OZONE

EPA Science Inventory

Ozone samples generated by UV photolysis and silent electric discharge upon air or oxygen were examined to determine if other oxidants were formed. Chemical and physical methods (IR and UV spectroscopy) failed to show the presence of such oxidants. Absence of such oxidants was al...

Oxidase catalysis via aerobically generated hypervalent iodine intermediates

NASA Astrophysics Data System (ADS)

Maity, Asim; Hyun, Sung-Min; Powers, David C.

2018-02-01

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

Studies on Effective Utilization of SOFC Exhaust Heat Using Thermoelectric Power Generation Technology

NASA Astrophysics Data System (ADS)

Terayama, Takeshi; Nagata, Susumu; Tanaka, Yohei; Momma, Akihiko; Kato, Tohru; Kunii, Masaru; Yamamoto, Atsushi

2013-07-01

Solid oxide fuel cells (SOFCs) are being researched around the world. In Japan, a compact SOFC system with rated alternative current (AC) power of 700 W has become available on the market, since the base load electricity demand for a standard home is said to be less than 700 W AC. To improve the generating efficiency of SOFC systems in the 700-W class, we focused on thermoelectric generation (TEG) technology, since there are a lot of temperature gradients in the system. Analysis based on simulations indicated the possibility of introducing thermoelectric generation at the air preheater, steam generator, and exhaust outlet. Among these options, incorporating a TEG heat exchanger comprising multiple CoSb3/SiGe-based TEG modules into the air preheater had potential to produce additional output of 37.5 W and an improvement in generating efficiency from 46% to 48.5%. Furthermore, by introducing thermoelectric generation at the other two locations, an increase in maximum output of more than 50 W and generating efficiency of 50% can be anticipated.

Comparative Genomics of Syntrophic Branched-Chain Fatty Acid Degrading Bacteria

PubMed Central

Narihiro, Takashi; Nobu, Masaru K.; Tamaki, Hideyuki; Kamagata, Yoichi; Sekiguchi, Yuji; Liu, Wen-Tso

2016-01-01

The syntrophic degradation of branched-chain fatty acids (BCFAs) such as 2-methylbutyrate and isobutyrate is an essential step in the production of methane from proteins/amino acids in anaerobic ecosystems. While a few syntrophic BCFA-degrading bacteria have been isolated, their metabolic pathways in BCFA and short-chain fatty acid (SCFA) degradation as well as energy conservation systems remain unclear. In an attempt to identify these pathways, we herein performed comparative genomics of three syntrophic bacteria: 2-methylbutyrate-degrading “Syntrophomonas wolfei subsp. methylbutyratica” strain JCM 14075T (=4J5T), isobutyrate-degrading Syntrophothermus lipocalidus strain TGB-C1T, and non-BCFA-metabolizing S. wolfei subsp. wolfei strain GöttingenT. We demonstrated that 4J5 and TGB-C1 both encode multiple genes/gene clusters involved in β-oxidation, as observed in the Göttingen genome, which has multiple copies of genes associated with butyrate degradation. The 4J5 genome possesses phylogenetically distinct β-oxidation genes, which may be involved in 2-methylbutyrate degradation. In addition, these Syntrophomonadaceae strains harbor various hydrogen/formate generation systems (i.e., electron-bifurcating hydrogenase, formate dehydrogenase, and membrane-bound hydrogenase) and energy-conserving electron transport systems, including electron transfer flavoprotein (ETF)-linked acyl-CoA dehydrogenase, ETF-linked iron-sulfur binding reductase, ETF dehydrogenase (FixABCX), and flavin oxidoreductase-heterodisulfide reductase (Flox-Hdr). Unexpectedly, the TGB-C1 genome encodes a nitrogenase complex, which may function as an alternative H2 generation mechanism. These results suggest that the BCFA-degrading syntrophic strains 4J5 and TGB-C1 possess specific β-oxidation-related enzymes for BCFA oxidation as well as appropriate energy conservation systems to perform thermodynamically unfavorable syntrophic metabolism. PMID:27431485

Effect of bicarbonate on iron-mediated oxidation of low-density lipoprotein

NASA Astrophysics Data System (ADS)

Arai, Hirofumi; Berlett, Barbara S.; Chock, P. Boon; Stadtman, Earl R.

2005-07-01

Oxidation of low-density lipoprotein (LDL) may play an important role in atherosclerosis. We studied the effects of bicarbonate/CO2 and phosphate buffer systems on metal ion-catalyzed oxidation of LDL to malondialdehyde (MDA) and to protein carbonyl and MetO derivatives. Our results revealed that LDL oxidation in mixtures containing free iron or heme derivatives was much greater in bicarbonate/CO2 compared with phosphate buffer. However, when copper was substituted for iron in these mixtures, the rate of LDL oxidation in both buffers was similar. Iron-catalyzed oxidation of LDL was highly sensitive to inhibition by phosphate. Presence of 0.3-0.5 mM phosphate, characteristic of human serum, led to 30-40% inhibition of LDL oxidation in bicarbonate/CO2 buffer. Iron-catalyzed oxidation of LDL to MDA in phosphate buffer was inhibited by increasing concentrations of albumin (10-200 μM), whereas MDA formation in bicarbonate/CO2 buffer was stimulated by 10-50 μM albumin but inhibited by higher concentrations. However, albumin stimulated the oxidation of LDL proteins to carbonyl derivatives at all concentrations examined in both buffers. Conversion of LDL to MDA in bicarbonate/CO2 buffer was greatly stimulated by ADP, ATP, and EDTA but only when EDTA was added at a concentration equal to that of iron. At higher than stoichiometric concentrations, EDTA prevented oxidation of LDL. Results of these studies suggest that interactions between bicarbonate and iron or heme derivatives leads to complexes with redox potentials that favor the generation of reactive oxygen species and/or to the generation of highly reactive CO2 anion or bicarbonate radical that facilitates LDL oxidation. Freely available online through the PNAS open access option.Abbreviations: LDL, low-density lipoprotein; MDA, malondialdehyde; MetO, methionine sulfoxide.

Microbial models of mammalian metabolism: production of novel alpha-diketone metabolites of warfarin and phenprocoumon using Aspergillus niger.

PubMed

Rizzo, J D; Davis, P J

1988-12-01

1. The coumarin anticoagulants warfarin and phenprocoumon were metabolized by Aspergillus niger via oxidative ring cleavage to yield the corresponding alpha-diketone metabolites. 2. Structural identification was based upon physical, spectral, and chromatographic comparisons of isolated metabolites and synthetic standards generated by the oxidative cleavage of warfarin or phenprocoumon with pyridinium chlorochromate. 3. This pathway of metabolism has been previously observed for coumarin anticoagulants in mammalian systems.

Inorganic nanostructured materials for high performance electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Sheng; Sun, Shouheng; You, Xiao-Zeng

2014-01-01

Electrochemical supercapacitors (ES) are a well-known energy storage system that has high power density, long life-cycle and fast charge-discharge kinetics. Nanostructured materials are a new generation of electrode materials with large surface area and short transport/diffusion path for ions and electrons to achieve high specific capacitance in ES. This mini review highlights recent developments of inorganic nanostructure materials, including carbon nanomaterials, metal oxide nanoparticles, and metal oxide nanowires/nanotubes, for high performance ES applications.

Inorganic nanostructured materials for high performance electrochemical supercapacitors.

PubMed

Liu, Sheng; Sun, Shouheng; You, Xiao-Zeng

2014-02-21

Electrochemical supercapacitors (ES) are a well-known energy storage system that has high power density, long life-cycle and fast charge-discharge kinetics. Nanostructured materials are a new generation of electrode materials with large surface area and short transport/diffusion path for ions and electrons to achieve high specific capacitance in ES. This mini review highlights recent developments of inorganic nanostructure materials, including carbon nanomaterials, metal oxide nanoparticles, and metal oxide nanowires/nanotubes, for high performance ES applications.

Solvent free oxidation of primary alcohols and diols using thymine iron(III) catalyst.

PubMed

Al-Hunaiti, Afnan; Niemi, Teemu; Sibaouih, Ahlam; Pihko, Petri; Leskelä, Markku; Repo, Timo

2010-12-28

In this study, we developed an efficient and selective iron-based catalyst system for the synthesis of ketones from secondary alcohols and carboxylic acids from primary alcohol. In situ generated iron catalyst of thymine-1-acetate (THA) and FeCl(3) under solvent-free condition exhibits high activity. As an example, 1-octanol and 2-octanol were oxidized to 1-octanoic acid and 2-octanone with 89% and 98% yields respectively.

Bartter/Gitelman syndromes as a model to study systemic oxidative stress in humans.

PubMed

Maiolino, Giuseppe; Azzolini, Matteo; Rossi, Gian Paolo; Davis, Paul A; Calò, Lorenzo A

2015-11-01

Reactive oxygen species (ROS) are intermediates in reduction-oxidation reactions that begin with the addition of one electron to molecular oxygen, generating the primary ROS superoxide, which in turn interacts with other molecules to produce secondary ROS, such as hydrogen peroxide, hydroxyl radical, and peroxynitrite. ROS are continuously produced during metabolic processes and are deemed to play an important role in cardiovascular diseases, namely, myocardial hypertrophy and fibrosis and atherosclerosis, via oxidative damage of lipids, proteins, and deoxyribonucleic acid. Angiotensin II (Ang II) is a potent vasoactive agent that also exerts mitogenic, proinflammatory, and profibrotic effects through several signaling pathways, in part involving ROS, particularly superoxide and hydrogen peroxide. Moreover, Ang II stimulates NADPH oxidases, leading to higher ROS generation and oxidative stress. Bartter/Gitelman syndrome patients, despite elevated plasma renin activity, Ang II, and aldosterone levels, exhibit reduced peripheral resistance, normal/low blood pressure, and blunted pressor effect of vasoconstrictors. In addition, notwithstanding the activation of the renin-angiotensin system and the increased plasma levels of Ang II, these patients display decreased production of ROS, reduced oxidative stress, and increased antioxidant defenses. In fact, Bartter/Gitelman syndrome patients are characterized by reduced levels of p22(phox) gene expression and undetectable plasma peroxynitrite levels, while showing increased plasma antioxidant power and expression of antioxidant enzymes, such as heme oxygenase-1. In conclusion, multifarious data suggest that Bartter and Gitelman syndrome patients are a model of low oxidative stress and high antioxidant defenses. The contribution offered by the study of these syndromes in elucidating the molecular mechanisms underlying this favorable status could offer chances for new therapeutic targets in disease characterized by high levels of reactive oxygen species. Copyright © 2015 Elsevier Inc. All rights reserved.

Tissue-Specific Inactivation of Type 2 Deiodinase Reveals Multilevel Control of Fatty Acid Oxidation by Thyroid Hormone in the Mouse

PubMed Central

Fonseca, Tatiana L.; Werneck-De-Castro, Joao Pedro; Castillo, Melany; Bocco, Barbara M.L.C.; Fernandes, Gustavo W.; McAninch, Elizabeth A.; Ignacio, Daniele L.; Moises, Caio C.S.; Ferreira, Alexandre; Gereben, Balázs

2014-01-01

Type 2 deiodinase (D2) converts the prohormone thyroxine (T4) to the metabolically active molecule 3,5,3′-triiodothyronine (T3), but its global inactivation unexpectedly lowers the respiratory exchange rate (respiratory quotient [RQ]) and decreases food intake. Here we used FloxD2 mice to generate systemically euthyroid fat-specific (FAT), astrocyte-specific (ASTRO), or skeletal-muscle-specific (SKM) D2 knockout (D2KO) mice that were monitored continuously. The ASTRO-D2KO mice also exhibited lower diurnal RQ and greater contribution of fatty acid oxidation to energy expenditure, but no differences in food intake were observed. In contrast, the FAT-D2KO mouse exhibited sustained (24 h) increase in RQ values, increased food intake, tolerance to glucose, and sensitivity to insulin, all supporting greater contribution of carbohydrate oxidation to energy expenditure. Furthermore, FAT-D2KO animals that were kept on a high-fat diet for 8 weeks gained more body weight and fat, indicating impaired brown adipose tissue (BAT) thermogenesis and/or inability to oxidize the fat excess. Acclimatization of FAT-D2KO mice at thermoneutrality dissipated both features of this phenotype. Muscle D2 does not seem to play a significant metabolic role given that SKM-D2KO animals exhibited no phenotype. The present findings are unique in that they were obtained in systemically euthyroid animals, revealing that brain D2 plays a dominant albeit indirect role in fatty acid oxidation via its sympathetic control of BAT activity. D2-generated T3 in BAT accelerates fatty acid oxidation and protects against diet-induced obesity. PMID:24487027

Tissue-specific inactivation of type 2 deiodinase reveals multilevel control of fatty acid oxidation by thyroid hormone in the mouse.

PubMed

Fonseca, Tatiana L; Werneck-De-Castro, Joao Pedro; Castillo, Melany; Bocco, Barbara M L C; Fernandes, Gustavo W; McAninch, Elizabeth A; Ignacio, Daniele L; Moises, Caio C S; Ferreira, Alexander R; Ferreira, Alexandre; Gereben, Balázs; Bianco, Antonio C

2014-05-01

Type 2 deiodinase (D2) converts the prohormone thyroxine (T4) to the metabolically active molecule 3,5,3'-triiodothyronine (T3), but its global inactivation unexpectedly lowers the respiratory exchange rate (respiratory quotient [RQ]) and decreases food intake. Here we used FloxD2 mice to generate systemically euthyroid fat-specific (FAT), astrocyte-specific (ASTRO), or skeletal-muscle-specific (SKM) D2 knockout (D2KO) mice that were monitored continuously. The ASTRO-D2KO mice also exhibited lower diurnal RQ and greater contribution of fatty acid oxidation to energy expenditure, but no differences in food intake were observed. In contrast, the FAT-D2KO mouse exhibited sustained (24 h) increase in RQ values, increased food intake, tolerance to glucose, and sensitivity to insulin, all supporting greater contribution of carbohydrate oxidation to energy expenditure. Furthermore, FAT-D2KO animals that were kept on a high-fat diet for 8 weeks gained more body weight and fat, indicating impaired brown adipose tissue (BAT) thermogenesis and/or inability to oxidize the fat excess. Acclimatization of FAT-D2KO mice at thermoneutrality dissipated both features of this phenotype. Muscle D2 does not seem to play a significant metabolic role given that SKM-D2KO animals exhibited no phenotype. The present findings are unique in that they were obtained in systemically euthyroid animals, revealing that brain D2 plays a dominant albeit indirect role in fatty acid oxidation via its sympathetic control of BAT activity. D2-generated T3 in BAT accelerates fatty acid oxidation and protects against diet-induced obesity.

Nitric oxide signaling: systems integration of oxygen balance in defense of cell integrity.

PubMed

Gong, Li; Pitari, Giovanni M; Schulz, Stephanie; Waldman, Scott A

2004-01-01

Nitric oxide has emerged as a ubiquitous signaling molecule subserving diverse pathophysiologic processes, including cardiovascular homeostasis and its decompensation in atherogenesis. Recent insights into molecular mechanisms regulating nitric oxide generation and the rich diversity of mechanisms by which it propagates signals reveal the role of this simple gas as a principle mediator of systems integration of oxygen balance. The molecular lexicon by which nitric oxide propagates signals encompasses the elements of posttranslational modification of proteins by redox-based nitrosylation of transition metal centers and free thiols. Spatial and temporal precision and specificity of signal initiation, amplification, and propagation are orchestrated by dynamic assembly of supramolecular complexes coupling nitric oxide production to upstream and downstream components in specific subcellular compartments. The concept of local paracrine signaling by nitric oxide over subcellular distances for short durations has expanded to include endocrine-like effects over anatomic spatial and temporal scales. From these insights emerges a role for nitric oxide in integrating system responses controlling oxygen supply and demand to defend cell integrity in the face of ischemic challenge. In this context, nitric oxide coordinates the respiratory cycle to acquire and deliver oxygen to target tissues by regulating hemoglobin function and vascular smooth muscle contractility and matches energy supply and demand by down-regulating energy-requiring functions while shifting metabolism to optimize energy production. Insights into mechanisms regulating nitric oxide production and signaling and their integration into responses mediating homeostasis place into specific relief the role of those processes in pathophysiology. Indeed, endothelial dysfunction associated with altered production of nitric oxide regulating tissue integrity contributes to the pathogenesis underlying atherogenesis. Moreover, this central role in pathophysiology identifies nitric oxide signaling as a key target for novel therapeutic interventions to minimize irreversible tissue damage associated with ischemic cardiovascular disease.

Generation of hydroxyl radicals and singlet oxygen during oxidation of rhododendrol and rhododendrol-catechol.

PubMed

Miyaji, Akimitsu; Gabe, Yu; Kohno, Masahiro; Baba, Toshihide

2017-03-01

The generation of hydroxyl radicals and singlet oxygen during the oxidation of 4-(4-hydroxyphenyl)-2-butanol (rhododendrol) and 4-(3,4-dihydroxyphenyl)-2-butanol (rhododendrol-catechol) with mushroom tyrosinase in a phosphate buffer (pH 7.4) was examined as the model for the reactive oxygen species generation via the two rhododendrol compounds in melanocytes. The reaction was performed in the presence of 5,5-dimethyl-1-pyrroline- N -oxide (DMPO) spin trap reagents for hydroxyl radical or 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP), an acceptor of singlet oxygen, and their electron spin resonances were measured. An increase in the electron spin resonances signal attributable to the adduct of DMPO reacting with the hydroxyl radical and that of 4-oxo-TEMP reacting with singlet oxygen was observed during the tyrosinase-catalyzed oxidation of rhododendrol and rhododendrol-catechol, indicating the generation of hydroxyl radical and singlet oxygen. Moreover, hydroxyl radical generation was also observed in the autoxidation of rhododendrol-catechol. We show that generation of intermediates during tyrosinase-catalyzed oxidation of rhododendrol enhances oxidative stress in melanocytes.

Effects of argan oil on the mitochondrial function, antioxidant system and the activity of NADPH- generating enzymes in acrylamide treated rat brain.

PubMed

Aydın, Birsen

2017-03-01

Argan oil (AO) is rich in minor compounds such as polyphenols and tocopherols which are powerful antioxidants. Acrylamide (ACR) has been classified as a neurotoxic agent in animals and humans. Mitochondrial oxidative stress and dysfunction is one of the most probable molecular mechanisms of neurodegenerative diseases. Female Sprague Dawley rats were exposed to ACR (50mg/kg i.p. three times a week), AO (6ml/kg,o.p, per day) or together for 30days. The activities of cytosolic enzymes such as xanthine oxidase (XO), glucose 6-phosphate dehydrogenase (G6PDH), glutathione-S-transferase (GST), mitochondrial oxidative stress, oxidative phosphorylation (OXPHOS) and tricarboxylic acid cycle (TCA) enzymes, mitochondrial metabolic function, adenosine triphosphate (ATP) level and acetylcholinesterase (AChE) activity were assessed in rat brain. Cytosolic and mitochondrial antioxidant enzymes were significantly diminished in the brains of rats treated with ACR compared to those in control. Besides, ACR treatment resulted in a significant reduction in brain ATP level, mitochondrial metabolic function, OXPHOS and TCA enzymes. Administration of AO restored both the cytosolic and mitochondrial oxidative stress by normalizing nicotinamide adenine dinucleotide phosphate (NADPH) generating enzymes. In addition, improved mitochondrial function primarily enhancing nicotinamide adenine dinucleotide (NADH) generated enzymes activities and ATP level in the mitochondria. The reason for AO's obvious beneficial effects in this study may be due to synergistic effects of its different bioactive compounds which is especially effective on mitochondria. Modulation of the brain mitochondrial functions and antioxidant systems by AO may lead to the development of new mitochondria-targeted antioxidants in the future. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Microbial desalination cell with sulfonated sodium poly(ether ether ketone) as cation exchange membranes for enhancing power generation and salt reduction.

PubMed

Moruno, Francisco Lopez; Rubio, Juan E; Atanassov, Plamen; Cerrato, José M; Arges, Christopher G; Santoro, Carlo

2018-06-01

Microbial desalination cell (MDC) is a bioelectrochemical system capable of oxidizing organics, generating electricity, while reducing the salinity content of brine streams. As it is designed, anion and cation exchange membranes play an important role on the selective removal of ions from the desalination chamber. In this work, sulfonated sodium (Na + ) poly(ether ether ketone) (SPEEK) cation exchange membranes (CEM) were tested in combination with quaternary ammonium chloride poly(2,6-dimethyl 1,4-phenylene oxide) (QAPPO) anion exchange membrane (AEM). Non-patterned and patterned (varying topographical features) CEMs were investigated and assessed in this work. The results were contrasted against a commercially available CEM. This work used real seawater from the Pacific Ocean in the desalination chamber. The results displayed a high desalination rate and power generation for all the membranes, with a maximum of 78.6±2.0% in salinity reduction and 235±7mWm -2 in power generation for the MDCs with the SPEEK CEM. Desalination rate and power generation achieved are higher with synthesized SPEEK membranes when compared with an available commercial CEM. An optimized combination of these types of membranes substantially improves the performances of MDC, making the system more suitable for real applications. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

46 CFR 63.01-3 - Scope and applicability.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING AUTOMATIC AUXILIARY... automatic auxiliary boilers, automatic heating boilers, automatic waste heat boilers, donkey boilers... control systems) used for the generation of steam and/or oxidation of ordinary waste materials and garbage...

46 CFR 63.01-3 - Scope and applicability.

Code of Federal Regulations, 2011 CFR

2011-10-01

... Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) MARINE ENGINEERING AUTOMATIC AUXILIARY... automatic auxiliary boilers, automatic heating boilers, automatic waste heat boilers, donkey boilers... control systems) used for the generation of steam and/or oxidation of ordinary waste materials and garbage...

DEVELOPMENT OF SULFATE RADICAL-BASED CHEMICAL OXIDATION PROCESSES FOR TREATMENT OF PCBS

EPA Science Inventory

This study investigates transition metal based activation of peroxymonosulfate for generation of highly reactive sulfate radicals to degrade Polychlorinated Biphenyls (PCBs) in contaminated aqueous and sediment systems. Environmental friendly transition metal iron (Fe (II), Fe (I...

Analysis of the Oxidative Stress Status in Nonspecific Vaginitis and Its Role in Vaginal Epithelial Cells Apoptosis

PubMed Central

Chen, Zhaojie; Zhang, Zhen; Zhang, Haiyan; Xie, Beibei

2015-01-01

Nonspecific vaginitis (NSV), also named bacterial vaginosis, is one of the most common genital system diseases in women during their reproductive years. The specific pathogenic mechanism of NSV is not clear yet. Upon the balance alteration, large amount of reactive oxidant species (ROS) is generated and accumulated in the genital tract, and thus resulting in oxidative stress, which has been reported to be an important trigger of mitochondrial pathway cell apoptosis. In this study, the antioxidant secretion level and antioxidant enzyme activity in the vaginal discharge were evaluated to analyze the oxidative status in the vaginal tract of NSV patients. The effect of oxidative stress on the vaginal mucosa epithelial cell apoptosis was then studied. The role of oxidative stress on NSV development was uncovered; thus open new direction for the prevention and treatment of NSV by providing antiradical agents was revealed. PMID:26558281

Green and Mild Oxidation: An Efficient Strategy toward Water-Dispersible Graphene.

PubMed

You, Xiaofei; Yang, Siwei; Li, Jipeng; Deng, Yuan; Dai, Lianqi; Peng, Xiong; Huang, Haoguang; Sun, Jing; Wang, Gang; He, Peng; Ding, Guqiao; Xie, Xiaoming

2017-01-25

Scalable fabrication of water-dispersible graphene (W-Gr) is highly desirable yet technically challenging for most practical applications of graphene. Herein, a green and mild oxidation strategy to prepare bulk W-Gr (dispersion, slurry, and powder) with high yield was proposed by fully exploiting structure defects of thermally reduced graphene oxide (TRGO) and oxidizing radicals generated from hydrogen peroxide (H 2 O 2 ). Owing to the increased carboxyl group from the mild oxidation process, the obtained W-Gr can be redispersed in low-boiling solvents with a reasonable concentration. Benefiting from the modified surface chemistry, macroscopic samples processed from the W-Gr show good hydrophilicity (water contact angle of 55.7°) and excellent biocompatibility, which is expected to be an alternative biomaterial for bone, vessel, and skin regeneration. In addition, the green and mild oxidation strategy is also proven to be effective for dispersing other carbon nanomaterials in a water system.

Pro-Oxidant Biological Effects of Inorganic Component of Petroleum: Vanadium and Oxidative Stress

DTIC Science & Technology

1996-08-01

independent existence. Pro-Oxidant Chemicals and Free Radicals Involved in Oxidative Stress Pro-Oxidant Chemicals Chemical and Metabolic Generation... metabolic reactions may generate primary free radicals (Fig. 1). Then, in an avalanche-type process, secondary free radicals and reactive oxygen species...vanadium absorption, distribution, metabolism , and disposition, and no pharmacokinetic model is available describing comparative kinetics and toxicity

Chemistry and liquid chromatography methods for the analyses of primary oxidation products of triacylglycerols.

PubMed

Zeb, A

2015-05-01

Triacylglycerols (TAGs) are one of the major components of the cells in higher biological systems, which can act as an energy reservoir in the living cells. The unsaturated fatty acid moiety is the key site of oxidation and formation of oxidation compounds. The TAG free radical generates several primary oxidation compounds. These include hydroperoxides, hydroxides, epidioxides, hydroperoxy epidioxides, hydroxyl epidioxides, and epoxides. The presence of these oxidized TAGs in the cell increases the chances of several detrimental processes. For this purpose, several liquid chromatography (LC) methods were reported in their analyses. This review is therefore focused on the chemistry, oxidation, extraction, and the LC methods reported in the analyses of oxidized TAGs. The studies on thin-layer chromatography were mostly focused on the total oxidized TAGs separation and employ hexane as major solvent. High-performance LC (HPLC) methods were discussed in details along with their merits and demerits. It was found that most of the HPLC methods employed isocratic elution with methanol and acetonitrile as major solvents with an ultraviolet detector. The coupling of HPLC with mass spectrometry (MS) highly increases the efficiency of analysis as well as enables reliable structural elucidation. The use of MS was found to be helpful in studying the oxidation chemistry of TAGs and needs to be extended to the complex biological systems.

Oxidation State Specific Generation of Arsines from Methylated Arsenicals Based on L- Cysteine Treatment in Buffered Media for Speciation Analysis by Hydride Generation - Automated Cryotrapping - Gas Chromatography-Atomic Absorption Spectrometry with the Multiatomizer

PubMed Central

Matoušek, Tomáš; Hernández-Zavala, Araceli; Svoboda, Milan; Langrová, Lenka; Adair, Blakely M.; Drobná, Zuzana; Thomas, David J.; Stýblo, Miroslav; Dědina, Jiří

2008-01-01

An automated system for hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l−1. Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of L-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the L-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species. PMID:18521190

Nitride Fuel Development Using Cryo-process Technique

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

O'Brien, Brandi M; Windes, William E

A new cryo-process technique has been developed for the fabrication of advanced fuel for nuclear systems. The process uses a new cryo-processing technique whereby small, porous microspheres (<2000 µm) are formed from sub-micron oxide powder. A simple aqueous particle slurry of oxide powder is pumped through a microsphere generator consisting of a vibrating needle with controlled amplitude and frequency. As the water-based droplets are formed and pass through the microsphere generator they are frozen in a bath of liquid nitrogen and promptly vacuum freeze-dried to remove the water. The resulting porous microspheres consist of half micron sized oxide particles heldmore » together by electrostatic forces and mechanical interlocking of the particles. Oxide powder microspheres ranging from 750 µm to 2000 µm are then converted into a nitride form using a high temperature fluidized particle bed. Carbon black can be added to the oxide powder before microsphere formation to augment the carbothermic reaction during conversion to a nitride. Also, the addition of ethyl alcohol to the aqueous slurry reduces the surface tension energy of the droplets resulting in even smaller droplets forming in the microsphere generator. Initial results from this new process indicate a lower impurity contamination in the final nitrides due to the single feed stream of particles, material handling and conversion are greatly simplified, a minimum of waste and personnel exposure are anticipated, and finally the conversion kinetics may be greatly increased because of the small oxide powder size (sub-micron) forming the porous microsphere. Thus far the fabrication process has been successful in demonstrating all of these improvements with surrogate ZrO2 powder. Further tests will be conducted in the future using the technique on UO2 powders.« less

Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Bloss, C.; Wagner, V.; Jenkin, M. E.; Volkamer, R.; Bloss, W. J.; Lee, J. D.; Heard, D. E.; Wirtz, K.; Martin-Reviejo, M.; Rea, G.; Wenger, J. C.; Pilling, M. J.

2005-03-01

The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature have been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE) to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and, where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

Development of a detailed chemical mechanism (MCMv3.1) for the atmospheric oxidation of aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Bloss, C.; Wagner, V.; Jenkin, M. E.; Volkamer, R.; Bloss, W. J.; Lee, J. D.; Heard, D. E.; Wirtz, K.; Martin-Reviejo, M.; Rea, G.; Wenger, J. C.; Pilling, M. J.

2004-09-01

The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature has been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE) to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

Mathematical modeling of nitrous oxide production in an anaerobic/oxic/anoxic process.

PubMed

Ding, Xiaoqian; Zhao, Jianqiang; Hu, Bo; Chen, Ying; Ge, Guanghuan; Li, Xiaoling; Wang, Sha; Gao, Kun; Tian, Xiaolei

2016-12-01

This study incorporates three currently known nitrous oxide (N 2 O) production pathways: ammonium-oxidizing bacteria (AOB) denitrification, incomplete hydroxylamine (NH 2 OH) oxidation, and heterotrophic denitrification on intracellular polymers, into a mathematical model to describe N 2 O production in an anaerobic/oxic/anoxic (AOA) process for the first time. The developed model was calibrated and validated by four experimental cases, then evaluated by two independent anaerobic/aerobic (AO) studies from literature. The modeling results displayed good agreement with the measured data. N 2 O was primarily generated in the aerobic stage by AOB denitrification (67.84-81.64%) in the AOA system. Smaller amounts of N 2 O were produced via incomplete NH 2 OH oxidation (15.61-32.17%) and heterotrophic denitrification on intracellular polymers (0-12.47%). The high nitrite inhibition on N 2 O reductase led to the increased N 2 O accumulation in heterotrophic denitrification on intracellular polymers. The new model was capable of modeling nitrification-denitrification dynamics and heterotrophic denitrification on intracellular polymers in the AOA system. Copyright © 2016 Elsevier Ltd. All rights reserved.

Monoterpene SOA - Contribution of first-generation oxidation products to formation and chemical composition

NASA Astrophysics Data System (ADS)

Mutzel, Anke; Rodigast, Maria; Iinuma, Yoshiteru; Böge, Olaf; Herrmann, Hartmut

2016-04-01

Investigation of the consecutive reactions of first-generation terpene oxidation products provides insight into the formation of secondary organic aerosol (SOA). To this end, OH radical reactions with α-pinene, β-pinene, and limonene were examined along with the OH-oxidation of nopinone as a β-pinene oxidation product and pinonaldehyde and myrtenal as α-pinene oxidation products. The SOA yield of β-pinene (0.50) was much higher than that of α-pinene (0.35) and the limonene/OH system (0.30). This is opposite to the ozonolysis SOA yields described in the literature. The growth curve of SOA from β-pinene shows the contribution of secondary reactions, such as further reaction of nopinone. This contribution (17%) and the high SOA yield of nopinone (0.24) might lead to the high SOA formation potential observed for β-pinene. The majority of the C9 oxidation products observed from β-pinene can be attributed to the consecutive reaction of nopinone, whereas in the case of pinonaldehyde, only a few α-pinene oxidation products were identified. Nopinone contributes significantly to the formation of pinic acid (51%), homoterpenylic acid (74%), and 3-methyl-1,2,3-butane-tricarboxylic acid (MBTCA, 88%) during β-pinene oxidation. The oxidation of pinonaldehyde was expected to produce important SOA markers, but only negligible amounts were identified. This indicates that their formation by oxidation of α-pinene must proceed via different pathways from the further oxidation of pinonaldehyde. Only pinonic acid and MBTCA were found in considerable amounts and were formed in α-pinene oxidation with 57% yield, while that for the pinonaldehyde/OH reaction was 33%. The lack of important SOA marker compounds might cause the low SOA yield (0.07) observed for pinonaldehyde. Based on the low SOA yield, pinonaldehyde contributes only 4.5% to α-pinene SOA. Myrtenal was identified among the gas-phase products of α-pinene oxidation. A majority of α-pinene SOA marker compounds was indeed formed by myrtenal oxidation, especially terebic acid (84%), pinic acid (76%), and diaterpenylic acid acetate (DTAA; 40%). In general, the contribution of myrtenal to α-pinene SOA is estimated to be as high as 23%. Among the detected compounds, homoterpenylic acid was positively identified as a new SOA marker compound, which was formed from β-pinene/OH and nopinone/OH but not from α-pinene/OH. A new reaction pathway yielding MBTCA was also identified in the β-pinene/OH system formed by the oxidation of nopinone, while in the case of α-pinene, the oxidation of pinonaldehyde yielded MBTCA.

Mechanisms underlying caloric restriction and life span regulation: implications for vascular aging

PubMed Central

Ungvari, Zoltan; Parrado-Fernandez, Cristina; Csiszar, Anna; de Cabo, Rafael

2008-01-01

This review focuses on the emerging evidence that attenuation of the production of reactive oxygen species (ROS) and inhibition of inflammatory pathways play a central role in the anti-aging cardiovascular effects of caloric restriction (CR). Particular emphasis is placed on the potential role of the plasma membrane redox system in CR-induced pathways responsible for sensing oxidative stress and increasing cellular oxidative stress resistance. We propose that CR increases bioavailability of NO, decreases vascular ROS generation, activates the Nrf2/ARE pathway inducing ROS detoxification systems, exerts anti-inflammatory effects and, thereby, suppresses initiation/progression of vascular disease that accompany aging. PMID:18340017

On-demand Hydrogen Production from Organosilanes at Ambient Temperature Using Heterogeneous Gold Catalysts

NASA Astrophysics Data System (ADS)

Mitsudome, Takato; Urayama, Teppei; Kiyohiro, Taizo; Maeno, Zen; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi

2016-11-01

An environmentally friendly (“green”), H2-generation system was developed that involved hydrolytic oxidation of inexpensive organosilanes as hydrogen storage materials with newly developed heterogeneous gold nanoparticle catalysts. The gold catalyst functioned well at ambient temperature under aerobic conditions, providing efficient production of pure H2. The newly developed size-selective gold nanoparticle catalysts could be separated easily from the reaction mixture containing organosilanes, allowing an on/off-switchable H2-production by the introduction and removal of the catalyst. This is the first report of an on/off-switchable H2-production system employing hydrolytic oxidation of inexpensive organosilanes without requiring additional energy.

Recovery Act: Demonstration of a SOFC Generator Fueled by Propane to Provide Electrical Power to Real World Applications

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

Bessette, Norman

The objective of this project provided with funds through the American Recovery and Reinvestment Act of 2009 (ARRA) was to demonstrate a Solid Oxide Fuel Cell (SOFC) generator capable of operation on propane fuel to improve efficiency and reduce emissions over commercially available portable generators. The key objectives can be summarized as: Development of two portable electrical generators in the 1-3kW range utilizing Solid Oxide Fuel Cells and propane fuel; The development and demonstration of a proof-of-concept electro-mechanical propane fuel interface that provides a user friendly capability for managing propane fuel; The deployment and use of the fuel cell portablemore » generators to power media production equipment over the course of several months at multiple NASCAR automobile racing events; The deployment and use of the fuel cell portable generators at scheduled events by first responders (police, fire) of the City of Folsom California; and Capturing data with regard to the systems’ ability to meet Department of Energy (DOE) Technical Targets and evaluating the ease of use and potential barriers to further adoption of the systems.« less

Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

PubMed

Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

2015-12-14

Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed.

Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst.

PubMed

McCann, Scott D; Lumb, Jean-Philip; Arndtsen, Bruce A; Stahl, Shannon S

2017-04-26

A homogeneous Cu-based catalyst system consisting of [Cu(MeCN) 4 ]PF 6 , N , N '-di- tert -butylethylenediamine (DBED), and p -( N , N -dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the "oxygenase"-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts.

Portable Nitric Oxide (NO) Generator Based on Electrochemical Reduction of Nitrite for Potential Applications in Inhaled NO Therapy and Cardiopulmonary Bypass Surgery.

PubMed

Qin, Yu; Zajda, Joanna; Brisbois, Elizabeth J; Ren, Hang; Toomasian, John M; Major, Terry C; Rojas-Pena, Alvaro; Carr, Benjamin; Johnson, Thomas; Haft, Jonathan W; Bartlett, Robert H; Hunt, Andrew P; Lehnert, Nicolai; Meyerhoff, Mark E

2017-11-06

A new portable gas phase nitric oxide (NO) generator is described for potential applications in inhaled NO (INO) therapy and during cardiopulmonary bypass (CPB) surgery. In this system, NO is produced at the surface of a large-area mesh working electrode by electrochemical reduction of nitrite ions in the presence of a soluble copper(II)-ligand electron transfer mediator complex. The NO generated is then transported into gas phase by either direct purging with nitrogen/air or via circulating the electrolyte/nitrite solution through a gas extraction silicone fiber-based membrane-dialyzer assembly. Gas phase NO concentrations can be tuned in the range of 5-1000 ppm (parts per million by volume for gaseous species), in proportion to a constant cathodic current applied between the working and counter electrodes. This new NO generation process has the advantages of rapid production times (5 min to steady-state), high Faraday NO production efficiency (ca. 93%), excellent stability, and very low cost when using air as the carrier gas for NO (in the membrane dialyzer configuration), enabling the development of potentially portable INO devices. In this initial work, the new system is examined for the effectiveness of gaseous NO to reduce the systemic inflammatory response (SIR) during CPB, where 500 ppm of NO added to the sweep gas of the oxygenator or to the cardiotomy suction air in a CPB system is shown to prevent activation of white blood cells (granulocytes and monocytes) during extracorporeal circulation with cardiotomy suction conducted with five pigs.

Advanced dry head-end reprocessing of light water reactor spent nuclear fuel

DOEpatents

Collins, Emory D; Delcul, Guillermo D; Hunt, Rodney D; Johnson, Jared A; Spencer, Barry B

2013-11-05

A method for reprocessing spent nuclear fuel from a light water reactor includes the step of reacting spent nuclear fuel in a voloxidation vessel with an oxidizing gas having nitrogen dioxide and oxygen for a period sufficient to generate a solid oxidation product of the spent nuclear fuel. The reacting step includes the step of reacting, in a first zone of the voloxidation vessel, spent nuclear fuel with the oxidizing gas at a temperature ranging from 200-450.degree. C. to form an oxidized reaction product, and regenerating nitrogen dioxide, in a second zone of the voloxidation vessel, by reacting oxidizing gas comprising nitrogen monoxide and oxygen at a temperature ranging from 0-80.degree. C. The first zone and the second zone can be separate. A voloxidation system is also disclosed.

Advanced dry head-end reprocessing of light water reactor spent nuclear fuel

DOEpatents

Collins, Emory D.; Delcul, Guillermo D.; Hunt, Rodney D.; Johnson, Jared A.; Spencer, Barry B.

2014-06-10

A method for reprocessing spent nuclear fuel from a light water reactor includes the step of reacting spent nuclear fuel in a voloxidation vessel with an oxidizing gas having nitrogen dioxide and oxygen for a period sufficient to generate a solid oxidation product of the spent nuclear fuel. The reacting step includes the step of reacting, in a first zone of the voloxidation vessel, spent nuclear fuel with the oxidizing gas at a temperature ranging from 200-450.degree. C. to form an oxidized reaction product, and regenerating nitrogen dioxide, in a second zone of the voloxidation vessel, by reacting oxidizing gas comprising nitrogen monoxide and oxygen at a temperature ranging from 0-80.degree. C. The first zone and the second zone can be separate. A voloxidation system is also disclosed.

Surface acoustic wave/silicon monolithic sensor/processor

NASA Technical Reports Server (NTRS)

Kowel, S. T.; Kornreich, P. G.; Nouhi, A.; Kilmer, R.; Fathimulla, M. A.; Mehter, E.

1983-01-01

A new technique for sputter deposition of piezoelectric zinc oxide (ZnO) is described. An argon-ion milling system was converted to sputter zinc oxide films in an oxygen atmosphere using a pure zinc oxide target. Piezoelectric films were grown on silicon dioxide and silicon dioxide overlayed with gold. The sputtered films were evaluated using surface acoustic wave measurements, X-ray diffraction, scanning electron microscopy, Auger electron spectroscopy, and resistivity measurements. The effect of the sputtering conditions on the film quality and the result of post-deposition annealing are discussed. The application of these films to the generation of surface acoustic waves is also discussed.

Cycle Analysis of Two-stage Planar SOFC Power Generation by Series Connection of Low and High Temperature SOFCs

NASA Astrophysics Data System (ADS)

Ohba, Takahiro; Takezawa, Shinya; Araki, Takuto; Onda, Kazuo; Sakaki, Yoshinori

Solid Oxide Fuel Cell (SOFC) can be composed by solid components, and high power generation efficiency of a whole cycle is obtained by using high temperature exhaust heat for fuel reforming and bottoming power generation. Recently, the low temperature SOFC, which runs in the temperature range of around 600°C or above, has been developed with the high efficiency of power generation. On the other hand, multi-stage power generation system has been proposed by the United States DOE. In this study, a power generation system of two-stage SOFC by series connection of low and high temperature SOFCs has been studied. Overpotential data for low-temperature SOFC used in this study are based on recent published data, and those for high temperature SOFC arhaihe based on our previous study. The analytical results show the two-stage SOFC power generation efficiency of 50.3% and the total power generation efficiency of 56.1% under a standard operating condition.

Phospholipid-templated silica nanocapsules as efficient polyenzymatic biocatalysts.

PubMed

Phuoc, Lai Truong; Laveille, Paco; Chamouleau, Françoise; Renard, Gilbert; Drone, Jullien; Coq, Bernard; Fajula, François; Galarneau, Anne

2010-09-28

Solid polyenzymatic biocatalysts have been designed by combining two immobilized enzymes, the first one allowing the in situ generation of H(2)O(2) from air and the second one performing an oxidation reaction. The in situ H(2)O(2) generation system is based on the reaction of glucose with air using a glucose oxidase (GOx). The optimization of the encapsulation of GOx into phospholipids-templated silica capsules (NPS) was performed. A bienzymatic system made of GOx and horseradish peroxidase (HRP) was studied. Optimal conditions for the activity of the GOx/HRP bienzymatic system have been determined for both homogeneous and heterogeneous conditions. The encapsulation in NPS materials increases the stability of both enzymes. The performance of the encapsulated bienzymatic GOx/HRP system in the model reaction of 4-aminoantipyridine with phenol is similar when the enzymes are immobilized separately in two NPS or coencapsulated in the same NPS. An excess of peroxidase compared to GOx ([HRP]/[GOx] = 5-10) is necessary to obtain the optimal activity. To show the potentiality of bienzymatic systems in real applications, HRP has been replaced by hemoglobin, which is known for its ability to oxidize polycyclic aromatic hydrocarbons (PAH) pollutants through a pseudoperoxidase pathway. A larger excess of Hb compared to GOx ([Hb]/[GOx] = 1000) was necessary to obtain the maximum PAH removal, as Hb is not a real peroxidase as HRP but a hemoprotein with some pseudoperoxidase activity. In opposite to real enzymes, the immobilization of Hb by adsorption in mesoporous silica is preferable as its encapsulation. Therefore, the bienzymatic system made of GOx encapsulated in NPS and Hb adsorbed in mesoporous silica has been used for the removal of 11 PAH from water. This heterogeneous bienzymatic system allows 64% of PAH removal from water using simple air as oxidant.

Photoionization of oxidized coenzyme Q in microemulsion: laser flash photolysis study in biomembrane-like system.

PubMed

Li, Kun; Wang, Mei; Wang, Jin; Zhu, Rongrong; Sun, Dongmei; Sun, Xiaoyu; Wang, Shi-Long

2013-01-01

Photoexcitation to generate triplet state has been proved to be the main photoreaction in homogeneous system for many benzoquinone derivatives, including oxidized coenzyme Q (CoQ) and its analogs. In the present study, microemulsion of CoQ, a heterogeneous system, is employed to mimic the distribution of CoQ in biomembrane. The photochemistry of CoQ(10) in microemulsion and cyclohexane is investigated and compared using laser flash photolysis and results show that CoQ(10) undergoes photoionization via a monophotonic process to generate radical cation of CoQ(10) in microemulsion and photoexcitation to generate excited triplet state in cyclohexane. Meanwhile, photoreactions of duroquinone (DQ) and CoQ(0) in microemulsion are also investigated to analyze the influence of molecular structure on the photochemistry of benzoquinone derivatives in microemulsion. Results suggest that photoexcitation, which is followed by excited state-involved hydrogen-abstraction reaction, is the main photoreaction for DQ and CoQ(0) in microemulsion. However, photoexcited CoQ(0) also leads to the formation of hydrated electrons. The isoprenoid side chain-involved high resonance stabilization is proposed to explain the difference in photoreactions of CoQ(0) and CoQ(10) in microemulsion. Considering that microemulsion is close to biomembrane system, its photoionization in microemulsion may be helpful to understand the real photochemistry of biological quinones in biomembrane system. © 2012 Tongji University. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

Solid Oxide Fuel Cells Operating on Alternative and Renewable Fuels

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

Wang, Xiaoxing; Quan, Wenying; Xiao, Jing

2014-09-30

This DOE project at the Pennsylvania State University (Penn State) initially involved Siemens Energy, Inc. to (1) develop new fuel processing approaches for using selected alternative and renewable fuels – anaerobic digester gas (ADG) and commercial diesel fuel (with 15 ppm sulfur) – in solid oxide fuel cell (SOFC) power generation systems; and (2) conduct integrated fuel processor – SOFC system tests to evaluate the performance of the fuel processors and overall systems. Siemens Energy Inc. was to provide SOFC system to Penn State for testing. The Siemens work was carried out at Siemens Energy Inc. in Pittsburgh, PA. Themore » unexpected restructuring in Siemens organization, however, led to the elimination of the Siemens Stationary Fuel Cell Division within the company. Unfortunately, this led to the Siemens subcontract with Penn State ending on September 23rd, 2010. SOFC system was never delivered to Penn State. With the assistance of NETL project manager, the Penn State team has since developed a collaborative research with Delphi as the new subcontractor and this work involved the testing of a stack of planar solid oxide fuel cells from Delphi.« less

Modeling and experimental performance of an intermediate temperature reversible solid oxide cell for high-efficiency, distributed-scale electrical energy storage

NASA Astrophysics Data System (ADS)

Wendel, Christopher H.; Gao, Zhan; Barnett, Scott A.; Braun, Robert J.

2015-06-01

Electrical energy storage is expected to be a critical component of the future world energy system, performing load-leveling operations to enable increased penetration of renewable and distributed generation. Reversible solid oxide cells, operating sequentially between power-producing fuel cell mode and fuel-producing electrolysis mode, have the capability to provide highly efficient, scalable electricity storage. However, challenges ranging from cell performance and durability to system integration must be addressed before widespread adoption. One central challenge of the system design is establishing effective thermal management in the two distinct operating modes. This work leverages an operating strategy to use carbonaceous reactant species and operate at intermediate stack temperature (650 °C) to promote exothermic fuel-synthesis reactions that thermally self-sustain the electrolysis process. We present performance of a doped lanthanum-gallate (LSGM) electrolyte solid oxide cell that shows high efficiency in both operating modes at 650 °C. A physically based electrochemical model is calibrated to represent the cell performance and used to simulate roundtrip operation for conditions unique to these reversible systems. Design decisions related to system operation are evaluated using the cell model including current density, fuel and oxidant reactant compositions, and flow configuration. The analysis reveals tradeoffs between electrical efficiency, thermal management, energy density, and durability.

Space Shuttle Main Engine structural analysis and data reduction/evaluation. Volume 3A: High pressure oxidizer turbo-pump preburner pump housing stress analysis report

NASA Technical Reports Server (NTRS)

Shannon, Robert V., Jr.

1989-01-01

The model generation and structural analysis performed for the High Pressure Oxidizer Turbopump (HPOTP) preburner pump volute housing located on the main pump end of the HPOTP in the space shuttle main engine are summarized. An ANSYS finite element model of the volute housing was built and executed. A static structural analysis was performed on the Engineering Analysis and Data System (EADS) Cray-XMP supercomputer

Mycogenic Mn(II) oxidation promotes remediation of acid mine drainage and other anthropogenically impacted environments

NASA Astrophysics Data System (ADS)

Santelli, C. M.; Chaput, D.; Hansel, C. M.; Burgos, W. D.

2014-12-01

Manganese is a pollutant in worldwide environments contaminated with metals and organics, such as acid mine drainage (AMD), freshwater ponds, and agricultural waste storage sites. Microorganisms contribute to the removal of dissolved Mn compounds in the environment by promoting Mn(II) oxidation reactions. The oxidation of Mn(II) results in the precipitation of sparingly soluble Mn(IV) oxide minerals, effectively removing the metal from the aqueous milieu (e.g., groundwater or wastewater streams). In recent years, our research has identified a diversity of Mn(II)-oxidizing fungi inhabiting these polluted environments, however their overall contribution to the remediation process in situ remains poorly understood. Here we present results of culture-based and Next Generation Sequencing (NGS) studies in AMD treatment systems actively remediating Mn and other metals where we profile the bacterial, fungal, algal and archaeal communities to determine the overall community diversity and to establish the relative abundance of known Mn(II) oxidizers. A variety of treatment systems with varying Mn-removal efficiencies were sampled to understand the relationship between remediation efficiency and microbial community composition and activity. Targeted-amplicon sequencing of DNA and RNA of the 16S rRNA genes (bacteria and archaea), 23S rRNA genes (algae) and ITS region (fungi) was performed using both 454 pyrosequencing and Illumina platforms. Results showed that only the fungal taxonomic profiles significantly differed between sites that removed the majority of influent Mn and those that did not. Specifically, Ascomycota (which include known Mn(II) oxidizers isolated from these treatment systems) dominated greater efficiency systems whereas less efficient systems were dominated by Basidiomycota. Furthermore, known Mn(II) oxidizers accounted for only a minor proportion of bacterial sequences but a far greater proportion of fungal sequences. These culture-independent studies lend further evidence to numerous culture-based studies (of AMD remediation systems here, as well as a variety of other metal-rich systems) that establish Mn(II)-oxidizing fungi as important contributors to the remediation of Mn, and likely other metals, in metal polluted environments.

Combining plasma gasification and solid oxide cell technologies in advanced power plants for waste to energy and electric energy storage applications.

PubMed

Perna, Alessandra; Minutillo, Mariagiovanna; Lubrano Lavadera, Antonio; Jannelli, Elio

2018-03-01

The waste to energy (WtE) facilities and the renewable energy storage systems have a strategic role in the promotion of the "eco-innovation", an emerging priority in the European Union. This paper aims to propose advanced plant configurations in which waste to energy plants and electric energy storage systems from intermittent renewable sources are combined for obtaining more efficient and clean energy solutions in accordance with the "eco-innovation" approach. The advanced plant configurations consist of an electric energy storage (EES) section based on a solid oxide electrolyzer (SOEC), a waste gasification section based on the plasma technology and a power generation section based on a solid oxide fuel cell (SOFC). The plant configurations differ for the utilization of electrolytic hydrogen and oxygen in the plasma gasification section and in the power generation section. In the first plant configuration IAPGFC (Integrated Air Plasma Gasification Fuel Cell), the renewable oxygen enriches the air stream, that is used as plasma gas in the gasification section, and the renewable hydrogen is used to enrich the anodic stream of the SOFC in the power generation section. In the second plant configuration IHPGFC (Integrated Hydrogen Plasma Gasification Fuel Cell) the renewable hydrogen is used as plasma gas in the plasma gasification section, and the renewable oxygen is used to enrich the cathodic stream of the SOFC in the power generation section. The analysis has been carried out by using numerical models for predicting and comparing the systems performances in terms of electric efficiency and capability in realizing the waste to energy and the electric energy storage of renewable sources. Results have highlighted that the electric efficiency is very high for all configurations (35-45%) and, thanks to the combination with the waste to energy technology, the storage efficiencies are very attractive (in the range 72-92%). Copyright © 2017 Elsevier Ltd. All rights reserved.

Photo-protection by 3-bromo-4, 5-dihydroxybenzaldehyde against ultraviolet B-induced oxidative stress in human keratinocytes.

PubMed

Hyun, Yu Jae; Piao, Mei Jing; Zhang, Rui; Choi, Yung Hyun; Chae, Sungwook; Hyun, Jin Won

2012-09-01

Exposure of the skin to ultraviolet B (UVB) radiation leads to epidermal damage and the generation of reactive oxygen species (ROS) in skin cells, including keratinocytes. Therefore, the photo-protective effect of 3-bromo-4, 5-dihydroxybenzaldehyde (BDB) against UVB was assessed in human HaCaT keratinocytes exposed to UVB radiation in vitro. BDB restored cell viability, which decreased upon exposure to UVB radiation. BDB exhibited scavenging activity against 1, 1-diphenyl-2-picrylhydrazyl radicals, intracellular ROS induced by hydrogen peroxide (H(2)O(2)) or UVB radiation, the superoxide anion generated by the xanthine/xanthine oxidase system, and the hydroxyl radical generated by the Fenton reaction (FeSO(4)+H(2)O(2)). Moreover, BDB absorbed UVB and decreased injury resulting from UVB-induced oxidative stress to lipids, proteins and DNA. Finally, BDB reduced UVB-induced apoptosis, as exemplified by fewer apoptotic bodies and a reduction in DNA fragmentation. Taken together, these results suggest that BDB protects human keratinocytes against UVB-induced oxidative stress by scavenging ROS and absorbing UVB rays, thereby reducing injury to cellular components. Copyright © 2012 Elsevier Inc. All rights reserved.

[The role of oxidative stress in pathogenesis of GBS].

PubMed

Dogonadze, S I; Ninua, N G; Gordeziani, M G; Kavlashvili, M S; Sanikidze, T V

2006-11-01

Axon degeneration accompanying its demielinization is a main course of neurological insufficiency typical for GBS. The mechanisms of axon degeneration, considered as the secondary result of serve inflammation are not established. We aimed to determine the role of oxidative metabolism in viral polyneuropathy pathogenesis. The activity of pro- and antioxidant systems of the body was studied by electron paramagnetic resonance (EPR) method. In blood and cerebrospinal fluid the intensive EPR signals of nitric oxide (NO), complexes of NO with nonhemic iron (HbNO), lypo- and superoxide radicals content noticeably increases, the signals of free Mn2+ and Fe2+ revealed, the activity of blood antioxidant enzymes, ceruloplasmin and katalasa increases (by 60%), superoxidedismitase's and glutation reductases activity decreases (by 20% and 70% correspondingly). It was considered, that inflammatory damage of nervous system induced by different infectious stimulus is initiated by activated immune cell proinflamatory agents (reactive oxygen and nitrogen species). Subsequently the oxidative stress, as result of accumulation of generators of reactive oxygen species, disordered intracellular metabolism products, contributes to axon demielinization and degeneration.

Emissivity of Candidate Materials for VHTR Applicationbs: Role of Oxidation and Surface Modification Treatments

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

Sridharan, Kumar; Allen, Todd; Anderson, Mark

The Generation IV (GEN IV) Nuclear Energy Systems Initiative was instituted by the Department of Energy (DOE) with the goal of researching and developing technologies and materials necessary for various types of future reactors. These GEN IV reactors will employ advanced fuel cycles, passive safety systems, and other innovative systems, leading to significant differences between these future reactors and current water-cooled reactors. The leading candidate for the Next Generation Nuclear Plant (NGNP) to be built at Idaho National Lab (INL) in the United States is the Very High Temperature Reactor (VHTR). Due to the high operating temperatures of the VHTR,more » the Reactor Pressure Vessel (RPV) will partially rely on heat transfer by radiation for cooling. Heat expulsion by radiation will become all the more important during high temperature excursions during off-normal accident scenarios. Radiant power is dictated by emissivity, a material property. The NGNP Materials Research and Development Program Plan [1] has identified emissivity and the effects of high temperature oxide formation on emissivity as an area of research towards the development of the VHTR.« less

Petrographic and Isotopic Evidence for Siderite Precursors to Iron Oxide Cements

NASA Astrophysics Data System (ADS)

Loope, D.

2015-12-01

The origin of iron oxide mineralization in the Navajo Sandstone on the Colorado Plateau is important because of the different forms of distinct self-organization exhibited by these systems, the potential importance of the cements as geochronometers, and their use as analogs for similar mineralization on other planets. We consider this mineralization to be the product of microbially mediated oxidation of siderite in evolving groundwater systems. Iron oxide grain coatings were dissolved and the iron precipitated as siderite during a reducing phase of diagenesis. Upon invasion by oxidizing waters, iron-oxidizing bacteria colonized the redox interface between siderite-cemented and porous sandstone. Precipitation of iron oxide at this interface generated acid that facilitated further siderite dissolution. One difficulty in testing this hypothesis is that siderite is destroyed by the cm-scale transport of iron during oxidation. There are two lines of evidence that support the presence of a siderite precursor in these systems. 1)Rhombic grains that we interpret to be iron oxide pseudomorphs after siderite occur where in-situ oxidation rather than dissolution of the siderite precursor has occurred. 2) The δ56Fe values of these iron oxide cements are typically negative. We have measured the δ56Fe value of Navajo Sandstone to be 0.2‰; a value in good agreement with previous workers (Chan et al., 2006; Busigny and Dauphas, 2007). Bleaching of the sandstones apparently results in near complete removal of Fe with little change in the δ56Fe values of the bulk sandstone. The δ56Fe values of iron oxide cements have a median value of -0.8‰; similar to the value we obtained from ferroan carbonate (-0.86‰). Iron oxide from samples that comprise largely rhombic grains has similar δ56Fe values (-0.5‰) to those obtained from cements produced by siderite dissolution and subsequent oxidation (-0.4‰). Our interpretation is that siderite precipitated from an aqueous solution in which the δ56Fe value was <0.2‰ yielding siderite with δ56Fe values that ranged upward from -1.4‰. Invasion of the Navajo by oxidizing waters resulted in microbially mediated oxidation of the siderite concretions. The strongly negative values of the Fe oxides result from the near-quantitative oxidation of the siderite in a closed system.

Regulation of Electrochemically Generated H2O2 in Situ from a Novel CB-PTFE Cathode for Transformation of Chlorine Benzene in Groundwater

NASA Astrophysics Data System (ADS)

Jiang, J.; Zhang, X.; Li, G.

2014-12-01

Fenton's reagents (H2O2 and Fe2+ catalyst commonly) have been widely used in soil and groundwater remediation. But the excessive H2O2 decomposition and the pH modification (acidification) problem have been limitations for Fenton based remediation strategies. The Electro-Fenton (E- Fenton) processes has been recently developed to solve the problems, in which Fe2+ or H2O2are generated in situ as continuing source of Fenton's reagents. In this study, a novel CB-PTFE cathode and a Fe cathode were employed to generate H2O2 and Fe2+ in situ simultaneously. The generated reactive oxidizing species, i.e., O2,H2O2 and hydroxyl radical (HO•), oxidized bio-refractory organics to nontoxic matters in groundwater. Automatic pH adjustments are achieved by appropriately arraying the electrodes. Laboratory batch tests and column tests for the E-Fenton oxidation and hybrid electrolysis system were conducted to evaluate the transformation efficiency of chlorine benzene. Results from batch experiments suggested the CB-PTFE cathode was effective for reducing O2 to H2O2. The H2O2 concentration reached 468 mg/L under the condition of pH 3.0 and 30mA/cm2 in 60 minutes, which was 5 and 10 times of that with a graphite and C-felt cathode. The removal efficiency of chlorine benzene reached 80% in 20 minutes. Both chlorine benzene degradation and H2O2 production increased with decreasing solution pH and increasing current density. The results from the columns tests proved that the in situ E-Fenton system is a feasible method for groundwater remediation.

A bio-inspired molecular water oxidation catalyst for renewable hydrogen generation: an examination of salt effects

NASA Astrophysics Data System (ADS)

Brimblecombe, Robin; Rotstein, Miriam; Koo, Annette; Dismukes, G. Charles; Swiegers, Gerhard F.; Spiccia, Leone

2009-08-01

Most transport fuels are derived from fossil fuels, generate greenhouse gases, and consume significant amounts of water in the extraction, purification, and/or burning processes. The generation of hydrogen using solar energy to split water, ideally from abundant water sources such as sea water or other non-potable sources, could potentially provide an unlimited, clean fuel for the future. Solar, electrochemical water splitting typically combines a photoanode at which water oxidation occurs, with a cathode for proton reduction to hydrogen. In recent work, we have found that a bioinspired tetra-manganese cluster catalyzes water oxidation at relatively low overpotentials (0.38 V) when doped into a Nafion proton conduction membrane deposited on a suitable electrode surface, and illuminated with visible light. We report here that this assembly is active in aqueous and organic electrolyte solutions containing a range of different salts in varying concentrations. Similar photocurrents were obtained using electrolytes containing 0.0 - 0.5 M sodium sulfate, sodium perchlorate or sodium chloride. A slight decline in photocurrent was observed for sodium perchlorate but only at and above 5.0 M concentration. In acetonitrile and acetone solutions containing 10% water, increasing the electrolyte concentration was found to result in leaching of the catalytic species from the membrane and a decrease in photocurrent. Leaching was not observed when the system was tested in an ionic liquid containing water, however, a lower photocurrent was generated than observed in aqueous electrolyte. We conclude that immersion of the membrane in an aqueous solution containing an electrolyte concentration of 0.05 - 0.5M represent good conditions for operation for the cubium/Nafion catalytic system.

Oxidation of DNA bases, deoxyribonucleosides and homopolymers by peroxyl radicals.

PubMed Central

Simandan, T; Sun, J; Dix, T A

1998-01-01

DNA base oxidation is considered to be a key event associated with disease initiation and progression in humans. Peroxyl radicals (ROO. ) are important oxidants found in cells whose ability to react with the DNA bases has not been characterized extensively. In this paper, the products resulting from ROO. oxidation of the DNA bases are determined by gas chromatography/MS in comparison with authentic standards. ROO. radicals oxidize adenine and guanine to their 8-hydroxy derivatives, which are considered biomarkers of hydroxyl radical (HO.) oxidations in cells. ROO. radicals also oxidize adenine to its hydroxylamine, a previously unidentified product. ROO. radicals oxidize cytosine and thymine to the monohydroxy and dihydroxy derivatives that are formed by oxidative damage in cells. Identical ROO. oxidation profiles are observed for each base when exposed as deoxyribonucleosides, monohomopolymers and base-paired dihomopolymers. These results have significance for the development, utilization and interpretation of DNA base-derived biomarkers of oxidative damage associated with disease initiation and propagation, and support the idea that the mutagenic potential of N-oxidized bases, when generated in cellular DNA, will require careful evaluation. Adenine hydroxylamine is proposed as a specific molecular probe for the activity of ROO. in cellular systems. PMID:9761719

Novel device for continuous spatial control and temporal delivery of nitric oxide for in vitro cell culture☆

PubMed Central

Romanowicz, Genevieve E.; He, Weilue; Nielsen, Matthew; Frost, Megan C.

2013-01-01

Nitric oxide (NO) is an ubiquitous signaling molecule of intense interest in many physiological processes. Nitric oxide is a highly reactive free radical gas that is difficult to deliver with precise control over the level and timing that cells actually experience. We describe and characterize a device that allows tunable fluxes and patterns of NO to be generated across the surface upon which cells are cultured. The system is based on a quartz microscope slide that allows for controlled light levels to be applied to a previously described photosensitive NO-releasing polydimethylsiloxane (PDMS). Cells are cultured in separate wells that are either NO-releasing or a chemically similar PDMS that does not release NO. Both wells are then top coated with DowCorning RTV-3140 PDMS and a polydopamine/gelatin layer to allow cells to grow in the culture wells. When the waveguide is illuminated, the surface of the quartz slide propagates light such that the photosensitive polymer is evenly irradiated and generates NO across the surface of the cell culture well and no light penetrates into the volume of the wells where cells are growing. Mouse smooth muscle cells (MOVAS) were grown in the system in a proof of principle experiment, whereby 60% of the cells were present in the NO-releasing well compared to control wells after 17 h. The compelling advantage of illuminating the NO-releasing polymers with the waveguide system is that light can be used to tunably control NO release while avoiding exposing cells to optical radiation. This device provides means to quantitatively control the surface flux, timing and duration of NO cells experience and allows for systematic study of cellular response to NO generated at the cell/surface interface in a wide variety of studies. PMID:24024168

Oxidative stress and antioxidative systems: recipes for successful data collection and interpretation.

PubMed

Noctor, Graham; Mhamdi, Amna; Foyer, Christine H

2016-05-01

Oxidative stress and reactive oxygen species (ROS) are common to many fundamental responses of plants. Enormous and ever-growing interest has focused on this research area, leading to an extensive literature that documents the tremendous progress made in recent years. As in other areas of plant biology, advances have been greatly facilitated by developments in genomics-dependent technologies and the application of interdisciplinary techniques that generate information at multiple levels. At the same time, advances in understanding ROS are fundamentally reliant on the use of biochemical and cell biology techniques that are specific to the study of oxidative stress. It is therefore timely to revisit these approaches with the aim of providing a guide to convenient methods and assisting interested researchers in avoiding potential pitfalls. Our critical overview of currently popular methodologies includes a detailed discussion of approaches used to generate oxidative stress, measurements of ROS themselves, determination of major antioxidant metabolites, assays of antioxidative enzymes and marker transcripts for oxidative stress. We consider the applicability of metabolomics, proteomics and transcriptomics approaches and discuss markers such as damage to DNA and RNA. Our discussion of current methodologies is firmly anchored to future technological developments within this popular research field. © 2016 John Wiley & Sons Ltd.

Protective and antioxidative effect of rubropunctatin against oxidative protein damage induced by metal catalyzed reaction.

PubMed

Dhale, Mohan A; Javagal, Manjunatha; Puttananjaiah, Mohan-Kumari H

2018-05-03

Monascus purpureus is known to produce several coloured secondary metabolites. In this study, M. purpureus CFR 410-11 mutant fermented with rice was dried and extracted in hexane for purification of pigment. The purity of the isolated pigment was confirmed by different chromatography techniques. The spectroscopic analysis revealed its structural identity as rubropunctatin. The antioxidant potencies of isolated rubropunctatin were evaluated. Rubropunctatin scavenged 16% 2, 2-diphenyl-1-picrylhydrazyl (DPPH) radical and inhibited 20% superoxide generation at 8 μg/ml concentration. The multiple antioxidant abilities of rubropunctatin were evidenced by its ferric reducing capacity also. The oxidative damage of BSA protein was induced by the metal catalyzed oxidation (MCO) by Fe 2+ /H 2 O 2 . The protective effects of rubropunctatin and M. purpureus (MTCC-410 and CFR 410-11) extracts were compared with glutathione and ascorbic acid. The M. purpureus extracts and rubropunctatin inhibited the formation of carbonyl content and protein oxidation assayed by SDS-PAGE. Rubropunctatin (42-169 μM) efficiently inhibited the protein oxidation compared to glutathione (48-195 μM) and ascorbic acid (85-340 μM) by scavenging the superoxide and hydroxyl radical generated in the system. Copyright © 2018 Elsevier B.V. All rights reserved.

A Role of Fluoride on Free Radical Generation and Oxidative Stress in BV-2 Microglia Cells

PubMed Central

Shuhua, Xi; Ziyou, Liu; Ling, Yan; Fei, Wang; Sun, Guifan

2012-01-01

The generation of ROS and lipid peroxidation has been considered to play an important role in the pathogenesis of chronic fluoride toxicity. In the present study, we observed that fluoride activated BV-2 microglia cell line by observing OX-42 expression in immunocytochemistry. Intracellular superoxide dismutase (SOD), glutathione (GSH), malondialdehyde (MDA), reactive oxygen species (ROS), superoxide anions (O2 ∙−), nitric oxide synthase (NOS), nitrotyrosine (NT) and nitric oxide (NO), NOS in cell medium were determined for oxidative stress assessment. Our study found that NaF of concentration from 5 to 20 mg/L can stimuli BV-2 cells to change into activated microglia displaying upregulated OX-42 expression. SOD activities significantly decreased in fluoride-treated BV-2 cells as compared with control, and MDA concentrations and contents of ROS and O2 ∙− increased in NaF-treated cells. Activities of NOS in cells and medium significantly increased with fluoride concentrations in a dose-dependent manner. NT concentrations also increased significantly in 10 and 50 mg/L NaF-treated cells compared with the control cells. Our present study demonstrated that toxic effects of fluoride on the central nervous system possibly partly ascribed to activiting of microglia, which enhanced oxidative stress induced by ROS and reactive nitrogen species. PMID:22933830

Acute ethanol intake induces superoxide anion generation and mitogen-activated protein kinase phosphorylation in rat aorta: A role for angiotensin type 1 receptor

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

Yogi, Alvaro; Callera, Glaucia E.; Mecawi, André S.

Ethanol intake is associated with increase in blood pressure, through unknown mechanisms. We hypothesized that acute ethanol intake enhances vascular oxidative stress and induces vascular dysfunction through renin–angiotensin system (RAS) activation. Ethanol (1 g/kg; p.o. gavage) effects were assessed within 30 min in male Wistar rats. The transient decrease in blood pressure induced by ethanol was not affected by the previous administration of losartan (10 mg/kg; p.o. gavage), a selective AT{sub 1} receptor antagonist. Acute ethanol intake increased plasma renin activity (PRA), angiotensin converting enzyme (ACE) activity, plasma angiotensin I (ANG I) and angiotensin II (ANG II) levels. Ethanol inducedmore » systemic and vascular oxidative stress, evidenced by increased plasma thiobarbituric acid-reacting substances (TBARS) levels, NAD(P)H oxidase‐mediated vascular generation of superoxide anion and p47phox translocation (cytosol to membrane). These effects were prevented by losartan. Isolated aortas from ethanol-treated rats displayed increased p38MAPK and SAPK/JNK phosphorylation. Losartan inhibited ethanol-induced increase in the phosphorylation of these kinases. Ethanol intake decreased acetylcholine-induced relaxation and increased phenylephrine-induced contraction in endothelium-intact aortas. Ethanol significantly decreased plasma and aortic nitrate levels. These changes in vascular reactivity and in the end product of endogenous nitric oxide metabolism were not affected by losartan. Our study provides novel evidence that acute ethanol intake stimulates RAS activity and induces vascular oxidative stress and redox-signaling activation through AT{sub 1}-dependent mechanisms. These findings highlight the importance of RAS in acute ethanol-induced oxidative damage. -- Highlights: ► Acute ethanol intake stimulates RAS activity and vascular oxidative stress. ► RAS plays a role in acute ethanol-induced oxidative damage via AT{sub 1} receptor activation. ► Translocation of p47phox and MAPKs phosphorylation are downstream effectors. ► Acute ethanol consumption increases the risk for acute vascular injury.« less

Oocyte exposure to ZnO nanoparticles inhibits early embryonic development through the γ-H2AX and NF-κB signaling pathways.

PubMed

Liu, Jing; Zhao, Yong; Ge, Wei; Zhang, Pengfei; Liu, Xinqi; Zhang, Weidong; Hao, Yanan; Yu, Shuai; Li, Lan; Chu, Meiqiang; Min, Lingjiang; Zhang, Hongfu; Shen, Wei

2017-06-27

The impacts of zinc oxide nanoparticles on embryonic development following oocyte stage exposure are unknown and the underlying mechanisms are sparsely understood. In the current investigation, intact nanoparticles were detected in ovarian tissue in vivo and cultured cells in vitro under zinc oxide nanoparticles treatment. Zinc oxide nanoparticles exposure during the oocyte stage inhibited embryonic development. Notably, in vitro culture data closely matched in vivo embryonic data, in that the impairments caused by Zinc oxide nanoparticles treatment passed through cell generations; and both gamma-H2AX and NF-kappaB pathways were involved in zinc oxide nanoparticles caused embryo-toxicity. Copper oxide and silicon dioxide nanoparticles have been used to confirm that particles are important for the toxicity of zinc oxide nanoparticles. The toxic effects of zinc oxide nanoparticles emanate from both intact nanoparticles and Zn2+. Our investigation along with others suggests that zinc oxide nanoparticles are toxic to the female reproductive system [ovaries (oocytes)] and subsequently embryo-toxic and that precaution should be taken regarding human exposure to their everyday use.

Oocyte exposure to ZnO nanoparticles inhibits early embryonic development through the γ-H2AX and NF-κB signaling pathways

PubMed Central

Liu, Jing; Zhao, Yong; Ge, Wei; Zhang, Pengfei; Liu, Xinqi; Zhang, Weidong; Hao, Yanan; Yu, Shuai; Li, Lan; Chu, Meiqiang; Min, Lingjiang; Zhang, Hongfu; Shen, Wei

2017-01-01

The impacts of zinc oxide nanoparticles on embryonic development following oocyte stage exposure are unknown and the underlying mechanisms are sparsely understood. In the current investigation, intact nanoparticles were detected in ovarian tissue in vivo and cultured cells in vitro under zinc oxide nanoparticles treatment. Zinc oxide nanoparticles exposure during the oocyte stage inhibited embryonic development. Notably, in vitro culture data closely matched in vivo embryonic data, in that the impairments caused by Zinc oxide nanoparticles treatment passed through cell generations; and both gamma-H2AX and NF-kappaB pathways were involved in zinc oxide nanoparticles caused embryo-toxicity. Copper oxide and silicon dioxide nanoparticles have been used to confirm that particles are important for the toxicity of zinc oxide nanoparticles. The toxic effects of zinc oxide nanoparticles emanate from both intact nanoparticles and Zn2+. Our investigation along with others suggests that zinc oxide nanoparticles are toxic to the female reproductive system [ovaries (oocytes)] and subsequently embryo-toxic and that precaution should be taken regarding human exposure to their everyday use. PMID:28487501

Vanadium distribution in rats and DNA cleavage by vanadyl complex: implication for vanadium toxicity and biological effects.

PubMed Central

Sakurai, H

1994-01-01

Vanadium ion is toxic to animals. However, vanadium is also an agent used for chemoprotection against cancers in animals. To understand both the toxic and beneficial effects we studied vanadium distribution in rats. Accumulation of vanadium in the liver nuclei of rats given low doses of compounds in the +4 or +5 oxidation state was greater than in the liver nuclei of rats given high doses of vanadium compounds or the vanadate (+5 oxidation state) compound. Vanadium was incorporated exclusively in the vanadyl (+4 oxidation state) form. We also investigated the reactions of vanadyl ion and found that incubation of DNA with vanadyl ion and hydrogen peroxide (H2O2) led to intense DNA cleavage. ESR spin trapping demonstrated that hydroxyl radicals are generated during the reactions of vanadyl ion and H2O2. Thus, we propose that the mechanism for vanadium-dependent toxicity and antineoplastic action is due to DNA cleavage by hydroxyl radicals generated in living systems. PMID:7843133

Thermoelectric properties and performance of flexible reduced graphene oxide films up to 3,000 K

NASA Astrophysics Data System (ADS)

Li, Tian; Pickel, Andrea D.; Yao, Yonggang; Chen, Yanan; Zeng, Yuqiang; Lacey, Steven D.; Li, Yiju; Wang, Yilin; Dai, Jiaqi; Wang, Yanbin; Yang, Bao; Fuhrer, Michael S.; Marconnet, Amy; Dames, Chris; Drew, Dennis H.; Hu, Liangbing

2018-02-01

The development of ultrahigh-temperature thermoelectric materials could enable thermoelectric topping of combustion power cycles as well as extending the range of direct thermoelectric power generation in concentrated solar power. However, thermoelectric operation temperatures have been restricted to under 1,500 K due to the lack of suitable materials. Here, we demonstrate a thermoelectric conversion material based on high-temperature reduced graphene oxide nanosheets that can perform reliably up to 3,000 K. After a reduction treatment at 3,300 K, the nanosheet film exhibits an increased conductivity to 4,000 S cm-1 at 3,000 K and a high power factor S2σ = 54.5 µW cm-1 K-2. We report measurements characterizing the film's thermoelectric properties up to 3,000 K. The reduced graphene oxide film also exhibits a high broadband radiation absorbance and can act as both a radiative receiver and a thermoelectric generator. The printable, lightweight and flexible film is attractive for system integration and scalable manufacturing.

Neutrophil extracellular traps enriched in oxidized mitochondrial DNA are interferogenic and contribute to lupus-like disease

PubMed Central

Lood, Christian; Blanco, Luz P.; Purmalek, Monica M.; Carmona-Rivera, Carmelo; De Ravin, Suk S.; Smith, Carolyne K.; Malech, Harry L.; Ledbetter, Jeffrey A.; Elkon, Keith B.; Kaplan, Mariana J.

2015-01-01

Neutrophil extracellular traps (NETs) are implicated in autoimmunity but how they are generated and their roles in sterile inflammation remain unclear. Ribonucleoprotein immune complexes, inducers of NETosis, require mitochondrial ROS for maximal NET stimulation. During this process, mitochondria become hypopolarized and translocate to the cell surface. Extracellular release of oxidized mitochondrial DNA is proinflammatory in vitro and, when injected into mice, stimulates type-I interferon (IFN) signaling through a pathway dependent on the DNA sensor, STING. Mitochondrial ROS is also necessary for spontaneous NETosis of low-density granulocytes from individuals with systemic lupus erythematosus (SLE). This was also observed in individuals with chronic granulomatous disease (CGD), which lack NADPH-oxidase activity, but still develop autoimmunity and type I-IFN signatures. Mitochondrial ROS inhibition in vivo reduces disease severity and type-I IFN responses in a mouse model of lupus. These findings highlight a role for mitochondria in the generation not only of NETs but also of pro-inflammatory oxidized mitochondrial DNA in autoimmune diseases. PMID:26779811

The Role of Oxidative Stress in Parkinson’s Disease

PubMed Central

Dias, Vera; Junn, Eunsung; Mouradian, M. Maral

2014-01-01

Oxidative stress plays an important role in the degeneration of dopaminergic neurons in Parkinson’s disease (PD). Disruptions in the physiologic maintenance of the redox potential in neurons interfere with several biological processes, ultimately leading to cell death. Evidence has been developed for oxidative and nitrative damage to key cellular components in the PD substantia nigra. A number of sources and mechanisms for the generation of reactive oxygen species (ROS) are recognized including the metabolism of dopamine itself, mitochondrial dysfunction, iron, neuroinflammatory cells, calcium, and aging. PD causing gene products including DJ-1, PINK1, parkin, alpha-synuclein and LRRK2 also impact in complex ways mitochondrial function leading to exacerbation of ROS generation and susceptibility to oxidative stress. Additionally, cellular homeostatic processes including the ubiquitin-proteasome system and mitophagy are impacted by oxidative stress. It is apparent that the interplay between these various mechanisms contributes to neurodegeneration in PD as a feed forward scenario where primary insults lead to oxidative stress, which damages key cellular pathogenetic proteins that in turn cause more ROS production. Animal models of PD have yielded some insights into the molecular pathways of neuronal degeneration and highlighted previously unknown mechanisms by which oxidative stress contributes to PD. However, therapeutic attempts to target the general state of oxidative stress in clinical trials have failed to demonstrate an impact on disease progression. Recent knowledge gained about the specific mechanisms related to PD gene products that modulate ROS production and the response of neurons to stress may provide targeted new approaches towards neuroprotection. PMID:24252804

Method for detection of extremely low concentration

DOEpatents

Andresen, Brian D.; Miller, Fred S.

2002-01-01

An ultratrace detector system for hand-held gas chromatography having high sensitivity, for example, to emissions generated during production of weapons, biological compounds, drugs, etc. The detector system is insensitive to water, air, helium, argon, oxygen, and CO.sub.2. The detector system is basically composed of a hand-held capillary gas chromatography (GC), an insulated heated redox-chamber, a detection chamber, and a vapor trap. For example, the detector system may use gas phase redox reactions and spectral absorption of mercury vapor. The gas chromatograph initially separates compounds that percolate through a bed of heated mercuric oxide (HgO) in a silica--or other metal--aerogel material which acts as an insulator. Compounds easily oxidized by HgO liberate atomic mercury that subsequently pass through a detection chamber which includes a detector cell, such as quartz, that is illuminated with a 254 nm ultra-violet (UV) mercury discharge lamp which generates the exact mercury absorption bands that are used to detect the liberated mercury atoms. Atomic mercury strongly absorbs 254 nm energy is therefore a specific signal for reducing compounds eluting from the capillary GC, whereafter the atomic mercury is trapped for example, in a silicon-aerogel trap.

Ultratrace detector for hand-held gas chromatography

DOEpatents

Andresen, Brian D.; Miller, Fred S.

1999-01-01

An ultratrace detector system for hand-held gas chromatography having high sensitivity, for example, to emissions generated during production of weapons, biological compounds, drugs, etc. The detector system is insensitive to water, air, helium, argon, oxygen, and C0.sub.2. The detector system is basically composed of a hand-held capillary gas chromatography (GC), an insulated heated redox-chamber, a detection chamber, and a vapor trap. For example, the detector system may use gas phase redox reactions and spectral absorption of mercury vapor. The gas chromatograph initially separates compounds that percolate through a bed of heated mercuric oxide (HgO) in a silica--or other metal--aerogel material which acts as an insulator. Compounds easily oxidized by HgO liberate atomic mercury that subsequently pass through a detection chamber which includes a detector cell, such as quartz, that is illuminated with a 254 nm ultra-violet (UV) mercury discharge lamp which generates the exact mercury absorption bands that are used to detect the liberated mercury atoms. Atomic mercury strongly absorbs 254 nm energy is therefore a specific signal for reducing compounds eluting from the capillary GC, whereafter the atomic mercury is trapped for example, in a silicon-aerogel trap.

Alkyl radical generation by an intramolecular homolytic substitution reaction between iron (II) and trialkylsulfonium groups.

PubMed

Jungen, Stefan; Chen, Peter

2018-05-16

Intramolecular, homolytic substitution reactions between iron (II) species and various trialkylsulfonium groups were directly observed in the gas phase upon collision induced dissociation. In spite of the notoriously low reduction potential of trialkylsulfonium species and the mismatched oxidation potential of iron (II), the reactions proceed at moderate collision energies, forming an alkyl radical as well as a thioether coordinated to the iron. In contrast to classical homolytic substitutions, the attacking radical is a "metalloradical", namely iron (II) that is oxidized to iron (III) during the reaction. With this process we demonstrate that the conceptually analogous, putative radical generation step in Radical S-Adenosyl Methionine Enzymes is possible and plausible. Further, we show that this kind of reaction only occurs in constrained systems with a defined geometry. Combining experimental measurements with DFT studies and NBO analyses allowed us to gain insights into the reactivity and transition states of these systems. Based on our findings, we challenge the notion of a collinear transition state in the radical generation step of Radical SAM Enzymes and propose it to be bent instead. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon balance in bioregenerative life support systems: some effects of system closure, waste management, and crop harvest index

NASA Technical Reports Server (NTRS)

Wheeler, Raymond M.

2003-01-01

In Advanced Life Support (ALS) systems with bioregenerative components, plant photosynthesis would be used to produce O2 and food, while removing CO2. Much of the plant biomass would be inedible and hence must be considered in waste management. This waste could be oxidized (e.g., incinerated or aerobically digested) to resupply CO2 to the plants, but this would not be needed unless the system were highly closed with regard to food. For example, in a partially closed system where some of the food is grown and some is imported, CO2 from oxidized waste when combined with crew and microbial respiration could exceed the CO2 removal capability of the plants. Moreover, it would consume some O2 produced from photosynthesis that could have been used by the crew. For partially closed systems it would be more appropriate to store or find other uses for the inedible biomass and excess carbon, such as generating soils or growing woody plants (e.g., dwarf fruit trees). Regardless of system closure, high harvest crops (i.e., crops with a high edible to total biomass ratio) would increase food production per unit area and O2 yields for systems where waste biomass is oxidized to recycle CO2. Such interlinking effects between the plants and waste treatment strategies point out the importance of oxidizing only that amount of waste needed to optimize system performance. Published by Elsevier Science Ltd on behalf of COSPAR.

Carbon balance in bioregenerative life support systems: some effects of system closure, waste management, and crop harvest index.

PubMed

Wheeler, Raymond M

2003-01-01

In Advanced Life Support (ALS) systems with bioregenerative components, plant photosynthesis would be used to produce O2 and food, while removing CO2. Much of the plant biomass would be inedible and hence must be considered in waste management. This waste could be oxidized (e.g., incinerated or aerobically digested) to resupply CO2 to the plants, but this would not be needed unless the system were highly closed with regard to food. For example, in a partially closed system where some of the food is grown and some is imported, CO2 from oxidized waste when combined with crew and microbial respiration could exceed the CO2 removal capability of the plants. Moreover, it would consume some O2 produced from photosynthesis that could have been used by the crew. For partially closed systems it would be more appropriate to store or find other uses for the inedible biomass and excess carbon, such as generating soils or growing woody plants (e.g., dwarf fruit trees). Regardless of system closure, high harvest crops (i.e., crops with a high edible to total biomass ratio) would increase food production per unit area and O2 yields for systems where waste biomass is oxidized to recycle CO2. Such interlinking effects between the plants and waste treatment strategies point out the importance of oxidizing only that amount of waste needed to optimize system performance. Published by Elsevier Science Ltd on behalf of COSPAR.

Carbon balance in bioregenerative life support systems: Some effects of system closure, waste management, and crop harvest index

NASA Astrophysics Data System (ADS)

Wheeler, Raymond M.

In Advanced Life Support (ALS) systems with bioregenerative components, plant photosynthesis would be used to produce O2 and food, while removing CO2. Much of the plant biomass would be inedible and hence must be considered in waste management. This waste could be oxidized (e.g., incinerated or aerobically digested) to resupply CO2 to the plants, but this would not be needed unless the system were highly closed with regard to food. For example, in a partially closed system where some of the food is grown and some is imported, CO2 from oxidized waste when combined with crew and microbial respiration could exceed the CO2 removal capability of the plants. Moreover, it would consume some O2 produced from photosynthesis that could have been used by the crew. For partially closed systems it would be more appropriate to store or find other uses for the inedible biomass and excess carbon, such as generating soils or growing woody plants (e.g., dwarf fruit trees). Regardless of system closure, high harvest crops (i.e., crops with a high edible to total biomass ratio) would increase food production per unit area and O2 yields for systems where waste biomass is oxidized to recycle CO2. Such interlinking effects between the plants and waste treatment strategies point out the importance of oxidizing only that amount of waste needed to optimize system performance.

Antioxidant Systems from Pepper (Capsicum annuum L.): Involvement in the Response to Temperature Changes in Ripe Fruits

PubMed Central

Mateos, Rosa M.; Jiménez, Ana; Román, Paloma; Romojaro, Félix; Bacarizo, Sierra; Leterrier, Marina; Gómez, Manuel; Sevilla, Francisca; del Río, Luis A.; Corpas, Francisco J.; Palma, José M.

2013-01-01

Sweet pepper is susceptible to changes in the environmental conditions, especially temperatures below 15 °C. In this work, two sets of pepper fruits (Capsicum annuum L.) which underwent distinct temperature profiles in planta were investigated. Accordingly, two harvesting times corresponding to each set were established: Harvest 1, whose fruits developed and ripened at 14.9 °C as average temperature; and Harvest 2, with average temperature of 12.4 °C. The oxidative metabolism was analyzed in all fruits. Although total ascorbate content did not vary between Harvests, a shift from the reduced to the oxidized form (dehydroascorbate), accompanied by a higher ascorbate peroxidase activity, was observed in Harvest 2 with respect to Harvest 1. Moreover, a decrease of the ascorbate-generating enzymatic system, the γ-galactono-lactone dehydrogenase, was found at Harvest 2. The activity values of the NADP-dependent dehydrogenases analyzed seem to indicate that a lower NADPH synthesis may occur in fruits which underwent lower temperature conditions. In spite of the important changes observed in the oxidative metabolism in fruits subjected to lower temperature, no oxidative stress appears to occur, as indicated by the lipid peroxidation and protein oxidation profiles. Thus, the antioxidative systems of pepper fruits seem to be involved in the response against temperature changes. PMID:23644886

Effects of alpha-lipoic acid on spatial learning and memory, oxidative stress, and central cholinergic system in a rat model of vascular dementia.

PubMed

Zhao, Ran-Ran; Xu, Fei; Xu, Xiao-Chen; Tan, Guo-Jun; Liu, Liang-Min; Wu, Ning; Zhang, Wen-Zhong; Liu, Ji-Xiang

2015-02-05

Brain oxidative stress due to chronic cerebral hypoperfusion was considered to be the major risk factor in the pathogenesis of vascular dementia. In this study, we investigated the protective efficacy of alpha-lipoic acid, an antioxidant, against vascular dementia in rats, as well as the potential mechanism. Bilateral common carotid arteries occlusion (BCCAO) induced severe cognitive deficits tested by Morris water maze (MWM), along with oxidative stress and disturbance of central cholinergic system. However, administration of alpha-lipoic acid (50mg/kg, i.p.) for 28 days significantly restored cognitive deficits induced by BCCAO. Biochemical determination revealed that alpha-lipoic acid markedly decreased the production of malondialdehyde (MDA) and the generation of reactive oxidative species (ROS), and increased the level of reduced glutathione (GSH) in the hippocampal tissue. Additionally, alpha-lipoic acid raised the level of acetylcholine (ACh) and choline acetyltransferase (ChAT) and decreased the activity of acetycholinesterase (AChE) in the hippocampus. These results indicated that treatment with alpha-lipoic acid significantly improved behavioral alterations, protected against oxidative stress, and restored central cholinergic system in the rat model of vascular dementia induced by BCCAO. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

A p-Type Zinc-Based Metal-Organic Framework.

PubMed

Shang, Congcong; Gautier, Romain; Jiang, Tengfei; Faulques, Eric; Latouche, Camille; Paris, Michael; Cario, Laurent; Bujoli-Doeuff, Martine; Jobic, Stéphane

2017-06-05

An original concept for the property tuning of semiconductors is demonstrated by the synthesis of a p-type zinc oxide (ZnO)-like metal-organic framework (MOF), (ZnC 2 O 3 H 2 ) n , which can be regarded as a possible alternative for ZnO, a natural n-type semiconductor. When small oxygen-rich organic linkers are introduced to the Zn-O system, oxygen vacancies and a deep valence-band maximum, the two obstacles for generating p-type behavior in ZnO, are restrained and raised, respectively. Further studies of this material on the doping and photoluminescence behaviors confirm its resemblance to metal oxides (MOs). This result answers the challenges of generating p-type behavior in an n-type-like system. This concept reveals that a new category of hybrid materials, with an embedded continuous metal-oxygen network, lies between the MOs and MOFs. It provides concrete support for the development of p-type hybrid semiconductors in the near future and, more importantly, the enrichment of tuning possibilities in inorganic semiconductors.

Integrated hydrocarbon reforming system and controls

DOEpatents

Clawson, Lawrence G.; Dorson, Matthew H.; Mitchell, William L.; Nowicki, Brian J.; Thijssen, Johannes; Davis, Robert; Papile, Christopher; Rumsey, Jennifer W.; Longo, Nathan; Cross, III, James C.; Rizzo, Vincent; Kleeburg, Gunther; Rindone, Michael; Block, Stephen G.; Sun, Maria; Morriseau, Brian D.; Hagan, Mark R.; Bowers, Brian

2003-11-04

A hydrocarbon reformer system including a first reactor configured to generate hydrogen-rich reformate by carrying out at least one of a non-catalytic thermal partial oxidation, a catalytic partial oxidation, a steam reforming, and any combinations thereof, a second reactor in fluid communication with the first reactor to receive the hydrogen-rich reformate, and having a catalyst for promoting a water gas shift reaction in the hydrogen-rich reformate, and a heat exchanger having a first mass of two-phase water therein and configured to exchange heat between the two-phase water and the hydrogen-rich reformate in the second reactor, the heat exchanger being in fluid communication with the first reactor so as to supply steam to the first reactor as a reactant is disclosed. The disclosed reformer includes an auxiliary reactor configured to generate heated water/steam and being in fluid communication with the heat exchanger of the second reactor to supply the heated water/steam to the heat exchanger.

Opportunities for functional oxides in yttrium oxide-titanium oxide-zirconium oxide system: Applications for novel thermal barrier coatings

NASA Astrophysics Data System (ADS)

Francillon, Wesley

This dissertation is an investigation of materials and processed under consideration for next generation thermal structural oxides with potential applications as thermal barrier coatings; wherein, high temperature stability and mechanical properties affect durability. Two notable next generation materials systems under investigation are pyrochlore and co-doped zirconia oxides. The motivation for this work is based on current limitations of the currently used thermal barrier material of yttria stabilized zirconia (YSZ) deposited by the plasma spray processes. The rapid quenching associated with the plasma spray process, results in a metastable structure that is a non-transformable tetragonal structure in the yttria partially stabilized zirconia system rather than the equilibrium anticipated two phase mixture of cubic and monoclinic phases. It has been shown that this metastable structure offers enhanced toughness and thus durability during thermomechanical cycling from the operating temperatures in excess of 1000C to ambient. However, the metastable oxides are susceptible to partitioning at temperatures greater than 1200C, thus resulting in a transformation of the tetragonal phase oxides. Transformations of the tetragonal prime phase into the parent cubic and tetragonal prime phase result in coating degradation. Several of the emerging oxides are based on rare earth additions to zirconia. However, there is limited information of the high temperature stability of these oxide coatings and more notably these compositions exhibit limited toughness for durable performance. A potential ternary composition based on the YSZ system that offers the ability to tailor the phase structure is based YO1.5-TiO2 -ZrO2. The ternary of YO1.5-TiO2-ZrO 2 has the current TBC composition of seven molar percent yttria stabilized zirconia, pyrochlore phase oxide and zirconia doped with yttria and titania additions (Ti-YSZ). The Ti-YSZ phase field is of interest because at equilibrium it is a single tetragonal phase. Thus, compositions are of single phase tetragonal phase, theoretically, should not undergo high temperature partitioning. Single Tetragonal phase oxides of Ti-YSZ also offer the possibility of enhanced toughness and higher temperature stability akin to those observed in yttria partially stabilized zirconia. Many pyrochlore oxides are under review because they have shown to have lower thermal conductivity than YSZ oxides. This study focused on chemically synthesizing homogeneous starting material compositions in a metastable state (preferably amorphous), following its evolution according to the phase hierarchy under conditions of kinetic constraints. The current equilibrium diagram of YO1.5-TiO2-ZrO 2 is based on theoretical calculations. One of the contributions of this work is the redefined phase fields in YO1.5-TiO2-ZrO 2 based on our experimental results. Investigated compositions were based on tie lines of Y2-xTi2ZrxO7+x/2 and Y2Ti2-yZryO7 representing substitution of Zr4+ for Y3+ and Zr4+ for Ti4+ respectively. More notably, we observed extended metastable phases in pyrochlore and fluorite oxides at low temperature. The significance of this result is that it offers a larger compositional range for investing pyrochlore oxides with associated high temperature phase stability for TBC applications. In tetragonal oxides, our results showed that Ti-YSZ results have slower partitioning kinetics in comparison to YSZ at high temperature. This study also emphasized the deposition of advanced ceramic coatings by plasma spray for tetragonal and pyrochlore systems, compositionally complex functional oxides that may potentially have lower thermal conductivity values compared to current YSZ oxides. Next generation thermal barrier coatings require powders with high chemical purity, chemical homogeneity, controlled particle size/shape and pertinent phase state. Thermal spray offers an avenue to create novel materials and deposits directly from the precursor and compositionally controlled powder feedstock. This study contributed to investigating an unexplored field that offers a variety of opportunities in materials synthesis that would not be possible by conventional methods. Understanding processing-microstructure-property correlations is of considerable importance in thermal spray of functional oxide materials. This thesis demonstrated by radio-frequency thermal spray that the complex pyrochlore oxide Y 2Ti2O7 could be deposited by directly injecting molecularly mixed precursors to form oxide coatings. Structural analysis revealed the metastable fluorite phase; however, with thermal treatments at relatively low temperature of 700°C the pyrochlore phase was obtained. For Ti-YSZ coatings, the tetragonal phase oxides were obtained with unique microstructures, however, the tetragonal prime destabilized at 1200°C. This dissertation explored novel oxide compositions through detailed structural analysis. The approach presented a comprehensive and integrated investigation as it pertains to phase evolution of oxides in powder feedstock to coating characteristics (phase/properties).

Ammonia Generation and Utilization in a Passive SCR (TWC+SCR) System on Lean Gasoline Engine

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

Prikhodko, Vitaly Y.; James E. Parks, II; Pihl, Josh A.

Lean gasoline engines offer greater fuel economy than the common stoichiometric gasoline engine, but the current three way catalyst (TWC) on stoichiometric engines is unable to control nitrogen oxide (NOX) emissions in oxidizing exhaust. For these lean gasoline engines, lean NOX emission control is required to meet existing Tier 2 and upcoming Tier 3 emission regulations set by the U.S. Environmental Protection Agency (EPA). While urea-based selective catalytic reduction (SCR) has proven effective in controlling NOX from diesel engines, the urea storage and delivery components can add significant size and cost. As such, onboard NH 3 production via a passivemore » SCR approach is of interest. In a passive SCR system, NH 3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean operation, NOX passes through the TWC and is reduced by the stored NH 3 on the SCR catalyst. In this work, a passive SCR system was evaluated on a 2.0-liter BMW lean burn gasoline direct injection engine to assess NH 3 generation over a Pd-only TWC and utilization over a Cu-based SCR catalyst. System NOX reduction efficiency and fuel efficiency improvement compared to stoichiometric engine operation were measured. A feedback control strategy based on cumulative NH 3 produced by the TWC during rich operation and NOX emissions during lean operation was implemented on the engine to control lean/rich cycle timing. At an SCR average inlet temperature of 350 °C, an NH 3:NOX ratio of 1.15:1 (achieved through longer rich cycle timing) resulted in 99.7 % NOX conversion. Increasing NH 3 generation further resulted in even higher NOX conversion; however, tailpipe NH 3 emissions resulted. At higher underfloor temperatures, NH 3 oxidation over the SCR limited NH 3 availability for NOX reduction. At the engine conditions studied, greater than 99 % NOX conversion was achieved with passive SCR while delivering fuel efficiency benefits ranging between 6-11 % compared with stoichiometric operation.« less

Ammonia Generation and Utilization in a Passive SCR (TWC+SCR) System on Lean Gasoline Engine

DOE PAGES

Prikhodko, Vitaly Y.; James E. Parks, II; Pihl, Josh A.; ...

2016-04-05

Lean gasoline engines offer greater fuel economy than the common stoichiometric gasoline engine, but the current three way catalyst (TWC) on stoichiometric engines is unable to control nitrogen oxide (NOX) emissions in oxidizing exhaust. For these lean gasoline engines, lean NOX emission control is required to meet existing Tier 2 and upcoming Tier 3 emission regulations set by the U.S. Environmental Protection Agency (EPA). While urea-based selective catalytic reduction (SCR) has proven effective in controlling NOX from diesel engines, the urea storage and delivery components can add significant size and cost. As such, onboard NH 3 production via a passivemore » SCR approach is of interest. In a passive SCR system, NH 3 is generated over a close-coupled TWC during periodic slightly rich engine operation and subsequently stored on an underfloor SCR catalyst. Upon switching to lean operation, NOX passes through the TWC and is reduced by the stored NH 3 on the SCR catalyst. In this work, a passive SCR system was evaluated on a 2.0-liter BMW lean burn gasoline direct injection engine to assess NH 3 generation over a Pd-only TWC and utilization over a Cu-based SCR catalyst. System NOX reduction efficiency and fuel efficiency improvement compared to stoichiometric engine operation were measured. A feedback control strategy based on cumulative NH 3 produced by the TWC during rich operation and NOX emissions during lean operation was implemented on the engine to control lean/rich cycle timing. At an SCR average inlet temperature of 350 °C, an NH 3:NOX ratio of 1.15:1 (achieved through longer rich cycle timing) resulted in 99.7 % NOX conversion. Increasing NH 3 generation further resulted in even higher NOX conversion; however, tailpipe NH 3 emissions resulted. At higher underfloor temperatures, NH 3 oxidation over the SCR limited NH 3 availability for NOX reduction. At the engine conditions studied, greater than 99 % NOX conversion was achieved with passive SCR while delivering fuel efficiency benefits ranging between 6-11 % compared with stoichiometric operation.« less

Proton translocation coupled to trimethylamine N-oxide reduction in anaerobically grown Escherichia coli.

PubMed Central

Takagi, M; Tsuchiya, T; Ishimoto, M

1981-01-01

Proton translocation coupled to trimethylamine N-oxide reduction was studied in Escherichia coli grown anaerobically in the presence of trimethylamine N-oxide. Rapid acidification of the medium was observed when trimethylamine N-oxide was added to anaerobic cell suspensions of E. coli K-10. Acidification was sensitive to the proton conductor 3,5-di-tert-butyl-4-hydroxybenzylidenemalononitrile (SF6847). No pH change was shown in a strain deficient in trimethylamine N-oxide reductase activity. The apparent H+/trimethylamine N-oxide ratio in cells oxidizing endogenous substrates was 3 to 4 g-ions of H+ translocated per mol of trimethylamine N-oxide added. The addition of trimethylamine N-oxide and formate to ethylenediaminetetraacetic acid-treated cell suspension caused fluorescence quenching of 3,3'-dipropylthiacarbocyanine [diS-C3-(5)], indicating the generation of membrane potential. These results indicate that the reduction of trimethylamine N-oxide in E. coli is catalyzed by an anaerobic electron transfer system, resulting in formation of a proton motive force. Trimethylamine N-oxide reductase activity and proton extrusion were also examined in chlorate-resistant mutants. Reduction of trimethylamine N-oxide occurred in chlC, chlG, and chlE mutants, whereas chlA, chlB, and chlD mutants, which are deficient in the molybdenum cofactor, could not reduce it. Protons were extruded in chlC and chlG mutants, but not in chlA, chlB, and chlD mutants. Trimethylamine N-oxide reductase activity in a chlD mutant was restored to the wild-type level by the addition of 100 microM molybdate to the growth medium, indicating that the same molybdenum cofactor as used by nitrate reductase is required for the trimethylamine N-oxide reductase system. PMID:7031034

Flume experiments elucidate relationships between stream morphology, hyporheic residence time, and nitrous oxide production

NASA Astrophysics Data System (ADS)

Quick, Annika; Farrell, Tiffany B.; Reeder, William Jeffrey; Feris, Kevin P.; Tonina, Daniele; Benner, Shawn G.

2015-04-01

The hyporheic zone is a potentially important producer of nitrous oxide, a powerful greenhouse gas. The location and magnitude of nitrous oxide generation within the hyporheic zone involves complex interactions between multiple nitrogen species, redox conditions, microbial communities, and hydraulics. To better understand nitrous oxide generation and emissions from streams, we conducted large-scale flume experiments in which we monitored pore waters along hyporheic flow paths within stream dune structures. Measurements of dissolved oxygen, ammonia, nitrate, nitrite, and dissolved nitrous oxide showed distinct spatial relationships reflecting redox changes along flow paths. Using residence times along a flow path, clear trends in oxygen conditions and nitrogen species were observed. Three dune sizes were modeled, resulting in a range of residence times, carbon reactivity levels and respiration rates. We found that the magnitude and location of nitrous oxide production in the hyporheic zone is related to nitrate loading, dune morphology, and residence time. Specifically, increasing exogenous nitrate levels in surface water to approximately 3 mg/L resulted in an increase in dissolved N2O concentrations greater than 500% (up to 10 µg/L N-N2O) in distinct zones of specific residence times. We also found, however, that dissolved N2O concentrations decreased to background levels further along the flow path due to either reduction of nitrous oxide to dinitrogen gas or degassing. The decrease in measurable N2O along a flow path strongly suggests an important relationship between dune morphology, residence time, and nitrous oxide emissions from within stream sediments. Relating streambed morphology and loading of nitrogen species allows for prediction of nitrous oxide production in the hyporheic zone of natural systems.

Structural characterization of electrochemically and in vitro biologically generated oxidation products of atorvastatin using UHPLC/MS/MS.

PubMed

Jirásko, Robert; Mikysek, Tomáš; Chagovets, Vitaliy; Vokřál, Ivan; Holčapek, Michal

2013-09-01

Ultrahigh-performance liquid chromatography coupled with high-mass-accuracy tandem mass spectrometry (UHPLC-MS-MS) has been used for elucidation of the structures of oxidation products of atorvastatin (AT), one of the most popular commercially available drugs. The purpose of the study was identification of AT metabolites in rat hepatocytes and comparison with electrochemically generated oxidation products. AT was incubated with rat hepatocytes for 24 h. Electrochemical oxidation of AT was performed by use of a three-electrode off-line system with a glassy carbon working electrode. Three supporting electrolytes (0.1 mol L(-1) H2SO4, 0.1 mol L(-1) HCl, and 0.1 mol L(-1) NaCl) were tested, and dependence on pH was also investigated. AT undergoes oxidation by a single irreversible process at approximately +1.0 V vs. Ag/AgCl electrode. The results obtained revealed a simple and relatively fast way of determining the type of oxidation and its position, on the basis of characteristic neutral losses (NLs) and fragment ions. Unfortunately, different products were obtained by electrochemical oxidation and biotransformation of AT. High-mass-accuracy measurement combined with different UHPLC-MS-MS scans, for example reconstructed ion-current chromatograms, constant neutral loss chromatograms, or exact mass filtering, enable rapid identification of drug-related compounds. β-Oxidation, aromatic hydroxylation of the phenylaminocarbonyl group, sulfation, AT lactone and glycol formation were observed in rat biotransformation samples. In contrast, a variety of oxidation reactions on the conjugated skeleton of isopropyl substituent of AT were identified as products of electrolysis.

Enhanced Oxidation Catalysts for Water Reclamation

NASA Technical Reports Server (NTRS)

Jolly, Clifford D.

1999-01-01

This effort seeks to develop and test high-performance, long operating life, physically stable catalysts for use in spacecraft water reclamation systems. The primary goals are to a) reduce the quantity of expendable water filters used to purify water aboard spacecraft, b) to extend the life of the oxidation catalysts used for eliminating organic contaminants in the water reclamation systems, and c) reduce the weight/volume of the catalytic oxidation systems (e.g. VRA) used. This effort is targeted toward later space station utilization and will consist of developing flight-qualifiable catalysts and long-term ground tests of the catalyst prior to their utilization in flight. Fixed -bed catalytic reactors containing 5% platinum on granular activated carbon have been subjected to long-term dynamic column tests to measure catalyst stability vs throughput. The data generated so far indicate that an order of magnitude improvement can be obtained with the treated catalysts vs the control catalyst, at only a minor loss (approx 10%) in the initial catalytic activity.

Development of a gravity-independent wastewater bioprocessor for advanced life support in space

NASA Technical Reports Server (NTRS)

Nashashibi-Rabah, Majda; Christodoulatos, Christos; Korfiatis, George P.; Janes, H. W. (Principal Investigator)

2005-01-01

Operation of aerobic biological reactors in space is controlled by a number of challenging constraints, mainly stemming from mass transfer limitations and phase separation. Immobilized-cell packed-bed bioreactors, specially designed to function in the absence of gravity, offer a viable solution for the treatment of gray water generated in space stations and spacecrafts. A novel gravity-independent wastewater biological processor, capable of carbon oxidation and nitrification of high-strength aqueous waste streams, is presented. The system, consisting of a fully saturated pressurized packed bed and a membrane oxygenation module attached to an external recirculation loop, operated continuously for over one year. The system attained high carbon oxidation efficiencies often exceeding 90% and ammonia oxidation reaching approximately 60%. The oxygen supply module relies on hydrophobic, nonporous, oxygen selective membranes, in a shell and tube configuration, for transferring oxygen to the packed bed, while keeping the gaseous and liquid phases separated. This reactor configuration and operating mode render the system gravity-independent and suitable for space applications.

Superoxide dismutases and glutaredoxins have a distinct role in the response of Candida albicans to oxidative stress generated by the chemical compounds menadione and diamide.

PubMed

Chaves, Guilherme Maranhão; da Silva, Walicyranison Plinio

2012-12-01

To cope with oxidative stress, Candida albicans possesses several enzymes involved in a number of biological processes, including superoxide dismutases (Sods) and glutaredoxins (Grxs). The resistance of C. albicans to reactive oxygen species is thought to act as a virulence factor. Genes such as SOD1 and GRX2, which encode for a Sod and Grx, respectively, in C. albicans are widely recognised to be important for pathogenesis. We generated a double mutant, Δgrx2/sod1, for both genes. This strain is very defective in hyphae formation and is susceptible to killing by neutrophils. When exposed to two compounds that generate reactive oxygen species, the double null mutant was susceptible to menadione and resistant to diamide. The reintegration of the SOD1 gene in the null mutant led to recovery in resistance to menadione, whereas reintegration of the GRX2 gene made the null mutant sensitive to diamide. Despite having two different roles in the responses to oxidative stress generated by chemical compounds, GRX2 and SOD1 are important for C. albicans pathogenesis because the double mutant Δgrx2/sod1 was very susceptible to neutrophil killing and was defective in hyphae formation in addition to having a lower virulence in an animal model of systemic infection.

Nitric oxide signals are interlinked with calcium signals in normal pancreatic stellate cells upon oxidative stress and inflammation.

PubMed

Jakubowska, Monika A; Ferdek, Pawel E; Gerasimenko, Oleg V; Gerasimenko, Julia V; Petersen, Ole H

2016-08-01

The mammalian diffuse stellate cell system comprises retinoid-storing cells capable of remarkable transformations from a quiescent to an activated myofibroblast-like phenotype. Activated pancreatic stellate cells (PSCs) attract attention owing to the pivotal role they play in development of tissue fibrosis in chronic pancreatitis and pancreatic cancer. However, little is known about the actual role of PSCs in the normal pancreas. These enigmatic cells have recently been shown to respond to physiological stimuli in a manner that is markedly different from their neighbouring pancreatic acinar cells (PACs). Here, we demonstrate the capacity of PSCs to generate nitric oxide (NO), a free radical messenger mediating, for example, inflammation and vasodilatation. We show that production of cytosolic NO in PSCs is unambiguously related to cytosolic Ca(2+) signals. Only stimuli that evoke Ca(2+) signals in the PSCs elicit consequent NO generation. We provide fresh evidence for the striking difference between signalling pathways in PSCs and adjacent PACs, because PSCs, in contrast to PACs, generate substantial Ca(2+)-mediated and NOS-dependent NO signals. We also show that inhibition of NO generation protects both PSCs and PACs from necrosis. Our results highlight the interplay between Ca(2+) and NO signalling pathways in cell-cell communication, and also identify a potential therapeutic target for anti-inflammatory therapies. © 2016 The Authors.

Heterogeneous Oxidation of Laboratory-generated Mixed Composition and Biomass Burning Particles

NASA Astrophysics Data System (ADS)

Lim, C. Y.; Sugrue, R. A.; Hagan, D. H.; Cappa, C. D.; Kroll, J. H.; Browne, E. C.

2016-12-01

Heterogeneous oxidation of organic aerosol (OA) can significantly transform the chemical and physical properties of particulate matter in the atmosphere, leading to changes to the chemical composition of OA and potential volatilization of organic compounds. It has become increasingly apparent that the heterogeneous oxidation kinetics of OA depend on the phase and morphology of the particles. However, most laboratory experiments to date have been performed on single-component, purely organic precursors, which may exhibit fundamentally different behavior than more complex particles in the atmosphere. Here we present laboratory studies of the heterogeneous oxidation of two more complex chemical systems: thin, organic coatings on inorganic seed particles and biomass burning OA. In the first system, squalane (C30H62), a model compound for reduced OA, is coated onto dry ammonium sulfate particles at various thicknesses (10-20 nm) and exposed to hydroxyl radical (OH) in a flow tube reactor. In the second, we use a semi-batch reactor to study the heterogeneous OH-initiated oxidation of biomass burning particles as a part of the 2016 FIREX campaign in Missoula, MT. The resulting changes in chemical composition are monitored with an Aerodyne High Resolution Time-of-flight Aerosol Mass Spectrometer (AMS) and a soot-particle AMS for the non-refractory and refractory systems, respectively. We show that the heterogeneous oxidation kinetics of these multicomponent particles are substantially different than that of the single-component particles. The oxidation of organic coatings is rapid, undergoing dramatic changes to carbon oxidation state and losing a significant amount of organic mass after relatively low OH exposures (equivalent to several days of atmospheric processing). In the case of biomass burning particles, the kinetics are complex, with different components (inferred by aerosol mass spectrometry) undergoing oxidation at different rates.

Solution Structures of Highly Active Molecular Ir Water-Oxidation Catalysts from Density Functional Theory Combined with High-Energy X-ray Scattering and EXAFS Spectroscopy.

PubMed

Yang, Ke R; Matula, Adam J; Kwon, Gihan; Hong, Jiyun; Sheehan, Stafford W; Thomsen, Julianne M; Brudvig, Gary W; Crabtree, Robert H; Tiede, David M; Chen, Lin X; Batista, Victor S

2016-05-04

The solution structures of highly active Ir water-oxidation catalysts are elucidated by combining density functional theory, high-energy X-ray scattering (HEXS), and extended X-ray absorption fine structure (EXAFS) spectroscopy. We find that the catalysts are Ir dimers with mono-μ-O cores and terminal anionic ligands, generated in situ through partial oxidation of a common catalyst precursor. The proposed structures are supported by (1)H and (17)O NMR, EPR, resonance Raman and UV-vis spectra, electrophoresis, etc. Our findings are particularly valuable to understand the mechanism of water oxidation by highly reactive Ir catalysts. Importantly, our DFT-EXAFS-HEXS methodology provides a new in situ technique for characterization of active species in catalytic systems.

Towards an Understanding of Energy Impairment in Huntington’s Disease Brain

PubMed Central

Dubinsky, Janet M.

2017-01-01

This review systematically examines the evidence for shifts in flux through energy generating biochemical pathways in Huntington’s disease (HD) brains from humans and model systems. Compromise of the electron transport chain (ETC) appears not to be the primary or earliest metabolic change in HD pathogenesis. Rather, compromise of glucose uptake facilitates glucose flux through glycolysis and may possibly decrease flux through the pentose phosphate pathway (PPP), limiting subsequent NADPH and GSH production needed for antioxidant protection. As a result, oxidative damage to key glycolytic and tricarboxylic acid (TCA) cycle enzymes further restricts energy production so that while basal needs may be met through oxidative phosphorylation, those of excessive stimulation cannot. Energy production may also be compromised by deficits in mitochondrial biogenesis, dynamics or trafficking. Restrictions on energy production may be compensated for by glutamate oxidation and/or stimulation of fatty acid oxidation. Transcriptional dysregulation generated by mutant huntingtin also contributes to energetic disruption at specific enzymatic steps. Many of the alterations in metabolic substrates and enzymes may derive from normal regulatory feedback mechanisms and appear oscillatory. Fine temporal sequencing of the shifts in metabolic flux and transcriptional and expression changes associated with mutant huntingtin expression remain largely unexplored and may be model dependent. Differences in disease progression among HD model systems at the time of experimentation and their varying states of metabolic compensation may explain conflicting reports in the literature. Progressive shifts in metabolic flux represent homeostatic compensatory mechanisms that maintain the model organism through presymptomatic and symptomatic stages. PMID:29125492

Mass-action model analysis of the apparent molar volume and heat capacity of pluronics in water and liposome suspensions at 25 °C.

PubMed

Quirion, François; Meilleur, Luc; Lévesque, Isabelle

2013-07-09

Pluronics are block copolymers composed of a central block of polypropylene oxide and two side chains of polyethylene oxide. They are used in water to generate aggregates and gels or added to phospholipid suspensions to prepare microparticles for drug delivery applications. The structure of these systems has been widely investigated. However, little is known about the mechanisms leading to these structures. This investigation compares the apparent molar volumes and heat capacities of Pluronics F38, F108, F127, P85, P104, and P103 at 25 °C in water and in the presence of lecithin liposomes. The changes in molar volumes, heat capacities, and enthalpies generated by a mass-action model are in good agreement with the loss of hydrophobic hydration of the polypropylene oxide central block of the Pluronics. However, the molecularity of the endothermic transitions is much smaller than the aggregation numbers reported in the literature for the same systems. It is suggested that Pluronics go through dehydration of their central block to form unimolecular or small entities having a hydrophobic polypropylene oxide core. In water, these entities would assemble athermally to form larger aggregates. In the presence of liposomes, they would be transferred into the hydrophobic lecithin bilayers of the liposomes. Light transmission experiments suggest that the liposome suspensions are significantly altered only when the added Pluronics are in the dehydrated state.

On the estimation of thermal strains developed during oxide growth

NASA Astrophysics Data System (ADS)

Sabau, Adrian S.; Wright, Ian G.

2009-07-01

This paper presents results for the strains and stresses in oxide scales under the conditions of temperature and pressure expected in typical steam boiler operation. These conditions are radically different from those typically encountered in laboratory testing and include features such as a thermal gradient across the tube wall, significant internal (steam) pressure, and cycling of both steam temperature and pressure. Critical examination of the assumptions of flat-plate geometry, which is usually made in calculating stresses and strains in oxide scales, indicated that only the component of the hoop strain that generates stress must be reported for the cylindrical case, and that the use of simple plane-strain is adequate for the system studied. Calculations were made for alloy T22 with a hypothetical, single-layered oxide with appropriate properties. Typical conditions associated with transition of the boiler from full to partial load involve a decrease in both steam temperature and pressure, and these two sources of stress generation were found to exert opposite effects. The relative magnitudes of the resulting strains were used to explain the trends in strain levels calculated when the effects of thermal expansion, temperature loading, and pressure loading were superimposed.

The role of folic acid and selenium against oxidative damage from ethanol in early life programming: a review.

PubMed

Ojeda, Luisa; Nogales, Fátima; Murillo, Luisa; Carreras, Olimpia

2018-04-01

There are disorders in children, covered by the umbrella term "fetal alcohol spectrum disorder" (FASD), that occur as result of alcohol consumption during pregnancy and lactation. They appear, at least in part, to be related to the oxidative stress generated by ethanol. Ethanol metabolism generates reactive oxygen species and depletes the antioxidant molecule glutathione (GSH), leading to oxidative stress and lipid and protein damage, which are related to growth retardation and neurotoxicity, thereby increasing the incidence of FASD. Furthermore, prenatal and postnatal exposure to ethanol in dams, as well as increasing oxidation in offspring, causes malnutrition of several micronutrients such as the antioxidant folic acid and selenium (Se), affecting their metabolism and bodily distribution. Although abstinence from alcohol is the only way to prevent FASD, it is possible to reduce its harmful effects with a maternal dietary antioxidant therapy. In this review, folic acid and Se have been chosen to be analyzed as antioxidant intervention systems related to FASD because, like ethanol, they act on the methionine metabolic cycle, being related to the endogenous antioxidants GSH and glutathione peroxidase. Moreover, several birth defects are related to poor folate and Se status.

Effect of curcumin against oxidation of biomolecules by hydroxyl radicals.

PubMed

Borra, Sai Krishna; Mahendra, Jaideep; Gurumurthy, Prema; Jayamathi; Iqbal, Shabeer S; Mahendra, Little

2014-10-01

Among various reactive oxygen species, hydroxyl radicals have the strongest chemical activity, which can damage a wide range of essential biomolecules such as lipids, proteins, and DNA. The objective of this study was to investigate the beneficial effects of curcumin on prevention of oxidative damage of biomolecules by hydroxyl radicals generated in in vitro by a Fenton like reaction. We have incubated the serum, plasma and whole blood with H2O2/Cu2+/ Ascorbic acid system for 4 hours at 37 0C and observed the oxidation of biomolecules like albumin, lipids, proteins and DNA. Curcumin at the concentrations of 50,100 and 200 μmoles, prevented the formation of ischemia modified albumin, MDA, protein carbonyls, oxidized DNA and increased the total antioxidant levels and GSH significantly. These observations suggest the hydroxyl radical scavenging potentials of curcumin and protective actions to prevent the oxidation of biomolecules by hydroxyl radicals.

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

Bose, A; Gardel, EJ; Vidoudez, C

Oxidation-reduction reactions underlie energy generation in nearly all life forms. Although most organisms use soluble oxidants and reductants, some microbes can access solid-phase materials as electron-acceptors or -donors via extracellular electron transfer. Many studies have focused on the reduction of solid-phase oxidants. Far less is known about electron uptake via microbial extracellular electron transfer, and almost nothing is known about the associated mechanisms. Here we show that the iron-oxidizing photoautotroph Rhodopseudomonas palustris TIE-1 accepts electrons from a poised electrode, with carbon dioxide as the sole carbon source/electron acceptor. Both electron uptake and ruBisCo form I expression are stimulated by light.more » Electron uptake also occurs in the dark, uncoupled from photosynthesis. Notably, the pioABC operon, which encodes a protein system essential for photoautotrophic growth by ferrous iron oxidation, influences electron uptake. These data reveal a previously unknown metabolic versatility of photoferrotrophs to use extracellular electron transfer for electron uptake.« less

Fluorescence intermittency originates from reclustering in two-dimensional organic semiconductors

NASA Astrophysics Data System (ADS)

Ruth, Anthony; Hayashi, Michitoshi; Zapol, Peter; Si, Jixin; McDonald, Matthew P.; Morozov, Yurii V.; Kuno, Masaru; Jankó, Boldizsár

2017-02-01

Fluorescence intermittency or blinking is observed in nearly all nanoscale fluorophores. It is characterized by universal power-law distributions in on- and off-times as well as 1/f behaviour in corresponding emission power spectral densities. Blinking, previously seen in confined zero- and one-dimensional systems has recently been documented in two-dimensional reduced graphene oxide. Here we show that unexpected blinking during graphene oxide-to-reduced graphene oxide photoreduction is attributed, in large part, to the redistribution of carbon sp2 domains. This reclustering generates fluctuations in the number/size of emissive graphenic nanoclusters wherein multiscale modelling captures essential experimental aspects of reduced graphene oxide's absorption/emission trajectories, while simultaneously connecting them to the underlying photochemistry responsible for graphene oxide's reduction. These simulations thus establish causality between currently unexplained, long timescale emission intermittency in a quantum mechanical fluorophore and identifiable chemical reactions that ultimately lead to switching between on and off states.

Role of Oxidative Stress as Key Regulator of Muscle Wasting during Cachexia.

PubMed

Ábrigo, Johanna; Elorza, Alvaro A; Riedel, Claudia A; Vilos, Cristian; Simon, Felipe; Cabrera, Daniel; Estrada, Lisbell; Cabello-Verrugio, Claudio

2018-01-01

Skeletal muscle atrophy is a pathological condition mainly characterized by a loss of muscular mass and the contractile capacity of the skeletal muscle as a consequence of muscular weakness and decreased force generation. Cachexia is defined as a pathological condition secondary to illness characterized by the progressive loss of muscle mass with or without loss of fat mass and with concomitant diminution of muscle strength. The molecular mechanisms involved in cachexia include oxidative stress, protein synthesis/degradation imbalance, autophagy deregulation, increased myonuclear apoptosis, and mitochondrial dysfunction. Oxidative stress is one of the most common mechanisms of cachexia caused by different factors. It results in increased ROS levels, increased oxidation-dependent protein modification, and decreased antioxidant system functions. In this review, we will describe the importance of oxidative stress in skeletal muscles, its sources, and how it can regulate protein synthesis/degradation imbalance, autophagy deregulation, increased myonuclear apoptosis, and mitochondrial dysfunction involved in cachexia.

Thyroid hormone-induced oxidative stress.

PubMed

Venditti, P; Di Meo, S

2006-02-01

Hypermetabolic state in hyperthyroidism is associated with tissue oxidative injury. Available data indicate that hyperthyroid tissues exhibit an increased ROS and RNS production. The increased mitochondrial ROS generation is a side effect of the enhanced level of electron carriers, by which hyperthyroid tissues increase their metabolic capacity. Investigations of antioxidant defence system have returned controversial results. Moreover, other thyroid hormone-linked biochemical changes increase tissue susceptibility to oxidative challenge, which exacerbates the injury and dysfunction they suffer under stressful conditions. Mitochondria, as a primary target for oxidative stress, might account for hyperthyroidism linked tissue dysfunction. This is consistent with the inverse relationship found between functional recovery of ischemic hyperthyroid hearts and mitochondrial oxidative damage and respiration impairment. However, thyroid hormone-activated mitochondrial mechanisms provide protection against excessive tissue dysfunction, including increased expression of uncoupling proteins, proteolytic enzymes and transcriptional coactivator PGC-1, and stimulate opening of permeability transition pores.

Mild zinc deficiency in male and female rats: early postnatal alterations in renal nitric oxide system and morphology.

PubMed

Tomat, Analia Lorena; Veiras, Luciana Cecilia; Aguirre, Sofía; Fasoli, Héctor; Elesgaray, Rosana; Caniffi, Carolina; Costa, María Ángeles; Arranz, Cristina Teresa

2013-03-01

Fetal and postnatal zinc deficiencies induce an increase in arterial blood pressure and impair renal function in male adult rats. We therefore hypothesized that these renal alterations are present in early stages of life and that there are sexual differences in the adaptations to this nutritional injury. The aim was to study the effects of moderate zinc deficiency during fetal life and lactation on renal morphology, oxidative stress, apoptosis, and the nitric oxide system in male and female rats at 21 d of life. Female Wistar rats received low (8 ppm) or control (30 ppm) zinc diets from the beginning of pregnancy to weaning. Glomerulus number, morphology, oxidative stress, apoptotic cells, nitric oxide synthase activity, and protein expression were evaluated in the kidneys of offspring at 21 d. Zinc deficiency decreased the nephron number, induced glomerular hypertrophy, increased oxidative damage, and decreased nitric oxide synthase activity in the male and female rat kidneys. Nitric oxide synthase activity was not affected by inhibitors of the neuronal or inducible isoforms, so nitric oxide was mainly generated by the endothelial isoenzyme. Gender differences were observed in glomerular areas and antioxidant enzyme activities. Zinc deficiency during fetal life and lactation induces an early decrease in renal functional units, associated with a decrease in nitric oxide activity and an increase in oxidative stress, which would contribute to increased arterial blood pressure and renal dysfunction in adulthood. The sexual differences observed in this model may explain the dissimilar development of hypertension and renal diseases in adult life. Copyright © 2013 Elsevier Inc. All rights reserved.

Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

2015-09-01

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data; and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the Statistical Oxidation Model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional UCD/CIT air quality model and applied to air quality episodes in California and the eastern US. The mass, composition and properties of SOA predicted using SOM are compared to SOA predictions generated by a traditional "two-product" model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation. Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than constrained multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which "ageing" reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least three times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these "hybrid" multi-generational schemes should be used with great caution in regional models.

Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model - Part 1: Assessing the influence of constrained multi-generational ageing

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Cappa, C. D.; Wexler, A. S.; Seinfeld, J. H.; Kleeman, M. J.

2016-02-01

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the statistical oxidation model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional University of California at Davis / California Institute of Technology (UCD/CIT) air quality model and applied to air quality episodes in California and the eastern USA. The mass, composition and properties of SOA predicted using SOM were compared to SOA predictions generated by a traditional two-product model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation.Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model, resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low-volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which ageing reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least 3 times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these hybrid multi-generational schemes should be used with great caution in regional models.

Quantitative detection of RO2 radicals and other products from cyclohexene ozonolysis with ammonium-CI3-TOF and acetate-CI-API-TOF

NASA Astrophysics Data System (ADS)

Hansel, A.; Scholz, W.; Mentler, B.; Fischer, L.; Berndt, T.

2017-12-01

The performance of the novel ammonium-CI3-TOF utilizing NH4+ adduct ion chemistry to measure quantitatively first generation oxidized product molecules (OMs) as well as highly oxidized organic molecules (HOMs) was investigated for the first time. The gas-phase ozonolysis of cyclohexene served as a test system in order to evaluate the capability of the detection systems. Experiments have been carried out in the TROPOS free-jet flow system at close to atmospheric conditions. Product ion signals were simultaneously observed by the ammonium-CI3-TOF and the acetate-CI-API-TOF. Both instruments are in remarkable good agreement within a factor of two for HOMs. For OMs not containing an OOH group the acetate technique can considerably underestimate OM concentrations by 2-3 orders of magnitude. First steps of cyclohexene ozonolysis generate ten different (m/z product peaks) main products comprising 92% of observed OMs. The remaining 8% are distributed over several (m/z peaks) minor products that can be attributed to HOMs, predominately to highly oxidized RO2 radicals. Summing up, observed ammonium-CI3-TOF products yield 4.9 x 109 molecules cm-³ in excellent agreement with the amount of reacted cyclohexene of 5.0 x 109 molecules cm-³ for reactant concentrations of [O3] = 2.25 x 1012 molecules cm-³ and [cyclohexene] = 2.0 x 1012 molecules cm-³ and a reaction time of 7.9 s. NH4+ adduct ion chemistry based CIMS techniques offer a unique opportunity for complete detection of the whole product distribution, and consequently, for a much better understanding of atmospheric oxidation processes.

Gas-Phase Oxidation via Ion/Ion Reactions: Pathways and Applications

NASA Astrophysics Data System (ADS)

Pilo, Alice L.; Zhao, Feifei; McLuckey, Scott A.

2017-06-01

Here, we provide an overview of pathways available upon the gas-phase oxidation of peptides and DNA via ion/ion reactions and explore potential applications of these chemistries. The oxidation of thioethers (i.e., methionine residues and S-alkyl cysteine residues), disulfide bonds, S-nitrosylated cysteine residues, and DNA to the [M+H+O]+ derivative via ion/ion reactions with periodate and peroxymono-sulfate anions is demonstrated. The oxidation of neutral basic sites to various oxidized structures, including the [M+H+O]+, [M-H]+, and [M-H-NH3]+ species, via ion/ion reactions is illustrated and the oxidation characteristics of two different oxidizing reagents, periodate and persulfate anions, are compared. Lastly, the highly efficient generation of molecular radical cations via ion/ion reactions with sulfate radical anion is summarized. Activation of the newly generated molecular radical peptide cations results in losses of various neutral side chains, several of which generate dehydroalanine residues that can be used to localize the amino acid from which the dehydroalanine was generated. The chemistries presented herein result in a diverse range of structures that can be used for a variety of applications, including the identification and localization of S-alkyl cysteine residues, the oxidative cleavage of disulfide bonds, and the generation of molecular radical cations from even-electron doubly protonated peptides. [Figure not available: see fulltext.

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

NASA Technical Reports Server (NTRS)

Huang, C. J.; Yeager, E.; Ogrady, W. E.

1975-01-01

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found.

Myeloperoxidase: a front-line defender against phagocytosed microorganisms

PubMed Central

Klebanoff, Seymour J.; Kettle, Anthony J.; Rosen, Henry; Winterbourn, Christine C.; Nauseef, William M.

2013-01-01

Successful immune defense requires integration of multiple effector systems to match the diverse virulence properties that members of the microbial world might express as they initiate and promote infection. Human neutrophils—the first cellular responders to invading microbes—exert most of their antimicrobial activity in phagosomes, specialized membrane-bound intracellular compartments formed by ingestion of microorganisms. The toxins generated de novo by the phagocyte NADPH oxidase and delivered by fusion of neutrophil granules with nascent phagosomes create conditions that kill and degrade ingested microbes. Antimicrobial activity reflects multiple and complex synergies among the phagosomal contents, and optimal action relies on oxidants generated in the presence of MPO. The absence of life-threatening infectious complications in individuals with MPO deficiency is frequently offered as evidence that the MPO oxidant system is ancillary rather than essential for neutrophil-mediated antimicrobial activity. However, that argument fails to consider observations from humans and KO mice that demonstrate that microbial killing by MPO-deficient cells is less efficient than that of normal neutrophils. We present evidence in support of MPO as a major arm of oxidative killing by neutrophils and propose that the essential contribution of MPO to normal innate host defense is manifest only when exposure to pathogens overwhelms the capacity of other host defense mechanisms. PMID:23066164

A multipumping flow system for in vitro screening of peroxynitrite scavengers.

PubMed

Ribeiro, Marta F T; Dias, Ana C B; Santos, João L M; Fernandes, Eduarda; Lima, José L F C; Zagatto, Elias A G

2007-09-01

Peroxynitrite anion is a reactive nitrogen species formed in vivo by the rapid, controlled diffusion reaction between nitric oxide and superoxide radicals. By reacting with several biological molecules, peroxynitrite may cause important cellular and tissue deleterious effects, which have been associated with many diseases. In this work, an automated flow-based procedure for the in vitro generation of peroxynitrite and subsequent screening of the scavenging activity of selected compounds is developed. This procedure involves a multipumping flow system (MPFS) and exploits the ability of compounds such as lipoic acid, dihydrolipoic acid, cysteine, reduced glutathione, oxidized glutathione, sulindac, and sulindac sulfone to inhibit the chemiluminescent reaction of luminol with peroxynitrite under physiological simulated conditions. Peroxynitrite was generated in the MPFS by the online reaction of acidified hydrogen peroxide with nitrite, followed by a subsequent stabilization by merging with a sodium hydroxide solution to rapidly quench the developing reaction. The pulsed flow and the timed synchronized insertion of sample and reagent solutions provided by the MPFS ensure the establishment of the reaction zone only inside the flow cell, thus allowing maximum chemiluminescence emission detection. The results obtained for the assayed compounds show that, with the exception of oxidized glutathione, all are highly potent scavengers of peroxynitrite at the studied concentrations.

CO2-Free Power Generation on an Iron Group Nanoalloy Catalyst via Selective Oxidation of Ethylene Glycol to Oxalic Acid in Alkaline Media

PubMed Central

Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Kitano, Sho; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Yamauchi, Miho

2014-01-01

An Fe group ternary nanoalloy (NA) catalyst enabled selective electrocatalysis towards CO2-free power generation from highly deliverable ethylene glycol (EG). A solid-solution-type FeCoNi NA catalyst supported on carbon was prepared by a two-step reduction method. High-resolution electron microscopy techniques identified atomic-level mixing of constituent elements in the nanoalloy. We examined the distribution of oxidised species, including CO2, produced on the FeCoNi nanoalloy catalyst in the EG electrooxidation under alkaline conditions. The FeCoNi nanoalloy catalyst exhibited the highest selectivities toward the formation of C2 products and to oxalic acid, i.e., 99 and 60%, respectively, at 0.4 V vs. the reversible hydrogen electrode (RHE), without CO2 generation. We successfully generated power by a direct EG alkaline fuel cell employing the FeCoNi nanoalloy catalyst and a solid-oxide electrolyte with oxygen reduction ability, i.e., a completely precious-metal-free system. PMID:25004118

Cerebrospinal fluid from subarachnoid haemorrhage patients causes excessive oxidative metabolism compared to vascular smooth muscle force generation.

PubMed

Pyne, G J; Cadoux-Hudson, T A; Clark, J F

2001-01-01

Cerebrospinal fluid (CSF) from subarachnoid haemorrhage (SAH) patients can stimulate vascular smooth muscle to generate force in vitro. CSF from SAH patients suffering from delayed ischaemic neurological deficits due to cerebral vasospasm can generate near maximal force in vitro and previous experiments have ascribed this generation of force to be a calcium mediated event. The intracellular calcium concentration has been demonstrated to rise during the vasospastic process. Calcium also stimulates oxidative metabolism as does adenosine diphosphate (ADP), the product of adenosine triphosphate (ATP) hydrolysis. Significant alteration in high energy metabolites such as ATP, ADP and phosphocreatine have also been demonstrated in various models of SAH mediated vasospasm. Vascular smooth muscle predominantly uses oxidative metabolism for force generation and reserves glycolytic metabolism for ion homeostasis. A decrease in oxidative metabolism during force generation would imply failing mitochondria and increased glycolytic high-energy phosphate supply. Increased oxidative metabolism would imply a decreased efficiency of the contractile apparatus or mitochondria. The aim of this study was to see if SAH CSF stimulation of porcine carotid artery oxidative metabolism was altered during force generation when compared with incremental calcium stimulation with potassium chloride depolarisation. CSF from patients (n = 10) who had subarachnoid haemorrhage stimulated force generation but with a significant 'right shift' in oxygen consumption. This 'right shift' is indicative of an increased energy cost for contractile work. These results suggest that vascular smooth muscle contractile apparatus, when stimulated by subarachnoid cerebrospinal fluid, is consuming excess adenosine triphosphate during force generation.

Effect of adsorbed films on friction of Al2O3-metal systems

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1976-01-01

The kinetic friction of polycrystalline Al2O3 sliding on Cu, Ni, and Fe in ultrahigh vacuum was studied as a function of the surface chemistry of the metal. Clean metal surfaces were exposed to O2, Cl2, C2H4, and C2H3Cl, and the change in friction due to the adsorbed species was observed. Auger electron spectroscopy assessed the elemental composition of the metal surface. It was found that the systems exposed to Cl2 exhibited low friction, interpreted as the van der Waals force between the Al2O3 and metal chloride. The generation of metal oxide by oxygen exposures resulted in an increase in friction, interpreted as due to strong interfacial bonds established by reaction of metal oxide with Al2O3 to form the complex oxide (spinel). The only effect of C2H4 was to increase the friction of the Fe system, but C2H3Cl exposures decreases friction in both Ni and Fe systems, indicating the dominance of the chlorine over the ethylene complex on the surface

Optoacoustic response from graphene-based solutions embedded in optical phantoms by using 905-nm high-power diode-laser assemblies

NASA Astrophysics Data System (ADS)

Leggio, Luca; Gallego, Daniel C.; Gawali, Sandeep Babu; Dadrasnia, Ehsan; Sánchez, Miguel; Rodríguez, Sergio; González, Marta; Carpintero, Guillermo; Osiński, Marek; Lamela, Horacio

2016-03-01

During the last two decades, optoacoustic imaging has been developed as a novel biomedical imaging technique based on the generation of ultrasound waves by means of laser light. In this work, we investigate the optoacoustic response from graphene-based solutions by using a compact and cost-effective system based on an assembly of several 905-nm pulsed high-power diode lasers coupled to a bundle of 200-μm diameter- core optical fibers. The coupled light is conveyed into a lens system and focused on an absorber consisting of graphene-based nanomaterials (graphene oxide, reduced graphene oxide, and reduced graphene-oxide/gold-nanoparticle hybrid, respectively) diluted in ethanol and hosted in slightly scattering optical phantoms. The high absorption of these graphene-based solutions suggests their potential future use in optoacoustic applications as contrast agents.

A thermodynamic approach for selecting operating conditions in the design of reversible solid oxide cell energy systems

NASA Astrophysics Data System (ADS)

Wendel, Christopher H.; Kazempoor, Pejman; Braun, Robert J.

2016-01-01

Reversible solid oxide cell (ReSOC) systems are being increasingly considered for electrical energy storage, although much work remains before they can be realized, including cell materials development and system design optimization. These systems store electricity by generating a synthetic fuel in electrolysis mode and subsequently recover electricity by electrochemically oxidizing the stored fuel in fuel cell mode. System thermal management is improved by promoting methane synthesis internal to the ReSOC stack. Within this strategy, the cell-stack operating conditions are highly impactful on system performance and optimizing these parameters to suit both operating modes is critical to achieving high roundtrip efficiency. Preliminary analysis shows the thermoneutral voltage to be a useful parameter for analyzing ReSOC systems and the focus of this study is to quantitatively examine how it is affected by ReSOC operating conditions. The results reveal that the thermoneutral voltage is generally reduced by increased pressure, and reductions in temperature, fuel utilization, and hydrogen-to-carbon ratio. Based on the thermodynamic analysis, many different combinations of these operating conditions are expected to promote efficient energy storage. Pressurized systems can achieve high efficiency at higher temperature and fuel utilization, while non-pressurized systems may require lower stack temperature and suffer from reduced energy density.

Effect of CoQ homologues on reactive oxygen generation by mitochondria.

PubMed

Imada, Isuke; Sato, Eisuke F; Kira, Yukimi; Inoue, Masayasu

2008-01-01

Effect of CoQ compounds (Qs) on reactive oxygen (ROS) generation by mitochondrial complex I was studied using rat liver mitochondria and chemiluminescence probe L012. Kinetic analysis revealed that short chain Qs, such as Q2 and idebenone enhanced ROS generation by mitochondrial NADH oxidase system by a succinate-inhibitable mechanism. Lipid peroxidation in mitochondrial membranes induced by NADH and iron was inhibited by short chain Qs. The inhibitory activity was enhanced by co-oxidation of succinate as determined by chemiluminescence method and by electron spin resonance spectroscopy. These results suggested that the reduced form of short chain Qs inhibited mitochondrial ROS generation and lipid peroxidation.

Nanowire mesh solar fuels generator

DOEpatents

Yang, Peidong; Chan, Candace; Sun, Jianwei; Liu, Bin

2016-05-24

This disclosure provides systems, methods, and apparatus related to a nanowire mesh solar fuels generator. In one aspect, a nanowire mesh solar fuels generator includes (1) a photoanode configured to perform water oxidation and (2) a photocathode configured to perform water reduction. The photocathode is in electrical contact with the photoanode. The photoanode may include a high surface area network of photoanode nanowires. The photocathode may include a high surface area network of photocathode nanowires. In some embodiments, the nanowire mesh solar fuels generator may include an ion conductive polymer infiltrating the photoanode and the photocathode in the region where the photocathode is in electrical contact with the photoanode.

Method of producing gaseous products using a downflow reactor

DOEpatents

Cortright, Randy D; Rozmiarek, Robert T; Hornemann, Charles C

2014-09-16

Reactor systems and methods are provided for the catalytic conversion of liquid feedstocks to synthesis gases and other noncondensable gaseous products. The reactor systems include a heat exchange reactor configured to allow the liquid feedstock and gas product to flow concurrently in a downflow direction. The reactor systems and methods are particularly useful for producing hydrogen and light hydrocarbons from biomass-derived oxygenated hydrocarbons using aqueous phase reforming. The generated gases may find used as a fuel source for energy generation via PEM fuel cells, solid-oxide fuel cells, internal combustion engines, or gas turbine gensets, or used in other chemical processes to produce additional products. The gaseous products may also be collected for later use or distribution.

Gaining electricity from in situ oxidation of hydrogen produced by fermentative cellulose degradation.

PubMed

Niessen, J; Schröder, U; Harnisch, F; Scholz, F

2005-01-01

To exploit the fermentative hydrogen generation and direct hydrogen oxidation for the generation of electric current from the degradation of cellulose. Utilizing the metabolic activity of the mesophilic anaerobe Clostridium cellulolyticum and the thermophilic Clostridium thermocellum we show that electricity generation is possible from cellulose fermentation. The current generation is based on an in situ oxidation of microbially synthesized hydrogen at platinum-poly(tetrafluoroaniline) (Pt-PTFA) composite electrodes. Current densities of 130 mA l(-1) (with 3 g cellulose per litre medium) were achieved in poised potential experiments under batch and semi-batch conditions. The presented results show that electricity generation is possible by the in situ oxidation of hydrogen, product of the anaerobic degradation of cellulose by cellulolytic bacteria. For the first time, it is shown that an insoluble complex carbohydrate like cellulose can be used for electricity generation in a microbial fuel cell. The concept represents a first step to the utilization of macromolecular biomass components for microbial electricity generation.

Hydroxyl radical and ferryl-generating systems promote gel network formation of myofibrillar protein.

PubMed

Xiong, Youling L; Blanchard, Suzanne P; Ooizumi, Tooru; Ma, Yuanyuan

2010-03-01

The objective of the study was to examine how oxidatively induced protein cross-linking would influence the gelation properties of myofibrillar protein (MP) under meat processing conditions. MP suspensions in 0.6 M NaCl at pH 6 were treated with an iron-catalyzed oxidizing system (IOS: 10 microM FeCl(3), 0.1 mM ascorbic acid, 0.05 to 5 mM H(2)O(2)) or a H(2)O(2)-activated metmyoglobin oxidizing system (MOS: 0.01 to 0.1 mM metmyoglobin/H(2)O(2)) that produced hydroxyl radical and ferryl species, respectively. Both oxidizing systems promoted MP thermal gelation, which was evidenced by rapid protein-protein interaction and the enhancement in storage modulus (elasticity) of the gel network as revealed by dynamic rheological testing in the 20 to 74 degrees C temperature range. This gelation-enhancing effect was attributed to the shift of myosin aggregation in the early stage of heating from predominantly head-head association (nonoxidized control samples) to prevalently tail-tail cross-linking through disulfide bonds. However, both hardness and water-holding capacity of chilled gels tended to decline when MP was exposed to >or=1 mM H(2)O(2) in IOS and to all concentrations of metmyoglobin in MOS. Microscopic examination confirmed a more porous structure in oxidized gels when compared with nonoxidized protein gels. The results demonstrated that mild oxidation altered the mode of myosin aggregation in favor of an elastic gel network formation, but it did not improve or had a negative effect on water-binding properties of MP gels. Mild oxidation promotes protein network formation and enhances gelation of myofibrillar protein under normal salt and pH conditions used in meat processing. This oxidative effect, which involves disulfide linkages, is somewhat similar to that in bakery product processing where oxidants are used to improve dough performance through gluten protein interaction.

Reactivity, chemoselectivity, and diastereoselectivity of the oxyfunctionalization of chiral allylic alcohols and derivatives in microemulsions: comparison of the chemical oxidation by the hydrogen peroxide/sodium molybdate system with the photooxygenation.

PubMed

Nardello, Véronique; Caron, Laurent; Aubry, Jean-Marie; Bouttemy, Sabine; Wirth, Thomas; Saha-Möller Chantu, R; Adam, Waldemar

2004-09-01

The chiral allylic alcohols 1a-d and their acetate (1e) and silyl ether (1f) derivatives have been oxidized by the H2O2/MoO4(2)- system, a convenient and efficient chemical source of singlet oxygen. This chemical peroxidation (formation of the allylic hydroperoxides 2) has been conducted in various media, which include aqueous solutions, organic solvents, and microemulsions. The reactivity, chemoselectivity, and diastereoselectivity of this chemical oxidation are compared to those of the sensitized photooxygenation, with the emphasis on preparative applications in microemulsion media. While a similar threo diastereoselectivity is observed for both modes of peroxidation, the chemoselectivity differs significantly, since in the chemical oxidation with the H2O2/MoO4(2)- system the undesirable epoxidation by the intermediary peroxomolybdate competes efficiently with the desirable peroxidation by the in situ generated singlet oxygen. A proper choice of the type of microemulsion and the reaction conditions furnishes a high chemoselectivity (up to 97%) in favor of threo-diastereoselective (up to 92%) peroxidation. Copyright 2004 American Chemical Society

P66SHC deletion improves fertility and progeric phenotype of late-generation TERC-deficient mice but not their short lifespan.

PubMed

Giorgio, Marco; Stendardo, Massimo; Migliaccio, Enrica; Pelicci, Pier Giuseppe

2016-06-01

Oxidative stress and telomere attrition are considered the driving factors of aging. As oxidative damage to telomeric DNA favors the erosion of chromosome ends and, in turn, telomere shortening increases the sensitivity to pro-oxidants, these two factors may trigger a detrimental vicious cycle. To check whether limiting oxidative stress slows down telomere shortening and related progeria, we have investigated the effect of p66SHC deletion, which has been shown to reduce oxidative stress and mitochondrial apoptosis, on late-generation TERC (telomerase RNA component)-deficient mice having short telomeres and reduced lifespan. Double mutant (TERC(-/-) p66SHC(-/-) ) mice were generated, and their telomere length, fertility, and lifespan investigated in different generations. Results revealed that p66SHC deletion partially rescues sterility and weight loss, as well as organ atrophy, of TERC-deficient mice, but not their short lifespan and telomere erosion. Therefore, our data suggest that p66SHC-mediated oxidative stress and telomere shortening synergize in some tissues (including testes) to accelerate aging; however, early mortality of late-generation mice seems to be independent of any link between p66SHC-mediated oxidative stress and telomere attrition. © 2016 The Authors. Aging Cell published by the Anatomical Society and John Wiley & Sons Ltd.

A Theoretical Solid Oxide Fuel Cell Model for Systems Controls and Stability Design

NASA Technical Reports Server (NTRS)

Kopasakis, George; Brinson, Thomas; Credle, Sydni

2008-01-01

As the aviation industry moves toward higher efficiency electrical power generation, all electric aircraft, or zero emissions and more quiet aircraft, fuel cells are sought as the technology that can deliver on these high expectations. The hybrid solid oxide fuel cell system combines the fuel cell with a micro-turbine to obtain up to 70% cycle efficiency, and then distributes the electrical power to the loads via a power distribution system. The challenge is to understand the dynamics of this complex multidiscipline system and the design distributed controls that take the system through its operating conditions in a stable and safe manner while maintaining the system performance. This particular system is a power generation and a distribution system, and the fuel cell and micro-turbine model fidelity should be compatible with the dynamics of the power distribution system in order to allow proper stability and distributed controls design. The novelty in this paper is that, first, the case is made why a high fidelity fuel cell mode is needed for systems control and stability designs. Second, a novel modeling approach is proposed for the fuel cell that will allow the fuel cell and the power system to be integrated and designed for stability, distributed controls, and other interface specifications. This investigation shows that for the fuel cell, the voltage characteristic should be modeled but in addition, conservation equation dynamics, ion diffusion, charge transfer kinetics, and the electron flow inherent impedance should also be included.

Effect of radical scavengers on the inactivation of papain by ascorbic acid in the presence of cupric ions.

PubMed

Kanazawa, H; Fujimoto, S; Ohara, A

1994-04-01

Incubation of papain (EC 3.4.22.2) with ascorbic acid (AsA) and Cu2+ in acetate buffer (pH 5.6) results in an irreversible loss of enzyme activity by site-specific generation of free radicals [H. Kanazawa, S. Fujimoto, A. Ohara, Biol. Pharm.Bull., 16, 11 (1993)]. In this study, the effect of some compounds, known free radical scavengers, on the relationship between the inactivation of papain by the Cu(2+)-AsA system and the oxidation of AsA was investigated. Catalase completely protected the enzyme from inactivation by the Cu(2+)-AsA system, although hydrogen peroxide (H2O2) by itself, known to be generated during the autoxidation of AsA, did not inactivate the enzyme. The oxidation of AsA was unaffected by catalase. Both thiourea and sodium thiocyanate completely protected the enzyme from inactivation, while AsA was partially oxidized only in the initial stage. In the presence of potassium iodide, both the inactivation of the enzyme and the oxidation of AsA were characterized by a rapid initial phase followed by a stable phase where no reaction took place and, subsequently, a slower phase. Histidine partially prevented the inactivation of the enzyme and the oxidation of AsA. The present results suggest that H2O2 serves as a source of secondary, highly reactive species, probably hydroxyl radicals, which are responsible for the inactivation, and that the protection from inactivation by some radical scavengers, such as thiourea, sodium thiocyanate, potassium iodide, and histidine, is based on the removal of metal ions (Cu2+ or Cu+) at the specific site of inactivation.

Obesity in aging exacerbates blood-brain barrier disruption, neuroinflammation, and oxidative stress in the mouse hippocampus: effects on expression of genes involved in beta-amyloid generation and Alzheimer's disease.

PubMed

Tucsek, Zsuzsanna; Toth, Peter; Sosnowska, Danuta; Gautam, Tripti; Mitschelen, Matthew; Koller, Akos; Szalai, Gabor; Sonntag, William E; Ungvari, Zoltan; Csiszar, Anna

2014-10-01

There is growing evidence that obesity has deleterious effects on the brain and cognitive function in the elderly population. However, the specific mechanisms through which aging and obesity interact to promote cognitive decline remain unclear. To test the hypothesis that aging exacerbates obesity-induced cerebromicrovascular damage and neuroinflammation, we compared young (7 months) and aged (24 months) high fat diet-fed obese C57BL/6 mice. Aging exacerbated obesity-induced systemic inflammation and blood-brain barrier disruption, as indicated by the increased circulating levels of proinflammatory cytokines and increased presence of extravasated immunoglobulin G in the hippocampus, respectively. Obesity-induced blood-brain barrier damage was associated with microglia activation, upregulation of activating Fc-gamma receptors and proinflammatory cytokines, and increased oxidative stress. Treatment of cultured primary microglia with sera derived from aged obese mice resulted in significantly more pronounced microglia activation and oxidative stress, as compared with treatment with young sera. Serum-induced activation and oxidative stress were also exacerbated in primary microglia derived from aged animals. Hippocampal expression of genes involved in regulation of the cellular amyloid precursor protein-dependent signaling pathways, beta-amyloid generation, and the pathogenesis of tauopathy were largely unaffected by obesity in aged mice. Collectively, obesity in aging is associated with a heightened state of systemic inflammation, which exacerbates blood-brain barrier disruption. The resulting neuroinflammation and oxidative stress in the mouse hippocampus likely contribute to the significant cognitive decline observed in aged obese animals. © The Author 2013. Published by Oxford University Press on behalf of The Gerontological Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Auxiliary power unit based on a solid oxide fuel cell and fuelled with diesel

NASA Astrophysics Data System (ADS)

Lawrence, Jeremy; Boltze, Matthias

An auxiliary power unit (APU) is presented that is fuelled with diesel, thermally self-sustaining, and based on a solid oxide fuel cell (SOFC). The APU is rated at 1 kW electrical, and can generate electrical power after a 3 h warm-up phase. System features include a "dry" catalytic partial oxidation (CPOX) diesel reformer, a 30 cell SOFC stack with an open cathode, and a porous-media afterburner. The APU does not require a supply of external water. The SOFC stack is an outcome of a development partnership with H.C. Starck GmbH and Fraunhofer IKTS, and is discussed in detail in an accompanying paper.

New spectrophotometric methods for the determinations of hydrogen sulfide present in the samples of lake water, industrial effluents, tender coconut, sugarcane juice and egg

NASA Astrophysics Data System (ADS)

Shyla, B.; Nagendrappa, G.

2012-10-01

The new methods are working on the principle that iron(III) is reduced to iron(II) by hydrogen sulfide, catechol and p-toluidine the system 1/hydrogen sulfide the system 2, in acidic medium followed by the reduced iron forming complex with 1,10-phenanthroline with λmax 510 nm. The other two methods are based on redox reactions between electrolytically generated manganese(III) sulfate taken in excess and hydrogen sulfide followed by the unreacted oxidant oxidizing diphenylamine λmax 570 the system 3/barium diphenylamine sulphonate λmax 540 nm, the system 4. The increase/decrease in the color intensity of the dye products of the systems 1 and 2 or 3 and 4 are proportional to the concentration of hydrogen sulfide with its quantification range 0.035-1.40 μg ml-1/0.14-1.40 μg ml-1.

Secondary organic aerosol formation from hydroxyl radical oxidation and ozonolysis of monoterpenes

NASA Astrophysics Data System (ADS)

Zhao, D. F.; Kaminski, M.; Schlag, P.; Fuchs, H.; Acir, I.-H.; Bohn, B.; Häseler, R.; Kiendler-Scharr, A.; Rohrer, F.; Tillmann, R.; Wang, M. J.; Wegener, R.; Wildt, J.; Wahner, A.; Mentel, Th. F.

2015-01-01

Oxidation by hydroxyl radical (OH) and ozonolysis are the two major pathways of daytime biogenic volatile organic compound (BVOC) oxidation and secondary organic aerosol (SOA) formation. In this study, we investigated the particle formation of several common monoterpenes (α-pinene, β-pinene and limonene) by OH-dominated oxidation, which has seldom been investigated. OH oxidation experiments were carried out in the SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction) chamber in Jülich, Germany, at low NOx (0.01 ~ 1 ppbV) and low ozone (O3) concentration (< 20 ppbV). OH concentration and total OH reactivity (kOH) were measured directly, and through this the overall reaction rate of total organics with OH in each reaction system was quantified. Multi-generation reaction process, particle growth, new particle formation (NPF), particle yield and chemical composition were analyzed and compared with that of monoterpene ozonolysis. Multi-generation products were found to be important in OH-dominated SOA formation. The relative role of functionalization and fragmentation in the reaction process of OH oxidation was analyzed by examining the particle mass and the particle size as a function of OH dose. We developed a novel method which quantitatively links particle growth to the reaction rate of OH with total organics in a reaction system. This method was also used to analyze the evolution of functionalization and fragmentation of organics in the particle formation by OH oxidation. It shows that functionalization of organics was dominant in the beginning of the reaction (within two lifetimes of the monoterpene) and fragmentation started to play an important role after that. We compared particle formation from OH oxidation with that from pure ozonolysis. In individual experiments, growth rates of the particle size did not necessarily correlate with the reaction rate of monoterpene with OH and O3. Comparing the size growth rates at the similar reaction rates of monoterpene with OH or O3 indicates that, generally, OH oxidation and ozonolysis had similar efficiency in particle growth. The SOA yield of α-pinene and limonene by ozonolysis was higher than that of OH oxidation. Aerosol mass spectrometry (AMS) shows SOA elemental composition from OH oxidation follows a slope shallower than -1 in the O / C vs. H / C diagram, also known as Van Krevelen diagram, indicating that oxidation proceeds without significant loss of hydrogen. SOA from OH oxidation had higher H / C ratios than SOA from ozonolysis. In ozonolysis, a process with significant hydrogen loss seemed to play an important role in SOA formation.

Production of nitric oxide using a microwave plasma torch and its application to fungal cell differentiation

NASA Astrophysics Data System (ADS)

Na, Young Ho; Kumar, Naresh; Kang, Min-Ho; Cho, Guang Sup; Choi, Eun Ha; Park, Gyungsoon; Uhm, Han Sup

2015-03-01

The generation of nitric oxide by a microwave plasma torch is proposed for its application to cell differentiation. A microwave plasma torch was developed based on basic kinetic theory. The analytical theory indicates that nitric oxide density is nearly proportional to oxygen molecular density and that the high-temperature flame is an effective means of generating nitric oxide. Experimental data pertaining to nitric oxide production are presented in terms of the oxygen input in units of cubic centimeters per minute. The apparent length of the torch flame increases as the oxygen input increases. The various levels of nitric oxide are observed depending on the flow rate of nitrogen gas, the mole fraction of oxygen gas, and the microwave power. In order to evaluate the potential of nitric oxide as an activator of cell differentiation, we applied nitric oxide generated from the microwave plasma torch to a model microbial cell (Neurospora crassa: non-pathogenic fungus). Germination and hyphal differentiation of fungal cells were not dramatically changed but there was a significant increase in spore formation after treatment with nitric oxide. In addition, the expression level of a sporulation related gene acon-3 was significantly elevated after 24 h upon nitric oxide treatment. Increase in the level of nitric oxide, nitrite and nitrate in water after nitric oxide treatment seems to be responsible for activation of fungal sporulation. Our results suggest that nitric oxide generated by plasma can be used as a possible activator of cell differentiation and development.

Generation and reactions of oxiranyllithiums by use of a flow microreactor system.

PubMed

Nagaki, Aiichiro; Takizawa, Eiji; Yoshida, Jun-ichi

2010-12-17

A flow microreactor system consisting of micromixers and microtubes provides an effective reactor for the generation and reactions of aryloxiranyllithiums without decomposition by virtue of short residence time and efficient temperature control. The deprotonation of styrene oxides with sBuLi can be conducted by using the flow microreactor system at -78 or -68 °C (whereas much lower temperatures (< -100 °C) are needed for the same reactions conducted under macrobatch conditions). The resulting α-aryloxiranyllithiums were allowed to react with electrophiles in the flow microreactor system at the same temperature. The sequential introduction of various electrophiles onto 2,3-diphenyloxiranes was also achieved by using an integrated flow microreactor, which serves as a powerful system for the stereoselective synthesis of tetrasubstituted epoxides.

Slab reformer

DOEpatents

Spurrier, Francis R.; DeZubay, Egon A.; Murray, Alexander P.; Vidt, Edward J.

1984-02-07

Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot comubstion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

Slab reformer

DOEpatents

Spurrier, Francis R.; DeZubay, Egon A.; Murray, Alexander P.; Vidt, Edward J.

1985-03-12

Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot combustion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

Slab reformer

NASA Technical Reports Server (NTRS)

Spurrier, Francis R. (Inventor); DeZubay, Egon A. (Inventor); Murray, Alexander P. (Inventor); Vidt, Edward J. (Inventor)

1984-01-01

Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot comubstion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

Slab reformer

NASA Technical Reports Server (NTRS)

Spurrier, Francis R. (Inventor); DeZubay, Egon A. (Inventor); Murray, Alexander P. (Inventor); Vidt, Edward J. (Inventor)

1985-01-01

Slab-shaped high efficiency catalytic reformer configurations particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot combustion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant.

Temperature and Nitric Oxide Generation in a Pulsed Arc Discharge Plasma

NASA Astrophysics Data System (ADS)

Namihira, T.; Sakai, S.; Matsuda, M.; D., Wang; Kiyan, T.; Akiyama, H.; Okamoto, K.; Toda, K.

2007-12-01

Nitric oxide (NO) is increasingly being used in medical treatments of high blood pressure, acute respiratory distress syndrome and other illnesses related to the lungs. Currently a NO inhalation system consists of a gas cylinder of N2 mixed with a high concentration of NO. This arrangement is potentially risky due to the possibility of an accidental leak of NO from the cylinder. The presence of NO in the air leads to the formation of nitric dioxide (NO2), which is toxic to the lungs. Therefore, an on-site generator of NO would be highly desirable for medical doctors to use with patients with lung disease. To develop the NO inhalation system without a gas cylinder, which would include a high concentration of NO, NAMIHIRA et al have recently reported on the production of NO from room air using a pulsed arc discharge. In the present work, the temperature of the pulsed arc discharge plasma used to generate NO was measured to optimize the discharge condition. The results of the temperature measurements showed the temperature of the pulsed arc discharge plasma reached about 10,000 K immediately after discharge initiation and gradually decreased over tens of microseconds. In addition, it was found that NO was formed in a discharge plasma having temperatures higher than 9,000 K and a smaller input energy into the discharge plasma generates NO more efficiently than a larger one.

Hydrogen Peroxide Probes Directed to Different Cellular Compartments

PubMed Central

Malinouski, Mikalai; Zhou, You; Belousov, Vsevolod V.; Hatfield, Dolph L.; Gladyshev, Vadim N.

2011-01-01

Background Controlled generation and removal of hydrogen peroxide play important roles in cellular redox homeostasis and signaling. We used a hydrogen peroxide biosensor HyPer, targeted to different compartments, to examine these processes in mammalian cells. Principal Findings Reversible responses were observed to various redox perturbations and signaling events. HyPer expressed in HEK 293 cells was found to sense low micromolar levels of hydrogen peroxide. When targeted to various cellular compartments, HyPer occurred in the reduced state in the nucleus, cytosol, peroxisomes, mitochondrial intermembrane space and mitochondrial matrix, but low levels of the oxidized form of the biosensor were also observed in each of these compartments, consistent with a low peroxide tone in mammalian cells. In contrast, HyPer was mostly oxidized in the endoplasmic reticulum. Using this system, we characterized control of hydrogen peroxide in various cell systems, such as cells deficient in thioredoxin reductase, sulfhydryl oxidases or subjected to selenium deficiency. Generation of hydrogen peroxide could also be monitored in various compartments following signaling events. Conclusions We found that HyPer can be used as a valuable tool to monitor hydrogen peroxide generated in different cellular compartments. The data also show that hydrogen peroxide generated in one compartment could translocate to other compartments. Our data provide information on compartmentalization, dynamics and homeostatic control of hydrogen peroxide in mammalian cells. PMID:21283738

Non-classical behaviour of higher valence dopants in chromium (III) oxide by a Cr vacancy compensation mechanism

NASA Astrophysics Data System (ADS)

Carey, John J.; Nolan, Michael

2017-10-01

Modification of metal oxides with dopants that have a stable oxidation in their parent oxides which is higher than the host system is expected to introduce extra electrons into the material to improve carrier mobility. This is essential for applications in catalysis, SOFCs and solar energy materials. Density functional theory calculations are used to investigate the change in electronic and geometric structure of chromium (III) oxide by higher valence dopants, namely; Ce, Ti, V and Zr. For single metal doping, we find that the dopants with variable oxidation states, Ce, Ti and V, adopt a valence state of  +3, while Zr dopant has a  +4 oxidation state and reduces a neighbouring Cr cation. Chromium vacancy formation is greatly enhanced for all dopants, and favoured over oxygen vacancy formation. The Cr vacancies generate holes which oxidise Ce, Ti and V from  +3 to  +4, while also oxidising lattice oxygen sites. For Zr doping, the generated holes oxidise the reduced Cr2+ cation back to Cr3+ and also two lattice oxygen atoms. Three metal atoms in the bulk lattice facilitate spontaneous Cr vacancy from charge compensation. A non-classical compensation mechanism is observed for Ce, Ti and V; all three metals are oxidised from  +3 to  +4, which explains experimental observations that these metals have a  +4 oxidation state in Cr2O3. Charge compensation of the three Zr metals proceeds by a classical higher valence doping mechanism; the three dopants reduce three Cr cations, which are subsequently charge compensated by a Cr vacancy oxidising three Cr2+ to Cr3+. The compensated structures are the correct ground state electronic structure for these doped systems, and used as a platform to investigate cation/anion vacancy formation. Unlike the single metal doped bulks, preference is now given for oxygen vacancy formation over Cr vacancy formation, indicating that the dopants increase the reducibility of Cr2O3 with Ce doping showing the strongest enhancement. The importance of the correct ground state in determining the formation of defects is emphasised.

Metabolic activation of sodium nitroprusside to nitric oxide in vascular smooth muscle.

PubMed

Kowaluk, E A; Seth, P; Fung, H L

1992-09-01

Sodium nitroprusside (SNP) is thought to exert its vasodilating activity, at least in part, by vascular activation to nitric oxide (NO), but the activation mechanism has not been delineated. This study has examined the potential for vascular metabolism of SNP to NO in bovine coronary arterial smooth muscle subcellular fractions using a sensitive and specific redox-chemiluminescence assay for NO. SNP was readily metabolized to NO in subcellular fractions, and the dominant site of metabolism appeared to be located in the membrane fractions. NO-generating activity was significantly enhanced by, but did not absolutely require, the addition of a NADPH-regenerating system, NADPH per se, NADH or cysteine. A correlation analysis of NO-generating activity (in the presence of a NADPH-regenerating system) with marker enzyme activities indicated that the SNP-directed NO-generating activity was primarily membrane-associated. Radiation inactivation target-size analysis revealed that the microsomal SNP-directed NO-generating activity was relatively insensitive to inactivation by radiation exposure, suggesting that the functioning catalytic unit might be quite small. A molecular weight of 5 to 11 kDa was estimated. NO-generating activity could be solubilized from the crude microsomes with 3-[(3-cholamidopropyl)- dimethylammonio]-1-propane sulfonate, and the solubilized extract was subjected to gel filtration chromatography. NO-generating activity was eluted in two peaks: one peak corresponding to an approximate molecular weight of 4 kDa, thus confirming the existence of a small molecular weight NO-generating activity, and a second activity peak corresponding to a molecular weight of 112 to 169 kDa, the functional significance of which is unclear at present.(ABSTRACT TRUNCATED AT 250 WORDS)

Regulation of cell function by methionine oxidation and reduction

PubMed Central

Hoshi, Toshinori; Heinemann, Stefan H

2001-01-01

Reactive oxygen species (ROS) are generated during normal cellular activity and may exist in excess in some pathophysiological conditions, such as inflammation or reperfusion injury. These molecules oxidize a variety of cellular constituents, but sulfur-containing amino acid residues are especially susceptible. While reversible cysteine oxidation and reduction is part of well-established signalling systems, the oxidation and the enzymatically catalysed reduction of methionine is just emerging as a novel molecular mechanism for cellular regulation. Here we discuss how the oxidation of methionine to methionine sulfoxide in signalling proteins such as ion channels affects the function of these target proteins. Methionine sulfoxide reductase, which reduces methionine sulfoxide to methionine in a thioredoxin-dependent manner, is therefore not only an enzyme important for the repair of age- or degenerative disease-related protein modifications. It is also a potential missing link in the post-translational modification cycle involved in the specific oxidation and reduction of methionine residues in cellular signalling proteins, which may give rise to activity-dependent plastic changes in cellular excitability. PMID:11179387

Steam Oxidation of FeCrAl and SiC in the Severe Accident Test Station (SATS)

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

Pint, Bruce A.; Unocic, Kinga A.; Terrani, Kurt A.

2015-08-01

Numerous research projects are directed towards developing accident tolerant fuel (ATF) concepts that will enhance safety margins in light water reactors (LWR) during severe accident scenarios. In the U.S. program, the high temperature steam oxidation performance of ATF solutions has been evaluated in the Severe Accident Test Station (SATS) at Oak Ridge National Laboratory (ORNL) since 2012 [1-3] and this facility continues to support those efforts in the ATF community. Compared to the current UO2/Zr-based alloy fuel system, alternative cladding materials can offer slower oxidation kinetics and a smaller enthalpy of oxidation that can significantly reduce the rate of heatmore » and hydrogen generation in the core during a coolant-limited severe accident [4-5]. Thus, steam oxidation behavior is a key aspect of the evaluation of ATF concepts. This report summarizes recent work to measure steam oxidation kinetics of FeCrAl and SiC specimens in the SATS.« less

A lithotrophic microbial fuel cell operated with pseudomonads-dominated iron-oxidizing bacteria enriched at the anode

PubMed Central

Nguyen, Thuy Thu; Luong, Tha Thanh Thi; Tran, Phuong Hoang Nguyen; Bui, Ha Thi Viet; Nguyen, Huy Quang; Dinh, Hang Thuy; Kim, Byung Hong; Pham, Hai The

2015-01-01

In this study, we attempted to enrich neutrophilic iron bacteria in a microbial fuel cell (MFC)-type reactor in order to develop a lithotrophic MFC system that can utilize ferrous iron as an inorganic electron donor and operate at neutral pHs. Electrical currents were steadily generated at an average level of 0.6 mA (or 0.024 mA cm–2 of membrane area) in reactors initially inoculated with microbial sources and operated with 20 mM Fe2+ as the sole electron donor and 10 ohm external resistance; whereas in an uninoculated reactor (the control), the average current level only reached 0.2 mA (or 0.008 mA cm–2 of membrane area). In an inoculated MFC, the generation of electrical currents was correlated with increases in cell density of bacteria in the anode suspension and coupled with the oxidation of ferrous iron. Cultivation-based and denaturing gradient gel electrophoresis analyses both show the dominance of some Pseudomonas species in the anode communities of the MFCs. Fluorescent in-situ hybridization results revealed significant increases of neutrophilic iron-oxidizing bacteria in the anode community of an inoculated MFC. The results, altogether, prove the successful development of a lithotrophic MFC system with iron bacteria enriched at its anode and suggest a chemolithotrophic anode reaction involving some Pseudomonas species as key players in such a system. The system potentially offers unique applications, such as accelerated bioremediation or on-site biodetection of iron and/or manganese in water samples. PMID:25712332

Assessment of the GECKO-A Modeling Tool and Simplified 3D Model Parameterizations for SOA Formation

NASA Astrophysics Data System (ADS)

Aumont, B.; Hodzic, A.; La, S.; Camredon, M.; Lannuque, V.; Lee-Taylor, J. M.; Madronich, S.

2014-12-01

Explicit chemical mechanisms aim to embody the current knowledge of the transformations occurring in the atmosphere during the oxidation of organic matter. These explicit mechanisms are therefore useful tools to explore the fate of organic matter during its tropospheric oxidation and examine how these chemical processes shape the composition and properties of the gaseous and the condensed phases. Furthermore, explicit mechanisms provide powerful benchmarks to design and assess simplified parameterizations to be included 3D model. Nevertheless, the explicit mechanism describing the oxidation of hydrocarbons with backbones larger than few carbon atoms involves millions of secondary organic compounds, far exceeding the size of chemical mechanisms that can be written manually. Data processing tools can however be designed to overcome these difficulties and automatically generate consistent and comprehensive chemical mechanisms on a systematic basis. The Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) has been developed for the automatic writing of explicit chemical schemes of organic species and their partitioning between the gas and condensed phases. GECKO-A can be viewed as an expert system that mimics the steps by which chemists might develop chemical schemes. GECKO-A generates chemical schemes according to a prescribed protocol assigning reaction pathways and kinetics data on the basis of experimental data and structure-activity relationships. In its current version, GECKO-A can generate the full atmospheric oxidation scheme for most linear, branched and cyclic precursors, including alkanes and alkenes up to C25. Assessments of the GECKO-A modeling tool based on chamber SOA observations will be presented. GECKO-A was recently used to design a parameterization for SOA formation based on a Volatility Basis Set (VBS) approach. First results will be presented.

Changes in the Antioxidant Systems as Part of the Signaling Pathway Responsible for the Programmed Cell Death Activated by Nitric Oxide and Reactive Oxygen Species in Tobacco Bright-Yellow 2 Cells1

PubMed Central

de Pinto, Maria Concetta; Tommasi, Franca; De Gara, Laura

2002-01-01

Nitric oxide (NO) has been postulated to be required, together with reactive oxygen species (ROS), for the activation of the hypersensitive reaction, a defense response induced in the noncompatible plant-pathogen interaction. However, its involvement in activating programmed cell death (PCD) in plant cells has been questioned. In this paper, the involvement of the cellular antioxidant metabolism in the signal transduction triggered by these bioactive molecules has been investigated. NO and ROS levels were singularly or simultaneously increased in tobacco (Nicotiana tabacum cv Bright-Yellow 2) cells by the addition to the culture medium of NO and/or ROS generators. The individual increase in NO or ROS had different effects on the studied parameters than the simultaneous increase in the two reactive species. NO generation did not cause an increase in phenylalanine ammonia-lyase (PAL) activity or induction of cellular death. It only induced minor changes in ascorbate (ASC) and glutathione (GSH) metabolisms. An increase in ROS induced oxidative stress in the cells, causing an oxidation of the ASC and GSH redox pairs; however, it had no effect on PAL activity and did not induce cell death when it was generated at low concentrations. In contrast, the simultaneous increase of NO and ROS activated a process of death with the typical cytological and biochemical features of hypersensitive PCD and a remarkable rise in PAL activity. Under the simultaneous generation of NO and ROS, the cellular antioxidant capabilities were also suppressed. The involvement of ASC and GSH as part of the transduction pathway leading to PCD is discussed. PMID:12376637

The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System.

PubMed

Angelini, Francesco; Pagano, Francesca; Bordin, Antonella; Milan, Marika; Chimenti, Isotta; Peruzzi, Mariangela; Valenti, Valentina; Marullo, Antonino; Schirone, Leonardo; Palmerio, Silvia; Sciarretta, Sebastiano; Murdoch, Colin E; Frati, Giacomo; De Falco, Elena

2017-01-01

Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS) in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human's current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject's profile will be discussed.

The Impact of Environmental Factors in Influencing Epigenetics Related to Oxidative States in the Cardiovascular System

PubMed Central

Angelini, Francesco; Pagano, Francesca; Bordin, Antonella; Milan, Marika; Valenti, Valentina; Marullo, Antonino; Schirone, Leonardo; Palmerio, Silvia; Sciarretta, Sebastiano; Frati, Giacomo

2017-01-01

Oxidative states exert a significant influence on a wide range of biological and molecular processes and functions. When their balance is shifted towards enhanced amounts of free radicals, pathological phenomena can occur, as the generation of reactive oxygen species (ROS) in tissue microenvironment or in the systemic circulation can be detrimental. Epidemic chronic diseases of western societies, such as cardiovascular disease, obesity, and diabetes correlate with the imbalance of redox homeostasis. Current advances in our understanding of epigenetics have revealed a parallel scenario showing the influence of oxidative stress as a major regulator of epigenetic gene regulation via modification of DNA methylation, histones, and microRNAs. This has provided both the biological link and a potential molecular explanation between oxidative stress and cardiovascular/metabolic phenomena. Accordingly, in this review, we will provide current insights on the physiological and pathological impact of changes in oxidative states on cardiovascular disorders, by specifically focusing on the influence of epigenetic regulation. A special emphasis will highlight the effect on epigenetic regulation of human's current life habits, external and environmental factors, including food intake, tobacco, air pollution, and antioxidant-based approaches. Additionally, the strategy to quantify oxidative states in humans in order to determine which biological marker could best match a subject's profile will be discussed. PMID:28607629

Pharmacological models and approaches for pathophysiological conditions associated with hypoxia and oxidative stress.

PubMed

Farías, Jorge G; Herrera, Emilio A; Carrasco-Pozo, Catalina; Sotomayor-Zárate, Ramón; Cruz, Gonzalo; Morales, Paola; Castillo, Rodrigo L

2016-02-01

Hypoxia is the failure of oxygenation at the tissue level, where the reduced oxygen delivered is not enough to satisfy tissue demands. Metabolic depression is the physiological adaptation associated with reduced oxygen consumption, which evidently does not cause any harm to organs that are exposed to acute and short hypoxic insults. Oxidative stress (OS) refers to the imbalance between the generation of reactive oxygen species (ROS) and the ability of endogenous antioxidant systems to scavenge ROS, where ROS overwhelms the antioxidant capacity. Oxidative stress plays a crucial role in the pathogenesis of diseases related to hypoxia during intrauterine development and postnatal life. Thus, excessive ROS are implicated in the irreversible damage to cell membranes, DNA, and other cellular structures by oxidizing lipids, proteins, and nucleic acids. Here, we describe several pathophysiological conditions and in vivo and ex vivo models developed for the study of hypoxic and oxidative stress injury. We reviewed existing literature on the responses to hypoxia and oxidative stress of the cardiovascular, renal, reproductive, and central nervous systems, and discussed paradigms of chronic and intermittent hypobaric hypoxia. This systematic review is a critical analysis of the advantages in the application of some experimental strategies and their contributions leading to novel pharmacological therapies. Copyright © 2015 Elsevier Inc. All rights reserved.

Second-Order Biomimicry: In Situ Oxidative Self-Processing Converts Copper(I)/Diamine Precursor into a Highly Active Aerobic Oxidation Catalyst

PubMed Central

2017-01-01

A homogeneous Cu-based catalyst system consisting of [Cu(MeCN)4]PF6, N,N′-di-tert-butylethylenediamine (DBED), and p-(N,N-dimethylamino)pyridine (DMAP) mediates efficient aerobic oxidation of alcohols. Mechanistic study of this reaction shows that the catalyst undergoes an in situ oxidative self-processing step, resulting in conversion of DBED into a nitroxyl that serves as an efficient cocatalyst for aerobic alcohol oxidation. Insights into this behavior are gained from kinetic studies, which reveal an induction period at the beginning of the reaction that correlates with the oxidative self-processing step, EPR spectroscopic analysis of the catalytic reaction mixture, which shows the buildup of the organic nitroxyl species during steady state turnover, and independent synthesis of oxygenated DBED derivatives, which are shown to serve as effective cocatalysts and eliminate the induction period in the reaction. The overall mechanism bears considerable resemblance to enzymatic reactivity. Most notable is the “oxygenase”-type self-processing step that mirrors generation of catalytic cofactors in enzymes via post-translational modification of amino acid side chains. This higher-order function within a synthetic catalyst system presents new opportunities for the discovery and development of biomimetic catalysts. PMID:28470049

Ferrous ion as a reducing agent in the generation of antibiofilm nitric oxide from a copper-based catalytic system.

PubMed

Wonoputri, Vita; Gunawan, Cindy; Liu, Sanly; Barraud, Nicolas; Yee, Lachlan H; Lim, May; Amal, Rose

2018-05-01

The work found that the electron-donating properties of ferrous ions (Fe 2+ ) can be used for the conversion of nitrite (NO 2 - ) into the biofilm-dispersing signal nitric oxide (NO) by a copper(II) complex (CuDTTCT) catalyst, a potentially applicable biofilm control technology for the water industries. The availability of Fe 2+ varied depending on the characteristics of the aqueous systems (phosphate- and carbonate-containing nitrifying bacteria growth medium, NBGM and phosphate buffered saline, PBS at pH 6 to 8, to simulate conditions typically present in the water industries) and was found to affect the production of NO from nitrite by CuDTTCT (casted into PVC). Greater amounts of NO were generated from the CuDTTCT-nitrite-Fe 2+ systems in PBS compared to those in NBGM, which was associated with the reduced extent of Fe 2+ -to-Fe 3+ autoxidation by the iron-precipitating moieties phosphates and carbonate in the former system. Further, acidic conditions at pH 6.0 were found to favor NO production from the catalytic system in both PBS and NBGM compared to neutral or basic pH (pH 7.0 or 8.0). Lower pH was shown to stabilize Fe 2+ and reduce its autoxidation to Fe 3+ . These findings will be beneficial for the potential implementation of the NO-generating catalytic technology and indeed, a 'non-killing' biofilm dispersal activity of CuDTTCT-nitrite-Fe 2+ was observed on nitrifying bacteria biofilms in PBS at pH 6. Copyright © 2018 Elsevier Inc. All rights reserved.

SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOFC

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

Steven Shaffer; Sean Kelly; Subhasish Mukerjee

2003-06-09

The objective of Phase I under this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with piped-in water (Demonstration System A); and Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustionmore » engine. This technical progress report covers work performed by Delphi from July through December 2002 under Department of Energy Cooperative Agreement DE-FC-02NT41246 for the 5 kW mass-market automotive (gasoline) auxiliary power unit. This report highlights technical results of the work performed under the following tasks for the automotive 5 kW system: Task 1--System Design and Integration; Task 2--Solid Oxide Fuel Cell Stack Developments; Task 3--Reformer Developments; Task 4--Development of Balance of Plant (BOP) Components; Task 5--Manufacturing Development (Privately Funded); Task 6--System Fabrication; and Task 7--System Testing.« less

Flammability Analysis For Actinide Oxides Packaged In 9975 Shipping Containers

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

Laurinat, James E.; Askew, Neal M.; Hensel, Steve J.

2013-03-21

Packaging options are evaluated for compliance with safety requirements for shipment of mixed actinide oxides packaged in a 9975 Primary Containment Vessel (PCV). Radiolytic gas generation rates, PCV internal gas pressures, and shipping windows (times to reach unacceptable gas compositions or pressures after closure of the PCV) are calculated for shipment of a 9975 PCV containing a plastic bottle filled with plutonium and uranium oxides with a selected isotopic composition. G-values for radiolytic hydrogen generation from adsorbed moisture are estimated from the results of gas generation tests for plutonium oxide and uranium oxide doped with curium-244. The radiolytic generation ofmore » hydrogen from the plastic bottle is calculated using a geometric model for alpha particle deposition in the bottle wall. The temperature of the PCV during shipment is estimated from the results of finite element heat transfer analyses.« less

The role of oxidative stress in the pathophysiology of hypertension.

PubMed

Rodrigo, Ramón; González, Jaime; Paoletto, Fabio

2011-04-01

Hypertension is considered to be the most important risk factor in the development of cardiovascular disease. An increasing body of evidence suggests that oxidative stress, which results in an excessive generation of reactive oxygen species (ROS), has a key role in the pathogenesis of hypertension. The modulation of the vasomotor system involves ROS as mediators of vasoconstriction induced by angiotensin II, endothelin-1 and urotensin-II, among others. The bioavailability of nitric oxide (NO), which is a major vasodilator, is highly dependent on the redox status. Under physiological conditions, low concentrations of intracellular ROS have an important role in the normal redox signaling maintaining vascular function and integrity. However, under pathophysiological conditions, increased levels of ROS contribute to vascular dysfunction and remodeling through oxidative damage. In human hypertension, an increase in the production of superoxide anions and hydrogen peroxide, a decrease in NO synthesis and a reduction in antioxidant bioavailability have been observed. In turn, antioxidants are reducing agents that can neutralize these oxidative and otherwise damaging biomolecules. The use of antioxidant vitamins, such as vitamins C and E, has gained considerable interest as protecting agents against vascular endothelial damage. Available data support the role of these vitamins as effective antioxidants that can counteract ROS effects. This review discusses the mechanisms involved in ROS generation, the role of oxidative stress in the pathogenesis of vascular damage in hypertension, and the possible therapeutic strategies that could prevent or treat this disorder.

Limitations in Using Chemical Oxidative Potential to Understand Oxidative Stress from Particulate Matter

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Wang, S.; Wang, X.; Kohl, L.; Chow, C. W.

2017-12-01

Particulate matter (PM) in the atmosphere is known to cause adverse cardiorespiratory health effects. It has been suggested that the ability of PM to generate oxidative stress leads to a proinflammatory response. In this work, we study the biological relevance of using a chemical oxidative potential (OP) assay to evaluate proinflammatory response in airway epithelial cells. Here we study the OPs of laboratory secondary organic aerosol (SOA) and metal mixtures, ambient PM from India, ash from the 2016 Alberta wildfires, and diesel exhaust particles. We use SOA derived from naphthalene and from monoterpenes as model systems for SOA. We measure OP using the dithiothreitol (DTT) assay, and cytosolic reactive oxygen species (ROS) production in BEAS-2B cell culture was measured using CellROX assay. We found that both SOA and copper show high OPs individually, but the OP of the combined SOA/copper mixture, which is more atmospherically relevant, was lower than either of the individual OPs. The reduced activity is attributed to chelation between metals and organic compounds using proton nuclear magnetic resonance. There is reasonable association between DTT activity and cellular ROS production within each particle type, but weak association across different particle types, suggesting that particle composition plays an important role in distinguishing between antioxidant consumption and ROS production. Our results highlight that while oxidative potential is a useful metric of PM's ability to generate oxidative stress, the chemical composition and cellular environment should be considered in understanding health impacts of PM.

Multicomponent kinetic analysis and theoretical studies on the phenolic intermediates in the oxidation of eugenol and isoeugenol catalyzed by laccase.

PubMed

Qi, Yan-Bing; Wang, Xiao-Lei; Shi, Ting; Liu, Shuchang; Xu, Zhen-Hao; Li, Xiqing; Shi, Xuling; Xu, Ping; Zhao, Yi-Lei

2015-11-28

Laccase catalyzes the oxidation of natural phenols and thereby is believed to initialize reactions in lignification and delignification. Numerous phenolic mediators have also been applied in laccase-mediator systems. However, reaction details after the primary O-H rupture of phenols remain obscure. In this work two types of isomeric phenols, EUG (eugenol) and ISO (trans-/cis-isoeugenol), were used as chemical probes to explore the enzymatic reaction pathways, with the combined methods of time-resolved UV-Vis absorption spectra, MCR-ALS, HPLC-MS, and quantum mechanical (QM) calculations. It has been found that the EUG-consuming rate is linear to its concentration, while the ISO not. Besides, an o-methoxy quinone methide intermediate, (E/Z)-4-allylidene-2-methoxycyclohexa-2,5-dienone, was evidenced in the case of EUG with the UV-Vis measurement, mass spectra and TD-DFT calculations; in contrast, an ISO-generating phenoxyl radical, a (E/Z)-2-methoxy-4-(prop-1-en-1-yl) phenoxyl radical, was identified in the case of ISO. Furthermore, QM calculations indicated that the EUG-generating phenoxyl radical (an O-centered radical) can easily transform into an allylic radical (a C-centered radical) by hydrogen atom transfer (HAT) with a calculated activation enthalpy of 5.3 kcal mol(-1) and then be fast oxidized to the observed eugenol quinone methide, rather than an O-radical alkene addition with barriers above 12.8 kcal mol(-1). In contrast, the ISO-generating phenoxyl radical directly undergoes a radical coupling (RC) process, with a barrier of 4.8 kcal mol(-1), while the HAT isomerization between O- and C-centered radicals has a higher reaction barrier of 8.0 kcal mol(-1). The electronic conjugation of the benzyl-type radical and the aromatic allylic radical leads to differentiation of the two pathways. These results imply that competitive reaction pathways exist for the nascent reactive intermediates generated in the laccase-catalyzed oxidation of natural phenols, which is important for understanding the lignin polymerization and may shed some light on the development of efficient laccase-mediator systems.

Solid oxide fuel cell generator

DOEpatents

Draper, Robert; George, Raymond A.; Shockling, Larry A.

1993-01-01

A solid oxide fuel cell generator has a pair of spaced apart tubesheets in a housing. At least two intermediate barrier walls are between the tubesheets and define a generator chamber between two intermediate buffer chambers. An array of fuel cells have tubes with open ends engaging the tubesheets. Tubular, axially elongated electrochemical cells are supported on the tubes in the generator chamber. Fuel gas and oxidant gas are preheated in the intermediate chambers by the gases flowing on the other side of the tubes. Gas leakage around the tubes through the tubesheets is permitted. The buffer chambers reentrain the leaked fuel gas for reintroduction to the generator chamber.

Study on the Treatment of Wastewater Generated at KSC (Kennedy Space Center) STS (Space Transport System) Operations and Projected Effects on the Design of the STS Hazardous Waste Management Facility at Vandenberg AFB, California.

DTIC Science & Technology

1983-10-01

carbon monoxide gas (mostly converted to carbon dioxide during afterburning), alu- minum oxide particles, and hydrogen chloride gas. Additionally, a great...colorimetrically or with an oxidation -reduction probe (ORP). The laboratory tests used a colorimetric indi- cator N.N.-Dimethyl-P-Phenylene Diamine Sulfate...in the composite wastewater sample under both quiescent and dynamic conditions to determine the corrosivity of the fluid . The procedures followed and

Characterization of the Terminal Iron(IV) Imides {[PhBPtBu2(pz’)]FeIV≡NAd}+

PubMed Central

Thomas, Christine M.; Mankad, Neal P.; Peters, Jonas C.

2008-01-01

New hybrid bis(phosphine)(pyrazole)borate tripodal ligands ([PhBPtBu2(pz’)]−) are reported that support pseudotetrahedral iron in the oxidation states +1, +2, +3, and +4. The higher oxidation states are stabilized by a terminal Fe≡NR linkage. Of particular interest is the generation and thorough characterization of an S = 1 FeIV≡NR+ imide cation using this new ligand system. The latter species can be observed electrochemically and spectroscopically, and its solid-state crystal structure is reported. PMID:16608321

Relationship between anode material, supporting electrolyte and current density during electrochemical degradation of organic compounds in water.

PubMed

Guzmán-Duque, Fernando L; Palma-Goyes, Ricardo E; González, Ignacio; Peñuela, Gustavo; Torres-Palma, Ricardo A

2014-08-15

Taking crystal violet (CV) dye as pollutant model, the electrode, electrolyte and current density (i) relationship for electro-degrading organic molecules is discussed. Boron-doped diamond (BDD) or Iridium dioxide (IrO2) used as anode materials were tested with Na2SO4 or NaCl as electrolytes. CV degradation and generated oxidants showed that degradation pathways and efficiency are strongly linked to the current density-electrode-electrolyte interaction. With BDD, the degradation pathway depends on i: If ii(lim), generated oxidants play a major role in the CV elimination. When IrO2 was used, CV removal was not dependent on i, but on the electrolyte. Pollutant degradation in Na2SO4 on IrO2 seems to occur via IrO3; however, in the presence of NaCl, degradation was dependent on the chlorinated oxidative species generated. In terms of efficiency, the Na2SO4 electrolyte showed better results than NaCl when BDD anodes were employed. On the contrary, NaCl was superior when combined with IrO2. Thus, the IrO2/Cl(-) and BDD/SO4(2-) systems were better at removing the pollutant, being the former the most effective. On the other hand, pollutant degradation with the BDD/SO4(2-) and IrO2/Cl(-) systems is favored at low and high current densities, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Hydrogen generation from natural gas for the fuel cell systems of tomorrow

NASA Astrophysics Data System (ADS)

Dicks, Andrew L.

In most cases hydrogen is the preferred fuel for use in the present generation of fuel cells being developed for commercial applications. Of all the potential sources of hydrogen, natural gas offers many advantages. It is widely available, clean, and can be converted to hydrogen relatively easily. When catalytic steam reforming is used to generate hydrogen from natural gas, it is essential that sulfur compounds in the natural gas are removed upstream of the reformer and various types of desulfurisation processes are available. In addition, the quality of fuel required for each type of fuel cell varies according to the anode material used, and the cell temperature. Low temperature cells will not tolerate high concentrations of carbon monoxide, whereas the molten fuel cell (MCFC) and solid oxide fuel cell (SOFC) anodes contain nickel on which it is possible to electrochemically oxidise carbon monoxide directly. The ability to internally reform fuel gas is a feature of the MCFC and SOFC. Internal reforming can give benefits in terms of increased electrical efficiency owing to the reduction in the required cell cooling and therefore parasitic system losses. Direct electrocatalysis of hydrocarbon oxidation has been the elusive goal of fuel cell developers over many years and recent laboratory results are encouraging. This paper reviews the principal methods of converting natural gas into hydrogen, namely catalytic steam reforming, autothermic reforming, pyrolysis and partial oxidation; it reviews currently available purification techniques and discusses some recent advances in internal reforming and the direct use of natural gas in fuel cells.

Segregated exhaust SOFC generator with high fuel utilization capability

DOEpatents

Draper, Robert; Veyo, Stephen E.; Kothmann, Richard E.

2003-08-26

A fuel cell generator contains a plurality of fuel cells (6) in a generator chamber (1) and also contains a depleted fuel reactor or a fuel depletion chamber (2) where oxidant (24,25) and fuel (81) is fed to the generator chamber (1) and the depleted fuel reactor chamber (2), where both fuel and oxidant react, and where all oxidant and fuel passages are separate and do not communicate with each other, so that fuel and oxidant in whatever form do not mix and where a depleted fuel exit (23) is provided for exiting a product gas (19) which consists essentially of carbon dioxide and water for further treatment so that carbon dioxide can be separated and is not vented to the atmosphere.

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

PubMed

Su, Yiming; Jassby, David; Song, Shikun; Zhou, Xuefei; Zhao, Hongying; Filip, Jan; Petala, Eleni; Zhang, Yalei

2018-06-05

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H 2 O 2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.

Inhibitory Effect of Dissolved Silica on the H2O2 Decomposition by Iron(III) and Manganese(IV) Oxides: Implications for H2O2-based In Situ Chemical Oxidation

PubMed Central

Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

2011-01-01

The decomposition of H2O2 on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H2O2, because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand and montmorillonite that were pre-equilibrated with 0.05 – 1.5 mM SiO2 were significantly less reactive toward H2O2 decomposition than their original counterparts, with the H2O2 loss rates inversely proportional to the SiO2 concentration. In the goethite/H2O2 system, the overall •OH yield, defined as the percentage of decomposed H2O2 producing •OH, was almost halved in the presence of 1.5 mM SiO2. Dissolved SiO2 also slows the H2O2 decomposition on manganese(IV) oxide. The presence of dissolved SiO2 results in greater persistence of H2O2 in groundwater, lower H2O2 utilization efficiency and should be considered in the design of H2O2-based treatment systems. PMID:22129132

Modeling of gas turbine - solid oxide fuel cell systems for combined propulsion and power on aircraft

NASA Astrophysics Data System (ADS)

Waters, Daniel Francis

This dissertation investigates the use of gas turbine (GT) engine integrated solid oxide fuel cells (SOFCs) to reduce fuel burn in aircraft with large electrical loads like sensor-laden unmanned air vehicles (UAVs). The concept offers a number of advantages: the GT absorbs many SOFC balance of plant functions (supplying fuel, air, and heat to the fuel cell) thereby reducing the number of components in the system; the GT supplies fuel and pressurized air that significantly increases SOFC performance; heat and unreacted fuel from the SOFC are recaptured by the GT cycle offsetting system-level losses; good transient response of the GT cycle compensates for poor transient response of the SOFC. The net result is a system that can supply more electrical power more efficiently than comparable engine-generator systems with only modest (<10%) decrease in power density. Thermodynamic models of SOFCs, catalytic partial oxidation (CPOx) reactors, and three GT engine types (turbojet, combined exhaust turbofan, separate exhaust turbofan) are developed that account for equilibrium gas phase and electrochemical reaction, pressure losses, and heat losses in ways that capture `down-the-channel' effects (a level of fidelity necessary for making meaningful performance, mass, and volume estimates). Models are created in a NASA-developed environment called Numerical Propulsion System Simulation (NPSS). A sensitivity analysis identifies important design parameters and translates uncertainties in model parameters into uncertainties in overall performance. GT-SOFC integrations reduce fuel burn 3-4% in 50 kW systems on 35 kN rated engines (all types) with overall uncertainty <1%. Reductions of 15-20% are possible at the 200 kW power level. GT-SOFCs are also able to provide more electric power (factors >3 in some cases) than generator-based systems before encountering turbine inlet temperature limits. Aerodynamic drag effects of engine-airframe integration are by far the most important limiter of the combined propulsion/electrical generation concept. However, up to 100-200 kW can be produced in a bypass ratio = 8, overall pressure ratio = 40 turbofan with little or no drag penalty. This study shows that it is possible to create cooperatively integrated GT-SOFC systems for combined propulsion and power with better overall performance than stand-alone components.

Systems-Level Feedbacks of NRF2 Controlling Autophagy upon Oxidative Stress Response

PubMed Central

Kapuy, Orsolya; Papp, Diána; Bánhegyi, Gábor

2018-01-01

Although the primary role of autophagy-dependent cellular self-eating is cytoprotective upon various stress events (such as starvation, oxidative stress, and high temperatures), sustained autophagy might lead to cell death. A transcription factor called NRF2 (nuclear factor erythroid-related factor 2) seems to be essential in maintaining cellular homeostasis in the presence of either reactive oxygen or nitrogen species generated by internal metabolism or external exposure. Accumulating experimental evidence reveals that oxidative stress also influences the balance of the 5′ AMP-activated protein kinase (AMPK)/rapamycin (mammalian kinase target of rapamycin or mTOR) signaling pathway, thereby inducing autophagy. Based on computational modeling here we propose that the regulatory triangle of AMPK, NRF2 and mTOR guaranties a precise oxidative stress response mechanism comprising of autophagy. We suggest that under conditions of oxidative stress, AMPK is crucial for autophagy induction via mTOR down-regulation, while NRF2 fine-tunes the process of autophagy according to the level of oxidative stress. We claim that the cellular oxidative stress response mechanism achieves an incoherently amplified negative feedback loop involving NRF2, mTOR and AMPK. The mTOR-NRF2 double negative feedback generates bistability, supporting the proper separation of two alternative steady states, called autophagy-dependent survival (at low stress) and cell death (at high stress). In addition, an AMPK-mTOR-NRF2 negative feedback loop suggests an oscillatory characteristic of autophagy upon prolonged intermediate levels of oxidative stress, resulting in new rounds of autophagy stimulation until the stress events cannot be dissolved. Our results indicate that AMPK-, NRF2- and mTOR-controlled autophagy induction provides a dynamic adaptation to altering environmental conditions, assuming their new frontier in biomedicine. PMID:29510589

Minerals Masquerading As Enzymes: Abiotic Oxidation Of Soil Organic Matter In An Iron-Rich Humid Tropical Forest Soil

NASA Astrophysics Data System (ADS)

Hall, S. J.; Silver, W. L.

2010-12-01

Oxidative reactions play an important role in decomposing soil organic matter fractions that resist hydrolytic degradation, and fundamentally affect the cycling of recalcitrant soil carbon across ecosystems. Microbial extracellular oxidative enzymes (e.g. lignin peroxidases and laccases) have been assumed to provide a dominant role in catalyzing soil organic matter oxidation, while other potential oxidative mechanisms remain poorly explored. Here, we show that abiotic reactions mediated by the oxidation of ferrous iron (Fe(II)) could explain high potential oxidation rates in humid tropical forest soils, which often contain high concentrations of Fe(II) and experience rapid redox fluctuations between anaerobic and aerobic conditions. These abiotic reactions could provide an additional mechanism to explain high rates of decomposition in these ecosystems, despite frequent oxygen deficits. We sampled humid tropical forest soils in Puerto Rico, USA from various topographic positions, ranging from well-drained ridges to riparian valleys that experience broad fluctuations in redox potential. We measured oxidative activity by adding the model humic compound L-DOPA to soil slurries, followed by colorimetric measurements of the supernatant solution over time. Dilute hydrogen peroxide was added to a subset of slurries to measure peroxidative activity. We found that oxidative and peroxidative activity correlated positively with soil Fe(II) concentrations, counter to prevailing theory that low redox potential should suppress oxidative enzymes. Boiling or autoclaving sub-samples of soil slurries to denature any enzymes present typically increased peroxidative activity and did not eliminate oxidative activity, further suggesting the importance of an abiotic mechanism. We found substantial differences in the oxidation products of the L-DOPA substrate generated by our soil slurries in comparison with oxidation products generated by a purified enzyme (mushroom tyrosinase). Tyrosinase generated a red compound (dopachrome) that is the target analyte of the traditional L-DOPA oxidative enzyme assay, whereas our soil slurries generated purple melanin-like compounds that were likely generated by more extensive oxidation. To investigate the importance of Fe(II) for L-DOPA oxidation, we added realistic concentrations of Fe(II) (equivalent to 10 - 500 μg Fe g-1 soil) to an L-DOPA buffer solution under oxic conditions, and found rates of L-DOPA oxidation comparable to those from soil slurries. Molecular oxygen and Fe(II) are known to generate strong oxidants via Fenton reactions. We decreased L-DOPA oxidation rates in soil slurries by adding catalase and superoxide-dismutase enzymes to scavenge reactive oxygen species, suggesting that a free-radical mechanism contributed to L-DOPA oxidation. We obtained similar results using another humic model compound, tetramethylbenzidine (TMB). Although abiotic oxidative reactions involving iron have been employed to degrade anthropogenic organic contaminants, this study is among the first to demonstrate their potential importance for oxidizing organic matter in natural ecosystems. In soils rich in Fe(II), abiotic reactions could complement, or even obviate, the role of microbial oxidative enzymes in degrading recalcitrant organic compounds.

The production of nitric oxide in the coeliac ganglion modulates the effect of cholinergic neurotransmission on the rat ovary during the preovulatory period.

PubMed

Delsouc, María B; Della Vedova, María C; Ramírez, Darío; Delgado, Silvia M; Casais, Marilina

2018-05-01

The aim of the present work was to investigate whether the nitric oxide produced by the nitric oxide/nitric oxide synthase (NO/NOS) system present in the coeliac ganglion modulates the effects of cholinergic innervation on oxidative status, steroidogenesis and apoptotic mechanisms that take place in the rat ovary during the first proestrous. An ex vivo Coeliac Ganglion- Superior Ovarian Nerve- Ovary (CG-SON-O) system was used. Cholinergic stimulation of the CG was achieved by 10 -6  M Acetylcholine (Ach). Furthermore, 400 μM Aminoguanidine (AG) - an inhibitor of inducible-NOS was added in the CG compartment in absence and presence of Ach. It was found that Ach in the CG compartment promotes apoptosis in ovarian tissue, probably due to the oxidative stress generated. AG in the CG compartment decreases the release of NO and progesterone, and increases the release of estradiol from the ovary. The CG co-treatment with Ach and AG counteracts the effects of the ganglionic cholinergic agonist on ovarian oxidative stress, increases hormone production and decreases Fas mRNA expression. These results suggest that NO is an endogenous modulator of cholinergic neurotransmission in CG, with implication in ovarian steroidogenesis and the apoptotic mechanisms that take place in the ovary during the preovulatory period in rats. Copyright © 2018 Elsevier Inc. All rights reserved.

From chemolithoautotrophs to electrolithoautotrophs: CO2 fixation by Fe(II)-oxidizing bacteria coupled with direct uptake of electrons from solid electron sources.

PubMed

Ishii, Takumi; Kawaichi, Satoshi; Nakagawa, Hirotaka; Hashimoto, Kazuhito; Nakamura, Ryuhei

2015-01-01

At deep-sea vent systems, hydrothermal emissions rich in reductive chemicals replace solar energy as fuels to support microbial carbon assimilation. Until recently, all the microbial components at vent systems have been assumed to be fostered by the primary production of chemolithoautotrophs; however, both the laboratory and on-site studies demonstrated electrical current generation at vent systems and have suggested that a portion of microbial carbon assimilation is stimulated by the direct uptake of electrons from electrically conductive minerals. Here we show that chemolithoautotrophic Fe(II)-oxidizing bacterium, Acidithiobacillus ferrooxidans, switches the electron source for carbon assimilation from diffusible Fe(2+) ions to an electrode under the condition that electrical current is the only source of energy and electrons. Site-specific marking of a cytochrome aa3 complex (aa3 complex) and a cytochrome bc1 complex (bc1 complex) in viable cells demonstrated that the electrons taken directly from an electrode are used for O2 reduction via a down-hill pathway, which generates proton motive force that is used for pushing the electrons to NAD(+) through a bc1 complex. Activation of carbon dioxide fixation by a direct electron uptake was also confirmed by the clear potential dependency of cell growth. These results reveal a previously unknown bioenergetic versatility of Fe(II)-oxidizing bacteria to use solid electron sources and will help with understanding carbon assimilation of microbial components living in electronically conductive chimney habitats.

From chemolithoautotrophs to electrolithoautotrophs: CO2 fixation by Fe(II)-oxidizing bacteria coupled with direct uptake of electrons from solid electron sources

PubMed Central

Ishii, Takumi; Kawaichi, Satoshi; Nakagawa, Hirotaka; Hashimoto, Kazuhito; Nakamura, Ryuhei

2015-01-01

At deep-sea vent systems, hydrothermal emissions rich in reductive chemicals replace solar energy as fuels to support microbial carbon assimilation. Until recently, all the microbial components at vent systems have been assumed to be fostered by the primary production of chemolithoautotrophs; however, both the laboratory and on-site studies demonstrated electrical current generation at vent systems and have suggested that a portion of microbial carbon assimilation is stimulated by the direct uptake of electrons from electrically conductive minerals. Here we show that chemolithoautotrophic Fe(II)-oxidizing bacterium, Acidithiobacillus ferrooxidans, switches the electron source for carbon assimilation from diffusible Fe2+ ions to an electrode under the condition that electrical current is the only source of energy and electrons. Site-specific marking of a cytochrome aa3 complex (aa3 complex) and a cytochrome bc1 complex (bc1 complex) in viable cells demonstrated that the electrons taken directly from an electrode are used for O2 reduction via a down-hill pathway, which generates proton motive force that is used for pushing the electrons to NAD+ through a bc1 complex. Activation of carbon dioxide fixation by a direct electron uptake was also confirmed by the clear potential dependency of cell growth. These results reveal a previously unknown bioenergetic versatility of Fe(II)-oxidizing bacteria to use solid electron sources and will help with understanding carbon assimilation of microbial components living in electronically conductive chimney habitats. PMID:26500609

Oxygen Reduction Reaction on Graphene in an Electro-Fenton System: In Situ Generation of H2 O2 for the Oxidation of Organic Compounds.

PubMed

Chen, Chen-Yu; Tang, Cheng; Wang, Hao-Fan; Chen, Cheng-Meng; Zhang, Xiaoyuan; Huang, Xia; Zhang, Qiang

2016-05-23

Fenton oxidation using an aqueous mixture of Fe(2+) and H2 O2 is a promising environmental remediation strategy. However, the difficulty of storage and shipment of concentrated H2 O2 and the generation of iron sludge limit its broad application. Therefore, highly efficient and cost-effective electrocatalysts are in great need. Herein, a graphene catalyst is proposed for the electro-Fenton process, in which H2 O2 is generated in situ by the two-electron reduction of the dissolved O2 on the cathode and then decomposes to generate (.) OH in acidic solution with Fe(2+) . The π bond of the oxygen is broken whereas the σ bond is generally preserved on the metal-free reduced graphene oxide owing to the high free energy change. Consequently, the oxygen is reduced to H2 O2 through a two-electron pathway. The thermally reduced graphene with a high specific surface area (308.8 m(2)  g(-1) ) and a large oxygen content (10.3 at %) exhibits excellent reactivity for the two-electron oxygen reduction reaction to H2 O2 . A highly efficient peroxide yield (64.2 %) and a remarkable decolorization of methylene blue (12 mg L(-1) ) of over 97 % in 160 min are obtained. The degradation of methylene blue with hydroxyl radicals generated in situ is described by a pseudo first-order kinetics model. This provides a proof-of-concept of an environmentally friendly electro-Fenton process using graphene for the oxygen reduction reaction in an acidic solution to generate H2 O2 . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Geochemical signatures of thermochemical sulfate reduction in controlled hydrous pyrolysis experiments

USGS Publications Warehouse

Zhang, T.; Ellis, G.S.; Walters, C.C.; Kelemen, S.R.; Wang, K.-s.; Tang, Y.

2008-01-01

A series of gold tube hydrous pyrolysis experiments was conducted in order to investigate the effect of thermochemical sulfate reduction (TSR) on gas generation, residual saturated hydrocarbon compositional alteration, and solid pyrobitumen formation. The intensity of TSR significantly depends on the H2O/MgSO4 mole ratio, the smaller the ratio, the stronger the oxidizing conditions. Under highly oxidizing conditions (MgSO4/hydrocarbon wt/wt 20/1 and hydrocarbon/H2O wt/wt 1/1), large amounts of H2S and CO2 are generated indicating that hydrocarbon oxidation coupled with sulfate reduction is the dominant reaction. Starting with a mixture of C21-C35 n-alkanes, these hydrocarbons are consumed totally at temperatures below the onset of hydrocarbon thermal cracking in the absence of TSR (400 ??C). Moreover, once the longer chain length hydrocarbons are oxidized, secondarily formed hydrocarbons, even methane, are oxidized to CO2. Using whole crude oils as the starting reactants, the TSR reaction dramatically lowers the stability of hydrocarbons leading to increases in gas dryness and gas/oil ratio. While their concentrations decrease, the relative distributions of n-alkanes do not change appreciably from the original composition, and consequently, are non-diagnostic for TSR. However, distinct molecular changes related to TSR are observed, Pr/n-C17 and Ph/n-C18 ratios decrease at a faster rate under TSR compared to thermal chemical alteration (TCA) alone. TSR promotes aromatization and the incorporation of sulfur and oxygen into hydrocarbons leading to a decrease in the saturate to aromatic ratio in the residual oil and in the generation of sulfur and oxygen rich pyrobitumen. These experimental findings could provide useful geochemical signatures to identify TSR in settings where TSR has occurred in natural systems. ?? 2008 Elsevier Ltd. All rights reserved.

Effects of water chemistry on arsenic removal from drinking water by electrocoagulation.

PubMed

Wan, Wei; Pepping, Troy J; Banerji, Tuhin; Chaudhari, Sanjeev; Giammar, Daniel E

2011-01-01

Exposure to arsenic through drinking water poses a threat to human health. Electrocoagulation is a water treatment technology that involves electrolytic oxidation of anode materials and in-situ generation of coagulant. The electrochemical generation of coagulant is an alternative to using chemical coagulants, and the process can also oxidize As(III) to As(V). Batch electrocoagulation experiments were performed in the laboratory using iron electrodes. The experiments quantified the effects of pH, initial arsenic concentration and oxidation state, and concentrations of dissolved phosphate, silica and sulfate on the rate and extent of arsenic removal. The iron generated during electrocoagulation precipitated as lepidocrocite (γ-FeOOH), except when dissolved silica was present, and arsenic was removed by adsorption to the lepidocrocite. Arsenic removal was slower at higher pH. When solutions initially contained As(III), a portion of the As(III) was oxidized to As(V) during electrocoagulation. As(V) removal was faster than As(III) removal. The presence of 1 and 4 mg/L phosphate inhibited arsenic removal, while the presence of 5 and 20 mg/L silica or 10 and 50 mg/L sulfate had no significant effect on arsenic removal. For most conditions examined in this study, over 99.9% arsenic removal efficiency was achieved. Electrocoagulation was also highly effective at removing arsenic from drinking water in field trials conducted in a village in Eastern India. By using operation times long enough to produce sufficient iron oxide for removal of both phosphate and arsenate, the performance of the systems in field trials was not inhibited by high phosphate concentrations. Copyright © 2010 Elsevier Ltd. All rights reserved.

Studies on oxidants and antioxidants with a brief glance at their relevance to the immune system.

PubMed

Amir Aslani, Banafsheh; Ghobadi, Sirous

2016-02-01

Free radical generation occurs continuously within cells as a consequence of common metabolic processes. However, in high concentrations, whether from endogenous or exogenous sources, free radicals can lead to oxidative stress; a harmful process that cause serious damages to all biomolecules in our body hence impairs cell functions and even results in cell death and diseased states. Oxidative injuries accumulate over time and participate in cancer development, cardiovascular and neurodegenerative disorders as well as aging. Nature has bestowed the human body with a complex web of antioxidant defense system including enzymatic antioxidants like glutathione peroxidase and glutathione reductase, catalase and superoxide dismutase as well as non-enzymatic antioxidants such as thiol antioxidants, melatonin, coenzyme Q, and metal chelating proteins, which are efficient enough to fight against excessive free radicals. Also, nutrient antioxidants such as vitamin C, vitamin E, carotenoids, polyphenols, and trace elements are known to have high antioxidant potency to assist in minimizing harmful effects of reactive species. The immune system is also extremely vulnerable to oxidant and antioxidant balance as uncontrolled free radical production can impair its function and defense mechanism. The present paper reviews the ways by which free radicals form in the body and promote tissue damage, as well as the role of the antioxidants defense mechanisms. Finally, we will have a brief glance at oxidants and antioxidants relevance to the immune system. Copyright © 2016 Elsevier Inc. All rights reserved.

Processing and Characterization of Sol-Gel Cerium Oxide Microspheres

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

McClure, Zachary D.; Padilla Cintron, Cristina

Of interest to space exploration and power generation, Radioisotope Thermoelectric Generators (RTGs) can provide long-term power to remote electronic systems without the need for refueling or replacement. Plutonium-238 (Pu-238) remains one of the more promising materials for thermoelectric power generation due to its high power density, long half-life, and low gamma emissions. Traditional methods for processing Pu-238 include ball milling irregular precipitated powders before pressing and sintering into a dense pellet. The resulting submicron particulates of Pu-238 quickly accumulate and contaminate glove boxes. An alternative and dust-free method for Pu-238 processing is internal gelation via sol-gel techniques. Sol-gel methodology createsmore » monodisperse and uniform microspheres that can be packed and pressed into a pellet. For this study cerium oxide microspheres were produced as a surrogate to Pu-238. The similar electronic orbitals between cerium and plutonium make cerium an ideal choice for non-radioactive work. Before the microspheres can be sintered and pressed they must be washed to remove the processing oil and any unreacted substituents. An investigation was performed on the washing step to find an appropriate wash solution that reduced waste and flammable risk. Cerium oxide microspheres were processed, washed, and characterized to determine the effectiveness of the new wash solution.« less

Nitric oxide mediates alginate oligosaccharides-induced root development in wheat (Triticum aestivum L.).

PubMed

Zhang, Yunhong; Liu, Hang; Yin, Heng; Wang, Wenxia; Zhao, Xiaoming; Du, Yuguang

2013-10-01

Alginate oligosaccharides (AOS), which are marine oligosaccharides, are involved in regulating plant root growth, but the promotion mechanism for AOS remains unclear. Here, AOS (10-80 mg L(-1)) were found to induce the generation of nitric oxide (NO) in the root system of wheat (Triticum aestivum L.), which promoted the formation and elongation of wheat roots in a dose-dependent manner. NO inhibitors suggested that nitrate reductase (NR), rather than nitric oxide synthase (NOS), was essential for AOS-induced root development. Further studies confirmed that AOS-induced NO generation in wheat roots by up-regulating the gene expression and enzyme activity of NR at the post-transcriptional level. The anatomy and RT-PCR results showed that AOS accelerated the division and growth of stele cells, leading to an increase in the ratio of stele area to root transverse area. This could be inhibited by the NR inhibitor, sodium tungstate, which indicated that NO catalyzed by the NR was involved in AOS regulation of root development. Taken together, in the early stage of AOS-induced root development, NO generation was a novel mechanism by which AOS regulated plant growth. The results also showed that this marine resource could be widely used for crop development. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Generator configuration for solid oxide fuel cells

DOEpatents

Reichner, Philip

1989-01-01

Disclosed are improvements in a solid oxide fuel cell generator 1 having a multiplicity of electrically connected solid oxide fuel cells 2, where a fuel gas is passed over one side of said cells and an oxygen-containing gas is passed over the other side of said cells resulting in the generation of heat and electricity. The improvements comprise arranging the cells in the configuration of a circle, a spiral, or folded rows within a cylindrical generator, and modifying the flow rate, oxygen concentration, and/or temperature of the oxygen-containing gases that flow to those cells that are at the periphery of the generator relative to those cells that are at the center of the generator. In these ways, a more uniform temperature is obtained throughout the generator.

Morphology and structure of TixOy nanoparticles generated by femtosecond laser ablation in water

NASA Astrophysics Data System (ADS)

Donėlienė, Jolanta; Rudzikas, Matas; Rades, Steffi; Dörfel, Ilona; Peplinski, Burkhard; Sahre, Mario; Pellegrino, Francesco; Maurino, Valter; Ulbikas, Juras; Galdikas, Algirdas; Hodoroaba, Vasile-Dan

2018-04-01

In this work femto-second pulsed laser ablation in liquid (PLAL) procedure for the generation of titanium oxide nanoparticles (NP) is reported with the purpose of understanding morphology and structure of the newly generated NPs. Ablation duration was varied for optimization of NP generation processes between 10 and 90 min. Surface morphology of NPs as well as their size and shape (distribution) were analysed by various complementary electron microscopy techniques, i.e. SEM, TSEM and TEM. The crystalline structure of titanium oxide particles was investigated by XRD (two instruments operated in different geometries) and HR-TEM. Concentration of generated titanium oxide NPs in liquid was analysed by ICP-MS. A mix of crystalline (mainly anatase), partly crystalline and amorphous spherical titanium oxide NPs can be reported having a mean size between 10 and 20 nm, which is rather independent of the laser ablation (LA) duration. A second component consisting of irregularly shaped, but crystalline titanium oxide nanostructures is co-generated in the LA water, with more pronounced occurrence at longer LA times. The provenance of this component is assigned to those spherical particles generated in suspension and passing through the converging laser beam, being hence subject to secondary irradiation effects, e. g. fragmentation.

Photolytic AND Catalytic Destruction of Organic Waste Water Pollutants

NASA Astrophysics Data System (ADS)

Torosyan, V. F.; Torosyan, E. S.; Kryuchkova, S. O.; Gromov, V. E.

2017-01-01

The system: water supply source - potable and industrial water - wastewater - sewage treatment - water supply source is necessary for water supply and efficient utilization of water resources. Up-to-date technologies of waste water biological treatment require for special microorganisms, which are technologically complex and expensive but unable to solve all the problems. Application of photolytic and catalytically-oxidizing destruction is quite promising. However, the most reagents are strong oxidizers in catalytic oxidation of organic substances and can initiate toxic substance generation. Methodic and scientific approaches to assess bread making industry influence on the environment have been developed in this paper in order to support forecasting and taking technological decisions concerning reduction of this influence. Destructive methods have been tested: ultra violet irradiation and catalytic oxidation for extraction of organic compounds from waste water by natural reagents.

Antioxidant Therapeutic Strategies for Cardiovascular Conditions Associated with Oxidative Stress

PubMed Central

Molina, Víctor M.; Carrasco, Rodrigo A.; Figueroa, Elías; Letelier, Pablo; Castillo, Rodrigo L.

2017-01-01

Oxidative stress (OS) refers to the imbalance between the generation of reactive oxygen species (ROS) and the ability to scavenge these ROS by endogenous antioxidant systems, where ROS overwhelms the antioxidant capacity. Excessive presence of ROS results in irreversible damage to cell membranes, DNA, and other cellular structures by oxidizing lipids, proteins, and nucleic acids. Oxidative stress plays a crucial role in the pathogenesis of cardiovascular diseases related to hypoxia, cardiotoxicity and ischemia–reperfusion. Here, we describe the participation of OS in the pathophysiology of cardiovascular conditions such as myocardial infarction, anthracycline cardiotoxicity and congenital heart disease. This review focuses on the different clinical events where redox factors and OS are related to cardiovascular pathophysiology, giving to support for novel pharmacological therapies such as omega 3 fatty acids, non-selective betablockers and microRNAs. PMID:28862654

Antioxidant Therapeutic Strategies for Cardiovascular Conditions Associated with Oxidative Stress.

PubMed

Farías, Jorge G; Molina, Víctor M; Carrasco, Rodrigo A; Zepeda, Andrea B; Figueroa, Elías; Letelier, Pablo; Castillo, Rodrigo L

2017-09-01

Oxidative stress (OS) refers to the imbalance between the generation of reactive oxygen species (ROS) and the ability to scavenge these ROS by endogenous antioxidant systems, where ROS overwhelms the antioxidant capacity. Excessive presence of ROS results in irreversible damage to cell membranes, DNA, and other cellular structures by oxidizing lipids, proteins, and nucleic acids. Oxidative stress plays a crucial role in the pathogenesis of cardiovascular diseases related to hypoxia, cardiotoxicity and ischemia-reperfusion. Here, we describe the participation of OS in the pathophysiology of cardiovascular conditions such as myocardial infarction, anthracycline cardiotoxicity and congenital heart disease. This review focuses on the different clinical events where redox factors and OS are related to cardiovascular pathophysiology, giving to support for novel pharmacological therapies such as omega 3 fatty acids, non-selective betablockers and microRNAs.

Mitochondrial generation of superoxide and hydrogen peroxide as the source of mitochondrial redox signaling.

PubMed

Brand, Martin D

2016-11-01

This review examines the generation of reactive oxygen species by mammalian mitochondria, and the status of different sites of production in redox signaling and pathology. Eleven distinct mitochondrial sites associated with substrate oxidation and oxidative phosphorylation leak electrons to oxygen to produce superoxide or hydrogen peroxide: oxoacid dehydrogenase complexes that feed electrons to NAD + ; respiratory complexes I and III, and dehydrogenases, including complex II, that use ubiquinone as acceptor. The topologies, capacities, and substrate dependences of each site have recently clarified. Complex III and mitochondrial glycerol 3-phosphate dehydrogenase generate superoxide to the external side of the mitochondrial inner membrane as well as the matrix, the other sites generate superoxide and/or hydrogen peroxide exclusively in the matrix. These different site-specific topologies are important for redox signaling. The net rate of superoxide or hydrogen peroxide generation depends on the substrates present and the antioxidant systems active in the matrix and cytosol. The rate at each site can now be measured in complex substrate mixtures. In skeletal muscle mitochondria in media mimicking muscle cytosol at rest, four sites dominate, two in complex I and one each in complexes II and III. Specific suppressors of two sites have been identified, the outer ubiquinone-binding site in complex III (site III Qo ) and the site in complex I active during reverse electron transport (site I Q ). These suppressors prevent superoxide/hydrogen peroxide production from a specific site without affecting oxidative phosphorylation, making them excellent tools to investigate the status of the sites in redox signaling, and to suppress the sites to prevent pathologies. They allow the cellular roles of mitochondrial superoxide/hydrogen peroxide production to be investigated without catastrophic confounding bioenergetic effects. They show that sites III Qo and I Q are active in cells and have important roles in redox signaling (e.g. hypoxic signaling and ER-stress) and in causing oxidative damage in a variety of biological contexts. Copyright © 2016 Elsevier Inc. All rights reserved.

Microfluidic electrochemical sensor for on-line monitoring of aerosol oxidative activity.

PubMed

Sameenoi, Yupaporn; Koehler, Kirsten; Shapiro, Jeff; Boonsong, Kanokporn; Sun, Yele; Collett, Jeffrey; Volckens, John; Henry, Charles S

2012-06-27

Particulate matter (PM) air pollution has a significant impact on human morbidity and mortality; however, the mechanisms of PM-induced toxicity are poorly defined. A leading hypothesis states that airborne PM induces harm by generating reactive oxygen species in and around human tissues, leading to oxidative stress. We report here a system employing a microfluidic electrochemical sensor coupled directly to a particle-into-liquid sampler (PILS) system to measure aerosol oxidative activity in an on-line format. The oxidative activity measurement is based on the dithiothreitol (DTT) assay, where, after being oxidized by PM, the remaining reduced DTT is analyzed by the microfluidic sensor. The sensor consists of an array of working, reference, and auxiliary electrodes fabricated in a poly(dimethylsiloxane)-based microfluidic device. Cobalt(II) phthalocyanine-modified carbon paste was used as the working electrode material, allowing selective detection of reduced DTT. The electrochemical sensor was validated off-line against the traditional DTT assay using filter samples taken from urban environments and biomass burning events. After off-line characterization, the sensor was coupled to a PILS to enable on-line sampling/analysis of aerosol oxidative activity. Urban dust and industrial incinerator ash samples were aerosolized in an aerosol chamber and analyzed for their oxidative activity. The on-line sensor reported DTT consumption rates (oxidative activity) in good correlation with aerosol concentration (R(2) from 0.86 to 0.97) with a time resolution of approximately 3 min.

Hydrogen measurement during steam oxidation using coupled thermogravimetric analysis and quadrupole mass spectrometry

DOE PAGES

Parkison, Adam J.; Nelson, Andrew Thomas

2016-01-11

An analytical technique is presented with the goal of measuring reaction kinetics during steam oxidation reactions for three cases in which obtaining kinetics information often requires a prohibitive amount of time and cost. The technique presented relies on coupling thermogravimetric analysis (TGA) with a quantitative hydrogen measurement technique using quadrupole mass spectrometry (QMS). The first case considered is in differentiating between the kinetics of steam oxidation reactions and those for simultaneously reacting gaseous impurities such as nitrogen or oxygen. The second case allows one to independently measure the kinetics of oxide and hydride formation for systems in which both ofmore » these reactions are known to take place during steam oxidation. The third case deals with measuring the kinetics of formation for competing volatile and non-volatile oxides during certain steam oxidation reactions. In order to meet the requirements of the coupled technique, a methodology is presented which attempts to provide quantitative measurement of hydrogen generation using QMS in the presence of an interfering fragmentation species, namely water vapor. This is achieved such that all calibrations and corrections are performed during the TGA baseline and steam oxidation programs, making system operation virtually identical to standard TGA. Benchmarking results showed a relative error in hydrogen measurement of 5.7–8.4% following the application of a correction factor. Lastly, suggestions are made for possible improvements to the presented technique so that it may be better applied to the three cases presented.« less

Hydrogen measurement during steam oxidation using coupled thermogravimetric analysis and quadrupole mass spectrometry

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

Parkison, Adam J.; Nelson, Andrew Thomas

An analytical technique is presented with the goal of measuring reaction kinetics during steam oxidation reactions for three cases in which obtaining kinetics information often requires a prohibitive amount of time and cost. The technique presented relies on coupling thermogravimetric analysis (TGA) with a quantitative hydrogen measurement technique using quadrupole mass spectrometry (QMS). The first case considered is in differentiating between the kinetics of steam oxidation reactions and those for simultaneously reacting gaseous impurities such as nitrogen or oxygen. The second case allows one to independently measure the kinetics of oxide and hydride formation for systems in which both ofmore » these reactions are known to take place during steam oxidation. The third case deals with measuring the kinetics of formation for competing volatile and non-volatile oxides during certain steam oxidation reactions. In order to meet the requirements of the coupled technique, a methodology is presented which attempts to provide quantitative measurement of hydrogen generation using QMS in the presence of an interfering fragmentation species, namely water vapor. This is achieved such that all calibrations and corrections are performed during the TGA baseline and steam oxidation programs, making system operation virtually identical to standard TGA. Benchmarking results showed a relative error in hydrogen measurement of 5.7–8.4% following the application of a correction factor. Lastly, suggestions are made for possible improvements to the presented technique so that it may be better applied to the three cases presented.« less

Cytosolic NADP(+)-dependent isocitrate dehydrogenase protects macrophages from LPS-induced nitric oxide and reactive oxygen species.

PubMed

Maeng, Oky; Kim, Yong Chan; Shin, Han-Jae; Lee, Jie-Oh; Huh, Tae-Lin; Kang, Kwang-il; Kim, Young Sang; Paik, Sang-Gi; Lee, Hayyoung

2004-04-30

Macrophages activated by microbial lipopolysaccharides (LPS) produce bursts of nitric oxide and reactive oxygen species (ROS). Redox protection systems are essential for the survival of the macrophages since the nitric oxide and ROS can be toxic to them as well as to pathogens. Using suppression subtractive hybridization (SSH) we found that cytosolic NADP(+)-dependent isocitrate dehydrogenase (IDPc) is strongly upregulated by nitric oxide in macrophages. The levels of IDPc mRNA and of the corresponding enzymatic activity were markedly increased by treatment of RAW264.7 cells or peritoneal macrophages with LPS or SNAP (a nitric oxide donor). Over-expression of IDPc reduced intracellular peroxide levels and enhanced the survival of H2O2- and SNAP-treated RAW264.7 macrophages. IDPc is known to generate NADPH, a cellular reducing agent, via oxidative decarboxylation of isocitrate. The expression of enzymes implicated in redox protection, superoxide dismutase (SOD) and catalase, was relatively unaffected by LPS and SNAP. We propose that the induction of IDPc is one of the main self-protection mechanisms of macrophages against LPS-induced oxidative stress.

Redox status in a model of cancer stem cells.

PubMed

Zaccarin, Mattia; Bosello-Travain, Valentina; Di Paolo, Maria Luisa; Falda, Marco; Maiorino, Matilde; Miotto, Giovanni; Piccolo, Stefano; Roveri, Antonella; Ursini, Fulvio; Venerando, Rina; Toppo, Stefano

2017-03-01

Reversible oxidation of Cys residues is a crucial element of redox homeostasis and signaling. According to a popular concept in oxidative stress signaling, the oxidation of targets of signals can only take place following an overwhelming of the cellular antioxidant capacity. This concept, however, ignores the activation of feedback mechanisms possibly leading to a paradoxical effect. In a model of cancer stem cells (CSC), stably overexpressing the TAZ oncogene, we observed that the increased formation of oxidants is associated with a globally more reduced state of proteins. Redox proteomics revealed that several proteins, capable of undergoing reversible redox transitions, are indeed more reduced while just few are more oxidized. Among the proteins more oxidized, G6PDH emerges as both more expressed and activated by oxidation. This accounts for the observed more reduced state of the NADPH/NADP + couple. The dynamic redox flux generating this apparently paradoxical effect is rationalized in a computational system biology model highlighting the crucial role of G6PDH activity on the rate of redox transitions eventually leading to the reduction of reversible redox switches. Copyright © 2016 Elsevier Inc. All rights reserved.

Exploring the Role of CYP3A4 Mediated Drug Metabolism in the Pharmacological Modulation of Nitric Oxide Production

PubMed Central

Pérez-del Palacio, José; Díaz, Caridad; Vergara, Noemí; Algieri, Francesca; Rodríguez-Nogales, Alba; de Pedro, Nuria; Rodríguez-Cabezas, M. Elena; Genilloud, Olga; Gálvez, Julio; Vicente, Francisca

2017-01-01

Nitric-oxide synthase, the enzyme responsible for mammalian nitric oxide generation, and cytochrome P450, the major enzymes involved in drug metabolism, share striking similarities. Therefore, it makes sense that cytochrome P450 drug mediated biotransformations might play an important role in the pharmacological modulation of nitric oxide synthase. In this work, we have undertaken an integrated in vitro assessment of the hepatic metabolism and nitric oxide modulation of previously described dual inhibitors (imidazoles and macrolides) of these enzymes in order assess the implication of CYP450 activities over production of nitric oxide. In vitro systems based in human liver microsomes and activated mouse macrophages were developed for these purposes. Additionally in vitro production the hepatic metabolites of dual inhibitor, roxithromycin, was investigated achieving the identification and isolation of main hepatic biotransformation products. Our results suggested that for some macrolide compounds, the cytochrome P450 3A4 derived drug metabolites have an important effect on nitric oxide production and might critically contribute to the pharmacological immunomodulatory activity observed. PMID:28446877

The PEMFC-integrated CO oxidation — a novel method of simplifying the fuel cell plant

NASA Astrophysics Data System (ADS)

Rohland, Bernd; Plzak, Vojtech

Natural gas and methanol are the most economical fuels for residential fuel cell power generators as well as for mobile PEM-fuel cells. However, they have to be reformed with steam into hydrogen, which is to be cleaned from CO by shift-reaction and by partial oxidation to a level of no more than 30 ppm CO. This level is set by the Pt/Ru-C-anode of the PEMFC. A higher partial oxidation reaction rate for CO than those of Pt/Ru-C can be achieved in an oxidic Au-catalyst system. In the Fe 2O 3-Au system, a reaction rate of 2·10 -3 mol CO/s g Au at 1000 ppm CO and 5% "air bleed" at 80°C is achieved. This high rate allows to construct a catalyst-sheet for each cell within a PEMFC-stack. Practical and theoretical current/voltage characteristics of PEMFCs with catalyst-sheet are presented at 1000 ppm CO in hydrogen with 5% "air bleed". This gives the possibility of simplifying the gas processor of the plant.

Role of oxidative metabolites of cocaine in toxicity and addiction: oxidative stress and electron transfer.

PubMed

Kovacic, Peter

2005-01-01

Cocaine is one of the principal drugs of abuse. Although impressive advances have been made, unanswered questions remain concerning mechanism of toxicity and addiction. Discussion of action mode usually centers on receptor binding and enzyme inhibition, with limited attention to events at the molecular level. This review provides extensive evidence in support of the hypothesis that oxidative metabolites play important roles comprising oxidative stress (OS), reactive oxygen species (ROS), and electron transfer (ET). The metabolites include norcocaine and norcocaine derivatives: nitroxide radical, N-hydroxy, nitrosonium, plus cocaine iminium and formaldehyde. Observed formation of ROS is rationalized by redox cycling involving several possible ET agents. Three potential ones are present in the form of oxidative metabolites, namely, nitroxide, nitrosonium, and iminium. Most attention has been devoted to the nitroxide-hydroxylamine couple which has been designated by various investigators as the principal source of ROS. The proximate ester substituent is deemed important for intramolecular stabilization of reactive intermediates. Reduction potential of nitroxide is in accord with plausibility of ET in the biological milieu. Toxicity by cocaine, with evidence for participation of OS, is demonstrated for many body components, including liver, central nervous system, cardiovascular system, reproductive system, kidney, mitochondria, urine, and immune system. Other adverse effects associated with ROS comprise teratogenesis and apoptosis. Examples of ROS generated are lipid peroxides and hydroxyl radical. Often observed were depletion of antioxidant defenses, and protection by added antioxidants, such as, thiol, salicylate, and deferoxamine. Considerable evidence supports the contention that oxidative ET metabolites of cocaine are responsible for much of the observed OS. Quite significantly, the pro-oxidant, toxic effects, including generation of superoxide and lipid peroxyl radicals, plus depletion of glutathione, elicited by nitroxide or the hydroxylamine derivative, were greater than for the parent drug. The formaldehyde metabolite also appears to play a role. Mechanistic similarity to the action of neurotoxin 3,3'-iminodipropionitrile is pointed out. A number of literature strategies for treatment of addiction are addressed. However, no effective interventions are currently available. An hypothesis for addiction is offered based on ET and ROS at low concentrations. Radicals may aid in cell signaling entailing redox processes which influence ion transport, neuromodulation, and transcription. Ideas are suggested for future work dealing with health promotion. These include use of AOs, both dietary and supplemental, trapping of the norcocaine metabolite by non-toxic complexing agents, and use of nitrones for capturing harmful radical species.

Malate-aspartate shuttle and exogenous NADH/cytochrome c electron transport pathway as two independent cytosolic reducing equivalent transfer systems.

PubMed

Abbrescia, Daniela Isabel; La Piana, Gianluigi; Lofrumento, Nicola Elio

2012-02-15

In mammalian cells aerobic oxidation of glucose requires reducing equivalents produced in glycolytic phase to be channelled into the phosphorylating respiratory chain for the reduction of molecular oxygen. Data never presented before show that the oxidation rate of exogenous NADH supported by the malate-aspartate shuttle system (reconstituted in vitro with isolated liver mitochondria) is comparable to the rate obtained on activation of the cytosolic NADH/cytochrome c electron transport pathway. The activities of these two reducing equivalent transport systems are independent of each other and additive. NADH oxidation induced by the malate-aspartate shuttle is inhibited by aminooxyacetate and by rotenone and/or antimycin A, two inhibitors of the respiratory chain, while the NADH/cytochrome c system remains insensitive to all of them. The two systems may simultaneously or mutually operate in the transfer of reducing equivalents from the cytosol to inside the mitochondria. In previous reports we suggested that the NADH/cytochrome c system is expected to be functioning in apoptotic cells characterized by the presence of cytochrome c in the cytosol. As additional new finding the activity of reconstituted shuttle system is linked to the amount of α-ketoglutarate generated inside the mitochondria by glutamate dehydrogenase rather than by aspartate aminotransferase. Copyright © 2011 Elsevier Inc. All rights reserved.

Solid State Energy Conversion Energy Alliance (SECA)

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

Hennessy, Daniel; Sibisan, Rodica; Rasmussen, Mike

2011-09-12

The overall objective is to develop a Solid Oxide Fuel Cell (SOFC) stack that can be economically produced in high volumes and mass customized for different applications in transportation, stationary power generation, and military market sectors. In Phase I, work will be conducted on system design and integration, stack development, and development of reformers for natural gas and gasoline. Specifically, Delphi-Battelle will fabricate and test a 5 kW stationary power generation system consisting of a SOFC stack, a steam reformer for natural gas, and balance-of-plant (BOP) components, having an expected efficiency of ≥ 35 percent (AC/LHV). In Phase II andmore » Phase III, the emphasis will be to improve the SOFC stack, reduce start-up time, improve thermal cyclability, demonstrate operation on diesel fuel, and substantially reduce materials and manufacturing cost by integrating several functions into one component and thus reducing the number of components in the system. In Phase II, Delphi-Battelle will fabricate and demonstrate two SOFC systems: an improved stationary power generation system consisting of an improved SOFC stack with integrated reformation of natural gas, and the BOP components, with an expected efficiency of ≥ 40 percent (AC/LHV), and a mobile 5 kW system for heavy-duty trucks and military power applications consisting of an SOFC stack, reformer utilizing anode tailgate recycle for diesel fuel, and BOP components, with an expected efficiency of ≥ 30 percent (DC/LHV). Finally, in Phase III, Delphi-Battelle will fabricate and test a 5 kW Auxiliary Power Unit (APU) for mass-market automotive application consisting of an optimized SOFC stack, an optimized catalytic partial oxidation (CPO) reformer for gasoline, and BOP components, having an expected efficiency of ≥ 30 percent (DC/LHV) and a factory cost of ≤ $400/kW.« less

Solid State Energy Conversion Energy Alliance (SECA)

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

Hennessy, Daniel; Sibisan, Rodica; Rasmussen, Mike

2011-09-12

The overall objective is to develop a solid oxide fuel cell (SOFC) stack that can be economically produced in high volumes and mass customized for different applications in transportation, stationary power generation, and military market sectors. In Phase I, work will be conducted on system design and integration, stack development, and development of reformers for natural gas and gasoline. Specifically, Delphi-Battelle will fabricate and test a 5 kW stationary power generation system consisting of a SOFC stack, a steam reformer for natural gas, and balance-of-plant (BOP) components, having an expected efficiency of 35 percent (AC/LHV). In Phase II and Phasemore » III, the emphasis will be to improve the SOFC stack, reduce start-up time, improve thermal cyclability, demonstrate operation on diesel fuel, and substantially reduce materials and manufacturing cost by integrating several functions into one component and thus reducing the number of components in the system. In Phase II, Delphi-Battelle will fabricate and demonstrate two SOFC systems: an improved stationary power generation system consisting of an improved SOFC stack with integrated reformation of natural gas, and the BOP components, with an expected efficiency of ≥40 percent (AC/LHV), and a mobile 5 kW system for heavy-duty trucks and military power applications consisting of an SOFC stack, reformer utilizing anode tailgate recycle for diesel fuel, and BOP components, with an expected efficiency of ≥30 percent (DC/LHV). Finally, in Phase III, Delphi-Battelle will fabricate and test a 5 kW Auxiliary Power Unit (APU) for mass-market automotive application consisting of an optimized SOFC stack, an optimized catalytic partial oxidation (CPO) reformer for gasoline, and BOP components, having an expected efficiency of 30 percent (DC/LHV) and a factory cost of ≤$400/kW.« less

Ferrocene functionalized graphene based electrode for the electro-Fenton oxidation of ciprofloxacin.

PubMed

Divyapriya, Govindaraj; Nambi, Indumathi; Senthilnathan, Jaganathan

2018-05-26

Ferrocene functionalized graphene based graphite felt electrode was firstly investigated for heterogeneous electro-Fenton oxidation of ciprofloxacin in neutral pH condition. Electrochemical reduction of Ferrocene functionalized graphene oxide (Fc-ErGO) was performed by cyclic voltammetry technique. At neutral pH condition, Fc-ErGO electrode (0.035 min ─1 ) exhibited ∼3 times and ∼9 times higher removal rates in comparison with plane ErGO (0.010 min ─1 ) and plane graphite felt (0.004 min ─1 ) electrodes respectively. The effect of pH and applied potential were studied for the degradation of ciprofloxacin in Fc-ErGO based electrode. Higher removal rate was observed at acidic pH (0.222 min ─1 ), whereas alkaline pH showed lower removal efficiency (0.014 min ─1 ). > 99% removal of ciprofloxacin was achieved with in 15 min and 120 min of reactions period at pH 3.0 and pH 7.0, respectively. H 2 O 2 generation was found to be high in plane ErGO electrode system in all of the pH conditions. Owing to the high redox ability of ferrocene, Fc-ErGO electrode generated high concentration of OH radicals (426 μM pH 3.0; 247 μM pH 7.0; 210 μM pH 9.0) than ErGO and plane graphite felt electrodes; The electrode reusability study was performed to understand the electrode stability. There was no significant change in removal efficiency even after the 5th cycle of reusability study at both acidic and neutral conditions. The possible mechanism of oxidation in Fc-ErGO based electro-Fenton process was also proposed based on the continuous monitoring of H 2 O 2 and OH radicals generated in the system. Copyright © 2018. Published by Elsevier Ltd.

Analysis of Halogen-Mercury Reactions in Flue Gas

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

Paula Buitrago; Geoffrey Silcox; Constance Senior

2010-01-01

Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using amore » wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation was observed at SO{sub 2} concentrations of 400 ppmv and higher. In contrast, SO{sub 2} concentrations as low as 50 ppmv significantly reduced mercury oxidation by bromine, this reduction could be due to both gas and liquid phase interactions between SO{sub 2} and oxidized mercury species. The simultaneous presence of chlorine and bromine in the flue gas resulted in a slight increase in mercury oxidation above that obtained with bromine alone, the extent of the observed increase is proportional to the chlorine concentration. The results of this study can be used to understand the relative importance of gas-phase mercury oxidation by bromine and chlorine in combustion systems. Two temperature profiles were tested: a low quench (210 K/s) and a high quench (440 K/s). For chlorine the effects of quench rate were slight and hard to characterize with confidence. Oxidation with bromine proved sensitive to quench rate with significantly more oxidation at the lower rate. The data generated in this program are the first homogeneous laboratory-scale data on bromine-induced oxidation of mercury in a combustion system. Five Hg-Cl and three Hg-Br mechanisms, some published and others under development, were evaluated and compared to the new data. The Hg-halogen mechanisms were combined with submechanisms from Reaction Engineering International for NO{sub x}, SO{sub x}, and hydrocarbons. The homogeneous kinetics under-predicted the levels of mercury oxidation observed in full-scale systems. This shortcoming can be corrected by including heterogeneous kinetics in the model calculations.« less

Self-Regulating Water-Separator System for Fuel Cells

NASA Technical Reports Server (NTRS)

Vasquez, Arturo; McCurdy, Kerri; Bradley, Karla F.

2007-01-01

proposed system would perform multiple coordinated functions in regulating the pressure of the oxidant gas (usually, pure oxygen) flowing to a fuelcell stack and in removing excess product water that is generated in the normal fuel-cell operation. The system could function in the presence or absence of gravitation, and in any orientation in a gravitational field. Unlike some prior systems for removing product water, the proposed system would not depend on hydrophobicity or hydrophilicity of surfaces that are subject to fouling and, consequently, to gradual deterioration in performance. Also unlike some prior systems, the proposed system would not include actively controlled electric motors for pumping; instead, motive power for separation and pumping away of product water would be derived primarily from the oxidant flow and perhaps secondarily from the fuel flow. The net effect of these and other features would be to make the proposed system more reliable and safer, relative to the prior systems. The proposed system (see figure) would include a pressure regulator and sensor in the oxidant supply just upstream from an ejector reactant pump. The pressure of the oxidant supply would depend on the consumption flow. In one of two control subsystems, the pressure of oxidant flowing from the supply to the ejector would be sensed and used to control the speed of a set of a reciprocating constant-displacement pump so that the volumetric flow of nominally incompressible water away from the system would slightly exceed the rate at which water was produced by the fuel cell(s). The two-phase (gas/liquid water) outlet stream from the fuel cell(s) would enter the water separator, a turbinelike centrifugal separator machine driven primarily by the oxidant gas stream. A second control subsystem would utilize feedback derived from the compressibility of the outlet stream: As the separator was emptied of liquid water, the compressibility of the pumped stream would increase. The compressibility would be sensed, and an increase in compressibility beyond a preset point (signifying a decrease in water content below an optimum low level) would cause the outflow from the reciprocating pump to be diverted back to the separator to recycle some water.

Direct observation of sequential oxidations of a titania-bound molecular proxy catalyst generated through illumination of molecular sensitizers

NASA Astrophysics Data System (ADS)

Chen, Hsiang-Yun; Ardo, Shane

2018-01-01

Natural photosynthesis uses the energy in sunlight to oxidize or reduce reaction centres multiple times, therefore preparing each reaction centre for a multiple-electron-transfer reaction that will ultimately generate stable reaction products. This process relies on multiple chromophores per reaction centre to quickly generate the active state of the reaction centre and to outcompete deleterious charge recombination. Using a similar design principle, we report spectroscopic evidence for the generation of a twice-oxidized TiO2-bound molecular proxy catalyst after low-intensity visible-light excitation of co-anchored molecular Ru(II)-polypyridyl dyes. Electron transfer from an excited dye to TiO2 generated a Ru(III) state that subsequently and repeatedly reacted with neighbouring Ru(II) dyes via self-exchange electron transfer to ultimately oxidize a distant co-anchored proxy catalyst before charge recombination. The largest yield for twice-oxidized proxy catalysts occurred when they were present at low coverage, suggesting that large dye/electrocatalyst ratios are also desired in dye-sensitized photoelectrochemical cells.

Slab reformer

DOEpatents

Spurrier, F.R.; DeZubay, E.A.; Murray, A.P.; Vidt, E.J.

1984-02-07

Slab-shaped high efficiency catalytic reformer configurations are disclosed particularly useful for generation of fuels to be used in fuel cell based generation systems. A plurality of structures forming a generally rectangular peripheral envelope are spaced about one another to form annular regions, an interior annular region containing a catalytic bed and being regeneratively heated on one side by a hot combustion gas and on the other side by the gaseous products of the reformation. An integrally mounted combustor is cooled by impingement of incoming oxidant. 14 figs.

Anaerobic nitrification-denitrification mediated by Mn-oxides in meso-tidal sediments: Implications for N2 and N2O production

NASA Astrophysics Data System (ADS)

Fernandes, Sheryl Oliveira; Javanaud, Cedric; Aigle, Axel; Michotey, Valérie D.; Guasco, Sophie; Deborde, Jonathan; Deflandre, Bruno; Anschutz, Pierre; Bonin, Patricia C.

2015-04-01

Field measurements in the Arcachon Bay (southwest France) indicated anaerobic production of NOx via nitrification, which was coupled to the reduction of Mn-oxides. To prove the occurrence of this process, laboratory microcosm experiments were set up. A 15N tracer-based approach was used to track if NOx produced through Mn-oxide-mediated anaerobic nitrification would be reduced to N2 via denitrification or anammox. We also hypothesized the generation of the potent greenhouse gas nitrous oxide (N2O) during nitrification-denitrification in the presence of Mn-oxides. The microcosms were prepared using sediment sectioned at varying depths (0-2.5, 2.5-4.5, 4.5-8.5, 8.5-12 and 12-17 cm) during two sampling campaigns in October (fall) and January (winter). Labeling with 15NO3- revealed low N2 production originating from NO3- in the water column (Pw), which did not increase significantly on amendment with Mn-oxides during both sampling periods. However, for both seasons, a significant increase of N2 produced via nitrification (Pn) was observed upon addition of Mn-oxides reaching 76-fold enhancement at ≤ 2.5 cm. To support these results, sediment slurries of October were subjected to amendment of 15NH4+, 14NO3- with or without addition of Mn-oxides. A substantial production of P15 (N2 production from 15NH4+) within 0-17 cm provided further evidence on nitrification-denitrification mediated by Mn-oxides probably with minimal intervention of anammox. In organically rich sediments, anaerobic nitrification-denitrification mediated by Mn-oxides could play an important role in lowering re-mineralized NH4+ levels in the benthic system. As hypothesized, significant production of N2O through the pathway was observed revealing newer mechanisms leading to the generation of the radiative gas.

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

2011-01-01

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Co3O4-based honeycombs as compact redox reactors/heat exchangers for thermochemical storage in the next generation CSP plants

NASA Astrophysics Data System (ADS)

Pagkoura, Chrysoula; Karagiannakis, George; Halevas, Eleftherios; Konstandopoulos, Athanasios G.

2016-05-01

Over the last years, several research groups have focused on developing efficient thermochemical heat storage (THS) systems, in-principle capable of being coupled with next generation high temperature Concentrated Solar Power plants. Among systems studied, the Co3O4/CoO redox system is a promising candidate. Currently, research efforts extend beyond basic level identification of promising materials to more application-oriented approaches aiming at validation of THS performance at pilot scale reactors. The present work focuses on the investigation of cobalt oxide based honeycomb structures as candidate reactors/heat exchangers to be employed for such purposes. In the evaluation conducted and presented here, cobalt oxide-based structures with different composition and geometrical characteristics were subjected to redox cycles in the temperature window between 800 and 1000°C under air flow. Basic aspects related to redox performance of each system are briefly discussed but the main focus lies on the evaluation of the segments structural stability after multi-cyclic operation. The latter is based on macroscopic visual observation and also supplemented by pre- (i.e. fresh samples) and post-characterization (i.e. after long term exposure) of extruded honeycombs via combined mercury porosimetry and SEM analysis.

Chemistry of the Konica Dry Color System

NASA Astrophysics Data System (ADS)

Suda, Yoshihiko; Ohbayashi, Keiji; Onodera, Kaoru

1991-08-01

While silver halide photosensitive materials offer superiority in image quality -- both in color and black-and-white -- they require chemical solutions for processing, and this can be a drawback. To overcome this, researchers turned to the thermal development of silver halide photographic materials, and met their first success with black-and-white images. Later, with the development of the Konica Dry Color System, color images were finally obtained from a completely dry thermal development system, without the use of water or chemical solutions. The dry color system is characterized by a novel chromogenic color image-forming technology and comprises four processes. (1) With the application of heat, a color developer precursor (CDP) decomposes to generate a p-phenylenediamine color developer (CD). (2) The CD then develops silver salts. (3) Oxidized CD then reacts with couplers to generate color image dyes. (4) Finally, the dyes diffuse from the system's photosensitive sheet to its image-receiving sheet. The authors have analyzed the kinetics of each of the system's four processes. In this paper, they report the kinetics of the system's first process, color developer (CD) generation.

A Noise and Emissions Assessment of the N3-X Transport

NASA Technical Reports Server (NTRS)

Berton, Jeffrey J.; Haller, William J.

2014-01-01

Analytical predictions of certification noise and exhaust emissions for NASA's N3-X - a notional, hybrid wingbody airplane - are presented in this paper. The N3-X is a 300-passenger concept transport propelled by an array of fans distributed spanwise near the trailing edge of the wingbody. These fans are driven by electric motors deriving power from twin generators driven by turboshaft engines. Turboelectric distributed hybrid propulsion has the potential to dramatically increase the propulsive efficiency of aircraft. The noise and exhaust emission estimates presented here are generated using NASA's conceptual design systems analysis tools with several key modifications to accommodate this unconventional architecture. These tools predict certification noise and the emissions of oxides of nitrogen by leveraging data generated from a recent analysis of the N3-X propulsion system.

Thiol oxidation by nitrosative stress: Cellular localization in human spermatozoa.

PubMed

Cabrillana, María E; Uribe, Pamela; Villegas, Juana V; Álvarez, Juan; Sánchez, Raúl; Fornés, Miguel W

2016-10-01

Peroxynitrite is a highly reactive nitrogen species and when it is generated at high levels it causes nitrosative stress, an important cause of impaired sperm function. High levels of peroxynitrite have been shown to correlate with decreased semen quality in infertile men. Thiol groups in sperm are mainly found in enzymes, antioxidant molecules, and structural proteins in the axoneme. Peroxynitrite primarily reacts with thiol groups of cysteine-containing proteins. Although it is well known that peroxynitrite oxidizes sulfhydryl groups in sperm, the subcellular localization of this oxidation remains unknown. The main objective of this study was to establish the subcellular localization of peroxynitrite-induced nitrosative stress in thiol groups and its relation to sperm motility in human spermatozoa. For this purpose, spermatozoa from healthy donors were exposed in vitro to 3-morpholinosydnonimine (SIN-1), a compound which generates peroxynitrite. In order to detect peroxynitrite and reduced thiol groups, the fluorescent probes, dihydrorhodamine 123 and monobromobimane (mBBr), were used respectively. Sperm viability was analyzed by propidium iodide staining. Peroxynitrite generation and thiol redox state were monitored by confocal microscopy whereas sperm viability was evaluated by flow cytometry. Sperm motility was analyzed by CASA using the ISAS(®) system. The results showed that exposure of human spermatozoa to peroxynitrite results in increased thiol oxidation which is mainly localized in the sperm head and principal piece regions. Thiol oxidation was associated with motility loss. The high susceptibility of thiol groups to peroxynitrite-induced oxidation could explain, at least in part, the negative effect of reactive nitrogen species on sperm motility. DHR: dihydrorhodamine 123; mBBr: monobromobimane ONOO(-): peroxynitrite RNS: reactive nitrogen species RFI: relative fluorescence intensity SIN-1: 3-morpholinosydnonimine CASA: Computer-Aided Sperm Analysis PARP: poli ADP ribose polimerasa VCL: curvilinear velocity VSL: straight-line velocity VAP: average path velocity PRDXs: peroxiredoxins ODF: outer dense fiber ODF1: outer dense fiber 1 PI: propidium iodide DMSO: dimethyl sulfoxide SD: standard deviation analysis of variance.

Large scale generation of micro-droplet array by vapor condensation on mesh screen piece

PubMed Central

Xie, Jian; Xu, Jinliang; He, Xiaotian; Liu, Qi

2017-01-01

We developed a novel micro-droplet array system, which is based on the distinct three dimensional mesh screen structure and sintering and oxidation induced thermal-fluid performance. Mesh screen was sintered on a copper substrate by bonding the two components. Non-uniform residue stress is generated along weft wires, with larger stress on weft wire top location than elsewhere. Oxidation of the sintered package forms micro pits with few nanograsses on weft wire top location, due to the stress corrosion mechanism. Nanograsses grow elsewhere to show hydrophobic behavior. Thus, surface-energy-gradient weft wires are formed. Cooling the structure in a wet air environment nucleates water droplets on weft wire top location, which is more “hydrophilic” than elsewhere. Droplet size is well controlled by substrate temperature, air humidity and cooling time. Because warp wires do not contact copper substrate and there is a larger conductive thermal resistance between warp wire and weft wire, warp wires contribute less to condensation but function as supporting structure. The surface energy analysis of drops along weft wires explains why droplet array can be generated on the mesh screen piece. Because the commercial material is used, the droplet system is cost effective and can be used for large scale utilization. PMID:28054635

Large scale generation of micro-droplet array by vapor condensation on mesh screen piece.

PubMed

Xie, Jian; Xu, Jinliang; He, Xiaotian; Liu, Qi

2017-01-05

We developed a novel micro-droplet array system, which is based on the distinct three dimensional mesh screen structure and sintering and oxidation induced thermal-fluid performance. Mesh screen was sintered on a copper substrate by bonding the two components. Non-uniform residue stress is generated along weft wires, with larger stress on weft wire top location than elsewhere. Oxidation of the sintered package forms micro pits with few nanograsses on weft wire top location, due to the stress corrosion mechanism. Nanograsses grow elsewhere to show hydrophobic behavior. Thus, surface-energy-gradient weft wires are formed. Cooling the structure in a wet air environment nucleates water droplets on weft wire top location, which is more "hydrophilic" than elsewhere. Droplet size is well controlled by substrate temperature, air humidity and cooling time. Because warp wires do not contact copper substrate and there is a larger conductive thermal resistance between warp wire and weft wire, warp wires contribute less to condensation but function as supporting structure. The surface energy analysis of drops along weft wires explains why droplet array can be generated on the mesh screen piece. Because the commercial material is used, the droplet system is cost effective and can be used for large scale utilization.

Large scale generation of micro-droplet array by vapor condensation on mesh screen piece

NASA Astrophysics Data System (ADS)

Xie, Jian; Xu, Jinliang; He, Xiaotian; Liu, Qi

2017-01-01

We developed a novel micro-droplet array system, which is based on the distinct three dimensional mesh screen structure and sintering and oxidation induced thermal-fluid performance. Mesh screen was sintered on a copper substrate by bonding the two components. Non-uniform residue stress is generated along weft wires, with larger stress on weft wire top location than elsewhere. Oxidation of the sintered package forms micro pits with few nanograsses on weft wire top location, due to the stress corrosion mechanism. Nanograsses grow elsewhere to show hydrophobic behavior. Thus, surface-energy-gradient weft wires are formed. Cooling the structure in a wet air environment nucleates water droplets on weft wire top location, which is more “hydrophilic” than elsewhere. Droplet size is well controlled by substrate temperature, air humidity and cooling time. Because warp wires do not contact copper substrate and there is a larger conductive thermal resistance between warp wire and weft wire, warp wires contribute less to condensation but function as supporting structure. The surface energy analysis of drops along weft wires explains why droplet array can be generated on the mesh screen piece. Because the commercial material is used, the droplet system is cost effective and can be used for large scale utilization.

Increased reactive oxygen species production during reductive stress: The roles of mitochondrial glutathione and thioredoxin reductases.

PubMed

Korge, Paavo; Calmettes, Guillaume; Weiss, James N

2015-01-01

Both extremes of redox balance are known to cause cardiac injury, with mounting evidence revealing that the injury induced by both oxidative and reductive stress is oxidative in nature. During reductive stress, when electron acceptors are expected to be mostly reduced, some redox proteins can donate electrons to O2 instead, which increases reactive oxygen species (ROS) production. However, the high level of reducing equivalents also concomitantly enhances ROS scavenging systems involving redox couples such as NADPH/NADP+ and GSH/GSSG. Here our objective was to explore how reductive stress paradoxically increases net mitochondrial ROS production despite the concomitant enhancement of ROS scavenging systems. Using recombinant enzymes and isolated permeabilized cardiac mitochondria, we show that two normally antioxidant matrix NADPH reductases, glutathione reductase and thioredoxin reductase, generate H2O2 by leaking electrons from their reduced flavoprotein to O2 when electron flow is impaired by inhibitors or because of limited availability of their natural electron acceptors, GSSG and oxidized thioredoxin. The spillover of H2O2 under these conditions depends on H2O2 reduction by peroxiredoxin activity, which may regulate redox signaling in response to endogenous or exogenous factors. These findings may explain how ROS production during reductive stress overwhelms ROS scavenging capability, generating the net mitochondrial ROS spillover causing oxidative injury. These enzymes could potentially be targeted to increase cancer cell death or modulate H2O2-induced redox signaling to protect the heart against ischemia/reperfusion damage. Copyright © 2015 Elsevier B.V. All rights reserved.

Method of making an apparatus for transpiration cooling of substrates such as turbine airfoils

DOEpatents

Alvin, Mary Anne; Anderson, Iver; Heidlof, Andy; White, Emma; McMordie, Bruce

2017-02-28

A method and apparatus for generating transpiration cooling using an oxidized porous HTA layer metallurgically bonded to a substrate having micro-channel architectures. The method and apparatus generates a porous HTA layer by spreading generally spherical HTA powder particles on a substrate, partially sintering under O.sub.2 vacuum until the porous HTA layer exhibits a porosity between 20% and 50% and a neck size ratio between 0.1 and 0.5, followed by a controlled oxidation generating an oxidation layer of alumina, chromia, or silica at a thickness of about 20 to about 500 nm. In particular embodiments, the oxidized porous HTA layer and the substrate comprise Ni as a majority element. In other embodiments, the oxidized porous HTA layer and the substrate further comprise Al, and in additional embodiments, the oxidized porous HTA layer and the substrate comprise .gamma.-Ni+.gamma.'-Ni.sub.3Al.

Repeatable hydrogen generation of 3D microporous nickel membrane using chemical milling

NASA Astrophysics Data System (ADS)

Seo, Keumyoung; Lim, Taekyung; Ju, Sanghyun

2018-05-01

In this study, we investigated a novel method of hydrogen generation through a chemical milling process. In the process of generating hydrogen with a thermochemical water-splitting method using a 3D microporous nickel membrane, the nickel surface is oxidized, leading to a decreased generation of hydrogen gas with time. To regenerate hydrogen from the oxidized catalysts, the oxidized metal surface was easily removed at room temperature, re-exposing a metal surface with abundant oxygen vacancies for continuous hydrogen generation. With this method, ~110 µmol · g‑1 of hydrogen gas was continuously produced per cycle. Since this method enabled us to create a fit state for hydrogen generation without extra heat, light, or electrical energy, it can solve the biggest commercialization challenge: inefficiency because the energy required for hydrogen generation is higher than the energy of the generated hydrogen.

Ecofriendly syntheses of phenothiazones and related structures facilitated by laccase – A comparative study

DOE PAGES

Cannatelli, Mark D.; Ragauskas, Arthur J.

2016-07-06

The biocatalytic synthesis of phenothiazones and related compounds has been achieved in an aqueous system under mild conditions facilitated by laccase oxidation. It was found that by coupling 2-aminothiophenol directly with 1,4-quinones, the product yields could be significantly increased compared to generating the 1,4-quinones in situ from the corresponding hydroquinones via laccase oxidation. However, laccase still proved to be pivotal for achieving highest product yields by catalyzing the final oxidation step. Furthermore, a difference in reactivity of aromatic and aliphatic amines toward 1,4-naphthoquinone is observed. Furthermore, this study provides a sustainable approach to the synthesis of a biologically important classmore » of compounds.« less

Lipid raft proteome reveals that oxidative phosphorylation system is associated with the plasma membrane.

PubMed

Kim, Bong-Woo; Lee, Chang Seok; Yi, Jae-Sung; Lee, Joo-Hyung; Lee, Joong-Won; Choo, Hyo-Jung; Jung, Soon-Young; Kim, Min-Sik; Lee, Sang-Won; Lee, Myung-Shik; Yoon, Gyesoon; Ko, Young-Gyu

2010-12-01

Although accumulating proteomic analyses have supported the fact that mitochondrial oxidative phosphorylation (OXPHOS) complexes are localized in lipid rafts, which mediate cell signaling, immune response and host-pathogen interactions, there has been no in-depth study of the physiological functions of lipid-raft OXPHOS complexes. Here, we show that many subunits of OXPHOS complexes were identified from the lipid rafts of human adipocytes, C2C12 myotubes, Jurkat cells and surface biotin-labeled Jurkat cells via shotgun proteomic analysis. We discuss the findings of OXPHOS complexes in lipid rafts, the role of the surface ATP synthase complex as a receptor for various ligands and extracellular superoxide generation by plasma membrane oxidative phosphorylation complexes.

Advanced oxidation process using hydrogen peroxide/microwave system for solubilization of phosphate.

PubMed

Liao, Ping Huang; Wong, Wayne T; Lo, Kwang Victor

2005-01-01

An advanced oxidation process (AOP) combining hydrogen peroxide and microwave heating was used for the solubilization of phosphate from secondary municipal sludge from an enhanced biological phosphorus removal process. The microwave irradiation is used as a generator agent of oxidizing radicals as well as a heating source in the process. This AOP process could facilitate the release of a large amount of the sludge-bound phosphorus from the sewage sludge. More than 84% of the total phosphorous could be released at a microwave heating time of 5 min at 170 degrees C. This innovative process has the potential of being applied to simple sludge treatment processes in domestic wastewater treatment and to the recovery of phosphorus from the wastewater.

Epitaxial growth and properties of doped transition metal and complex oxide films.

PubMed

Chambers, Scott A

2010-01-12

The detailed science and technology of crystalline oxide film growth using vacuum methods is reviewed and discussed with an eye toward gaining fundamental insights into the relationships between growth process and parameters, film and interface structure and composition, and electronic, magnetic and photochemical properties. The topic is approached first from a comparative point of view based on the most widely used growth methods, and then on the basis of specific material systems that have generated very high levels of interest. Emphasis is placed on the wide diversity of structural, electronic, optical and magnetic properties exhibited by oxides, and the fascinating results that this diversity of properties can produce when combined with the degrees of freedom afforded by heteroepitaxy.

Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

PubMed

Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

2014-06-01

Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., α-FeOOH, γ-FeOOH, α-Fe2O3 and γ-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or α-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments. Copyright © 2014 Elsevier Inc. All rights reserved.

Interdependence of tetrapyrrole metabolism, the generation of oxidative stress and the mitigative oxidative stress response

PubMed Central

Busch, Andrea W.U.; Montgomery, Beronda L.

2015-01-01

Tetrapyrroles are involved in light harvesting and light perception, electron-transfer reactions, and as co-factors for key enzymes and sensory proteins. Under conditions in which cells exhibit stress-induced imbalances of photosynthetic reactions, or light absorption exceeds the ability of the cell to use photoexcitation energy in synthesis reactions, redox imbalance can occur in photosynthetic cells. Such conditions can lead to the generation of reactive oxygen species (ROS) associated with alterations in tetrapyrrole homeostasis. ROS accumulation can result in cellular damage and detrimental effects on organismal fitness, or ROS molecules can serve as signals to induce a protective or damage-mitigating oxidative stress signaling response in cells. Induced oxidative stress responses include tetrapyrrole-dependent and -independent mechanisms for mitigating ROS generation and/or accumulation. Thus, tetrapyrroles can be contributors to oxidative stress, but are also essential in the oxidative stress response to protect cells by contributing to detoxification of ROS. In this review, we highlight the interconnection and interdependence of tetrapyrrole metabolism with the occurrence of oxidative stress and protective oxidative stress signaling responses in photosynthetic organisms. PMID:25618582

An ethanol extract of Piper betle Linn. mediates its anti-inflammatory activity via down-regulation of nitric oxide.

PubMed

Ganguly, Sudipto; Mula, Soumyaditya; Chattopadhyay, Subrata; Chatterjee, Mitali

2007-05-01

The leaves of Piper betle (locally known as Paan) have long been in use in the Indian indigenous system of medicine for the relief of pain; however, the underlying molecular mechanisms of this effect have not been elucidated. The anti-inflammatory and immunomodulatory effects of an ethanolic extract of the leaves of P. betle (100 mg kg(-1); PB) were demonstrated in a complete Freund's adjuvant-induced model of arthritis in rats with dexamethasone (0.1 mg kg(-1)) as the positive control. At non-toxic concentrations of PB (5-25 microg mL(-1)), a dose-dependent decrease in extracellular production of nitric oxide in murine peritoneal macrophages was measured by the Griess assay and corroborated by flow cytometry using the nitric oxide specific probe, 4,5-diaminofluorescein-2 diacetate. This decreased generation of reactive nitrogen species was mediated by PB progressively down-regulating transcription of inducible nitric oxide synthase in macrophages, and concomitantly causing a dose-dependent decrease in the expression of interleukin-12 p40, indicating the ability of PB to down-regulate T-helper 1 pro-inflammatory responses. Taken together, the anti-inflammatory and anti-arthrotic activity of PB is attributable to its ability to down-regulate the generation of reactive nitrogen species, thus meriting further pharmacological investigation.

Malondialdehyde epitopes as targets of immunity and the implications for atherosclerosis

PubMed Central

Binder, Christoph J.

2018-01-01

Accumulating evidence suggests that oxidation-specific epitopes (OSEs) constitute a novel class of damage-associated molecular patterns (DAMPs) generated during high oxidative stress but also in the physiological process of apoptosis. To deal with the potentially harmful consequences of such epitopes, the immune system has developed several mechanisms to protect from OSEs and to orchestrate their clearance, including IgM natural antibodies and both cellular and membrane-bound receptors. Here, we focus on malondialdehyde (MDA) epitopes as prominent examples of OSEs that trigger both innate and adaptive immune responses. First, we review the mechanism of MDA generation, the different types of adducts on various biomolecules and provide relevant examples for physiological carriers of MDA such as apoptotic cells, microvesicles (MV) or oxidized low-density lipoproteins (LDL). Based on recent insights, we argue that MDA epitopes contribute to the maintenance of homeostatic functions by acting as markers of elevated oxidative stress and tissue damage. We discuss multiple lines of evidence that MDA epitopes are pro-inflammatory and thus important targets of innate and adaptive immune responses. Finally, we illustrate the relevance of MDA epitopes in human pathologies by describing their capacity to drive inflammatory processes in atherosclerosis and highlighting protective mechanisms of immunity that could be exploited for therapeutic purposes. PMID:27235680

Bioinspired catalytic generation of high-valent cobalt-oxo species by the axially coordinated CoPc on pyridine-functionalized MWCNTs for the elimination of organic contaminants

NASA Astrophysics Data System (ADS)

Li, Nan; Wang, Ying; Wu, Chenren; Lu, Wangyang; Pei, Kemei; Chen, Wenxing

2018-03-01

Enzymes have always been a source of inspiration for the design and improvement of catalysts. Many examples are occurring in heme/non-heme metalloenzymes with the generation of active high-valent metal-oxo intermediates that are controlled by the surrounding amino acids/protein and axial residue ligands, facilitating the efficient oxidation of substrates in biochemical processes. Here, the high-valent cobalt-oxo species have been formed during the heterolysis of H2O2 activated by the bioinspired catalyst, axially coordinated cobalt phthalocyanine (CoPc) on pyridine-functionalized multi-walled carbon nanotubes (MWCNTs-Py), characterized by ultraviolet-visible and X-ray photoelectron spectroscopy. Formation process of the active cobalt-oxo species has been further confirmed by electrospray ionization mass spectrometry analysis and the results from the density functional theory (B3LYP/6-311G) calculations. Such high-valent cobalt-oxo species exhibit high reactivity and enough persistence for the oxidation of the target substrate, C.I. Acid Red 1. The oxidation products are nearly biodegradable small molecules identified by ultra-performance liquid chromatography/high-definition mass spectrometry. This strategy provides a foundation on developing efficient and persistent catalytic system, in particular oxidation processes based on the complex catalysts with N4 macrocycle structures.

Oxidant-induced DNA damage of target cells.

PubMed Central

Schraufstätter, I; Hyslop, P A; Jackson, J H; Cochrane, C G

1988-01-01

In this study we examined the leukocytic oxidant species that induce oxidant damage of DNA in whole cells. H2O2 added extracellularly in micromolar concentrations (10-100 microM) induced DNA strand breaks in various target cells. The sensitivity of a specific target cell was inversely correlated to its catalase content and the rate of removal of H2O2 by the target cell. Oxidant species produced by xanthine oxidase/purine or phorbol myristate acetate-stimulated monocytes induced DNA breakage of target cells in proportion to the amount of H2O2 generated. These DNA strand breaks were prevented by extracellular catalase, but not by superoxide dismutase. Cytotoxic doses of HOCl, added to target cells, did not induce DNA strand breakage, and myeloperoxidase added extracellularly in the presence of an H2O2-generating system, prevented the formation of DNA strand breaks in proportion to its H2O2 degrading capacity. The studies also indicated that H2O2 formed hydroxyl radical (.OH) intracellularly, which appeared to be the most likely free radical responsible for DNA damage: .OH was detected in cells exposed to H2O2; the DNA base, deoxyguanosine, was hydroxylated in cells exposed to H2O2; and intracellular iron was essential for induction of DNA strand breaks. PMID:2843565

Increased Advanced Oxidation Protein Products Generation by Cyclosporine-A and Angiotensin II in Human Gingival Fibroblasts – Ex-vivo Study

PubMed Central

Subbarayan, Rajasekaran; Ajitkumar, Supraja; Murugan Girija, Dinesh

2017-01-01

Introduction Cyclosporin-A (CsA), an immunosuppressant, induces renal fibrosis and Renin Angiotensin System (RAS) is known to play a major role. CsA has the potential to increase the oxidative stress; specifically through the Advanced Oxidation Protein Products (AOPP) which could possibly stimulate fibrosis. A similar type of pathology occurs even in the gingiva known as CsA Induced Gingival Overgrowth (CIGO). Aim This study was undertaken to estimate the AOPP generation by Human Gingival Fibroblasts (HGF) under the influence of CsA and Angiotensin II (Ang II). Materials and Methods Six healthy gingival tissue samples were obtained during crown lengthening procedure and primary HGF were cultured using enzymatic digestion method. The ideal non-cytotoxic concentrations of CsA and Ang II were identified using cytotoxicity assay. Later, HGF were incubated with CsA and Ang II for 12 hours and AOPP assay was performed at zero and one hour interval. Results There was a statistically significant increase in AOPP production in both the CsA and Ang II when compared to the control group with a p value<0.05. Conclusion CsA can induce oxidative stress and preventing/controlling it may be necessary to prevent untoward effect of the drug. PMID:28274044

The NADPH oxidase inhibitor apocynin (acetovanillone) induces oxidative stress

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

Riganti, Chiara; Costamagna, Costanzo; Bosia, Amalia

Apocynin (acetovanillone) is often used as a specific inhibitor of NADPH oxidase. In N11 glial cells, apocynin induced, in a dose-dependent way, a significant increase of both malonyldialdehyde level (index of lipid peroxidation) and lactate dehydrogenase release (index of a cytotoxic effect). Apocynin evoked also, in a significant way, an increase of H{sub 2}O{sub 2} concentration and a decrease of the intracellular glutathione/glutathione disulfide ratio, accompanied by augmented efflux of glutathione and glutathione disulfide. Apocynin induced the activation of both pentose phosphate pathway and tricarboxylic acid cycle, which was blocked when the cells were incubated with glutathione together with apocynin.more » The cell incubation with glutathione prevented also the apocynin-induced increase of malonyldialdehyde generation and lactate dehydrogenase leakage. Apocynin exerted an oxidant effect also in a cell-free system: indeed, in aqueous solution, it evoked a faster oxidation of the thiols glutathione and dithiothreitol, and elicited the generation of reactive oxygen species, mainly superoxide anions. Our results suggest that apocynin per se can induce an oxidative stress and exert a cytotoxic effect in N11 cells and other cell types, and that some effects of apocynin in in vitro and in vivo experimental models should be interpreted with caution.« less

[Antioxidative activities of two metabolites of cultured marine fungus, Halorosellinia oceanicum 323 in vitro].

PubMed

Luo, Jinghui; Yang, Yingbao; Lin, Yongcheng; Chen, Zhiliang; Jiang, Guangce

2004-03-01

To investigate the antioxidative effects of 323-A and 323-B, two isomers extracted from the metabolites of cultured marine fungus, Halorosellinia oceanicum 323 in vitro. NADH-PMS-NBT system was used to produce superoxide free radical (O2*-), EDTANa2-Fe(II)-H2O2 system to generate hydroxyl free radical (*OH), H2O2 to stimulate oxidative hemolysis of erythrocytes of rats, Cys-Fe2+ to induce malondialdehyde (MDA) production in homogenates, and ferrous-ascorbic acid system to increase the turbidity of mitochondria suspension in the liver of rats. And the antioxidative activities of 323-A and 323-B were studied. 323-A and 323-B not only scavenge O2*- and *OH produced by the experimental systems directly, but also inhibit H2O2 stimulated oxidative hemolysis of erythrocytes of rats, depress MDA production in homogenates induced by Cys-Fe2+ system, and reduce the turbidity of mitochondria suspension in the liver of rats increased by ferrous-ascorbic acid system in vitro. 323-A and 323-B showed comprehensive cleaning actions on free radicals and protective effects on the functions of tissues and cells against oxidative lesion. The results suggested that the marine microorganic metabolites might be a novel and profound source of antioxidative reagents.

Mathematical Modeling of Ammonia Electro-Oxidation on Polycrystalline Pt Deposited Electrodes

NASA Astrophysics Data System (ADS)

Diaz Aldana, Luis A.

The ammonia electrolysis process has been proposed as a feasible way for electrochemical generation of fuel grade hydrogen (H2). Ammonia is identified as one of the most suitable energy carriers due to its high hydrogen density, and its safe and efficient distribution chain. Moreover, the fact that this process can be applied even at low ammonia concentration feedstock opens its application to wastewater treatment along with H 2 co-generation. In the ammonia electrolysis process, ammonia is electro-oxidized in the anode side to produce N2 while H2 is evolved from water reduction in the cathode. A thermodynamic energy requirement of just five percent of the energy used in hydrogen production from water electrolysis is expected from ammonia electrolysis. However, the absence of a complete understanding of the reaction mechanism and kinetics involved in the ammonia electro-oxidation has not yet allowed the full commercialization of this process. For that reason, a kinetic model that can be trusted in the design and scale up of the ammonia electrolyzer needs to be developed. This research focused on the elucidation of the reaction mechanism and kinetic parameters for the ammonia electro-oxidation. The definition of the most relevant elementary reactions steps was obtained through the parallel analysis of experimental data and the development of a mathematical model of the ammonia electro-oxidation in a well defined hydrodynamic system, such as the rotating disk electrode (RDE). Ammonia electro-oxidation to N 2 as final product was concluded to be a slow surface confined process where parallel reactions leading to the deactivation of the catalyst are present. Through the development of this work it was possible to define a reaction mechanism and values for the kinetic parameters for ammonia electro-oxidation that allow an accurate representation of the experimental observations on a RDE system. Additionally, the validity of the reaction mechanism and kinetic parameters were supplemented by means of process scale up, performance evaluation, and hydrodynamic analysis in a flow cell electrolyzer. An adequate simulation of the flow electrolyzer performance was accomplished using the obtained kinetic parameters.

A comparison of the phototoxic potency of six types of TiO2 nanoparticles

EPA Science Inventory

Nanoparticles,such as nano-TiO2, are often photo active and can become photo toxic by the generation of reactive oxygen species (ROS) and free-radical oxidative damage to surrounding tissues. Because the retina is the only part of the central nervous system directly exposed to li...

Redox mediators modify end product distribution in biomass fermentations by mixed ruminal microbes in vitro

USDA-ARS?s Scientific Manuscript database

The fermentation system of mixed ruminal bacteria is capable of generating large amounts of short-chain volatile fatty acids (VFA) via the carboxylate platform in vitro. These VFAs are subject to elongation to larger, more energy-dense products through reverse beta-oxidation. This study examined the...

ADVANCES IN BIOTREATMENT OF ACID MINE DRAINAGE AND BIORECOVERY OF METALS: 2. MEMBRANE BIOREACTOR SYSTEM FOR SULFATE REDUCTION

EPA Science Inventory

Acid-mine drainage (AMD) is a severe pollution problem attributed to past mining activities. AMD is an acidic, metal-bearing wastewater generated by the oxidation of metal sulfides to sulfates by Thiobacillus bacteria in both the active and abandoned mining operations. The wastew...

MODULATION OF THE CYTOTOXICITY AND GENOTOXICITY OF THE DRINKING WATER DBP IODOACETIC ACID BY SUPPRESSORS OF OXIDATIVE STRESS

EPA Science Inventory

Drinking water disinfection by-products (DBPs) are generated by the chemical disinfection of water and may pose a hazard to the public health. Previously we demonstrated that iodoacetic acid was the most cytotoxic and genotoxic DBP analyzed in a mammalian cell system. Little is k...

Nitric oxide negatively regulates mammalian adult neurogenesis

NASA Astrophysics Data System (ADS)

Packer, Michael A.; Stasiv, Yuri; Benraiss, Abdellatif; Chmielnicki, Eva; Grinberg, Alexander; Westphal, Heiner; Goldman, Steven A.; Enikolopov, Grigori

2003-08-01

Neural progenitor cells are widespread throughout the adult central nervous system but only give rise to neurons in specific loci. Negative regulators of neurogenesis have therefore been postulated, but none have yet been identified as subserving a significant role in the adult brain. Here we report that nitric oxide (NO) acts as an important negative regulator of cell proliferation in the adult mammalian brain. We used two independent approaches to examine the function of NO in adult neurogenesis. In a pharmacological approach, we suppressed NO production in the rat brain by intraventricular infusion of an NO synthase inhibitor. In a genetic approach, we generated a null mutant neuronal NO synthase knockout mouse line by targeting the exon encoding active center of the enzyme. In both models, the number of new cells generated in neurogenic areas of the adult brain, the olfactory subependyma and the dentate gyrus, was strongly augmented, which indicates that division of neural stem cells in the adult brain is controlled by NO and suggests a strategy for enhancing neurogenesis in the adult central nervous system.

Insulin regulates its own delivery to skeletal muscle by feed-forward actions on the vasculature

PubMed Central

Wang, Hong; Upchurch, Charles T.; Liu, Zhenqi

2011-01-01

Insulin, at physiological concentrations, regulates the volume of microvasculature perfused within skeletal and cardiac muscle. It can also, by relaxing the larger resistance vessels, increase total muscle blood flow. Both of these effects require endothelial cell nitric oxide generation and smooth muscle cell relaxation, and each could increase delivery of insulin and nutrients to muscle. The capillary microvasculature possesses the greatest endothelial surface area of the body. Yet, whether insulin acts on the capillary endothelial cell is not known. Here, we review insulin's actions at each of three levels of the arterial vasculature as well as recent data suggesting that insulin can regulate a vesicular transport system within the endothelial cell. This latter action, if it occurs at the capillary level, could enhance insulin delivery to muscle interstitium and thereby complement insulin's actions on arteriolar endothelium to increase insulin delivery. We also review work that suggests that this action of insulin on vesicle transport depends on endothelial cell nitric oxide generation and that insulin's ability to regulate this vesicular transport system is impaired by inflammatory cytokines that provoke insulin resistance. PMID:21610226

Distributed Optical Fiber Sensors with Ultrafast Laser Enhanced Rayleigh Backscattering Profiles for Real-Time Monitoring of Solid Oxide Fuel Cell Operations.

PubMed

Yan, Aidong; Huang, Sheng; Li, Shuo; Chen, Rongzhang; Ohodnicki, Paul; Buric, Michael; Lee, Shiwoo; Li, Ming-Jun; Chen, Kevin P

2017-08-24

This paper reports a technique to enhance the magnitude and high-temperature stability of Rayleigh back-scattering signals in silica fibers for distributed sensing applications. With femtosecond laser radiation, more than 40-dB enhancement of Rayleigh backscattering signal was generated in silica fibers using 300-nJ laser pulses at 250 kHz repetition rate. The laser-induced Rayleigh scattering defects were found to be stable from the room temperature to 800 °C in hydrogen gas. The Rayleigh scatter at high temperatures was correlated to the formation and modification of nanogratings in the fiber core. Using optical fibers with enhanced Rayleigh backscattering profiles as distributed temperature sensors, we demonstrated real-time monitoring of solid oxide fuel cell (SOFC) operations with 5-mm spatial resolution at 800 °C. Information gathered by these fiber sensor tools can be used to verify simulation results or operated in a process-control system to improve the operational efficiency and longevity of SOFC-based energy generation systems.

Generation of reactive oxygen species and oxidative stress in Escherichia coli and Staphylococcus aureus by a novel semiconductor catalyst

NASA Astrophysics Data System (ADS)

Chow, K. L.; Mak, N. K.; Wong, M. H.; Zhou, X. F.; Liang, Y.

2011-03-01

The objective of this study was to investigate antimicrobial mechanisms of a new catalytic material (charge transfer auto oxidation-reduction type catalyst, CT catalyst) that may have great potential for application in water/wastewater treatment. Generation of reactive oxygen species (ROS) in bacteria-free solution, induction of ROS and oxidative damage in bacteria (including E. coli and S. aureus) were examined for the CT catalyst. The results showed that significantly higher ( p < 0.05, via t-test) amount of hydroxyl radicals was generated by the CT catalyst compared with the control, particularly after 6 h of contact time that more than twice of the amount of the control was produced. The generation of ROS in the bacteria was greater under higher pH and temperature levels, which closely related with the oxidative damage in cells. The results indicated that CT catalyst induced oxidative damage in the bacteria might serve as an important mechanism interpreting the anti-microbial function of the CT catalyst.

Magnetohydrodynamics (MHD) Engineering Test Facility (ETF) 200 MWe power plant Conceptual Design Engineering Report (CDER)

NASA Technical Reports Server (NTRS)

1981-01-01

The reference conceptual design of the magnetohydrodynamic (MHD) Engineering Test Facility (ETF), a prototype 200 MWe coal-fired electric generating plant designed to demonstrate the commercial feasibility of open cycle MHD, is summarized. Main elements of the design, systems, and plant facilities are illustrated. System design descriptions are included for closed cycle cooling water, industrial gas systems, fuel oil, boiler flue gas, coal management, seed management, slag management, plant industrial waste, fire service water, oxidant supply, MHD power ventilating

Magnetohydrodynamics (MHD) Engineering Test Facility (ETF) 200 MWe power plant Conceptual Design Engineering Report (CDER)

NASA Astrophysics Data System (ADS)

1981-09-01

The reference conceptual design of the magnetohydrodynamic (MHD) Engineering Test Facility (ETF), a prototype 200 MWe coal-fired electric generating plant designed to demonstrate the commercial feasibility of open cycle MHD, is summarized. Main elements of the design, systems, and plant facilities are illustrated. System design descriptions are included for closed cycle cooling water, industrial gas systems, fuel oil, boiler flue gas, coal management, seed management, slag management, plant industrial waste, fire service water, oxidant supply, MHD power ventilating

SOLID STATE ENERGY CONVERSION ALLIANCE DELPHI SOLID OXIDE FUEL CELL

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

Steven Shaffer; Sean Kelly; Subhasish Mukerjee

2004-05-07

The objective of this project is to develop a 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. During Phase I, the following will be accomplished: Develop and demonstrate technology transfer efforts on a 5 kW stationary distributed power generation system that incorporates steam reforming of natural gas with the option of piped-in water (Demonstration System A). Initiate development of a 5 kW system for later mass-market automotive auxiliary power unit application, which will incorporate Catalytic Partial Oxidation (CPO) reforming of gasoline, with anode exhaust gas injected into an ultra-lean burn internal combustion engine.more » This technical progress report covers work performed by Delphi from July 1, 2003 to December 31, 2003, under Department of Energy Cooperative Agreement DE-FC-02NT41246. This report highlights technical results of the work performed under the following tasks: Task 1 System Design and Integration; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant (BOP) Components; Task 5 Manufacturing Development (Privately Funded); Task 6 System Fabrication; Task 7 System Testing; Task 8 Program Management; Task 9 Stack Testing with Coal-Based Reformate; and Task 10 Technology Transfer from SECA CORE Technology Program. In this reporting period, unless otherwise noted Task 6--System Fabrication and Task 7--System Testing will be reported within Task 1 System Design and Integration. Task 8--Program Management, Task 9--Stack Testing with Coal Based Reformate, and Task 10--Technology Transfer from SECA CORE Technology Program will be reported on in the Executive Summary section of this report.« less

Vibroconvective mixing applied to vertical Bridgman growth

NASA Astrophysics Data System (ADS)

Zawilski, Kevin T.; Claudia, M.; Custodio, C.; DeMattei, Robert C.; Feigelson, Robert S.

2003-10-01

A promising method for stirring melts during vertical Bridgman growth is the coupled vibrational stirring (CVS) method. It involves the application of low frequency vibrations to the outside of the growth ampoule and produces strong flows emanating from the fluid surface. Although the technique was pioneered a number of years ago, previous studies have not provided sufficient information to explain how to control CVS generated flows in a particular system. This paper examines both the fluid flow produced by CVS and the effect of these flows on a model oxide growth system. CVS generated flows were studied using tracer particles in a water/glycerin system. The particle velocities were measured as a function of distance from the fluid surface. A large velocity gradient, decreasing from the surface, was found to be present. The velocity profile produced was dependent on the vibrational amplitude and frequency, the crucible diameter, and the fluid viscosity. The effects of CVS flows on the crystal growth interface were studied using NaNO 3 as a model oxide. Under non-growth conditions (i.e. no furnace or crucible translation), the solid-liquid interface position was found to be a strong function of vibrational frequency once CVS generated flows approached the interface. During crystal growth, undesirable growth rate fluctuations were found as the growth interface moved into regions of increasing fluid flow. This data suggests that a control system in which CVS flows are continuously decreased during growth to maintain a constant flow rate in the vicinity of the growth interface is necessary in order to prevent or reduce growth rate fluctuations.

Electrochemically assisted fabrication of size-exclusion films of organically modified silica and application to the voltammetry of phospholipids.

PubMed

Mehdi, B Layla; Rutkowska, Iwona A; Kulesza, Pawel J; Cox, James A

2013-06-01

Modification of electrodes with nm-scale organically modified silica films with pores diameters controlled at 10- and 50-nm is described. An oxidation catalyst, mixed-valence ruthenium oxide with cyano crosslinks or gold nanoparticles protected by dirhodium-substituted phosophomolybdate (AuNP-Rh 2 PMo 11 ), was immobilized in the pores. These systems comprise size-exclusion films at which the biological compounds, phosphatidylcholine and cardiolipin, were electrocatalytically oxidized without interference from surface-active concomitants such as bovine serum albumin. 10-nm pores were obtained by adding generation-4 poly(amidoamine) dendrimer, G4-PAMAM, to a (CH 3 ) 3 SiOCH 3 sol. 50-nm pores were obtained by modifying a glassy carbon electrode (GC) with a sub-monolayer film of aminopropyltriethoxylsilane, attaching 50-nm diameter poly(styrene sulfonate), PSS, spheres to the protonated amine, transferring this electrode to a (CH 3 ) 3 SiOCH 3 sol, and electrochemically generating hydronium at uncoated GC sites, which catalyzed ormosil growth around the PSS. Voltammetry of Fe(CN) 6 3- and Ru(NH 3 ) 6 3+ demonstrated the absence of residual charge after removal of the templating agents. With the 50-nm system, the pore structure was sufficiently defined to use layer-by-layer electrostatic assembly of AuNP-Rh 2 PMo 11 therein. Flow injection amperometry of phosphatidylcholine and cardiolipin demonstrated analytical utility of these electrodes.

Obesity, Oxidative Stress, Adipose Tissue Dysfunction, and the Associated Health Risks: Causes and Therapeutic Strategies.

PubMed

Manna, Prasenjit; Jain, Sushil K

2015-12-01

Obesity is gaining acceptance as a serious primary health burden that impairs the quality of life because of its associated complications, including diabetes, cardiovascular diseases, cancer, asthma, sleep disorders, hepatic dysfunction, renal dysfunction, and infertility. It is a complex metabolic disorder with a multifactorial origin. Growing evidence suggests that oxidative stress plays a role as the critical factor linking obesity with its associated complications. Obesity per se can induce systemic oxidative stress through various biochemical mechanisms, such as superoxide generation from NADPH oxidases, oxidative phosphorylation, glyceraldehyde auto-oxidation, protein kinase C activation, and polyol and hexosamine pathways. Other factors that also contribute to oxidative stress in obesity include hyperleptinemia, low antioxidant defense, chronic inflammation, and postprandial reactive oxygen species generation. In addition, recent studies suggest that adipose tissue plays a critical role in regulating the pathophysiological mechanisms of obesity and its related co-morbidities. To establish an adequate platform for the prevention of obesity and its associated health risks, understanding the factors that contribute to the cause of obesity is necessary. The most current list of obesity determinants includes genetic factors, dietary intake, physical activity, environmental and socioeconomic factors, eating disorders, and societal influences. On the basis of the currently identified predominant determinants of obesity, a broad range of strategies have been recommended to reduce the prevalence of obesity, such as regular physical activity, ad libitum food intake limiting to certain micronutrients, increased dietary intake of fruits and vegetables, and meal replacements. This review aims to highlight recent findings regarding the role of oxidative stress in the pathogenesis of obesity and its associated risk factors, the role of dysfunctional adipose tissue in development of these risk factors, and potential strategies to regulate body weight loss/gain for better health benefits.

Functional K(ATP) channels in the rat retinal microvasculature: topographical distribution, redox regulation, spermine modulation and diabetic alteration.

PubMed

Ishizaki, Eisuke; Fukumoto, Masanori; Puro, Donald G

2009-05-15

The essential task of the circulatory system is to match blood flow to local metabolic demand. However, much remains to be learned about this process. To better understand how local perfusion is regulated, we focused on the functional organization of the retinal microvasculature, which is particularly well adapted for the local control of perfusion. Here, we assessed the distribution and regulation of functional K(ATP) channels whose activation mediates the hyperpolarization induced by adenosine. Using microvascular complexes freshly isolated from the rat retina, we found a topographical heterogeneity in the distribution of functional K(ATP) channels; capillaries generate most of the K(ATP) current. The initiation of K(ATP)-induced responses in the capillaries supports the concept that the regulation of retinal perfusion is highly decentralized. Additional study revealed that microvascular K(ATP) channels are redox sensitive, with oxidants increasing their activity. Furthermore, the oxidant-mediated activation of these channels is driven by the polyamine spermine, whose catabolism produces oxidants. In addition, our observation that spermine-dependent oxidation occurs predominately in the capillaries accounts for why they generate most of the K(ATP) current detected in retinal microvascular complexes. Here, we also analysed retinal microvessels of streptozotocin-injected rats. We found that soon after the onset of diabetes, an increase in spermine-dependent oxidation at proximal microvascular sites boosts their K(ATP) current and thereby virtually eliminates the topographical heterogeneity of functional K(ATP) channels. We conclude that spermine-dependent oxidation is a previously unrecognized mechanism by which this polyamine modulates ion channels; in addition to a physiological role, spermine-dependent oxidation may also contribute to microvascular dysfunction in the diabetic retina.

Elemental mercury oxidation in an electrostatic precipitator enhanced with in situ soft X-ray irradiation.

PubMed

Jing, He; Wang, Xiaofei; Wang, Wei-Ning; Biswas, Pratim

2015-04-01

Corona discharge based techniques are promising approaches for oxidizing elemental mercury (Hg0) in flue gas from coal combustion. In this study, in-situ soft X-rays were coupled to a DC (direct current) corona-based electrostatic precipitator (ESP). The soft X-rays significantly enhanced Hg0 oxidation, due to generation of electrons from photoionization of gas molecules and the ESP electrodes. This coupling technique worked better in the positive corona discharge mode because more electrons were in the high energy region near the electrode. Detailed mechanisms of Hg0 oxidation are proposed and discussed based on ozone generation measurements and Hg0 oxidation behavior observations in single gas environments (O2, N2, and CO2). The effect of O2 concentration in flue gas, as well as the effects of particles (SiO2, TiO2, and KI) was also evaluated. In addition, the performance of a soft X-rays coupled ESP in Hg0 oxidations was investigated in a lab-scale coal combustion system. With the ESP voltage at +10 kV, soft X-ray enhancement, and KI addition, mercury oxidation was maximized. Mercury is a significant-impact atmospheric pollutant due to its toxicity. Coal-fired power plants are the primary emission sources of anthropogenic releases of mercury; hence, mercury emission control from coal-fired power plant is important. This study provides an alternative mercury control technology for coal-fired power plants. The proposed electrostatic precipitator with in situ soft X-rays has high efficiency on elemental mercury conversion. Effects of flue gas conditions (gas compositions, particles, etc.) on performance of this technology were also evaluated, which provided guidance on the application of the technology for coal-fired power plant mercury control.

Obesity, Oxidative Stress, Adipose Tissue Dysfunction, and the Associated Health Risks: Causes and Therapeutic Strategies

PubMed Central

Manna, Prasenjit

2015-01-01

Abstract Obesity is gaining acceptance as a serious primary health burden that impairs the quality of life because of its associated complications, including diabetes, cardiovascular diseases, cancer, asthma, sleep disorders, hepatic dysfunction, renal dysfunction, and infertility. It is a complex metabolic disorder with a multifactorial origin. Growing evidence suggests that oxidative stress plays a role as the critical factor linking obesity with its associated complications. Obesity per se can induce systemic oxidative stress through various biochemical mechanisms, such as superoxide generation from NADPH oxidases, oxidative phosphorylation, glyceraldehyde auto-oxidation, protein kinase C activation, and polyol and hexosamine pathways. Other factors that also contribute to oxidative stress in obesity include hyperleptinemia, low antioxidant defense, chronic inflammation, and postprandial reactive oxygen species generation. In addition, recent studies suggest that adipose tissue plays a critical role in regulating the pathophysiological mechanisms of obesity and its related co-morbidities. To establish an adequate platform for the prevention of obesity and its associated health risks, understanding the factors that contribute to the cause of obesity is necessary. The most current list of obesity determinants includes genetic factors, dietary intake, physical activity, environmental and socioeconomic factors, eating disorders, and societal influences. On the basis of the currently identified predominant determinants of obesity, a broad range of strategies have been recommended to reduce the prevalence of obesity, such as regular physical activity, ad libitum food intake limiting to certain micronutrients, increased dietary intake of fruits and vegetables, and meal replacements. This review aims to highlight recent findings regarding the role of oxidative stress in the pathogenesis of obesity and its associated risk factors, the role of dysfunctional adipose tissue in development of these risk factors, and potential strategies to regulate body weight loss/gain for better health benefits. PMID:26569333

High-fat diet induces skeletal muscle oxidative stress in a fiber type-dependent manner in rats.

PubMed

Pinho, Ricardo A; Sepa-Kishi, Diane M; Bikopoulos, George; Wu, Michelle V; Uthayakumar, Abinas; Mohasses, Arta; Hughes, Meghan C; Perry, Christopher G R; Ceddia, Rolando B

2017-09-01

This study investigated the effects of high-fat (HF) diet on parameters of oxidative stress among muscles with distinct fiber type composition and oxidative capacities. To accomplish that, male Wistar rats were fed either a low-fat standard chow (SC) or a HF diet for 8 weeks. Soleus, extensor digitorum longus (EDL), and epitrochlearis muscles were collected and mitochondrial H 2 O 2 (mtH 2 O 2 ) emission, palmitate oxidation, and gene expression and antioxidant system were measured. Chronic HF feeding enhanced fat oxidation in oxidative and glycolytic muscles. It also caused a significant reduction in mtH 2 O 2 emission in the EDL muscle, although a tendency towards a reduction was also found in the soleus and epitrochlearis muscles. In the epitrochlearis, HF diet increased mRNA expression of the NADPH oxidase complex; however, this muscle also showed an increase in the expression of antioxidant proteins, suggesting a higher capacity to generate and buffer ROS. The soleus muscle, despite being highly oxidative, elicited H 2 O 2 emission rates equivalent to only 20% and 35% of the values obtained for EDL and epitrochlearis muscles, respectively. Furthermore, the Epi muscle with the lowest oxidative capacity was the second highest in H 2 O 2 emission. In conclusion, it appears that intrinsic differences related to the distribution of type I and type II fibers, rather than oxidative capacity, drove the activity of the anti- and pro-oxidant systems and determine ROS production in different skeletal muscles. This also suggests that the impact of potentially deleterious effects of ROS production on skeletal muscle metabolism/function under lipotoxic conditions is fiber type-specific. Copyright © 2017. Published by Elsevier Inc.

Free radicals generated during oxidation of green tea polyphenols: electron paramagnetic resonance spectroscopy combined with density functional theory calculations.

PubMed

Severino, Joyce Ferreira; Goodman, Bernard A; Kay, Christopher W M; Stolze, Klaus; Tunega, Daniel; Reichenauer, Thomas G; Pirker, Katharina F

2009-04-15

Electron paramagnetic resonance spectroscopy and density functional theory calculations have been used to investigate the redox properties of the green tea polyphenols (GTPs) (-)-epigallocatechin gallate (EGCG), (-)-epigallocatechin (EGC), and (-)-epicatechin gallate (ECG). Aqueous extracts of green tea and these individual phenols were autoxidized at alkaline pH and oxidized by superoxide anion (O(2)(-)) radicals in dimethyl sulfoxide. Several new aspects of the free radical chemistry of GTPs were revealed. EGCG can be oxidized on both the B and the D ring. The B ring was the main oxidation site during autoxidation, but the D ring was the preferred site for O(2)(-) oxidation. Oxidation of the D ring was followed by structural degradation, leading to generation of a radical identical to that of oxidized gallic acid. Alkaline autoxidation of green tea extracts produced four radicals that were related to products of the oxidation of EGCG, EGC, ECG, and gallic acid, whereas the spectra from O(2)(-) oxidation could be explained solely by radicals generated from EGCG. Assignments of hyperfine coupling constants were made by DFT calculations, allowing the identities of the radicals observed to be confirmed.

Functional Studies on Oligotropha carboxidovorans Molybdenum-Copper CO Dehydrogenase Produced in Escherichia coli.

PubMed

Kaufmann, Paul; Duffus, Benjamin R; Teutloff, Christian; Leimkühler, Silke

2018-04-30

The Mo/Cu-dependent CO dehydrogenase (CODH) from Oligotropha carboxidovorans is an enzyme that is able to catalyze both the oxidation of CO to CO 2 and the oxidation of H 2 to protons and electrons. Despite the close to atomic resolution structure (1.1 Å), significant uncertainties have remained with regard to the reaction mechanism of substrate oxidation at the unique Mo/Cu center, as well as the nature of intermediates formed during the catalytic cycle. So far, the investigation of the role of amino acids at the active site was hampered by the lack of a suitable expression system that allowed for detailed site-directed mutagenesis studies at the active site. Here, we report on the establishment of a functional heterologous expression system of O. carboxidovorans CODH in Escherichia coli. We characterize the purified enzyme in detail by a combination of kinetic and spectroscopic studies and show that it was purified in a form with characteristics comparable to those of the native enzyme purified from O. carboxidovorans. With this expression system in hand, we were for the first time able to generate active-site variants of this enzyme. Our work presents the basis for more detailed studies of the reaction mechanism for CO and H 2 oxidation of Mo/Cu-dependent CODHs in the future.