Oxidative degradation of lignin by photochemical and chemical radical generating systems

International Nuclear Information System (INIS)

Gold, M.H.; Kutsuki, H.; Morgan, M.A.

1983-01-01

Oxidation of specifically radiolabeled 14 C-lignins by UV/H 2 O 2 , Fenton's reagent, photosensitizing riboflavin, UV- and γ-irradiation was examined. In the presence of UV/H 2 O 2 , a hydroxyl radical (radicalOH) generating system, 14 C-methoxy, 2-[ 14 C-sidechain] and 14 C-ring labeled lignin were rapidly and extensively degraded as measured by gel filtration of the reaction products on Sephadex LH-20. This suggested that exposure to radicalOH leads to rapid, nonspecific lignin degradation. Rapid degradation of 14 C-methoxy, 2-[ 14 C-sidechain] and 14 C-ring labeled lignin also occurred in the presence of the radicalOH generating system, Fenton's reagent, confirming the primary role of radicalOH in these reactions. Photosensitizing riboflavin, also capable of effecting transformation of organic compounds via Type I hydrogen radical abstractions, caused extensive oxidative degradation of 14 C-methoxy labeled lignin and significant degradation of 2-[ 14 C-sidechain] and 14 C-ring labeled lignin. In addition, UV- and γ-irradiation caused slower but extensive degradation of the polymers, probably via radical type mechanisms. All of these results indicate that radicalOH as well as organic radical generating systems are effective agents for the purpose of degrading this heterogeneous, optically inactive and random biopolymer. (author)

A large capacity turbine generator for nuclear power generation

International Nuclear Information System (INIS)

Maeda, Susumu; Miki, Takahiro; Suzuki, Kazuichi

2000-01-01

In future large capacity nuclear power plant, capacity of a generator to be applied will be 1800 MVA of the largest class in the world. In response to this, the Mitsubishi Electric Co., Ltd. began to carry out element technology verification of a four-pole large capacity turbine generator mainly using upgrading technique of large capacity, since 1994 fiscal year. And, aiming at reliability verification of the 1800 MVA class generator, a model generator with same cross-section as that of an actual one was manufactured, to carry out some verifications on its electrified tests, and so on. Every performance evaluation result of tests on the model generator were good, and high reliability to design and manufacturing technique of the 1800 MVA class generator could be verified. In future, on the base of these technologies, further upgrading of reliability on the large capacity turbine generator for nuclear power generation is intended to be carried out. (G.K.)

A novel property of gold nanoparticles: Free radical generation under microwave irradiation

International Nuclear Information System (INIS)

Paudel, Nava Raj; Shvydka, Diana; Parsai, E. Ishmael

2016-01-01

Purpose: Gold nanoparticles (GNPs) are known to be effective mediators in microwave hyperthermia. Interaction with an electromagnetic field, large surface to volume ratio, and size quantization of nanoparticles (NPs) can lead to increased cell killing beyond pure heating effects. The purpose of this study is to explore the possibility of free radical generation by GNPs in aqueous media when they are exposed to a microwave field. Methods: A number of samples with 500 mM 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in 20 ppm GNP colloidal suspensions were scanned with an electron paramagnetic resonance (EPR)/electron spin resonance spectrometer to generate and detect free radicals. A fixed (9.68 GHz) frequency microwave from the spectrometer has served for both generation and detection of radicals. EPR spectra obtained as first derivatives of intensity with the spectrometer were double integrated to get the free radical signal intensities. Power dependence of radical intensity was studied by applying various levels of microwave power (12.5, 49.7, and 125 mW) while keeping all other scan parameters the same. Free radical signal intensities from initial and final scans, acquired at the same power levels, were compared. Results: Hydroxyl radical (OH⋅) signal was found to be generated due to the exposure of GNP–DMPO colloidal samples to a microwave field. Intensity of OH⋅ signal thus generated at 12.5 mW microwave power for 2.8 min was close to the intensity of OH⋅ signal obtained from a water–DMPO sample exposed to 1.5 Gy ionizing radiation dose. For repeated scans, higher OH⋅ intensities were observed in the final scan for higher power levels applied between the initial and the final scans. Final intensities were higher also for a shorter time interval between the initial and the final scans. Conclusions: Our results observed for the first time demonstrate that GNPs generate OH⋅ radicals in aqueous media when they are exposed to a microwave field. If OH�

A novel property of gold nanoparticles: Free radical generation under microwave irradiation.

Science.gov (United States)

Paudel, Nava Raj; Shvydka, Diana; Parsai, E Ishmael

2016-04-01

Gold nanoparticles (GNPs) are known to be effective mediators in microwave hyperthermia. Interaction with an electromagnetic field, large surface to volume ratio, and size quantization of nanoparticles (NPs) can lead to increased cell killing beyond pure heating effects. The purpose of this study is to explore the possibility of free radical generation by GNPs in aqueous media when they are exposed to a microwave field. A number of samples with 500 mM 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in 20 ppm GNP colloidal suspensions were scanned with an electron paramagnetic resonance (EPR)/electron spin resonance spectrometer to generate and detect free radicals. A fixed (9.68 GHz) frequency microwave from the spectrometer has served for both generation and detection of radicals. EPR spectra obtained as first derivatives of intensity with the spectrometer were double integrated to get the free radical signal intensities. Power dependence of radical intensity was studied by applying various levels of microwave power (12.5, 49.7, and 125 mW) while keeping all other scan parameters the same. Free radical signal intensities from initial and final scans, acquired at the same power levels, were compared. Hydroxyl radical (OH⋅) signal was found to be generated due to the exposure of GNP-DMPO colloidal samples to a microwave field. Intensity of OH⋅ signal thus generated at 12.5 mW microwave power for 2.8 min was close to the intensity of OH⋅ signal obtained from a water-DMPO sample exposed to 1.5 Gy ionizing radiation dose. For repeated scans, higher OH⋅ intensities were observed in the final scan for higher power levels applied between the initial and the final scans. Final intensities were higher also for a shorter time interval between the initial and the final scans. Our results observed for the first time demonstrate that GNPs generate OH⋅ radicals in aqueous media when they are exposed to a microwave field. If OH⋅ radicals can be generated close to

A novel property of gold nanoparticles: Free radical generation under microwave irradiation

Energy Technology Data Exchange (ETDEWEB)

Paudel, Nava Raj, E-mail: nrpaudel@yahoo.com [Department of Radiation Oncology, The University of Toledo Medical Center, Toledo, Ohio 43614 and Department of Radiation Oncology, University of Arkansas for Medical Sciences, Little Rock, Arkansas 72205 (United States); Shvydka, Diana; Parsai, E. Ishmael [Department of Radiation Oncology, The University of Toledo Medical Center, Toledo, Ohio 43614 (United States)

2016-04-15

Purpose: Gold nanoparticles (GNPs) are known to be effective mediators in microwave hyperthermia. Interaction with an electromagnetic field, large surface to volume ratio, and size quantization of nanoparticles (NPs) can lead to increased cell killing beyond pure heating effects. The purpose of this study is to explore the possibility of free radical generation by GNPs in aqueous media when they are exposed to a microwave field. Methods: A number of samples with 500 mM 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in 20 ppm GNP colloidal suspensions were scanned with an electron paramagnetic resonance (EPR)/electron spin resonance spectrometer to generate and detect free radicals. A fixed (9.68 GHz) frequency microwave from the spectrometer has served for both generation and detection of radicals. EPR spectra obtained as first derivatives of intensity with the spectrometer were double integrated to get the free radical signal intensities. Power dependence of radical intensity was studied by applying various levels of microwave power (12.5, 49.7, and 125 mW) while keeping all other scan parameters the same. Free radical signal intensities from initial and final scans, acquired at the same power levels, were compared. Results: Hydroxyl radical (OH⋅) signal was found to be generated due to the exposure of GNP–DMPO colloidal samples to a microwave field. Intensity of OH⋅ signal thus generated at 12.5 mW microwave power for 2.8 min was close to the intensity of OH⋅ signal obtained from a water–DMPO sample exposed to 1.5 Gy ionizing radiation dose. For repeated scans, higher OH⋅ intensities were observed in the final scan for higher power levels applied between the initial and the final scans. Final intensities were higher also for a shorter time interval between the initial and the final scans. Conclusions: Our results observed for the first time demonstrate that GNPs generate OH⋅ radicals in aqueous media when they are exposed to a microwave field. If OH�

Investigating free radical generation in HepG2 cells using immuno-spin trapping.

Science.gov (United States)

Horinouchi, Yuya; Summers, Fiona A; Ehrenshaft, Marilyn; Kawazoe, Kazuyoshi; Tsuchiya, Koichiro; Tamaki, Toshiaki; Mason, Ronald P

2014-10-01

Oxidative stress can induce the generation of free radicals, which are believed to play an important role in both physiological and pathological processes and a number of diseases such as cancer. Therefore, it is important to identify chemicals which are capable of inducing oxidative stress. In this study, we evaluated the ability of four environmental chemicals, aniline, nitrosobenzene (NB), N,N-dimethylaniline (DMA) and N,N-dimethyl-4-nitrosoaniline (DMNA), to induce free radicals and cellular damage in the hepatoma cell line HepG2. Cytotoxicity was assessed using lactate dehydrogenase (LDH) assays and morphological changes were observed using phase contrast microscopy. Free radicals were detected by immuno-spin trapping (IST) in in-cell western experiments or in confocal microscopy experiments to determine the subcellular localization of free radical generation. DMNA induced free radical generation, LDH release and morphological changes in HepG2 cells whereas aniline, NB and DMA did not. Confocal microscopy showed that DMNA induced free radical generation mainly in the cytosol. Preincubation of HepG2 cells with N-acetylcysteine and 2,2'-dipyridyl significantly prevented free radical generation upon subsequent incubation with DMNA, whereas preincubation with apocynin and dimethyl sulfoxide did not. These results suggest that DMNA induces oxidative stress and that reactive oxygen species, metals and free radical generation play a critical role in DMNA-induced cytotoxicity. Copyright © 2014. Published by Elsevier Inc.

Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation.

Science.gov (United States)

Zhang, Tao; Chen, Yin; Wang, Yuru; Le Roux, Julien; Yang, Yang; Croué, Jean-Philippe

2014-05-20

Peroxydisulfate (PDS) is an appealing oxidant for contaminated groundwater and toxic industrial wastewaters. Activation of PDS is necessary for application because of its low reactivity. Present activation processes always generate sulfate radicals as actual oxidants which unselectively oxidize organics and halide anions reducing oxidation capacity of PDS and producing toxic halogenated products. Here we report that copper oxide (CuO) can efficiently activate PDS under mild conditions without producing sulfate radicals. The PDS/CuO coupled process is most efficient at neutral pH for decomposing a model compound, 2,4-dichlorophenol (2,4-DCP). In a continuous-flow reaction with an empty-bed contact time of 0.55 min, over 90% of 2,4-DCP (initially 20 μM) and 90% of adsorbable organic chlorine (AOCl) can be removed at the PDS/2,4-DCP molar ratio of 1 and 4, respectively. Based on kinetic study and surface characterization, PDS is proposed to be first activated by CuO through outer-sphere interaction, the rate-limiting step, followed by a rapid reaction with 2,4-DCP present in the solution. In the presence of ubiquitous chloride ions in groundwater/industrial wastewater, the PDS/CuO oxidation shows significant advantages over sulfate radical oxidation by achieving much higher 2,4-DCP degradation capacity and avoiding the formation of highly chlorinated degradation products. This work provides a new way of PDS activation for contaminant removal.

Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation

KAUST Repository

Zhang, Tao

2014-05-20

Peroxydisulfate (PDS) is an appealing oxidant for contaminated groundwater and toxic industrial wastewaters. Activation of PDS is necessary for application because of its low reactivity. Present activation processes always generate sulfate radicals as actual oxidants which unselectively oxidize organics and halide anions reducing oxidation capacity of PDS and producing toxic halogenated products. Here we report that copper oxide (CuO) can efficiently activate PDS under mild conditions without producing sulfate radicals. The PDS/CuO coupled process is most efficient at neutral pH for decomposing a model compound, 2,4-dichlorophenol (2,4-DCP). In a continuous-flow reaction with an empty-bed contact time of 0.55 min, over 90% of 2,4-DCP (initially 20 μM) and 90% of adsorbable organic chlorine (AOCl) can be removed at the PDS/2,4-DCP molar ratio of 1 and 4, respectively. Based on kinetic study and surface characterization, PDS is proposed to be first activated by CuO through outer-sphere interaction, the rate-limiting step, followed by a rapid reaction with 2,4-DCP present in the solution. In the presence of ubiquitous chloride ions in groundwater/industrial wastewater, the PDS/CuO oxidation shows significant advantages over sulfate radical oxidation by achieving much higher 2,4-DCP degradation capacity and avoiding the formation of highly chlorinated degradation products. This work provides a new way of PDS activation for contaminant removal. © 2014 American Chemical Society.

Particle size-dependent radical generation from wildland fire smoke

International Nuclear Information System (INIS)

Leonard, Stephen S.; Castranova, Vince; Chen, Bean T.; Schwegler-Berry, Diane; Hoover, Mark; Piacitelli, Chris; Gaughan, Denise M.

2007-01-01

Firefighting, along with construction, mining and agriculture, ranks among the most dangerous occupations. In addition, the work environment of firefighters is unlike that of any other occupation, not only because of the obvious physical hazards but also due to the respiratory and systemic health hazards of smoke inhalation resulting from combustion. A significant amount of research has been devoted to studying municipal firefighters; however, these studies may not be useful in wildland firefighter exposures, because the two work environments are so different. Not only are wildland firefighters exposed to different combustion products, but their exposure profiles are different. The combustion products wildland firefighters are exposed to can vary greatly in characteristics due to the type and amount of material being burned, soil conditions, temperature and exposure time. Smoke inhalation is one of the greatest concerns for firefighter health and it has been shown that the smoke consists of a large number of particles. These smoke particles contain intermediates of hydrogen, carbon and oxygen free radicals, which may pose a potential health risk. Our investigation looked into the involvement of free radicals in smoke toxicity and the relationship between particle size and radical generation. Samples were collected in discrete aerodynamic particle sizes from a wildfire in Alaska, preserved and then shipped to our laboratory for analysis. Electron spin resonance was used to measure carbon-centered as well as hydroxyl radicals produced by a Fenton-like reaction with wildfire smoke. Further study of reactive oxygen species was conducted using analysis of cellular H 2 O 2 generation, lipid peroxidation of cellular membranes and DNA damage. Results demonstrate that coarse size-range particles contained more carbon radicals per unit mass than the ultrafine particles; however, the ultrafine particles generated more ·OH radicals in the acellular Fenton-like reaction. The

Optimization of free radical scavenging capacity and pH of Hylocereus polyrhizus peel by Response Surface Methodology

Science.gov (United States)

Putranto, A. W.; Dewi, S. R.; Puspitasari, Y.; Nuriah, F. A.

2018-03-01

Red dragon fruit (Hylocereus polyrhizus) peel, a by-product of juice processing, contains a high antioxidant that can be used for nutraceuticals. Hence, it is important to extract and investigate its antioxidant stability. The aim of this study was to optimize the free radical scavenging capacity and pH of H. polyrhizus peel extract using Central Composite Design (CCD) under Response Surface Methodology (RSM). The extraction of H. polyrhizus peel was done by using green-Pulsed Electric Field (PEF)-assisted extraction method. Factors optimized were electric field strength (kV/cm) and extraction time (seconds). The result showed that the correlation between responses (free radical-scavenging capacity and pH) and two factors was quadratic model. The optimum conditions was obtained at the electric field strength of 3.96 kV/cm, and treatment time of 31.9 seconds. Under these conditions, the actual free radical-scavenging capacity and pH were 75.86 ± 0.2 % and 4.8, respectively. The verification model showed that the actual values are in accordance with the predicted values, and have error rate values of free radical-scavenging capacity and pH responses were 0.1% and 3.98%, respectively. We suggest to extract the H. polyrhizus peel using a green and non-thermal extraction technology, PEF-assisted extraction, for research, food applications and nutraceuticals industry.

Fragmentation characteristics of the unstable [CH3 CO][radical sign] radicals generated by neutralization of [CH3CO]+ cations

Science.gov (United States)

Hop, C. E. C. A.; Holmes, J. L.

1991-03-01

The stability and fragmentation characteristics of [CH3 CO][radical sign] radicals, generated by vertical charge exchange between acetyl cations and permanent gases or metal vapours (He, Xe, NO, Cd, Na and K), were examined mass spectrometrically. Two dissociation reactions were observed, the losses of CH[radical sign]3 and H[radical sign]. The H[radical sign] loss reaction, the higher energy dissociation, became of greater importance as the exothermicity of the charge exchange was increased. Based on the analysis of the kinetic energy releases it was concluded that these decompositions arose from the population of two excited states of the [CH3 CO][radical sign] radical.

Generation and detection of the cyclohexadienyl radical in phosphonium ionic liquids.

Science.gov (United States)

Lauzon, J M; Arseneau, D J; Brodovitch, J C; Clyburne, J A C; Cormier, P; McCollum, B; Ghandi, K

2008-10-21

The formation of the cyclohexadienyl radical, C(6)H(6)Mu, in ionic and molecular solvents has been compared. This is the first time that a muoniated free radical is reported in an ionic liquid. In marked contrast to molecular liquids, free radical generation in ionic liquids is significantly enhanced. Comparison of the hyperfine interactions in the ionic liquid and in molecular solvents and with theoretical calculations, suggests significant and unforeseen solvent interaction with the cyclohexadienyl radical.

Photoswitching of triplet-triplet annihilation upconversion with photo-generated radical from hexaphenylbiimidazole

Energy Technology Data Exchange (ETDEWEB)

Mahmood, Zafar [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Toffoletti, Antonio [Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo, 1, 35131 Padova (Italy); Zhao, Jianzhang, E-mail: zhaojzh@dlut.edu.cn [State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Barbon, Antonio, E-mail: antonio.barbon@unipd.it [Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo, 1, 35131 Padova (Italy)

2017-03-15

Photoirradiation generated radical from hexaphenyl-biimidazole (HPBI) was used for reversible switching of triplet-triplet annihilation (TTA) upconversion, based on quenching of the photosensitizer triplet state by radical-triplet pair mechanism. Upon 365 nm irradiation, the TTA upconversion in a system composed by a boron-dipyrromethene (BODIPY) derivative and perylene, was completely switched off due to quenching of triplet state of photosensitizer by photogenerated radical from HPBI. The upconversion was recovered after leaving the samples in darkness, due to regeneration of HPBI Dimer. The photophysical process involved in the photochromism and photoswitching of TTA upconversion were studied with steady-state UV–vis absorption spectroscopy, nanosecond transient absorption spectroscopy and EPR spectroscopy. - Graphical abstract: Radical-switched TTA upconversion was achieved with reversible quenching of the triplet state by photo-generated stable organic radical from photochromic hexaphenylbiimidazole.

Radicals of DNA and DNA nucleotides generated by ionising radiation

International Nuclear Information System (INIS)

Przybytniak, G.

2004-01-01

A first stage of cell processes leading to DNA damage of initiated by radical reactions. In a model system such transformations were generated by ionising radiation which involves production of electron loss and electron gain centers of the substrate and radical formation. Using cryogenic ESR spectroscopy it was found that the DNA nucleotides, which convert to radical anions upon electron capture undergo the separation of unpaired spin and charge due to protonation. Circular and linear dichroism studies enabled to conclude that iron ions(III) induce strong changes in the DNA helical structure indicating their coordination with nitrogen bases. The repair of DNA radicals produced via radiolytic oxidation, i.e. the guanine radical cation and the allyl type radical of thymine, is possible at elevated temperatures due to the involvement of sulphydryl groups. The influence of the thiol charge is then limited

Antioxidant and Free Radical Scavenging Capacity of Seed and Shell Essential Oils Extracted from Abrus precatorius (L

Directory of Open Access Journals (Sweden)

Sunday O. Okoh

2014-04-01

Full Text Available Essential oils from plants have been proven safe as natural antioxidants, and few are already marketed as digestive enhancers as well as in prevention of several degenerative diseases. This study evaluated the antioxidant capacity of seed and shell essential oils of Abrus precatorius (L, a herb used for ethno-medicinal practices in Nigeria. The essential oils were obtained by hydro-distillation. The ability of the oils to act as hydrogen/electrons donor or scavenger of radicals were determined by in-vitro antioxidant assays using 2,2-diphenyl-2-picryl-hydrazyl free radical (DPPH. scavenging; 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid (ABTS radical scavenging; lipid peroxide and nitric oxide radicals scavenging assays. The IC50 of the seed and shell oils (2.10 mg/mL and 1.20 mg/mL respectively showed that antioxidant activity is higher than that for the standard drugs (3.20 mg/mL and 3.40 mg/mL for the nitric oxide scavenging assay. The lipid peroxidation radical activity of the oils were similar to vitamin C, weak DPPH and ABTS radical scavenging activities were discovered in comparison to vitamin C and rutin. Generally, in the four antioxidant assays, a significant correlation existed between concentrations of the oils and percentage inhibition of free radicals and lipid peroxidation. The composition of A. precatorius essential oils reported earlier may account for their antioxidant capacity.

Free radical generation from an aniline derivative in HepG2 cells: a possible captodative effect.

Science.gov (United States)

Horinouchi, Yuya; Summers, Fiona A; Ehrenshaft, Marilyn; Mason, Ronald P

2015-01-01

Xenobiotic metabolism can induce the generation of protein radicals, which are believed to play an important role in the toxicity of chemicals and drugs. It is therefore important to identify chemical structures capable of inducing macromolecular free radical formation in living cells. In this study, we evaluated the ability of four structurally related environmental chemicals, aniline, nitrosobenzene, N,N-dimethylaniline, and N,N-dimethyl-4-nitrosoaniline (DMNA), to induce free radicals and cellular damage in the hepatoma cell line HepG2. Cytotoxicity was assessed using lactate dehydrogenase assays, and morphological changes were observed using phase contrast microscopy. Protein free radicals were detected by immuno-spin trapping using in-cell western experiments and confocal microscopy to determine the subcellular locale of free radical generation. DMNA induced free radical generation, lactate dehydrogenase release, and morphological changes in HepG2 cells, whereas aniline, nitrosobenzene, N,N-dimethylaniline did not. Confocal microscopy showed that DMNA induced free radical generation mainly in the cytosol. Preincubation of HepG2 cells with N-acetylcysteine and 2,2'-dipyridyl significantly prevented free radical generation on subsequent incubation with DMNA, whereas preincubation with apocynin and dimethyl sulfoxide had no effect. These results suggest that DMNA is metabolized to reactive free radicals capable of generating protein radicals which may play a critical role in DMNA toxicity. We propose that the captodative effect, the combined action of the electron-releasing dimethylamine substituent, and the electron-withdrawing nitroso substituent, leads to a thermodynamically stabilized radical, facilitating enhanced protein radical formation by DMNA. Copyright © 2014 Elsevier Inc. All rights reserved.

Analysis of Ethyl Acetate Extract of Enzymatic Hydrolysate from High Purity Oleuropein and DPPH Radical Scavenging Capacity

Science.gov (United States)

Yuan, Jiaojiao; Li, Bing; Qin, Frank G. F.; Tu, Junling

2018-01-01

High purify oleuropein (81.04% OL) was hydrolyzed by hemicellulase and phenols was existed in the ethyl acetate extract of enzymatic hydrolysate (EAE). The results presented that there were hydroxytyrosol (HT), tyrosol, caffeic acid, 3,4-dihydroxybenzoic acid, 3,4-dihydroxy phenylacetic acid in EAE by HPLC, and HT content was 19.36%. Antioxidant activities (DPPH radical scavenging capacity) were all added as the samples concentration increased, and dose-effect relationships also existed. HT possessed the highest DPPH radical scavenging capacity, followed by Vc, and eugenol, OL, caffeic acid, 3,4-dihydroxy phenylacetic acid and 3,4-dihydroxybenzoic acid.

Applicability of an improved Trolox equivalent antioxidant capacity (TEAC) assay for evaluation of antioxidant capacity measurements of mixtures

NARCIS (Netherlands)

Berg, R. van den; Haenen, G.R.M.M.; Berg, H. van den; Bast, A.

1999-01-01

The TEAC (Trolox equivalent antioxidant capacity) assay is based on scavenging of 2,2'-azinobis-(3- ethylbenzothiazoline-6-sulfonate) radical anions (ABTS(.-)). In this report we describe a modification based on pre-generation of the ABTS radical anions with a thermolabile azo compound, 2,2'-azobis-

Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system.

Science.gov (United States)

Huang, Xiaoqiang; Luo, Shipeng; Burghaus, Olaf; Webster, Richard D; Harms, Klaus; Meggers, Eric

2017-10-01

We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation.

Iron release from ferritin and lipid peroxidation by radiolytically generated reducing radicals

International Nuclear Information System (INIS)

Reif, D.W.; Schubert, J.; Aust, S.D.

1988-01-01

Iron is involved in the formation of oxidants capable of damaging membranes, protein, and DNA. Using 137 Cs gamma radiation, we investigated the release of iron from ferritin and concomitant lipid peroxidation by radiolytically generated reducing radicals, superoxide and the carbon dioxide anion radical. Both radicals released iron from ferritin with similar efficiencies and iron mobilization from ferritin required an iron chelator. Radiolytically generated superoxide anion resulted in peroxidation of phospholipid liposomes as measured by malondialdehyde formation only when ferritin was included as an iron source and the released iron was found to be chelated by the phospholipid liposomes

The scavenging of free radical and oxygen species activities and hydration capacity of collagen hydrolysates from walleye pollock ( Theragra chalcogramma) skin

Science.gov (United States)

Zhuang, Yongliang; Li, Bafang; Zhao, Xue

2009-06-01

Fish skin collagen hydrolysates (FSCH) were prepared from walleye pollock ( Theragra chalcogramma) using a mixture of enzymes, namely trypsin and flavourzyme. The degree of hydrolysis of the skin collagen was 27.3%. FSCH was mainly composed of low-molecular-weight peptides and the relative proportion of <1000Da fraction was 70.6%. Free radical and oxygen species scavenging activities of FSCH were investigated in four model systems, including diphenylpicrylhy-drazyl radical (DPPH), superoxide anion radical, hydroxyl radical and hydrogen peroxide model, and compared with that of a native antioxidant, reduced glutathione (GSH). FSCH was also evaluated by water-absorbing and water-holding capacity. The results showed that FSCH was able to scavenge free radical and oxygen species significantly and to enhance water-absorbing and water-holding capacity remarkably. Therefore, FSCH may have potential applications in the medicine and food industries.

A Brief Review on Electro-generated Hydroxyl Radical for Organic Wastewater Mineralization

Directory of Open Access Journals (Sweden)

Ervin Nurhayati

2016-05-01

Full Text Available Hydroxyl radical is a highly reactive oxidizing agent that can be electrochemically generated on the surface of Boron doped diamond (BDD anode. Once generated, this radical will non-selectively mineralize organic pollutants to carbon dioxide, water and organic anions as the oxidation products. Its application in Advanced Oxidation Process (AOP to degrade nonbiodegradable even the recalcitrant pollutants in wastewater has been increasingly studied and even applied.

Generation of OH Radical by Ultrasonic Irradiation in Batch and Circulatory Reactor

Science.gov (United States)

Fang, Yu; Shimizu, Sayaka; Yamamoto, Takuya; Komarov, Sergey

2018-03-01

Ultrasonic technology has been widely investigated in the past as one of the advance oxidation processes to treat wastewater, in this process acoustic cavitation causes generation of OH radical, which play a vital role in improving the treatment efficiency. In this study, OH radical formation rate was measured in batch and circulatory reactor by using Weissler reaction at various ultrasound output power. It is found that the generation rate in batch reactor is higher than that in circulatory reactor at the same output power. The generation rate tended to be slower when output power exceeds 137W. The optimum condition for circulatory reactor was found to be 137W output and 4L/min flow rate. Results of aluminum foil erosion test revealed a strong dependence of cavitation zone length on the ultrasound output power. This is assumed to be one of the reasons why the generation rate of HO radicals becomes slower at higher output power in circulatory reactor.

Effects of the components in rice flour on thermal radical generation under microwave irradiation.

Science.gov (United States)

Lin, Lufen; Huang, Luelue; Fan, Daming; Hu, Bo; Gao, Yishu; Lian, Huizhang; Zhao, Jianxin; Zhang, Hao; Chen, Wei

2016-12-01

The relationships between radical generation under microwave irradiation and the components of various types of rice flour were investigated. Electron paramagnetic resonance (EPR) spectroscopy was used to characterize the radicals found in rice flour samples. The EPR spectra revealed that several types of radical (carbon-centered, tyrosyl and semiquinone) were localized in the starch and protein fractions of the rice flour. The signal intensity of the free radicals was observed to increase exponentially with increasing microwave power and residence time. The rice bran samples exhibited the greatest free radical signal intensity, followed by the brown rice samples and the white rice samples. This finding was consistent for both the native and the microwaved samples. The ratio of rice starch to rice protein also played an important role in the generation of radicals. Copyright © 2016 Elsevier B.V. All rights reserved.

Quantitative detection of plasma-generated radicals in liquids by electron paramagnetic resonance spectroscopy

International Nuclear Information System (INIS)

Tresp, H; Hammer, M U; Winter, J; Reuter, S; Weltmann, K-D

2013-01-01

In this paper the qualitative and quantitative detection of oxygen radicals in liquids after plasma treatment with an atmospheric pressure argon plasma jet by electron paramagnetic resonance spectroscopy is investigated. Absolute values for · OH and O 2 ·- radical concentration and their net production rate in plasma-treated liquids are determined without the use of additional scavenging chemicals such as superoxide dismutase (SOD) or mannitol (D-MAN). The main oxygen-centred radical generation in PBS was found to originate from the superoxide radical. It is shown that hidden parameters such as the manufacturer of chemical components could have a big influence on the comparability and reproducibility of the results. Finally, the effect of a shielding gas device for the investigated plasma jet with a shielding gas composition of varying oxygen-to-nitrogen ratio on radical generation after plasma treatment of phosphate-buffered saline solution was investigated. (paper)

Antioxidant capacity and oxygen radical diseases in the preterm newborn.

Science.gov (United States)

Rogers, S; Witz, G; Anwar, M; Hiatt, M; Hegyi, T

2000-06-01

Bronchopulmonary dysplasia, intraventricular hemorrhage, necrotizing enterocolitis, and retinopathy of prematurity may be different manifestations of oxygen radical diseases of prematurity (ORDP). To test the hypothesis that the antioxidant capacity of cord blood serum will predict risk of ORDP. An inception cohort of premature neonates was followed up from birth until discharge or death to determine if outcome was related to cord blood serum antioxidant capacity, as determined by a manual assay measuring the relative inhibition of oxidation of 2,2'-azino-di-(3-ethylbenzthiazoline)-6 sulfonic acid (ABTS). Possible correlations between antioxidant capacity and various perinatal factors were also tested. Level 3 newborn intensive care unit. All inborn very low-birth-weight neonates from whom cord blood was available and for whom maternal consent was obtained were included. Newborns who died in the first week of life or who had major congenital malformations were excluded. A convenience sample of newborns weighing more than 1500 g was used to perfect assay and explore confounders. Significant ORDP was defined as the presence of intraventricular hemorrhage greater than grade 2, retinopathy of prematurity greater than stage 1, bronchopulmonary dysplasia at the postconceptional age of 36 weeks, or necrotizing enterocolitis with the hypothesis that neonates with ORDP will have lower antioxidant capacity in cord blood serum. Serum antioxidant capacity at birth correlated with gestational age for the entire sample of 41 neonates and for the 26 neonates born before 32 weeks' gestation. After correction for gestational age, cord serum antioxidant capacity did not correlate with maternal smoking, preeclampsia, chorioamnionitis, cord pH Apgar scores, or any of the ORDP studied. Cord serum antioxidant capacity correlates with gestational age but does not predict ORDP risk.

Reactions of carbon radicals generated by 1,5-transposition of reactive centers

Directory of Open Access Journals (Sweden)

ZIVORAD CEKOVIC

2005-03-01

Full Text Available Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the d-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.

Generation of various radicals in nitrogen plasma and their behavior in media

International Nuclear Information System (INIS)

Uhm, Han S.

2015-01-01

Research on the generation of radicals in nitrogen plasma shows that the most dominant radicals are excited nitrogen molecules in the metastable state of N 2 (A 3 ∑ u + ). Hydroxyl molecules are generated from the dissociation of water molecules upon contact with excited nitrogen molecules. The estimated densities of various radicals in nitrogen plasma with an electron temperature of 1 eV are presented in this study. The behavior of these radicals in media is also investigated. Excited nitrogen molecules in the N 2 (A 3 ∑ u + ) state from a plasma jet are injected into water, after which the molecules disappear instantaneously within a few tens of nm, producing hydroxyl molecules. Hydrogen peroxide, hydrogen dioxide, and nitrogen monoxide molecules can diffuse much deeper into water, implying the possibility that a chemical reaction between hydrogen dioxide and nitrogen monoxide molecules produces hydroxyl molecules in deep water, even though density in this case may not be very high

Effect of processing on phenolic acids composition and radical scavenging capacity of barley pasta.

Science.gov (United States)

De Paula, Rosanna; Rabalski, Iwona; Messia, Maria Cristina; Abdel-Aal, El-Sayed M; Marconi, Emanuele

2017-12-01

Phenolic acids, total phenolics content and DPPH radical scavenging capacity in raw ingredients, fresh and dried spaghetti, and in uncooked and cooked spaghetti were evaluated and compared with semolina spaghetti as a reference. Ferulic acid was the major phenolic acid found in the free and bound phenolic extracts in all the investigated pasta samples. The addition of barley flour into pasta at incorporation levels of 30, 50 and 100% increased phenolic acids and total phenolics content. Pasta processing did not significantly affect the total phenolics content and free radical scavenging capacity, but a significant reduction in total phenolic acids measured by HPLC was found. Drying process differently affected individual phenolic compounds in the free and bound fractions, and thus, the total phenolic acids content. Free vanillic, caffeic and p-coumaric acids did not significantly change, while p-hydroxybenzoic and ferulic acids of the free extracts showed higher values compared to the corresponding fresh pasta. Cooking did not greatly affect total phenolic acids, more leading to conserving free and bound phenolic compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Radical Scavenging Capacity of Methanolic Phillyrea latifolia L. Extract: Anthocyanin and Phenolic Acids Composition of Fruits

Directory of Open Access Journals (Sweden)

Naciye Erkan

2013-01-01

Full Text Available Radical scavenging capacity of a crude methanolic extract from the fruits of Phillyrea latifolia L., commonly known as green olive tree or mock privet, was investigated with reference to anthocyanin standards, as flavonoids, and phenolic acid standards, as phenylpropanoids. Characterization with high performance liquid chromatography-diode array detection (HPLC-DAD indicated the presence of keracyanin, kuromanin, cyanidin, ferulic acid, caffeic acid and rosmarinic acid at amounts of 289.1, 90.4, 191.4, 225.2, 221.2 and 190.1 mg/100 g fresh weight (FW of fruits, respectively. Chlorogenic and p-coumaric acids were found to exist in lower amounts. Trolox equivalent antioxidant capacity (TEAC and IC50 values of the plant extract were found to be 1.8 mM Trolox equivalents (TE/g FW of fruits and 69.4 µg/mL, respectively, indicating the close radical scavenging activity of the extract to those of keracyanin and p-coumaric acid. The crude methanolic P. latifolia L. fruit extract was seen to be fairly potent in radical scavenging. Total phenolic content (TPC of the plant extract was found to be 1652.9 mg gallic acid equivalent (GAE/100 g FW of fruits.

Determining the local origin of hydroxyl radical generation during phacoemulsification.

Science.gov (United States)

Aust, Steven D; Terry, Scott; Hebdon, Thomas; Gunderson, Broc; Terry, Michael; Dimalanta, Ramon

2011-06-01

To determine the local origin of hydroxyl radicals during phacoemulsification using an ultrasonic phacoemulsification device that includes longitudinal and torsional modalities. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. Experimental study. Experiments were conducted using the Infiniti Vision System and Ozil handpiece. Hydroxyl radical concentrations during longitudinal and torsional phacoemulsification were quantitated as malondialdehyde (MDA) determined spectrophotometrically using the deoxyribose assay. The difference between the total concentration found in the aspirated solution at steady-state concentrations and the pre-aspirate levels deductively determined the concentration of MDA formed along the interior of the sonicating tip. The time to reach 50% of steady state as a function of reaction vessel volume was determined. The mean maximum for torsional ultrasound at 100% amplitude was 7.70 nM ± 0.38 (SD), 91.1% of which was generated outside the tip. During longitudinal ultrasound at 100% power, MDA concentration in the aspirated solution was 29.5 ± 0.3 nM, 71.6% of which was generated outside the tip. The time (seconds) to reach 50% of maximum for longitudinal ultrasound using 5 mL, 10 mL, and 20 mL reaction vessels was 12.6 ± 1.5, 21.0 ± 1.5, and 25.3 ± 3.4, respectively. Although a significantly greater proportion of the hydroxyl radicals generated during ultrasound modality were formed outside the phaco tip (91.1% torsional; 71.6% longitudinal), torsional ultrasound generated only about one-fourth the amount of MDA as longitudinal ultrasound in total and about one-third that generated outside the tip (7.02 nM versus 21.1 nM). No author has a financial or proprietary interest in any material or method mentioned. Additional disclosures are found in the footnotes. Copyright © 2011 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.

Degradation of acetic acid with sulfate radical generated by persulfate ions photolysis.

Science.gov (United States)

Criquet, Justine; Leitner, Nathalie Karpel Vel

2009-09-01

The photolysis of S(2)O(8)(2-) was studied for the removal of acetic acid in aqueous solution and compared with the H(2)O(2)/UV system. The SO(4)(-) radicals generated from the UV irradiation of S(2)O(8)(2-) ions yield a greater mineralization of acetic acid than the ()OH radicals. Acetic acid is oxidized by SO(4)(-) radicals without significant formation of intermediate by-products. Increasing system pH results in the formation of ()OH radicals from SO(4)(-) radicals. Maximum acetic acid degradation occurred at pH 5. The results suggest that above this pH, competitive reactions with the carbon mineralized inhibit the reaction of the solute with SO(4)(-) and also ()OH radicals. Scavenging effects of two naturally occurring ions were tested; in contrast to HCO(3)(-) ions, the presence of Cl(-) ions enhances the efficiency of the S(2)O(8)(2-)/UV process towards the acetate removal. It is attributed to the formation of the Cl() radical and its great reactivity towards acetate.

Isomerization of Second-Generation Isoprene Peroxy Radicals

DEFF Research Database (Denmark)

D'Ambro, Emma L.; Møller, Kristian Holten; Lopez-Hilfiker, Felipe D.

2017-01-01

kinetics box model, we find that to explain the behavior of low-volatility products and SOA mass yields relative to input H2O2 concentrations, the second-generation dihydroxy hydroperoxy peroxy radical (C5H11O6·) must undergo an intramolecular H-shift with a net forward rate constant of order 0.1 s-1...... products under atmospheric conditions and, thus, on the importance of nonreactive gas-particle partitioning of isoprene oxidation products as an SOA source....

Polyphenol contents and radical scavenging capacities of red maple (Acer rubrum L.) extracts.

Science.gov (United States)

Royer, Mariana; Diouf, Papa Niokhor; Stevanovic, Tatjana

2011-09-01

The crude ethanol and water extracts of different red maple (Acer rubrum L.) tissues: whole branches (WB), wood of branches (BW), bark of branches (BB), stem bark (SB) and whole twigs (T), were examined in order to determine their phenolic contents as well as their radical scavenging capacities. The total phenols (TP), total extractable tanins (TET) and non-precipitable phenols (NPP), were determined by combination of spectrophotometric and precipitation methods, while total flavonoids, hydroxy cinanmic acids and proanthocyanidins were determined spectrophotometrically. The radical scavenging activities of the extracts were determined against five reactive oxygen species (ROS): superoxide anion (O(2)(·-)), hydroxyl radical (HO(·)), peroxyl radical (ROO(·)), hypochlorite ion (ClO(-)), and hydrogen peroxide (H(2)O(2)) and one reactive nitrogen species (RNS): nitric oxide (NO). The extracts of stem bark were significantly more efficient (exhibiting the highest antioxidant efficiencies, AE) than the other studied extracts against all ROS (at p<0.05, Duncan statistical tests), except against NO. The correlation coefficients determined between total phenolic (TP) content and antiradical efficiencies were R(2)=0.12 for O(2)(·-); R(2)=0.29 for HO(·); R(2)=0.40 for H(2)O(2); R(2)=0.86 for ROO(·); R(2)=0.03 for NO(·) and R(2)=0.73 for ClO(-). Our results indicate potential utilisation of extracts as natural antioxidants. Copyright © 2011 Elsevier Ltd. All rights reserved.

World nuclear generating capacity 1993/94

International Nuclear Information System (INIS)

Anon.

1994-01-01

This article is the annual summary of world nuclear generating capacity for 1994. A global summary is first provided, reviewing total installed capacity and growth in installed capacity over the next five years. A more detailed discussion of the nuclear efforts in 34 countries follows, with a tabular listing of nuclear projects in each of these countries. The listing includes reactor supplier, reactor type, size, current status, and date of commercial operation

Micrococcus radiodurans surface exonuclease. Dimer to monomer conversion by ionizing radiation-generated aqueous free radicals

Energy Technology Data Exchange (ETDEWEB)

Mitchel, R E.J.

1980-01-01

Micrococcus radiodurans possesses an exonuclease firmly bound to a middle cell wall membrane layer. Aqueous OH/sup -/ radicals generated chemically or by ionizing radiation cause the immediate release of this enzyme into the surrounding medium. The enzyme is located in a hydrophobic site and can also be released by aqueous n-butanol. When extracted by this solvent it is a non-covalently linked dimer and has a molecular weight of 260,000 as determined by gel filtration. When released by radiation generated OH/sup -/ radicals, the enzyme initially appears in solution as the dimer but is rapidly split by further aqueous radical attack into two 130,000 molecular weight subunits. Hydroxyl radicals are most effective but reducing radicals are also able to monomerize the enzyme. Only the released dimer enzyme is subject to free radical monomerization. Bound dimer enzyme is not split prior to release. No detectable loss of activity or change in catalytic properties accompanies the free radical cleavage of the enzyme. Both subunits of the dimer enzyme possess a tightly bound metal ion (probably Ca/sup 2 +/) required for activity. The monomer but not the dimer enzyme will bind to an anion exchanger. The monomer is susceptible to loss of its metal ion, and consequent inactivation, when exposed to the exchanger in the absence of Ca/sup 2 +/. Besides providing information on some of the immediate non-lethal effects of ionizing radiation, the behavior of this enzyme system demonstrates a potential cellular mechanism by which internally or externally generated free radicals could be utilized by the cell to control various enzymic reactions.

Multiple free-radical scavenging (MULTIS) capacity in cattle serum.

Science.gov (United States)

Sueishi, Yoshimi; Kamogawa, Erisa; Kimura, Anna; Kitahara, Go; Satoh, Hiroyuki; Asanuma, Taketoshi; Oowada, Shigeru

2017-01-01

Multiple free-radical scavenging (MULTIS) activity in cattle and human sera was evaluated with electron spin resonance spectroscopy. Scavenging rates against six active species, namely hydroxyl radical, superoxide anion, alkoxyl radical, alkylperoxyl radical, methyl radical, and singlet oxygen were quantified. The difference in the electron spin resonance signal intensity in the presence and absence of the serum was converted into the scavenging rates. Comparative MULTIS measurements were made in sera from eight beef cattle, three fetal calves and fifteen healthy human volunteers. Further, we determined the MULTIS value of albumin, the most abundant component in serum. MULTIS values in cattle sera indicated higher scavenging activity against most free radical species tested than human sera. In particular, cattle serum scavenging activities against superoxide and methyl radical were higher than human serum by 2.6 and 3.7 fold, respectively. In cattle serum, albumin appears to play a dominant role in MULTIS activity, but in human serum that is not the case. Previous data indicated that the abundance of uric acid in bovine blood is nearly 80% less than humans; however, this difference does not explain the deviation in MULTIS profile.

Effect of flavoring chemicals on free radical formation in electronic cigarette aerosols.

Science.gov (United States)

Bitzer, Zachary T; Goel, Reema; Reilly, Samantha M; Elias, Ryan J; Silakov, Alexey; Foulds, Jonathan; Muscat, Joshua; Richie, John P

2018-05-20

Flavoring chemicals, or flavorants, have been used in electronic cigarettes (e-cigarettes) since their inception; however, little is known about their toxicological effects. Free radicals present in e-cigarette aerosols have been shown to induce oxidative stress resulting in damage to proliferation, survival, and inflammation pathways in the cell. Aerosols generated from e-liquid solvents alone contain high levels of free radicals but few studies have looked at how these toxins are modulated by flavorants. We investigated the effects of different flavorants on free radical production in e-cigarette aerosols. Free radicals generated from 49 commercially available e-liquid flavors were captured and analyzed using electron paramagnetic resonance (EPR). The flavorant composition of each e-liquid was analyzed by gas chromatography mass spectroscopy (GCMS). Radical production was correlated with flavorant abundance. Ten compounds were identified and analyzed for their impact on free radical generation. Nearly half of the flavors modulated free radical generation. Flavorants with strong correlations included β-damascone, δ-tetradecalactone, γ-decalactone, citral, dipentene, ethyl maltol, ethyl vanillin, ethyl vanillin PG acetal, linalool, and piperonal. Dipentene, ethyl maltol, citral, linalool, and piperonal promoted radical formation in a concentration-dependent manner. Ethyl vanillin inhibited the radical formation in a concentration dependent manner. Free radical production was closely linked with the capacity to oxidize biologically-relevant lipids. Our results suggest that flavoring agents play an important role in either enhancing or inhibiting the production of free radicals in flavored e-cigarette aerosols. This information is important for developing regulatory strategies aimed at reducing potential harm from e-cigarettes. Copyright © 2018 Elsevier Inc. All rights reserved.

Reliability payments to generation capacity in electricity markets

International Nuclear Information System (INIS)

Olsina, Fernando; Pringles, Rolando; Larisson, Carlos; Garcés, Francisco

2014-01-01

Electric power is a critical input to modern economies. Generation adequacy and security of supply in power systems running under competition are currently topics of high concern for consumers, regulators and governments. In a market setting, generation investments and adequacy can only be achieved by an appropriate regulatory framework that sets efficient remuneration to power capacity. Theoretically, energy-only electricity markets are efficient and no additional mechanism is needed. Nonetheless, the energy-only market design suffers from serious drawbacks. Therefore, jointly with the evolution of electricity markets, many remunerating mechanisms for generation capacity have been proposed. Explicit capacity payment was the first remunerating approach implemented and perhaps still the most applied. However, this price-based regulation has been applied no without severe difficulties and criticism. In this paper, a new reliability payment mechanism is envisioned. Capacity of each generating unit is paid according to its effective contribution to overall system reliability. The proposed scheme has many attractive features and preserves the theoretical efficiency properties of energy-only markets. Fairness, incentive compatibility, market power mitigation and settlement rules are investigated in this work. The article also examines the requirements for system data and models in order to implement the proposed capacity mechanism. A numerical example on a real hydrothermal system serves for illustrating the practicability of the proposed approach and the resulting reliability payments to the generation units. - Highlights: • A new approach for remunerating supply reliability provided by generation units is proposed. • The contribution of each generating unit to lessen power shortfalls is determined by simulations. • Efficiency, fairness and incentive compatibility of the proposed reliability payment are assessed

Capacity value evaluation of photovoltaic power generation

International Nuclear Information System (INIS)

Kurihara, I.

1993-01-01

The paper presents an example of capacity value (kW-value) evaluation of photovoltaic generation from power companies generation planning point of view. The method actually applied to evaluate the supplying capability of conventional generation plants is briefly described. 21 figs, 1 tab

Spin trapping study on the nature of radicals generated by X radiolysis and peroxidation of linolenic acid

International Nuclear Information System (INIS)

Azizova, O.A.; Osipov, A.N.; Zubarev, V.E.; Yakhyaev, A.V.; Vladimirov, Yu.A.; Savov, V.M.; Kagan, V.E.

1983-01-01

The radicals of linolenic acid and their spin adducts (SA) with PBN formed during X radiolysis of linolenic acid and in lipid peroxidation with ferrous ions were investigated and identified. It was found that in the absence of oxygen in pure linolenic acid at 77 K X irradiation produces alkyl and carboxyl radicals. In the presence of the spin trap alkyl radical spin adducts were formed. Irradiation of linolenic acid in the presence of oxygen at 77 K also resulted in the formation of alkyl radicals. These radicals were transformed into peroxy radicals in the interaction of alkyl radical with oxygen upon heating to 117 K. In the presence of spin trap X irradiation of linolenic acid and heating of the sample up to 300 K gave rise to EPR spectra of SA alkyl and unidentified radicals. Lipid peroxidation of linolenic acid induced by ferrous ions in the presence of spin trap also formed radicals and SA of linolenic acid. The spectral parameters of SA generated with ferrous ions in lipid peroxidation and of those generated during X radiolysis do not differ. The similarity of spectral parameters of SA in these two cases suggests a similarity in the structure of linolenic acid radicals. (author)

Photodynamically generated bovine serum albumin radicals

DEFF Research Database (Denmark)

Silvester, J A; Timmins, G S; Davies, Michael Jonathan

1998-01-01

Porphyrin-sensitized photoxidation of bovine serum albumin (BSA) results in oxidation of the protein at (at least) two different, specific sites: the Cys-34 residue giving rise to a thiyl radical (RS.); and one or both of the tryptophan residues (Trp-134 and Trp-214) resulting in the formation...... of tertiary carbon-centred radicals and disruption of the tryptophan ring system. In the case of porphyrins such as hematoporphyrin, which bind at specific sites on BSA, these species appear to arise via long-range transfer of damage within the protein structure, as the binding site is some distance from...... the ultimate site of radical formation. This transfer of damage is shown to depend on a number of factors including the conformation of the protein, the presence of blocking groups and pH. Alteration of the protein conformation results in radical formation at additional (or alternative) sites, as does blocking...

Capacity expansion model of wind power generation based on ELCC

Science.gov (United States)

Yuan, Bo; Zong, Jin; Wu, Shengyu

2018-02-01

Capacity expansion is an indispensable prerequisite for power system planning and construction. A reasonable, efficient and accurate capacity expansion model (CEM) is crucial to power system planning. In most current CEMs, the capacity of wind power generation is considered as boundary conditions instead of decision variables, which may lead to curtailment or over construction of flexible resource, especially at a high renewable energy penetration scenario. This paper proposed a wind power generation capacity value(CV) calculation method based on effective load-carrying capability, and a CEM that co-optimizes wind power generation and conventional power sources. Wind power generation is considered as decision variable in this model, and the model can accurately reflect the uncertainty nature of wind power.

Power generation capacity planning under budget constraint in developing countries

International Nuclear Information System (INIS)

Afful-Dadzie, Anthony; Afful-Dadzie, Eric; Awudu, Iddrisu; Banuro, Joseph Kwaku

2017-01-01

Highlights: • A long term stochastic GEP model with budget constraint is developed. • Model suitable for analyzing GEP problems in developing countries. • Model determines optimal mix, size and timing of future generation capacity needs. • A real case study of the Ghana GEP problem was employed. • Insufficient budget leads to costly generation capacity expansion plans. - Abstract: This paper presents a novel multi-period stochastic optimization model for studying long-term power generation capacity planning in developing countries. A stylized model is developed to achieve three objectives: (1) to serve as a tool for determining optimal mix, size and timing of power generation types in the face of budget constraint, (2) to help decision makers appreciate the consequences of capacity expansion decisions on level of unserved electricity demand and its attendant impact on the national economy, and (3) to encourage the habit of periodic savings towards new generation capacity financing. The problem is modeled using a stochastic mixed-integer linear programming (MILP) technique under demand uncertainty. The effectiveness of the model, together with valuable insights derived from considering different levels of budget constraints are demonstrated using Ghana as a case study. The results indicate that at an annual savings equivalent to 0.75% of GDP, Ghana could finance the needed generation capacity to meet approximately 95% of its annual electricity demand between 2016 and 2035. Additionally, it is observed that as financial constraint becomes tighter, decisions on the mix of new generation capacities tend to be more costly compared to when sufficient funds are available.

Free radicals generated by radiolysis of aqueous solutions

International Nuclear Information System (INIS)

Schwarz, H.A.

1981-01-01

The free radicals produced in the radiolysis of aqueous solutions span the range of redox potentials from -2.9 to +2.65 volts. The identity and nature of these radicals were discussed. Most of the discussion was results obtained with low LET radiation sources ( 60 Co gamma radiation or electron accelerators). Water radiolysis provides the synthesis of many radicals and radical ions in aqueous solution. The primary radicals, e/sub aq/ - H, OH, are well characterized. The radical population can be made to be 90% pure OH (or O - ) if N 2 O solutions are irradiated, the remaining 10% being H atoms. 55% of the radicals can be converted to H atoms in acid solution or in neutral phosphate solutions(e/sub aq/ - reacts with H 2 PO 4- to produce H). The remaining 45% (OH radicals) are difficult to convert to H by reaction with H 2 , due to the slow rate of the reaction. About 100 atmospheres of H 2 are required to do the conversion in less than 10 - 6 sec. 3 figures, 3 tables. (DP)

Essays on investment planning in electricity generating capacity

Science.gov (United States)

Gonzalez-Gomez, Jorge

In the first part of this study we develop and analyze two mathematical models that incorporate a time changing demand for electricity and uncertainty of input prices. The first model highlights the shortcomings in assuming a constant plant utilization under uncertainty of input prices and the effects of such assumption on the optimal investment in electricity generating capacity in a simple two period model. The second model presents sufficient restrictions to the optimal investment in electricity generating capacity problem to allow for a recursive solution. The necessary restrictions are extremely limiting to the extend that we found a solution for very simple scenarios. In our opinion, the problem is better handled in a case by case basis rather than under a general dynamic framework. Following the spirit of our conclusions of the first part of our study, in the second part we provide a methodology to simulate long-term natural gas prices, we analyze the investment prospects of nuclear and natural gas generating capacity in Mexico and provide a constraint approach for the optimal generation of hydroelectric plants in the Mexican hydroelectric system. These three problems belong to the solution of the optimal investment in electricity generating capacity in Mexico. To simulate the uncertainty of natural gas prices, we assume that natural gas prices are the sum of two stochastic processes: short-term and long-term variability. We characterize the short-term variability of natural gas prices using an Exponential General Autoregressive Conditional Heteroskedastic (EGARCH) model. The uncertainty of the long-term variability of natural gas prices is based on the long-term natural gas prices scenarios of the National Energy Modeling System of the Energy Information Administration. Equipped with a methodology to simulate long-term natural gas prices, we investigate the investment prospects of nuclear and natural gas generating capacity in Mexico using the levelized

Generation of hydroxyl radicals by urban suspended particulate air matter. The role of iron ions

Science.gov (United States)

Valavanidis, Athanasios; Salika, Anastasia; Theodoropoulou, Anna

Recent epidemiologic studies showed statistical associations between particulate air pollution in urban areas and increased morbidity and mortality, even at levels well within current national air quality standards. Inhalable particulate matter (PM 10) can penetrate into the lower airways where they can cause acute and chronic lung injury by generating toxic oxygen free radicals. We tested inhalable total suspended particulates (TSP) from the Athens area, diesel and gasoline exhaust particles (DEP and GED), and urban street dusts, by Electron Paramagnetic Resonance (EPR). All particulates can generate hydroxyl radicals (HO ṡ), in aqueous buffered solutions, in the presence of hydrogen peroxide. Results showed that oxidant generating activity is related with soluble iron ions. Leaching studies showed that urban particulate matter can release large amounts of Fe 3+ and lesser amounts of Fe 2+, as it was shown from other studies. Direct evidence of HO ṡ was confirmed by spin trapping with DMPO and measurement of DMPO-OH adduct by EPR. Evidence was supported with the use of chelator (EDTA), which increases the EPR signal, and the inhibition of the radical generating activity by desferrioxamine or/and antioxidants ( D-mannitol, sodium benzoate).

Cupric ion reducing antioxidant capacity assay for antioxidants in human serum and for hydroxyl radical scavengers.

Science.gov (United States)

Apak, Reşat; Güçlü, Kubilay; Ozyürek, Mustafa; Bektaşoğlu, Burcu; Bener, Mustafa

2010-01-01

, for which the FRAP (ferric reducing antioxidant potency) test is basically nonresponsive. The additivity of absorbances of all the tested antioxidants confirmed that antioxidants in the CUPRAC test do not chemically interact among each other so as to cause an intensification or quenching of the theoretically expected absorbance, and that a total antioxidant capacity (TAC) assay of serum is possible. As a distinct advantage over other electron-transfer based assays (e.g., Folin, FRAP, ABTS, DPPH), CUPRAC is superior in regard to its realistic pH close to the physiological pH, favorable redox potential, accessibility and stability of reagents, and applicability to lipophilic antioxidants as well as hydrophilic ones. The CUPRAC procedure can also assay hydroxyl radicals, being the most reactive oxygen species (ROS). As a more convenient, efficient, and less costly alternative to HPLC/electrochemical detection techniques and to the nonspecific, low-yield TBARS test, we use p-aminobenzoate, 2,4- and 3,5-dimethoxybenzoate probes for detecting hydroxyl radicals generated from an equivalent mixture of [Fe(II)+EDTA] with hydrogen peroxide. The produced hydroxyl radicals attack both the probe and the water-soluble antioxidants in 37 degrees C-incubated solutions for 2 h. The CUPRAC absorbance of the ethylacetate extract due to the reduction of Cu(II)-neocuproine reagent by the hydroxylated probe decreases in the presence of (.)OH scavengers, the difference being proportional to the scavenging ability of the tested compound. The developed method is less lengthy, more specific, and of a higher yield than the classical TBARS assay.

Toll-Like Receptor-Mediated Free Radical Generation in Clonorchis sinensis Excretory-Secretory Product-Treated Cholangiocarcinoma Cells.

Science.gov (United States)

Bahk, Young Yil; Pak, Jhang Ho

2016-10-01

Clonorchiasis, caused by direct contact with Clonorchis sinensis worms and their excretory-secretory products (ESPs), is associated with chronic inflammation, malignant changes in bile ducts, and even cholangiocarcinogenesis. Our previous report revealed that intracellular free radicals enzymatically generated by C. sinensis ESPs cause NF-κB-mediated inflammation in human cholangiocarcinoma cells (HuCCT1). Therefore, the present study was conducted to examine the role of upstream Toll-like receptors (TLRs) on the initial host innate immune responses to infection. We found that treatment of HuCCT1 cells with native ESPs induced changes in TLR mRNA levels in a time-dependent manner, concomitant with the generation of free radicals. ESP-mediated free radical generation was markedly attenuated by preincubation of the cells with TLR1-4-neutralizing antibodies, indicating that at least TLR1 through 4 participate in stimulation of the host innate immune responses. These findings indicate that free radicals triggered by ESPs are critically involved in TLR signal transduction. Continuous signaling by this pathway may function in initiating C. sinensis infection-associated inflammation cascades, a detrimental event leading to progression to more severe hepatobiliary diseases.

HFE gene variants and iron-induced oxygen radical generation in idiopathic pulmonary fibrosis.

Science.gov (United States)

Sangiuolo, Federica; Puxeddu, Ermanno; Pezzuto, Gabriella; Cavalli, Francesco; Longo, Giuliana; Comandini, Alessia; Di Pierro, Donato; Pallante, Marco; Sergiacomi, Gianluigi; Simonetti, Giovanni; Zompatori, Maurizio; Orlandi, Augusto; Magrini, Andrea; Amicosante, Massimo; Mariani, Francesca; Losi, Monica; Fraboni, Daniela; Bisetti, Alberto; Saltini, Cesare

2015-02-01

In idiopathic pulmonary fibrosis (IPF), lung accumulation of excessive extracellular iron and macrophage haemosiderin may suggest disordered iron homeostasis leading to recurring microscopic injury and fibrosing damage. The current study population comprised 89 consistent IPF patients and 107 controls. 54 patients and 11 controls underwent bronchoalveolar lavage (BAL). Haemosiderin was assessed by Perls' stain, BAL fluid malondialdehyde (MDA) by high-performance liquid chromatography, BAL cell iron-dependent oxygen radical generation by fluorimetry and the frequency of hereditary haemochromatosis HFE gene variants by reverse dot blot hybridisation. Macrophage haemosiderin, BAL fluid MDA and BAL cell unstimulated iron-dependent oxygen radical generation were all significantly increased above controls (pHFE allelic variants was markedly higher in IPF compared with controls (40.4% versus 22.4%, OR 2.35, p=0.008) and was associated with higher iron-dependent oxygen radical generation (HFE variant 107.4±56.0, HFE wild type (wt) 59.4±36.4 and controls 16.7±11.8 fluorescence units per 10(5) BAL cells; p=0.028 HFE variant versus HFE wt, p=0.006 HFE wt versus controls). The data suggest iron dysregulation associated with HFE allelic variants may play an important role in increasing susceptibility to environmental exposures, leading to recurring injury and fibrosis in IPF. Copyright ©ERS 2015.

Free radical scavenging and total antioxidant capacity of root extracts of Anchomanes difformis Engl. (Araceae).

Science.gov (United States)

Aliyu, Abubakar B; Ibrahim, Mohammed A; Musa, Aliyu M; Musa, Aisha O; Kiplimo, Joyce J; Oyewale, Adebayo O

2013-01-01

Antioxidants activities from plants sources have attracted a wide range of interest across the world in recent times. This is due to growing concern for safe and alternative sources of antioxidants. The free radical scavenging activity using 1,1-diphenyl-2-picrylhydrazyl radical (DPPH), reducing power assay, total antioxidant capacity of the phosphomolybdenum method and the total phenolics content using the Folin-Ciocalteu reagent were carried out on the acetone, n-butanol and methanol root extracts of Anchomanes difformis. The results of the total phenolics content expressed in mg/100 g of gallic acid equivalent (GAE) showed that the n-butanol extract has significantly (p extracts. All the extracts displayed strong concentration dependent radical scavenging activity. It was also observed that the n-butanol extract showed higher activity of 70.87% and 78.59% at low concentrations of 31.25 microg/mL and 62.5 microg/mL, respectively, than methanol and acetone extracts. The results also showed that the n-butanol extract has strongest reducing ability which is comparable to that of gallic acid at all the concentrations tested. Phytochemical screening on the extracts revealed the presence of flavonoids, saponins, and tannins. The results suggest that n-butanol extract of the plant is very rich in antioxidant compounds worthy of further investigations.

Screening of free radical scavenging capacity and antioxidant activities of Rosmarinus officinalis extracts with focus on location and harvesting times

NARCIS (Netherlands)

Yesil Celiktas, O.; Girgin, G.; Orhan, H.; Wichers, H.J.; Bedir, E.; Vardar Sukan, F.

2007-01-01

Methanolic extracts from the leaves of Rosmarinus officinalis (rosemary) harvested from different locations of Turkey at four different times of the year were analyzed by HPLC, and their radical scavenging capacities and antioxidant activities were studied by various assays. The amounts of carnosol,

Induction of oxygen free radical generation in human monocytes by lipoprotein(a)

DEFF Research Database (Denmark)

Riis Hansen, P; Kharazmi, A; Jauhiainen, M

1994-01-01

The mechanism behind the association of elevated plasma lipoprotein(a) [Lp(a)] levels with atherosclerotic disease is unknown. In the present study, Lp(a) induced generation of oxygen free radicals by monocytes from selected healthy individuals in vitro. This observation may provide a link between...

Free radical generation in post-irradiation period: an evidence from the conversion of xanthine dehydrogenase into xanthine oxidase

International Nuclear Information System (INIS)

Kale, R.K.

2003-01-01

Xanthine oxidoreductase (XOR) system which consists of xanthine dehydrogenase (XDH) and xathine oxidase (XO), is one of the major sources of free radicals in biological systems. XOR system is pre-dominantly present as XDH in the normal tissue and converts into free radical generating XO-Form in the damaged tissue. Therefore, XO-Form of XOR system, is expected to be mainly found in the radiolytically damaged tissue. In such an event, XO may catalyze the generation of free radicals and potentiate the radiation effects in post-irradiation period. Recent findings on the effect of ionizing radiation on XOR system in the liver of mice, peroxidative damage and lactate dehydrogenase support this possibility. From these results it has been hypothized that free radical generating systems could be activated in the radiolytically damaged cell and in turn contribute to the cause and complications of late effects and their persistence in post-irradiation period. This aspect may have great significance in understanding the radiation - induced damages. It may also have serious implication in various fields like radiation therapy, health physics, carcinogenesis, space travelling radiation exposures and post nuclear accident care. Further, it is suggested that efforts need to be made to search more system(s) which could be activated particularly at lower doses of radiation and generate free radicals in post-irradiation period

Antioxidant Effects of Herbal Tea Leaves from Yacon (Smallanthus sonchifolius) on Multiple Free Radical and Reducing Power Assays, Especially on Different Superoxide Anion Radical Generation Systems.

Science.gov (United States)

Sugahara, Shintaro; Ueda, Yuto; Fukuhara, Kumiko; Kamamuta, Yuki; Matsuda, Yasushi; Murata, Tatsuro; Kuroda, Yasuhiro; Kabata, Kiyotaka; Ono, Masateru; Igoshi, Keiji; Yasuda, Shin

2015-11-01

Yacon (Smallanthus sonchifolius), a native Andean plant, has been cultivated as a crop and locally used as a traditional folk medicine for the people suffering from diabetes and digestive/renal disorders. However, the medicinal properties of this plant and its processed foods have not been completely established. This study investigates the potent antioxidative effects of herbal tea leaves from yacon in different free radical models and a ferric reducing model. A hot-water extract exhibited the highest yield of total polyphenol and scavenging effect on 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical among four extracts prepared with hot water, methanol, ethanol, and ethylacetate. In addition, a higher reducing power of the hot-water extract was similarly demonstrated among these extracts. Varying concentrations of the hot-water extract resulted in different scavenging activities in four synthetic free radical models: DPPH radical (EC50 28.1 μg/mL), 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) cation radical (EC50 23.7 μg/mL), galvinoxyl radical (EC50 3.06 μg/mL), and chlorpromazine cation radical (EC50 475 μg/mL). The yacon tea-leaf extract further demonstrated superoxide anion (O2(-)) radical scavenging effects in the phenazine methosulfate-NADH-nitroblue tetrazolium (EC50 64.5 μg/mL) and xanthine oxidase assay systems (EC50 20.7 μg/mL). Subsequently, incubating human neutrophilic cells in the presence of the tea-leaf extract could suppress the cellular O2(-) radical generation (IC50 65.7 μg/mL) in a phorbol 12-myristate 13-acetate-activated cell model. These results support yacon tea leaves may be a good source of natural antioxidants for preventing O2(-) radical-mediated disorders. Yacon has been considered to be a potent alternative food source for patients who require a dietary cure in regional area, while the leaf part has been provided and consumed as an herbal tea in local markets. We demonstrated here potent antioxidative effects of the tea

Free radical generation induced by ultrasound in red wine and model wine: An EPR spin-trapping study.

Science.gov (United States)

Zhang, Qing-An; Shen, Yuan; Fan, Xue-Hui; Martín, Juan Francisco García; Wang, Xi; Song, Yun

2015-11-01

Direct evidence for the formation of 1-hydroxylethyl radicals by ultrasound in red wine and air-saturated model wine is presented in this paper. Free radicals are thought to be the key intermediates in the ultrasound processing of wine, but their nature has not been established yet. Electron paramagnetic resonance (EPR) spin trapping with 5,5-dimethyl-l-pyrrolin N-oxide (DMPO) was used for the detection of hydroxyl free radicals and 1-hydroxylethyl free radicals. Spin adducts of hydroxyl free radicals were detected in DMPO aqueous solution after sonication while 1-hydroxylethyl free radical adducts were observed in ultrasound-processed red wine and model wine. The latter radical arose from ethanol oxidation via the hydroxyl radical generated by ultrasound in water, thus providing the first direct evidence of the formation of 1-hydroxylethyl free radical in red wine exposed to ultrasound. Finally, the effects of ultrasound frequency, ultrasound power, temperature and ultrasound exposure time were assessed on the intensity of 1-hydroxylethyl radical spin adducts in model wine. Copyright © 2015 Elsevier B.V. All rights reserved.

Generation capacity expansion planning in deregulated electricity markets

Science.gov (United States)

Sharma, Deepak

With increasing demand of electric power in the context of deregulated electricity markets, a good strategic planning for the growth of the power system is critical for our tomorrow. There is a need to build new resources in the form of generation plants and transmission lines while considering the effects of these new resources on power system operations, market economics and the long-term dynamics of the economy. In deregulation, the exercise of generation planning has undergone a paradigm shift. The first stage of generation planning is now undertaken by the individual investors. These investors see investments in generation capacity as an increasing business opportunity because of the increasing market prices. Therefore, the main objective of such a planning exercise, carried out by individual investors, is typically that of long-term profit maximization. This thesis presents some modeling frameworks for generation capacity expansion planning applicable to independent investor firms in the context of power industry deregulation. These modeling frameworks include various technical and financing issues within the process of power system planning. The proposed modeling frameworks consider the long-term decision making process of investor firms, the discrete nature of generation capacity addition and incorporates transmission network modeling. Studies have been carried out to examine the impact of the optimal investment plans on transmission network loadings in the long-run by integrating the generation capacity expansion planning framework within a modified IEEE 30-bus transmission system network. The work assesses the importance of arriving at an optimal IRR at which the firm's profit maximization objective attains an extremum value. The mathematical model is further improved to incorporate binary variables while considering discrete unit sizes, and subsequently to include the detailed transmission network representation. The proposed models are novel in the

Calorimetric and spectroscopic properties of small globular proteins (bovine serum albumin, hemoglobin) after free radical generation

International Nuclear Information System (INIS)

Farkas, N.; Belagyi, J.; Lorinczy, D.

2003-01-01

Mild oxidation of -SH-containing proteins (serum albumin, hemoglobin) by Ce(IV)-ions in the presence of the spin trap phenyl-tert-butylnitrone (PBN) resulted in the appearance of strongly immobilized nitroxide free radicals which evidences the formation of thiyl radicals on the thiol site of the proteins. In hydroxyl free radical generating system a fraction of strongly immobilized nitroxide radicals was also detected in these proteins, which implies that the oxidation of a fraction of the thiol groups was also involved in the free radical reaction. According to the differential scanning calorimetry (DSC) experiments the melting processes of the proteins were calorimetrically irreversible, therefore the two-state kinetic model was used to evaluate the experiments. The results support the view that site-specific interaction of SH-containing proteins with hydroxyl and thiyl free radicals is able to modify the internal dynamics of proteins and affect the conformation of large molecules

Neuroprotection by Radical Avoidance: Search for Suitable Agents

Directory of Open Access Journals (Sweden)

Rüdiger Hardeland

2009-12-01

Full Text Available Neurodegeneration is frequently associated with damage by free radicals. However, increases in reactive oxygen and nitrogen species, which may ultimately lead to neuronal cell death, do not necessarily reflect its primary cause, but can be a consequence of otherwise induced cellular dysfunction. Detrimental processes which promote free radical formation are initiated, e.g., by disturbances in calcium homeostasis, mitochondrial malfunction, and an age-related decline in the circadian oscillator system. Free radicals generated at high rates under pathophysiological conditions are insufficiently detoxified by scavengers. Interventions at the primary causes of dysfunction, which avoid secondary rises in radical formation, may be more efficient. The aim of such approaches should be to prevent calcium overload, to reduce mitochondrial electron dissipation, to support electron transport capacity, and to avoid circadian perturbations. l-Theanine and several amphiphilic nitrones are capable of counteracting excitotoxicity and/or mitochondrial radical formation. Resveratrol seems to promote mitochondrial biogenesis. Mitochondrial effects of leptin include attenuation of electron leakage. Melatonin combines all the requirements mentioned, additionally regulates anti- and pro-oxidant enzymes and is, with few exceptions, very well tolerated. In this review, the perspectives, problems and limits of drugs are compared which may be suitable for reducing the formation of free radicals.

8760-Based Method for Representing Variable Generation Capacity Value in Capacity Expansion Models: Preprint

Energy Technology Data Exchange (ETDEWEB)

Frew, Bethany A [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Cole, Wesley J [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Sun, Yinong [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Mai, Trieu T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Richards, James [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2017-08-01

Capacity expansion models (CEMs) are widely used to evaluate the least-cost portfolio of electricity generators, transmission, and storage needed to reliably serve demand over the evolution of many years or decades. Various CEM formulations are used to evaluate systems ranging in scale from states or utility service territories to national or multi-national systems. CEMs can be computationally complex, and to achieve acceptable solve times, key parameters are often estimated using simplified methods. In this paper, we focus on two of these key parameters associated with the integration of variable generation (VG) resources: capacity value and curtailment. We first discuss common modeling simplifications used in CEMs to estimate capacity value and curtailment, many of which are based on a representative subset of hours that can miss important tail events or which require assumptions about the load and resource distributions that may not match actual distributions. We then present an alternate approach that captures key elements of chronological operation over all hours of the year without the computationally intensive economic dispatch optimization typically employed within more detailed operational models. The updated methodology characterizes the (1) contribution of VG to system capacity during high load and net load hours, (2) the curtailment level of VG, and (3) the potential reductions in curtailments enabled through deployment of storage and more flexible operation of select thermal generators. We apply this alternate methodology to an existing CEM, the Regional Energy Deployment System (ReEDS). Results demonstrate that this alternate approach provides more accurate estimates of capacity value and curtailments by explicitly capturing system interactions across all hours of the year. This approach could be applied more broadly to CEMs at many different scales where hourly resource and load data is available, greatly improving the representation of challenges

The role of proteins in damage induced by free radicals

International Nuclear Information System (INIS)

Gebicki, J.M.

1996-01-01

The initial consequence of oxidative stress in living organisms is chemical modification of cell components. Recently increasing attention in this area has been paid to the modification of proteins. A form of protein modification which has been studied in some detail only recently is peroxidation. In the last 8 years, we and our collaborators have shown that a range of isolated proteins acquire hydroperoxide groups when exposed to a range of biologically plausible oxidants. These include HO free radicals generated by radiation or in the Fenton reaction, peroxyl radicals, oxidants released by activated neutrophils, and peroxynitrite. In more complex systems, we also found protein peroxides in the apo B component of LDL treated with 20 μM Cu ++ , and in irradiated blood serum. These observations suggest that the formation of protein peroxides is a possible consequence of oxidative stress in vivo. A remarkable feature of the process of protein peroxidation is its high efficiency. This is most easily measured with proteins oxidized by radiation-generated free radicals. It was found that, for some proteins, peroxide yields reached 40% of the numbers of HO radicals generated. Thus in effect, almost half of these radicals can be converted to the much more long-lived protein peroxide groups. If they, in turn, have the capacity to damage other molecules, the major oxidative pathway in vivo may have the sequence: free radical ? protein peroxide ? another oxidized molecule. This hypothesis was tested by studying the ability of protein peroxides to react with selected molecules and the results are briefly discussed. Clearly, these effects are specific to individual proteins. More generally, amino acid and protein peroxides were found to be a potential source of a range of free radicals when reduced by Fe ++ . If this turns out to be a common phenomenon, protein peroxides may prove to be a major source of oxidative damage

The role of proteins in damage induced by free radicals

Energy Technology Data Exchange (ETDEWEB)

Gebicki, J.M. [Macquarie Univ., North Ryde, NSW (Australia). School of Biological Sciences

1996-12-31

The initial consequence of oxidative stress in living organisms is chemical modification of cell components. Recently increasing attention in this area has been paid to the modification of proteins. A form of protein modification which has been studied in some detail only recently is peroxidation. In the last 8 years, we and our collaborators have shown that a range of isolated proteins acquire hydroperoxide groups when exposed to a range of biologically plausible oxidants. These include HO free radicals generated by radiation or in the Fenton reaction, peroxyl radicals, oxidants released by activated neutrophils, and peroxynitrite. In more complex systems, we also found protein peroxides in the apo B component of LDL treated with 20 {mu}M Cu{sup ++}, and in irradiated blood serum. These observations suggest that the formation of protein peroxides is a possible consequence of oxidative stress in vivo. A remarkable feature of the process of protein peroxidation is its high efficiency. This is most easily measured with proteins oxidized by radiation-generated free radicals. It was found that, for some proteins, peroxide yields reached 40% of the numbers of HO radicals generated. Thus in effect, almost half of these radicals can be converted to the much more long-lived protein peroxide groups. If they, in turn, have the capacity to damage other molecules, the major oxidative pathway in vivo may have the sequence: free radical ? protein peroxide ? another oxidized molecule. This hypothesis was tested by studying the ability of protein peroxides to react with selected molecules and the results are briefly discussed. Clearly, these effects are specific to individual proteins. More generally, amino acid and protein peroxides were found to be a potential source of a range of free radicals when reduced by Fe{sup ++}. If this turns out to be a common phenomenon, protein peroxides may prove to be a major source of oxidative damage.

Modification of DNA bases in mammalian chromatin by radiation-generated free radicals

International Nuclear Information System (INIS)

Gajewski, E.; Rao, G.; Nackerdien, Z.; Dizdaroglu, M.

1990-01-01

Modification of DNA bases in mammalian chromatin in aqueous suspension by ionizing radiation generated free radicals was investigated. Argon, air, N2O, and N2O/O2 were used for saturation of the aqueous system in order to provide different radical environments. Radiation doses ranging from 20 to 200 Gy (J.kg-1) were used. Thirteen products resulting from radical interactions with pyrimidines and purines in chromatin were identified and quantitated by using the technique of gas chromatography/mass spectrometry with selected-ion monitoring after acidic hydrolysis and trimethylsilylation of chromatin. The methodology used permitted analysis of the modified bases directly in chromatin without the necessity of isolation of DNA from chromatin first. The results indicate that the radical environment provided by the presence of different gases in the system had a substantial effect on the types of products and their quantities. Some products were produced only in the presence of oxygen, whereas other products were detected only in the absence of oxygen. Products produced under all four gaseous conditions were also observed. Generally, the presence of oxygen in the system increased the yields of the products with the exception of formamidopyrimidines. Superoxide radical formed in the presence of air, and to a lesser extent in the presence of N2O/O2, had no effect on product formation. The presence of oxygen dramatically increased the yields of 8-hydroxypurines, whereas the yields of formamidopyrimidines were not affected by oxygen, although these products result from respective oxidation and reduction of the same hydroxyl-adduct radicals of purines. The yields of the products were much lower than those observed previously with DNA

Efficient peroxydisulfate activation process not relying on sulfate radical generation for water pollutant degradation

KAUST Repository

Zhang, Tao; Chen, Yin; Wang, Yuru; Le Roux, Julien; Yang, Yang; Croue, Jean-Philippe

2014-01-01

Peroxydisulfate (PDS) is an appealing oxidant for contaminated groundwater and toxic industrial wastewaters. Activation of PDS is necessary for application because of its low reactivity. Present activation processes always generate sulfate radicals

DPPH and oxygen free radicals as pro-oxidant of biomolecules.

Science.gov (United States)

Letelier, María Eugenia; Molina-Berríos, Alfredo; Cortés-Troncoso, Juan; Jara-Sandoval, José; Holst, Marianne; Palma, Karina; Montoya, Margarita; Miranda, Dante; González-Lira, Víctor

2008-03-01

Numerous investigations exist about the alterations that oxygen free radicals can provoke on biomolecules; these modifications can be prevented and/or reversed by different antioxidants agents. On the other hand, 2,2-diphenyl-1-picrylhydrazyl radical (DPPH), a stable nitrogen synthetic radical, is used to evaluate the antioxidant capacity of medicinal herbal products; however, the structural changes that this radical provoke on the herbal active principles are not clear yet. In this work, we compared the redox reactivity of oxygen free radicals and DPPH radical on phospholipids and protein thiol groups present in rat liver microsomes. Cu2+/ascorbate was used as generator system of oxygen free radical and as antioxidant, an extract of Buddleja globosa's leaves. Cu2+/ascorbate provoked microsomal lipid peroxidation, microsomal thiols oxidation and oxygen consumption; all of these phenomena were inhibited by B. globosa extract. On the other hand, DPPH was bleached in different extension by the herbal extract and phosphatidyl choline; beside, DPPH decreased microsomal thiols content, but this phenomenon were not prevented by the herbal extract. Furthermore, DPPH did not induce oxygen consumption and neither modified the oxygen consumption induced by Cu2+/ascorbate. Distinct redox mechanisms may explain the differences between the reactivity of DPPH and oxygen free radicals on biomolecules, which is discussed.

Manipulating radicals: Using cobalt to steer radical reactions

OpenAIRE

Chirilă, A.

2017-01-01

This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

Oxidative generation of guanine radicals by carbonate radicals and their reactions with nitrogen dioxide to form site specific 5-guanidino-4-nitroimidazole lesions in oligodeoxynucleotides.

Science.gov (United States)

Joffe, Avrum; Mock, Steven; Yun, Byeong Hwa; Kolbanovskiy, Alexander; Geacintov, Nicholas E; Shafirovich, Vladimir

2003-08-01

A simple photochemical approach is described for synthesizing site specific, stable 5-guanidino-4-nitroimidazole (NIm) adducts in single- and double-stranded oligodeoxynucleotides containing single and multiple guanine residues. The DNA sequences employed, 5'-d(ACC CG(1)C G(2)TC CG(3)C G(4)CC) and 5'-d(ACC CG(1)C G(2)TC C), were a portion of exon 5 of the p53 tumor suppressor gene, including the codons 157 (G(2)) and 158 (G(3)) mutation hot spots in the former sequence with four Gs and the codon 157 (G(2)) mutation hot spot in the latter sequence with two Gs. The nitration of oligodeoxynucleotides was initiated by the selective photodissociation of persulfate anions to sulfate radicals induced by UV laser pulses (308 nm). In aqueous solutions, of bicarbonate and nitrite anions, the sulfate radicals generate carbonate anion radicals and nitrogen dioxide radicals by one electron oxidation of the respective anions. The guanine residue in the oligodeoxynucleotide is oxidized by the carbonate anion radical to form the neutral guanine radical. While the nitrogen dioxide radicals do not react with any of the intact DNA bases, they readily combine with the guanine radicals at either the C8 or the C5 positions. The C8 addition generates the well-known 8-nitroguanine (8-nitro-G) lesions, whereas the C5 attack produces unstable adducts, which rapidly decompose to NIm lesions. The maximum yields of the nitro products (NIm + 8-nitro-G) were typically in the range of 20-40%, depending on the number of guanine residues in the sequence. The ratio of the NIm to 8-nitro-G lesions gradually decreases from 3.4 in the model compound, 2',3',5'-tri-O-acetylguanosine, to 2.1-2.6 in the single-stranded oligodeoxynucleotides and to 0.8-1.1 in the duplexes. The adduct of the 5'-d(ACC CG(1)C G(2)TC C) oligodeoxynucleotide containing the NIm lesion in codon 157 (G(2)) was isolated in HPLC-pure form. The integrity of this adduct was established by a detailed analysis of exonuclease digestion

Optimum capacity determination of stand-alone hybrid generation system considering cost and reliability

International Nuclear Information System (INIS)

Chen, Hung-Cheng

2013-01-01

Highlights: ► This paper presents a methodology for the installation capacity optimization. ► Hybrid generation system is optimized by application of adaptive genetic algorithm. ► A cost investigation is made under various conditions and component characteristics. ► The optimization scheme is validated to meet the annual power load demand. -- Abstract: The aim of this work is to present an optimization methodology for the installation capacity of a stand-alone hybrid generation system, taking into consideration the cost and reliability. Firstly, on the basis of derived steady state models of a wind generator (WG), a photovoltaic array (PV), a battery and an inverter, the hybrid generation system is modeled for the purpose of capacity optimization. Secondly, the power system is analyzed for determining both the system structure and the operation control strategy. Thirdly, according to hourly weather database of wind speed, temperature and solar irradiation, annual power generation capacity is estimated for the system match design in order that an annual power load demand can be met. The capacity determination of a hybrid generation system becomes complicated as a result of the uncertainty in the renewable energy together with load demand and the nonlinearity of system components. Aimed at the power system reliability and the cost minimization, the capacity of a hybrid generation system is optimized by application of an adaptive genetic algorithm (AGA) to individual power generation units. A total cost investigation is made under various conditions, such as wind generator power curves, battery discharge depth and the loss of load probability (LOLP). At the end of this work, the capacity of a hybrid generation system is optimized at two installation sites, namely the offshore Orchid Island and Wuchi in Taiwan. The optimization scheme is validated to optimize power capacities of a photovoltaic array, a battery and a wind turbine generator with a relative

Developing SyrinOX total antioxidant capacity assay for measuring antioxidants in humans.

Science.gov (United States)

Prasetyo, Endry N; Knes, Otto; Nyanhongo, Gibson S; Guebitz, Georg M

2013-02-01

Accurate monitoring of the antioxidant status or of oxidative stress in patients is still a big challenge in clinical laboratories. This study investigates the possibility of applying a newly developed total antioxidant capacity assay method based on laccase or peroxidase oxidized syringaldazine [Tetramethoxy azobismethylene quinone (TMAMQ)] which is referred to here as SyrinOX, as a diagnostic tool for monitoring both oxidative stress and antioxidant status in patients. Attempts to adapt the Randox total antioxidant procedure [simultaneous incubation of the radical generating system (metmyoglobin and H(2) O(2) ) and antioxidant sample] for SyrinOX were abandoned after it was discovered that the H(2) O(2) reacted with enzymatically generated TMAMQ and ABTS radicals at a rate of 6.4 × 10(-2) /μM/s and 5.7 × 10(-3) /μM/s respectively. Thus this study for the first time demonstrates the negative effects of H(2) O(2) in the Randox system. This leads to erroneous results because the total antioxidant values obtained are the sum of radicals reduced by antioxidants plus those reacting with the radical generating system. Therefore they should be avoided not only for this particular method but also when using other similar methods. Consequently, SyrinOX is best applied using a three-step approach involving, production of TMAMQ, recovery and purification (free from enzyme and other impurities) and then using TMAMQ for measuring the total antioxidant capacity of samples. Using this approach, the reaction conditions for application of SyrinOX when measuring the total antioxidant capacity of plasma sample were determined to be 50% (v/v) ethanol/50 mM sodium succinate buffer pH 5.5, between 20 and 25 °C for at least 1 h. © 2012 The Authors. International Journal of Experimental Pathology © 2012 International Journal of Experimental Pathology.

Free radical scavenging activities of yellow gentian (Gentiana lutea L.) measured by electron spin resonance.

Science.gov (United States)

Kusar, A; Zupancic, A; Sentjurc, M; Baricevic, D

2006-10-01

Yellow gentian (Gentiana lutea L.) is a herbal species with a long-term use in traditional medicine due to its digestive and stomachic properties. This paper presents an investigation of the free radical scavenging activity of methanolic extracts of yellow gentian leaves and roots in two different systems using electron spin resonance (ESR) spectrometry. Assays were based on the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH) and the superoxide radicals (O2*-) generated by the xanthine/xanthine oxidase (X/XO) system. The results of gentian methanolic extracts were compared with the antioxidant capacity of synthetic antioxidant butylated hydroxyanisole (BHA). This study proves that yellow gentian leaves and roots exhibit considerable antioxidant properties, expressed either by their capability to scavenge DPPH or superoxide radicals.

Electric generating capacity planning: A nonlinear programming approach

Energy Technology Data Exchange (ETDEWEB)

Yakin, M.Z.; McFarland, J.W.

1987-02-01

This paper presents a nonlinear programming approach for long-range generating capacity expansion planning in electrical power systems. The objective in the model is the minimization of total cost consisting of investment cost plus generation cost for a multi-year planning horizon. Reliability constraints are imposed by using standard and practical reserve margin requirements. State equations representing the dynamic aspect of the problem are included. The electricity demand (load) and plant availabilities are treated as random variables, and the method of cumulants is used to calculate the expected energy generated by each plant in each year of the planning horizon. The resulting model has a (highly) nonlinear objective function and linear constraints. The planning model is solved over the multiyear planning horizon instead of decomposing it into one-year period problems. This approach helps the utility decision maker to carry out extensive sensitivity analysis easily. A case study example is provided using EPRI test data. Relationships among the reserve margin, total cost and surplus energy generating capacity over the planning horizon are explored by analyzing the model.

Anticancer system created by acrolein and hydroxyl radical generated in enzymatic oxidation of spermine and other biochemical reactions.

Science.gov (United States)

Alarcon, R A

2012-10-01

A hypothesis suggesting the existence of a ubiquitous physiological anticancer system created by two highly reactive oxidative stress inducers with anticancer properties, acrolein and hydroxyl radical, is reported in this communication. Both components can originate separately or together in several biochemical interactions, among them, the enzymatic oxidation of the polyamine spermine, which appear to be their main source. The foundations of this hypothesis encompass our initial search for growth-inhibitors or anticancer compounds in biological material leading to the isolation of spermine, a polyamine that became highly cytotoxic through the generation of acrolein, when enzymatically oxidized. Findings complemented with pertinent literature data by other workers and observed anticancer activities by sources capable of producing acrolein and hydroxyl radical. This hypothesis obvious implication: spermine enzymatic oxidations or other biochemical interactions that would co-generate acrolein and hydroxyl radical, the anticancer system components, should be tried as treatments for any given cancer. The biochemical generation of acrolein observed was totally unexpected, since this aldehyde was known; as a very toxic and highly reactive xenobiotic chemical produced in the pyrolysis of fats and other organic material, found as an atmospheric pollutant, in tobacco smoke and car emissions, and mainly used as a pesticide or aquatic herbicide. Numerous studies on acrolein, considered after our work a biological product, as well, followed. In them, acrolein widespread presence, its effects on diverse cellular proteins, such as, growth factors, and its anticancer activities, were additionally reported. Regarding hydroxyl radical, the second component of the proposed anticancer system, and another cytotoxic product in normal cell metabolism, it co-generates with acrolein in several biochemical interactions, occurrences suggesting that these products might jointly fulfill some

World nuclear generating capacity and uranium requirements to 2005

International Nuclear Information System (INIS)

Anon.

1991-01-01

The outlook for the world nuclear power industry through 2005 is more positive than some may believe. Installed nuclear electric generating capacity is forecast to grow at an average rate of 2.4 percent per year, and reach 448 gigawatts electric (GWe) by 2005. Consequently, annual world uranium requirements also will grow, reaching over 200 million pounds equivalent U 3 O 8 by 2005. This article presents data and summarizes installed nuclear generating capacity and charts its increase as a function of time through the year 2005. This data is also charted by reactor type as well as reactor status: under construction, planned, or estimated future construction. In a similar fashion, the data is also charted by country and continent. Historical and projected data is also given for capacity factor

The electricity generation adequacy problem: Assessing dynamic effects of capacity remuneration mechanisms

International Nuclear Information System (INIS)

Hary, Nicolas; Rious, Vincent; Saguan, Marcelo

2016-01-01

Following liberalization reforms, the ability of power markets to provide satisfactory incentives for capacity investments has become a major concern. In particular, current energy markets can exhibit a phenomenon of investment cycles, which generate phases of under and over-capacity, and hence additional costs and risks for generation adequacy. To cope with these issues, new mechanisms, called capacity remuneration mechanisms (CRM), have been (or will be) implemented. This paper assesses the dynamic effects of two CRMs, the capacity market and the strategic reserve mechanism, and studies to what extent they can reduce the investment cycles. Generation costs and shortage costs of both mechanisms are also compared to conclude on their effectivity and economic efficiency. A simulation model, based on system dynamics, is developed to study the functioning of both CRMs and the related investment decisions. The results highlight the benefits of deploying CRMs to solve the adequacy issue: shortages are strongly reduced compared to an energy-only market. Besides, the capacity market appears to be more beneficial, since it experiences fewer shortages and generation costs are lower. These comparisons can be used by policy makers (in particular in Europe, where these two CRMs are mainly debated) to determine which CRM to adopt. - Highlights: •A study of the dynamic effects of CRMs on generation investments is provided. •Capacity market and strategic reserve mechanism are compared. •Both CRMs reduce the cyclical tendencies prone to appear in energy-only market. •The capacity market experiences fewer shortages and generation costs are lower.

Generation capacity adequacy in deregulated markets : options for Alberta

International Nuclear Information System (INIS)

Ayres, M.

2004-01-01

The Canadian Energy Research Institute (CERI) is a Calgary-based non-profit organization that conducts studies on energy and related environmental issues to help Canadian business and government organizations. This paper summarized the information in a two volume CERI study report which assessed generation capacity issues in deregulated electricity markets in Canada. The study observed the restructuring experience in several jurisdictions and described how, or if, energy-only markets are succeeding in ensuring capacity additions. Supply-side and demand-side mechanisms have been proposed as solutions to address these problems. Theoretical and practical issues of adequacy that are most relevant from a Canadian perspective were presented. In fully developed energy markets, the price of energy reflects scarcity. When generating resources are abundant prices are low. Since investment decisions are based on price expectations, it is unlikely that deregulated markets in their current state can offer adequate generation for the long term. It was concluded that long-term investment will occur with competitive markets and by adding a capacity mechanism to the market design. tabs., figs

Diphthamide biosynthesis requires an organic radical generated by an iron-sulphur enzyme

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yang; Zhu, Xuling; Torelli, Andrew T; Lee, Michael; Dzikovski, Boris; Koralewski, Rachel M; Wang, Eileen; Freed, Jack; Krebs, Carsten; Ealick, Steve E; Lin, Hening [Cornell; (Penn)

2010-08-30

Archaeal and eukaryotic translation elongation factor 2 contain a unique post-translationally modified histidine residue called diphthamide, which is the target of diphtheria toxin. The biosynthesis of diphthamide was proposed to involve three steps, with the first being the formation of a C-C bond between the histidine residue and the 3-amino-3-carboxypropyl group of S-adenosyl-l-methionine (SAM). However, further details of the biosynthesis remain unknown. Here we present structural and biochemical evidence showing that the first step of diphthamide biosynthesis in the archaeon Pyrococcus horikoshii uses a novel iron-sulphur-cluster enzyme, Dph2. Dph2 is a homodimer and each of its monomers can bind a [4Fe-4S] cluster. Biochemical data suggest that unlike the enzymes in the radical SAM superfamily, Dph2 does not form the canonical 5'-deoxyadenosyl radical. Instead, it breaks the C_γ,Met-S bond of SAM and generates a 3-amino-3-carboxypropyl radical. Our results suggest that P. horikoshii Dph2 represents a previously unknown, SAM-dependent, [4Fe-4S]-containing enzyme that catalyses unprecedented chemistry.

Total free radical species and oxidation equivalent in polluted air.

Science.gov (United States)

Wang, Guoying; Jia, Shiming; Niu, Xiuli; Tian, Haoqi; Liu, Yanrong; Chen, Xuefu; Li, Lan; Zhang, Yuanhang; Shi, Gaofeng

2017-12-31

Free radicals are the most important chemical intermediate or agent of the atmosphere and influenced by thousands of reactants. The free radicals determine the oxidizing power of the polluted air. Various gases present in smog or haze are oxidants and induce organ and cellular damage via generation of free radical species. At present, however, the high variability of total free radicals in polluted air has prevented the detection of possible trends or distributions in the concentration of those species. The total free radicals are a kind of contaminants with colorless, tasteless characteristics, and almost imperceptible by human body. Here we present total free radical detection and distribution characteristics, and analyze the effects of total free radicals in polluted air on human health. We find that the total free radical values can be described by not only a linear dependence on ozone at higher temperature period, but also a linear delay dependence on particulate matter at lower temperature period throughout the measurement period. The total free radical species distribution is decrease from west to east in Lanzhou, which closely related to the distribution of the air pollutants. The total free radical oxidation capacity in polluted air roughly matches the effects of tobacco smoke produced by the incomplete combustion of a controlled amount of tobacco in a smoke chamber. A relatively unsophisticated chromatographic fingerprint similarity is used for indicating preliminarily the effect of total free radicals in polluted air on human health. Copyright © 2017 Elsevier B.V. All rights reserved.

On option purchase agreements for new generation capacity

International Nuclear Information System (INIS)

Ramesh, V.C.

1996-01-01

Given the increasing competition in the power generation sector, and the resulting uncertainty surrounding long-term investments in new generation projects, utilities are beginning to hedge their risks using financial instruments called options. The purpose of this paper is to explain, in a tutorial fashion, the issues involved in an option contract for new generation capacity (long-term firm energy). Particular emphasis is placed on the valuation of such options. The concepts are explained with illustrative examples

Generation capacity adequacy in interdependent electricity markets

International Nuclear Information System (INIS)

Cepeda, Mauricio; Finon, Dominique

2011-01-01

This paper deals with the practical problems related to long-term security of supply in regional electricity markets with transmission constraints. Differences between regulatory policies and market designs in terms of generation adequacy policies may distort the normal functioning of the neighboring markets, as well as the reliability of supply. We test the effect of heterogeneous regulatory design between two interdependent markets: energy-only market, price-capped market without capacity mechanisms and price-capped markets with forward capacity contracts obligation. We rely on a long-term market simulation model in system dynamics that characterizes expansion decision in a competitive regime. The results show that differences in market designs affect both price and reliability of supply in the two markets. We examine both the short and long terms effect, and how free-riding may occur where capacity adequacy policies are adopted in one market but not the other. The main finding is that the lack of harmonization between local markets in policies to ensure capacity adequacy may lead to undesirable side effects. - Research highlights: → We model the long-term dynamic of two interdependent markets. → We examine both the short and long terms effect of heterogeneous regulatory design: energy-only market, price-capped market without capacity mechanisms and price-capped markets with forward capacity contracts obligation. → Differences in market designs affect both price and reliability of supply in the two markets. → Lack of harmonization between local markets in policies to ensure capacity adequacy may lead to undesirable side effects. → Free-riding may occur where capacity adequacy policies are adopted in one market but not the other.

Neutrophil superoxide-anion generating capacity in chronic smoking ...

Indian Academy of Sciences (India)

Unknown

To this purpose, we randomly assigned 128 male chronic smokers (37 ± 21 pack years of smoking) ... Secondly, in non-smoking human subjects we have recently shown ... therapy in chronic smoking affects superoxide generating capacity of ...

Merchant interconnector projects by generators in the EU: Profitability and allocation of capacity

International Nuclear Information System (INIS)

Koten, Silvester van

2012-01-01

When building a cross-border transmission line (a so-called interconnector) as a for-profit (merchant) project, where the regulator has required that capacity allocation be done non-discriminatorily by explicit auction, the identity of the investor can affect the profitability of the interconnector project and, once operational, the resulting allocation of its capacity. Specifically, when the investor is a generator (hereafter the integrated generator) who also can use the interconnector to export its electricity to a distant location, then, once operational, the integrated generator will bid more aggressively in the allocation auctions to increase the auction revenue and thus its profits. As a result, the integrated generator is more likely to win the auction and the capacity is sold for a higher price. This lowers the allocative efficiency of the auction, but it increases the expected ex-ante profitability of the merchant interconnector project. Unaffiliated, independent generators, however, are less likely to win the auction and, in any case, pay a higher price, which dramatically lowers their revenues from exporting electricity over this interconnector. - Highlights: ► A merchant interconnector owned by an electricity generator needs special attention of regulators. ► Even when allocation of the capacity is done by auctions, the generator will make a large profit. ► The generator will also decrease the allocation of capacity to competitors by bidding aggressively.

Free radical generation by non-equilibrium atmospheric pressure plasma in alcohol-water mixtures: an EPR-spin trapping study

Science.gov (United States)

Uchiyama, Hidefumi; Ishikawa, Kenji; Zhao, Qing-Li; Andocs, Gabor; Nojima, Nobuyuki; Takeda, Keigo; Krishna, Murali C.; Ishijima, Tatsuo; Matsuya, Yuji; Hori, Masaru; Noguchi, Kyo; Kondo, Takashi

2018-03-01

Free radical species in aqueous solution—various alcohol-water reaction mixtures—by exposure to non-equilibrium cold atmospheric pressure Ar plasma (CAP), were monitored using electron paramagnetic resonance spin-trapping techniques with 3, 5-dibromo-4-nitrosobenzene sulfonate as a water soluble nitroso spin trap. The major radical species were formed by H-abstraction from alcohol molecules due to ·OH radicals. In the ethanol-water mixture ·CH2CH2OH produced by H abstraction from CH3 group of the ethanol and ·CH3 radicals were detected. The latter was due to the decomposition of unstable CH3·CHOH to form the ·CH3 radicals and the stable formaldehyde by C-C bond fission. These intermediates are similar to those observed by reaction with ·OH radicals generation in the H2O2-UV photolysis of the reaction mixtures. The evidence of ·CH3 radical formation in the pyrolytic decomposition of the reaction mixtures by exposure to ultrasound or in methane irradiated with microwave plasma have been reported previously. However, the pyrolytic ·CH3 radicals were not found in both plasma and H2O2-UV photolysis condition. These results suggests that free radicals produced by Ar-CAP are most likely due to the reaction between abundant ·OH radicals and alcohol molecules.

Demonstration using EPR spin-trapping of an oxygen-dependent, carbon-centered free radical generated by soybean lipoxygenase

International Nuclear Information System (INIS)

Carpenter, M.F.; Smith, F.L.

1986-01-01

Purified prostaglandin synthase produces a carbon-centered, oxygen-dependent free radical which they have shown forms a spin-trapped adduct with 4-POBN and has characteristic hyperfine spin coupling constants (hfsc). As production of this radical is cyclooxygenase-dependent, additional studies on radical production were done using soybean lipoxygenase. The latter generates a lipid substrate-derived free radical trapped by the EPR spin trap 4-POBN [α-(4-pyridyl 1-oxide)N-tert-butyl nitrone]. With linoleate as substrate, the hfsc are a/sub N/ = 15.5 G, a/sub β//sup H/ = 2.7 G. This signal is inhibited by ETYA, various antioxidants and heat inactivation of the enzyme. Additional hfsc are not seen when the enzyme is incubated in an 17 O 2 atmosphere, but the signal is inhibited by anaerobeosis. Substitution of 13 C 18 carbon free fatty acids from Chlorella pyrenoisdosa for linoleate produces 2 new lines for each of the original 6 observed with 12 C substrate; the new spectrum has hfsc of a/sub N/ = 16.0 G, a/sub β//sup H/ = 2.4 G, a/sub β/ 13 C = 4.2 G. This demonstrates that the radical is carbon centered and oxygen-dependent and appears not to be the same radical formed by enzymic hydrogen abstraction from the lipid substrate. This radical and the prostaglandin synthase-dependent radical appear to be nearly identical

Enhancement of carboxylic acid degradation with sulfate radical generated by persulfate activation.

Science.gov (United States)

Criquet, J; Nebout, P; Karpel Vel Leitner, N

2010-01-01

The aim of this work was to investigate the generation of sulfate radical for the removal of two carboxylic acids in aqueous solution: acetic and citric acids. From photochemical and radiolytic processes, kinetics of the degradation of these two carboxylic acids was studied as a function of the pH of the solution. It was shown that the maximum of acetic acid degradation occurred at pH 5. Above this pH, competitive reactions with the carbon mineralized inhibit the reaction of with the solute. In the case of citric acid, pH has only a little effect on the kinetic of citric acid degradation. The determination of mineralization yields shows several differences depending on carboxylic acids and pH. The degradation of both carboxylic acids was also studied in the radiolysis process whether with or without persulfate addition. A comparison of the processes of sulfate radical production is presented.

Free radical scavenging actions of three Trifolium species in the protection of blood plasma antioxidant capacity in vitro.

Science.gov (United States)

Kolodziejczyk-Czepas, Joanna; Nowak, Pawel; Moniuszko-Szajwaj, Barbara; Kowalska, Iwona; Stochmal, Anna

2015-01-01

Three clover [Trifolium L. (Leguminosae)] species were selected on the basis of data from traditional medicine, phytochemical profiles, and agricultural significance. The in vitro evaluations of free radical scavenging properties, ferric reducing abilities, and antioxidant effects of extracts from T. pratense L. (crude extract and phenolic fraction), T. pallidum L., and T. scabrum L. (phenolic fractions) were performed. Activities of the Trifolium extracts were determined at their final concentrations of 1.5-50 µg/ml. Free radical scavenging properties of methanol extract solutions were estimated by the reduction of DPPH(•) and ABTS(•) radicals. Measurements of the total antioxidant capacity (TAC) were carried out to assess the antioxidant activities of the extracts in human blood plasma under conditions of oxidative stress, induced by 200 μM peroxynitrite. The phenolic fraction of T. pratense displayed the strongest ABTS(•) and DPPH(•) radical scavenging effects (EC50 value of 21.69 and 12.27 µg/ml, respectively). The EC50 value for T. pallidum extract attained 29.77 and 30.06 µg/ml. The two remaining extracts were less potent scavengers (EC50 value higher than 50 µg/ml). Similar differences were obtained during evaluation of the ferric reducing abilities. Analysis of antioxidant properties of the extracts in blood plasma did not provide such evident differences in their actions, however, it indicated that the T. pratense phenolic fraction displayed the strongest effect. The examined Trifolium extracts partly protected blood plasma and enhanced its non-enzymatic antioxidant defense against harmful action of peroxynitrite in vitro.

Prevention of alloimmunization by ultraviolet-B irradiation. Inactivation of leukocytes and the generation of active oxygen and radicals

International Nuclear Information System (INIS)

Takahashi, Tsuneo; Mogi, Yuko; Sekiguchi, Sadayoshi; Akasaka, Junichi; Kamo, Naoki; Kuwabara, Mikinori.

1994-01-01

UV-B irradiation of platelet concentrates (PC) has been tried in several institutes to inactivate leukocytes in PC and prevent alloimmunization on platelet transfusion. However, the mechanism of inactivation of leukocytes contaminating PC has not been fully understood. It is known that UV-B light is absorbed by photosensitizers in cells and produces active oxygen and radicals, such as singlet oxygen, superioxide anions and hydroxyl radicals. These active oxygen or radicals should injure cellular components and this could cause the suppression of cellular functions. In this study, we investigated the relationships among UV-B irradiation, free radical generation and leukocyte inactivation. We found the evidence that active oxygen and radicals were produced in peripheral blood mononuclear cells by UV-B irradiation. UV-B irradiation suppressed the stimulatory function of leukocytes in a mixed lymphocyte reaction (MLR), and the suppression depended on the dosage of UV-B. Even a low dosage of UV-B, 10 J/m 2 , could inhibit the MLR if the irradiated cells were incubated at 37degC for 24 hours before co-culture with responder cells. Treatments of cells with the exogenous singlet oxygen or superoxide anions also caused suppression of the stimulatory function in the MLR, inhibition of capping formation of HLA-DR antigens, and an increase of intracellular free Ca 2+ levels as did the UV-B treatment. These results indicate that the active oxygen or radicals generated in UV-B-irradiated leukocytes could be one of the causes of leukocyte inactivation. (author0

Muconaldehyde formation from 14C-benzene in a hydroxyl radical generating system

Energy Technology Data Exchange (ETDEWEB)

Latriano, L.; Zaccaria, A.; Goldstein, B.D.; Witz, G.

1985-01-01

It has recently been proposed that muconaldehyde, a six carbon, alpha, beta-unsaturated dialdehyde, may be a hematotoxic metabolite of benzene. The present studies indicate that trans, trans-muconaldehyde is formed from benzene in vitro in a hydroxyl radical (.OH) generating system containing ascorbate, ferrous sulfate and EDTA in phosphate buffer, pH 6.7. Muconaldehyde formed from benzene in the .OH generating system was identified by trapping it with thiobarbituric acid (TBA), which results in the formation of an adduct with a 495 nm absorption maximum and a 510 nm fluorescence emission maximum. These maxima were identical to those observed after reacting authentic trans, trans-muconaldehyde with TBA. This finding was supported by thin layer chromatography and solid phase extraction studies. In those studies benzene-derived muconaldehyde cochromatographed with the muconaldehyde/TBA standard. Analyses of the products from the .OH generating system using high performance liquid chromatography (HPLC) confirm that trans, trans-muconaldehyde is a product of benzene ring fission. Regardless of whether or not TBA was used for trapping, samples from the .OH system incubated with benzene contained a peak which cochromatographed with the muconaldehyde standard. The radioactivity profile of fractions collected during HPLC analysis demonstrates 14C-benzene to be the source of the trans, trans-muconaldehyde. The role of hydroxyl radicals in the formation of muconaldehyde was investigated by using dimethyl sulfoxide, mannitol, and ethanol as .OH scavengers. These scavengers, at concentrations of 10 and 100 mM, were found to cause a dose-dependent decrease in the formation of muconaldehyde.

Effects of Actinobacillus pleuropneumoniae cytotoxins on generation of oxygen radicals by porcine neutrophils

Directory of Open Access Journals (Sweden)

Simson Tarigan

1999-03-01

Full Text Available Cytotoxins produced by Actinobacillus pleuropneumoniae (App suggested to be the most important pathogenic and virulent factors for this organism. However, the mechanisms on how the cytotoxins contribute to the disease process remain unclear. The purpose of this study is to investigate the effect of the cytotoxins on the oxidative-burst metabolism of porcine neutrophils. In this study, neutrophils were firstly loaded with an oxidative probe dichlorofluorescin diacetate (DCFHDA then expose to cytotoxins. Cells producing oxygen radicals emitted fluorescence and its intensity was measured with a FACScan flow cytometer. All cytotoxins derived from either App serotypes producing ApxI and ApxII, App serotypes producing ApxII only, or App serotypes producing ApxII and ApxIII were capable of stimulating neutrophils for oxygen-radical generation. However, compared with phorbol myristate acetate (PMA, App cytotoxins were much weaker as stimulants for oxygen radicals. In addition, Apx preparation stimulated an oxidative-burst metabolism of neutrophils at a low, narrow range of Apx doses. At higher doses, the toxins inhibit the oxidative burst metabolism. The effects of cytotoxins produced by App during infection on recruited neutrophils into the lungs are assumed to be comparable to those observed in this in vitro study. Neutrophils, and other host cells, adjacent to the bacteria become lysis due to high toxin concentration, whereas those at some distance to the bacteria produce oxygen radicals which in turn cause tissue damage or necrosis.

Scenarios of Expansion to Electric Generation Capacity

Directory of Open Access Journals (Sweden)

José Somoza-Cabrera

2017-06-01

Full Text Available We show the building scenarios of expansion to electric generation capacity enough to supply the demand to 2050. We were using the LEAP facility (Long-range Energy Alternatives Planning System, to simulate dispatch of electricity at minimum cost. Finally, we show the cost-benefice analysis of the technologies availability, included externality and CO2 emission limited. However that we included the externals cost in this analysis, it results insufficient to closed gap between fossil and renewable technologies of electric generation. Nevertheless, in some opportunities the renewable options had very important participations in the minimal cost scenario of expansion.

Radical scavenging potentials of single and combinatorial herbal formulations in vitro

Directory of Open Access Journals (Sweden)

Okey A. Ojiako

2016-04-01

Full Text Available Reactive oxygen and nitrogen species (RONS are involved in deleterious/beneficial biological processes. The present study sought to investigate the capacity of single and combinatorial herbal formulations of Acanthus montanus, Emilia coccinea, Hibiscus rosasinensis, and Asystasia gangetica to act as superoxide radicals (SOR, hydrogen peroxide (HP, nitric oxide radical (NOR, hydroxyl radical (HR, and 2,2-diphenyl-1-picrylhydrazyl (DPPH radical antagonists using in vitro models. The herbal extracts were single herbal formulations (SHfs, double herbal formulations (DHfs, triple herbal formulations (THfs, and a quadruple herbal formulation (QHf. The phytochemical composition and radical scavenging capacity index (SCI of the herbal formulations were measured using standard methods. The flavonoids were the most abundant phytochemicals present in the herbal extracts. The SCI50 defined the concentration (μg/mL of herbal formulation required to scavenge 50% of the investigated radicals. The SHfs, DHfs, THfs, and QHf SCI50 against the radicals followed the order HR > SOR > DPPH radical > HP > NOR. Although the various herbal formulations exhibited ambivalent antioxidant activities in terms of their radical scavenging capabilities, a broad survey of the results of the present study showed that combinatorial herbal formulations (DHfs, THfs, and QHf appeared to exhibit lower radical scavenging capacities than those of the SHfs in vitro.

The role of melanin as protector against free radicals in skin and its role as free radical indicator in hair

Science.gov (United States)

Herrling, Thomas; Jung, Katinka; Fuchs, Jürgen

2008-05-01

Throughout the body, melanin is a homogenous biological polymer containing a population of intrinsic, semiquinone-like radicals. Additional extrinsic free radicals are reversibly photo-generated by UV and visible light. Melanin photochemistry, particularly the formation and decay of extrinsic radicals, has been the subject of numerous electron spin resonance (ESR) spectroscopy studies. Several melanin monomers exist, and the predominant monomer in a melanin polymer depends on its location within an organism. In skin and hair, melanin differs in content of eumelanin or pheomelanin. Its bioradical character and its susceptibility to UV irradiation makes melanin an excellent indicator for UV-related processes in both skin and hair. The existence of melanin in skin is strongly correlated with the prevention against free radicals/ROS generated by UV radiation. Especially in the skin melanin (mainly eumelanin) ensures the only natural UV protection by eliminating the generated free radicals/ROS. Melanin in hair can be used as a free radical detector for evaluating the efficacy of hair care products. The aim of this study was to investigate the suitability of melanin as protector of skin against UV generated free radicals and as free radical indicator in hair.

Financing investment in new electricity generation capacity in Northwest Europe. Policy brief

Energy Technology Data Exchange (ETDEWEB)

Ozdemir, O.; De Joode, J.; Koutstaal, P.R. [ECN Policy Studies, Amsterdam (Netherlands)

2013-05-15

Current Northwest European electricity markets are designed as 'energy-only' markets. In an energy-only market the price received for electricity produced is set by the marginal generation unit and potentially leaves the owners of these units with 'missing money': i.e. money that is required to recover investment cost. With a much higher penetration of intermittent electricity sources such as wind and solar PV, these markets may not be capable of providing sufficient incentives for investment in generation capacity, because operating hours and scarcity rents for peak and mid-merit order capacity will be considerably reduced. There are a number of options available to address this missing money problem. First of all, options should be explored which focus on improving the existing electricity markets. These options include increasing flexibility in both supply and demand improving the profitability of investments, for example by means of removing (implicit) price caps and allowing for long-term contracts. Next to these options which can help increase the revenue for generation investments some form of capacity mechanism such as capacity payments or capacity markets could be introduced. These capacity mechanisms have attracted considerable attention in recent years, both in the literature and in the policy debate, with a number of countries considering the introduction of such mechanisms. However, unilateral introduction of capacity mechanisms in integrated electricity markets can have a considerable impact on cross border electricity flows and investment decisions. It might negatively affect security of supply in neighbouring countries and will result in price differences between consumers within a country which have to bear the costs of capacity mechanisms and those outside those countries. Moreover, unilateral capacity mechanisms can disrupt the functioning of the internal energy market. Before the implementation of capacity mechanisms

Damage induced by hydroxyl radicals generated in the hydration layer of γ-irradiated frozen aqueous solution of DNA

International Nuclear Information System (INIS)

Ohshima, Hideki; Matsuda, Akira; Kuwabara, Mikinori; Iida, Yoshiharu.

1996-01-01

Aqueous DNA solutions with or without the spin trap α-phenyl-N-tert-butylnitrone (PBN) were exposed to γ-rays at 77 K. After thawing the solutions, three experiments were carried out to confirm the generation of OH radicals in the hydration layer of DNA and to examine whether they act as an inducer of DNA strand breaks and base alterations. Observation with the EZR-spin tapping method showed ESR signals from PBN-OH adducts in the solution containing PBN and DNA, but there were few signals in the solution containing PBN alone, suggesting that reactive OH radicals were produced in the hydration layer of γ-irradiated DNA and were effectively scavenged by PBN, and that unreactive OH radicals were produced in the free water layer of γ-irradiated DNA. Agarose gel electrophoresis of DNA proved that PBN had no effect on the formation of strand breaks, whereas examination with the high-performance liquid chromatography-eloctrochemical detection (HPLC-ECD) method showed that PBN suppressed the formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG). From these results it was concluded that OH radicals generated in the hydration layer of γ-irradiated DNA did not induce DNA strand breaks but induced base alterations. (author)

Generation capacity issues in deregulated markets : a Canadian perspective, volume 1

International Nuclear Information System (INIS)

Ayres, M.; Brereton, B.; Czamanski, D.; Van Melle, B.; Penman, A.

2004-01-01

A study was conducted by the Canadian Energy Research Institute (CERI) to assess generation capacity issues in deregulated electricity markets in Canada. This first volume is based on observations of the restructuring experience in several jurisdictions. It describes how, or if, energy-only markets are succeeding in ensuring capacity additions, and under what conditions. Supply-side and demand-side mechanisms have been proposed as solutions to address these problems. The report focuses on theoretical and practical issues of adequacy that are most relevant from a Canadian perspective. In fully developed energy markets, the price of energy reflects scarcity. Prices are low when generating resources are abundant, and owners make investment decisions based on price expectations. Although deregulated markets may theoretically offer a solution to the capacity adequacy problem, experience has shown that it is not easy to make the rules that make markets operate efficiently. It was concluded that it seems unlikely that deregulated markets in their current state will be able to offer adequate generation for the long term. The challenge lies in moving to competitive markets that encourage long term investment, and adding a capacity mechanism to the market design. refs., tabs., figs

In situ generation of a hydroxyl radical by nanoporous activated carbon derived from rice husk for environmental applications: kinetic and thermodynamic constants.

Science.gov (United States)

Karthikeyan, S; Sekaran, G

2014-03-07

The objective of this investigation is to evaluate the hydroxyl radical (˙OH) generation using nanoporous activated carbon (NPAC), derived from rice husk, and dissolved oxygen in water. The in situ production of the ˙OH radical was confirmed through the DMPO spin trapping method in EPR spectroscopy and quantitative determination by a deoxyribose assay procedure. NPAC served as a heterogeneous catalyst to degrade 2-deoxy-d-ribose (a reference compound) using hydroxyl radical generated from dissolved oxygen in water at temperatures in the range 313-373 K and pH 6, with first order rate constants (k = 9.2 × 10(-2) min(-1), k = 1.2 × 10(-1) min(-1), k = 1.3 × 10(-1) min(-1) and k = 1.68 × 10(-1) min(-1)). The thermodynamic constants for the generation of hydroxyl radicals by NPAC and dissolved oxygen in water were ΔG -1.36 kJ mol(-1) at 313 K, ΔH 17.73 kJ mol(-1) and ΔS 61.01 J mol(-1) K(-1).

Artifacts Generated During Azoalkane Peroxy Radical Oxidative Stress Testing of Pharmaceuticals Containing Primary and Secondary Amines.

Science.gov (United States)

Nefliu, Marcela; Zelesky, Todd; Jansen, Patrick; Sluggett, Gregory W; Foti, Christopher; Baertschi, Steven W; Harmon, Paul A

2015-12-01

We report artifactual degradation of pharmaceutical compounds containing primary and secondary amines during peroxy radical-mediated oxidative stress carried out using azoalkane initiators. Two degradation products were detected when model drug compounds dissolved in methanol/water were heated to 40°C with radical initiators such as 2,2'-azobis(2-methylpropionitrile) (AIBN). The primary artifact was identified as an α-aminonitrile generated from the reaction of the amine group of the model drug with formaldehyde and hydrogen cyanide, generated as byproducts of the stress reaction. A minor artifact was generated from the reaction between the amine group and isocyanic acid, also a byproduct of the stress reaction. We report the effects of pH, initiator/drug molar ratio, and type of azoalkane initiator on the formation of these artifacts. Mass spectrometry and nuclear magnetic resonance were used for structure elucidation, whereas mechanistic studies, including stable isotope labeling experiments, cyanide analysis, and experiments exploring the effects of butylated hydroxyanisole addition, were employed to support the degradation pathways. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

The impacts of renewable energy policies on renewable energy sources for electricity generating capacity

Science.gov (United States)

Koo, Bryan Bonsuk

Electricity generation from non-hydro renewable sources has increased rapidly in the last decade. For example, Renewable Energy Sources for Electricity (RES-E) generating capacity in the U.S. almost doubled for the last three year from 2009 to 2012. Multiple papers point out that RES-E policies implemented by state governments play a crucial role in increasing RES-E generation or capacity. This study examines the effects of state RES-E policies on state RES-E generating capacity, using a fixed effects model. The research employs panel data from the 50 states and the District of Columbia, for the period 1990 to 2011, and uses a two-stage approach to control endogeneity embedded in the policies adopted by state governments, and a Prais-Winsten estimator to fix any autocorrelation in the panel data. The analysis finds that Renewable Portfolio Standards (RPS) and Net-metering are significantly and positively associated with RES-E generating capacity, but neither Public Benefit Funds nor the Mandatory Green Power Option has a statistically significant relation to RES-E generating capacity. Results of the two-stage model are quite different from models which do not employ predicted policy variables. Analysis using non-predicted variables finds that RPS and Net-metering policy are statistically insignificant and negatively associated with RES-E generating capacity. On the other hand, Green Energy Purchasing policy is insignificant in the two-stage model, but significant in the model without predicted values.

Semen cryopreservation and radical reduction capacity of seminal fluid in captive African lion (Panthera leo).

Science.gov (United States)

Luther, I; Jakop, U; Lueders, I; Tordiffe, A; Franz, C; Schiller, J; Kotze, A; Müller, K

2017-02-01

Optimizing cryopreservation protocols for nondomestic felids contributes to the successful development of assisted reproduction techniques and genetic resource banking. In this study, we describe a simple cryopreservation procedure for African lion (Panthera leo) ejaculates, which was tested with different packaging options and different sperm numbers per dose. By applying urethral catheterization and electroejaculation, 17 ejaculates with greater than 20% motile and greater than 5% progressively motile sperm were collected. A lyophilized extender (a modified egg yolk-Tes-Tris-fructose-glycerol medium) was rehydrated and added in one step at ambient temperature (∼25 °C) to semen, which was prediluted in cell culture medium M199. After slow cooling of insulated samples to 15 °C in a refrigerator (4 °C), the samples were fast frozen over the surface of liquid nitrogen or in a dry shipper. Aliquots of 300 μL containing 20 × 10 6 sperm were frozen in cryovials and in 0.5-mL straws. Differences were observed in the total motility after thawing between vial (31.5 ± 14.1%) and straw freezing (20.1 ± 8.6%). However, the subpopulations of vital (22.7 ± 7.8% for vial and 19.8 ± 8.5% for straw) and progressively motile (10.0 ± 7.9% for vial and 10.0 ± 6.4% for straw) sperm after washing and 1 hour incubation at 38 °C were of similar magnitude, velocity, and linearity for both packaging options. After freezing of five ejaculates with 20, 60, and 100 × 10 6 sperm per dose, best results were achieved at the lowest concentration. In general, post-thaw results were highly variable (2.2% and 56.5% total motility) and not correlated to motility or morphology of the fresh semen. To further characterize semen quality, we assessed the protective potential of seminal fluid against oxidative stress, which might be challenged on freeze thawing. The capacity of seminal fluid to reduce radicals was measured in 10 semen samples by electron spin resonance

Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

Directory of Open Access Journals (Sweden)

R. Volkamer

2010-07-01

Full Text Available A detailed analysis of OH, HO₂ and RO₂ radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA. During spring of 2003 (MCMA-2003 field campaign an extensive set of measurements was collected to quantify time-resolved RO_x (sum of OH, HO₂, RO₂ radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1 was constrained by measurements of (1 concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO, formaldehyde (HCHO, ozone (O₃, glyoxal (CHOCHO, and other oxygenated volatile organic compounds (OVOCs; (2 respective photolysis-frequencies (J-values; (3 concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated and oxidants, i.e., OH- and NO₃ radicals, O₃; and (4 NO, NO₂, meteorological and other parameters. The RO_x production rate was calculated directly from these observations; the MCM was used to estimate further RO_x production from unconstrained sources, and express overall RO_x production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO₂ and HO₂ radicals into OH radicals.

Daytime radical production is found to be about 10–25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: Oxygenated VOC other than HCHO about 33%; HCHO and O₃ photolysis each about 20%; O₃/alkene reactions and HONO photolysis each about 12%, other sources <3%. Nitryl chloride photolysis could potentially contribute ~15% additional radicals, while NO₂* + water makes – if any – a very small contribution (~2%. The peak radical production of ~7.5 10⁷ molec cm⁻³ s⁻¹ is

Neutrophil superoxide-anion generating capacity in chronic smoking ...

Indian Academy of Sciences (India)

We investigated whether long-term -tocopherol therapy in chronic smoking affects superoxide generating capacity of neutrophils ex vivo. To this purpose, we randomly assigned 128 male chronic smokers (37 ± 21 pack years of smoking) to treatment with placebo ( = 64) or -tocopherol (400 IU dL--tocopherol daily, ...

The Challenges to Human Resources Development of Libraries in Times of Radical and Generational Changes.

Science.gov (United States)

Muller, Uta

Librarianship has undergone a radical change in recent years, which will be continued in the future. Whereas previously the administration of media was most important, nowadays an ever increasing willingness to provide a service is required. In addition to the essential restructuring of libraries, a generational change is taking place within the…

Functionalized graphene quantum dots loaded with free radicals combined with liquid chromatography and tandem mass spectrometry to screen radical scavenging natural antioxidants from Licorice and Scutellariae.

Science.gov (United States)

Wang, Guoying; Niu, XiuLi; Shi, Gaofeng; Chen, Xuefu; Yao, Ruixing; Chen, Fuwen

2014-12-01

A novel screening method was developed for the detection and identification of radical scavenging natural antioxidants based on a free radical reaction combined with liquid chromatography with tandem mass spectrometry. Functionalized graphene quantum dots were prepared for loading free radicals in the complex screening system. The detection was performed with and without a preliminary exposure of the samples to specific free radicals on the functionalized graphene quantum dots, which can facilitate charge transfer between free radicals and antioxidants. The difference in chromatographic peak areas was used to identify potential antioxidants. This is a novel approach to simultaneously evaluate the antioxidant power of a component versus a free radical, and to identify it in a vegetal matrix. The structures of the antioxidants in the samples were identified using tandem mass spectrometry and comparison with standards. Fourteen compounds were found to possess potential antioxidant activity, and their free radical scavenging capacities were investigated. The order of scavenging capacity of 14 compounds was compared according to their free radical scavenging rate. 4',5,6,7-Tetrahydroxyflavone (radical scavenging rate: 0.05253 mL mg(-1) s(-1) ) showed the strongest capability for scavenging free radicals. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Free radical transfer in polymers

International Nuclear Information System (INIS)

Sonntag, C. von; Bothe, E.; Ulanski, P.

1998-01-01

For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N 2 O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO 2 -elimination. This prevents a scission of the polymer chain in the

Formation of Nanoparticles Controlled by the Yield and Properties of the γ-Generated Radicals

International Nuclear Information System (INIS)

Chen, Q.

2009-01-01

In the past two decades, nanoparticles have attracted much attention because of their novel properties. Among the numerous synthetic methods, ionizing irradiation, which is simple and can take at normal temperature and pressure, even at low temperature, is a powerful method for preparing metals, alloys, metal oxides, metal chalcogenides, metal halides and insoluble sulphate nanoparticles. In this method, dose rate is always used to affect the shape, component and size of synthesized nanoparticles. In addition, to eliminate the effect of ·OH on the formation of nanoparticles, alcohol (such as isopropyl alcohol) is always added and a lot of reductive radicals with wide range of reduction potentials are generated. At the same time, these radicals transformed from ·OH can also reduce the reactant, which have been used to control the growth of nanoparticles. However, so far, most nanoparticles synthesized by ionizing irradiation are spherical. In our previous work, ''solid'' BaSO 4 microspheres, mainly consisting of quasi-spherical nanoparticles, have been synthesized by precipitating Ba 2+ ions with SO 4 2- ions, which were generated from the reduction of K 2 S 2 O 8 in the presence of EDTA under N 2 atmosphere by γ-irradiation

Mismatch of wind power capacity and generation: causing factors, GHG emissions and potential policy responses

NARCIS (Netherlands)

Subtil Lacerda, J.; van den Bergh, J.C.J.M.

2016-01-01

Policies to assure combatting climate change and realising energy security have stimulated a rapid growth in global installed capacity of renewable energy generation. The expansion of power generation from renewables, though, has so far lagged behind the growth in generation capacity. This indicates

Pyrimidine nucleobase radical reactivity in DNA and RNA

Science.gov (United States)

Greenberg, Marc M.

2016-11-01

Nucleobase radicals are major products of the reactions between nucleic acids and hydroxyl radical, which is produced via the indirect effect of ionizing radiation. The nucleobase radicals also result from hydration of cation radicals that are produced via the direct effect of ionizing radiation. The role that nucleobase radicals play in strand scission has been investigated indirectly using ionizing radiation to generate them. More recently, the reactivity of nucleobase radicals resulting from formal hydrogen atom or hydroxyl radical addition to pyrimidines has been studied by independently generating the reactive intermediates via UV-photolysis of synthetic precursors. This approach has provided control over where the reactive intermediates are produced within biopolymers and facilitated studying their reactivity. The contributions to our understanding of pyrimidine nucleobase radical reactivity by this approach are summarized.

Long-term need for new generating capacity

International Nuclear Information System (INIS)

Bloomster, C.H.; Merrill, E.T.

1987-03-01

Electricity demand should continue to grow at about the same rate as GNP, creating a need for large amounts of new generating capacity by the year 2000. Only coal and nuclear at this time have the abundant domestic resources and assured technology to meet this need. However, large increase in both coal and nuclear usage will not be acceptable to society without solutions to many of the problems that now deter their increased usage. For coal, the problems center around the safety and environmental impacts of increased coal mining and coal combustion. For nuclear the problems center around reactor safety, radioactive waste disposal, financial risk, and nuclear materials safeguards. The fuel requirements and waste generation for coal plants are orders of magnitude greater than for nuclear. Technology improvements and waste management practices must be pursued to mitigate environmental and safety impacts from electricity generation. 26 refs., 14 figs., 23 tabs

Fate of free radicals generated during one-electron reductions of 4-alkyl-1,4-peroxyquinols by cytochrome P-450

International Nuclear Information System (INIS)

Yumibe, N.P.; Thompson, J.A.

1988-01-01

Free radicals resulting from the one-electron reduction and subsequent homolytic cleavage of oxygen-oxygen bonds by heme proteins are likely to be responsible for some aspects of the toxicity of organic hydroperoxides. In the present work, effects of the 4-alkyl substituent of 2,6-di-tert-butyl-4-alkyl-4-hydroperoxycytohexa-2,5-dienones on radical production were investigated with microsomal cytochrome P-450 from rat liver. Quinoxy radicals from homolysis of the peroxyquinols underwent β-scission to produce a quinone and an alkyl radical, and this process occurred with increasing frequency as the stability of the alkyl radical increased. The fate of benzyl and 2-phenylethyl radicals generated from the appropriately substituted peroxyquinols was investigated also. The former was converted to benzyl alcohol, benzaldehyde, and toluene and the latter to 2-phenylethanol, phenylacetaldehyde, ethylbenzene, styrene, and benzaldehyde. Oxygen-18 labeling studies demonstrate that 80-85% of the benzyl alcohol incorporated oxygen from the hydroperoxide and the balance from molecular oxygen. This indicates that the predominant reaction pathway involved recombination between the benzyl radical and the iron-bound hydroxyl radical of the P-450 intermediate complex. By contrast, about 50% of 2-phenylethanol from the 2-phenylethyl radical incorporated oxygen from water and the balance from O 2 . Two alternative mechanisms are proposed to explain the formation of 2-phenylethanol that contained oxygen from water and the concurrent formation of styrene: (a) oxygen exchange of the P-450 intermediate with water, followed by hydrogen abstraction and radical recombination reactions with the P-450 complex, or (b) oxidation of the radical to the 2-phenylethyl cation followed by proton elimination and hydration

Lipid-derived free radical production in superantigen-induced interstitial pneumonia

Science.gov (United States)

Miyakawa, Hisako; Mason, Ronald P.; Jiang, JinJie; Kadiiska, Maria B.

2009-01-01

We studied the free radical generation involved in the development of interstitial pneumonia (IP) in an animal model of autoimmune disease. We observed an electron spin resonance (ESR) spectrum of α-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) radical adducts detected in the lipid extract of lungs in autoimmune-prone mice after intratracheal instillation of staphylococcal enterotoxin B. The POBN adducts detected by ESR were paralleled by infiltration of macrophages and neutrophils in the bronchoalveolar lavage fluid. To further investigate the mechanism of free radical generation, mice were pretreated with the macrophage toxicant gadolinium chloride, which significantly suppressed the radical generation. Free radical generation was also decreased by pretreatment with the xanthine oxidase (XO) inhibitor allopurinol, the iron chelator Desferal, and the inducible nitric oxide synthase (iNOS) inhibitor 1400W. Histopathologically, these drugs significantly reduced both the cell infiltration to alveolar septal walls and the synthesis of pulmonary collagen fibers. Experiments with NADPH oxidase knockout mice showed that NADPH oxidase did not contribute to lipid radical generation. These results suggest that lipid-derived carbon-centered free radical production is important in the manifestation of IP and that a macrophage toxicant, an XO inhibitor, an iron chelator, and an iNOS inhibitor protect against both radical generation and the manifestation of IP. PMID:19376221

Loading of free radicals on the functional graphene combined with liquid chromatography-tandem mass spectrometry screening method for the detection of radical-scavenging natural antioxidants.

Science.gov (United States)

Wang, Guoying; Shi, Gaofeng; Chen, Xuefu; Chen, Fuwen; Yao, Ruixing; Wang, Zhenju

2013-11-13

A novel free radical reaction combined with liquid chromatography electrospray ionization tandem mass spectrometry (FRR-LC-PDA-ESI/APCI-MS/MS) screening method was developed for the detection and identification of radical-scavenging natural antioxidants. Functionalized graphene was prepared by chemical method for loading free radicals (superoxide radical, peroxyl radical and PAHs free radical). Separation was performed with and without a preliminary exposure of the sample to specific free radicals on the functionalized graphene, which can facilitate reaction kinetics (charge transfers) between free radicals and potential antioxidants. The difference in chromatographic peak areas is used to identify potential antioxidants. The structure of the antioxidants in one sample (Swertia chirayita) is identified using MS/MS and comparison with standards. Thirteen compounds were found to possess potential antioxidant activity, and their free radical-scavenging capacities were investigated. The thirteen compounds were identified as 1,3,5-trihydroxyxanthone-8-O-β-D-glucopyranoside (PD1), norswertianin (PD2), 1,3,5,8-tetrahydroxyxanthone (PD3), 3, 3', 4', 5, 8-penta hydroxyflavone-6-β-D-glucopyranosiduronic acid-6'-pentopyranose-7-O-glucopyranoside (PD4), 1,5,8-trihydroxy-3-methoxyxanthone (PD5), swertiamarin (PS1), 2-C-β-D-glucopyranosyl-1,3,7-trihydroxylxanthone (PS2), 1,3,7-trihydroxylxanthone-8-O-β-D-glucopyranoside (PL1), 1,3,8-trihydroxyl xanthone-5-O-β-D-glucopyranoside (PL2), 1,3,7-trihydroxy-8-methoxyxanthone (PL3), 1,2,3-trihydroxy-7,8-dimethoxyxanthone (PL4), 1,8-dihydroxy-2,6-dimethoxy xanthone (PL5) and 1,3,5,8-tetramethoxydecussatin (PL6). The reactivity and SC50 values of those compounds were investigated, respectively. PD4 showed the strongest capability for scavenging PAHs free radical; PL4 showed prominent scavenging capacities in the lipid peroxidation processes; it was found that all components in S. chirayita exhibited weak reactivity in the superoxide

Short-term optimal wind power generation capacity in liberalized electricity markets

International Nuclear Information System (INIS)

Olsina, Fernando; Roescher, Mark; Larisson, Carlos; Garces, Francisco

2007-01-01

Mainly because of environmental concerns and fuel price uncertainties, considerable amounts of wind-based generation capacity are being added to some deregulated power systems. The rapid wind development registered in some countries has essentially been driven by strong subsidizing programs. Since wind investments are commonly isolated from market signals, installed wind capacity can be higher than optimal, leading to distortions of the power prices with a consequent loss of social welfare. In this work, the influence of wind generation on power prices in the framework of a liberalized electricity market has been assessed by means of stochastic simulation techniques. The developed methodology allows investigating the maximal wind capacity that would be profitably deployed if wind investments were subject to market conditions only. For this purpose, stochastic variables determining power prices are accurately modeled. A test system resembling the size and characteristics of the German power system has been selected for this study. The expected value of the optimal, short-term wind capacity is evaluated for a considerable number of random realizations of power prices. The impact of dispersing the wind capacity over statistical independent wind sites has also been evaluated. The simulation results reveal that fuel prices, installation and financing costs of wind investments are very influential parameters on the maximal wind capacity that might be accommodated in a market-based manner

Heat wave generates questions about Ontario's generation capacity

International Nuclear Information System (INIS)

Horne, D.

2005-01-01

Concerns regarding Ontario's power generation capacity were raised following a major blackout which occurred in August 2003. Power demand reached 26,170 MW during the weeks leading to the blackout, forcing the Independent Electricity System Operator (IESO) to ask residents to reduce electricity use during the day. The grid operator had also issued a forecast that Toronto could face rolling blackouts during times of heavy power demand. Ontario power consumption records were set in June and July of 2003 due to a heat wave, with hourly demand exceeding 25,000 MW on 53 occasions. Ontario was forced to import up to 3,400 MW (13 per cent of its power needs) from neighbouring provinces and the United States. During that period, the price of power had risen sharply to over 30 cents a kilowatt hour, although household consumers were still charged in the 5 to 10 cent range per kilowatt hour. However, it was noted that taxpayers will eventually bear the cost of importing power. The IESO noted that importing electricity is cheaper than the generation available in Ontario and that it is more economical to import, based on the market clearing price of all generators. In 2004, the IESO purchased 6 per cent of their electricity from the United States. That figure is expected to increase for 2005. Ontario generators produced 26.9 million MWh more in the summer of 2005 than during the same period in 2004 to meet electricity demand levels. It was noted that although importing power presently meets peak demand, the IESO agrees there is a need for new generation within Ontario. In addition to restarting Ontario's Pickering and Bruce nuclear facilities, more than 3,300 MW of new gas-fired generation is under construction or approved, and more than 9,000 MW are in various stages of approval. This paper discussed the effect of high energy costs on industry and Ontario's ability to meet future electricity demand in comparison to neighbouring jurisdictions. Issues regarding grid maintenance

Antioxidant capacity of anthocyanins from acerola genotypes

Directory of Open Access Journals (Sweden)

Vera Lúcia Arroxelas Galvão De Lima

2011-03-01

Full Text Available Anthocyanins from 12 acerola genotypes cultivated at the Active Germplasm Bank at Federal Rural University of Pernambuco were isolated for antioxidant potential evaluation. The antioxidant activity and radical scavenging capacity of the anthocyanin isolates were measured according to the β-carotene bleaching method and 1,1-diphenyl-2-picrylhydrazyl (DPPH free radical scavenging assay, respectively. The antioxidant activity varied from 25.58 to 47.04% at 0.2 mg.mL-1, and it was measured using the β-carotene bleaching method. The free radical scavenging capacity increased according to the increase in concentration and reaction time by the DPPH assay. At 16.7 μg.mL-1 concentration and after 5 minutes and 2 hours reaction time, the percentage of scavenged radicals varied from 36.97 to 63.92% and 73.27 to 94.54%, respectively. Therefore, the antioxidant capacity of acerola anthocyanins varied amongst acerola genotypes and methods used. The anthocyanins present in this fruit may supply substantial dietary source of antioxidant which may promote health and produce disease prevention effects.

Loading capacity of various filters for lithium fire generated aerosols

International Nuclear Information System (INIS)

Jeppson, D.W.; Barreca, J.R.

1980-01-01

The lithium aerosol loading capacity of a prefilter, HEPA filters and a sand and gravel bed filter was determined. The test aerosol was characterized and was generated by burning lithium in an unlimited air atmosphere. Correlation to sodium aerosol loading capacities were made to relate existing data to lithium aerosol loadings under varying conditions. This work is being conducted in support of the fusion reactor safety program. The lithium aerosol was generated by burning lithium pools, up to 45 kgs, in a 340 m 3 low humidity air atmosphere to supply aerosol to recirculating filter test loops. The aerosol was sampled to determine particle size, mass concentrations and chemical species. The dew point and gas concentrations were monitored throughout the tests. Loop inlet aerosol mass concentrations ranged up to 5 gr/m 3 . Chemical compounds analyzed to be present in the aerosol include Li 2 O, LiOH, and Li 2 CO 3 . HEPA filters with and without separators and a prefilter and HEPA filter in series were loaded with 7.8 to 11.1 kg/m 2 of aerosol at a flow rate of 1.31 m/sec and 5 kPa pressure drop. The HEPA filter loading capacity was determined to be greater at a lower flow rate. The loading capacity increased from 0.4 to 2.8 kg by decreasing the flow rate from 1.31 to 0.26 m/sec for a pressure drop of 0.11 kPa due to aerosol buildup. The prefilter tested in series with a HEPA did not increase the total loading capacity significantly for the same total pressure drop. Separators in the HEPA had only minor effect on loading capacity. The sand and gravel bed filter loaded to 0.50 kg/m 2 at an aerosol flow rate of 0.069 m/sec and final pressure drop of 6.2 kPa. These loading capacities and their dependence on test variables are similar to those reported for sodium aerosols except for the lithium aerosol HEPA loading capacity dependence upon flow rate

Free radical scavenging capacity, anticandicidal effect of bioactive compounds from Sida cordifolia L., in combination with nystatin and clotrimazole and their effect on specific immune response in rats.

Science.gov (United States)

Ouédraogo, Maurice; Konaté, Kiessoun; Lepengué, Alexis Nicaise; Souza, Alain; M'Batchi, Bertrand; Sawadogo, Laya L

2012-12-26

Infectious diseases caused by fungi are still a major threat to public health, despite numerous efforts by researchers. Use of ethnopharmacological knowledge is one attractive way to reduce empiricism and enhance the probability of success in new drug-finding efforts. In this work, the total alkaloid compounds (AC) from Sida cordifolia L. (Malvaceae) have been investigated for their free radical scavenging capacity, antifungal and immunostimulatory properties. The antifungal activity was investigated against five candida strains using the microplate dilution method and the Fractional Inhibitory Concentration Index (FICI) of compounds was evaluated. The antioxidant activity of the samples was evaluate using three separate methods, at last, the immunostimulatory effect on immunosuppressed wistar rats was performed. As for the antifungal activity, result varied according to microorganism. The results obtained in this antifungal activity were interesting and indicated a synergistic effect between alkaloid compounds and the antifungal references such as Nystatin and Clotrimazole. Antioxidant capacity noticed that the reduction capacity of DPPH radicals obtained the best result comparatively to the others methods of free radical scavenging. Our results showed a low immunostimulatory effect and this result could be explained by the lack of biologically active antioxidants such as polyphenol compounds lowly contained in the alkaloid compounds. The results of this study showed that alkaloid compounds in combination with antifungal references (Nystatin and Clotrimazole) exhibited antimicrobial effects against candida strains tested. The results supported the utilization of these plants in infectious diseases particularly in treatment of candida infections.

Strong Generative Capacity and the Empirical Base of Linguistic Theory

Directory of Open Access Journals (Sweden)

Dennis Ott

2017-09-01

Full Text Available This Perspective traces the evolution of certain central notions in the theory of Generative Grammar (GG. The founding documents of the field suggested a relation between the grammar, construed as recursively enumerating an infinite set of sentences, and the idealized native speaker that was essentially equivalent to the relation between a formal language (a set of well-formed formulas and an automaton that recognizes strings as belonging to the language or not. But this early view was later abandoned, when the focus of the field shifted to the grammar's strong generative capacity as recursive generation of hierarchically structured objects as opposed to strings. The grammar is now no longer seen as specifying a set of well-formed expressions and in fact necessarily constructs expressions of any degree of intuitive “acceptability.” The field of GG, however, has not sufficiently acknowledged the significance of this shift in perspective, as evidenced by the fact that (informal and experimentally-controlled observations about string acceptability continue to be treated as bona fide data and generalizations for the theory of GG. The focus on strong generative capacity, it is argued, requires a new discussion of what constitutes valid empirical evidence for GG beyond observations pertaining to weak generation.

Formation of Nanoparticles Controlled by the Yield and Properties of the γ-Generated Radicals

Energy Technology Data Exchange (ETDEWEB)

Chen, Q. [Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing (China)

2009-07-01

In the past two decades, nanoparticles have attracted much attention because of their novel properties. Among the numerous synthetic methods, ionizing irradiation, which is simple and can take at normal temperature and pressure, even at low temperature, is a powerful method for preparing metals, alloys, metal oxides, metal chalcogenides, metal halides and insoluble sulphate nanoparticles. In this method, dose rate is always used to affect the shape, component and size of synthesized nanoparticles. In addition, to eliminate the effect of ·OH on the formation of nanoparticles, alcohol (such as isopropyl alcohol) is always added and a lot of reductive radicals with wide range of reduction potentials are generated. At the same time, these radicals transformed from ·OH can also reduce the reactant, which have been used to control the growth of nanoparticles. However, so far, most nanoparticles synthesized by ionizing irradiation are spherical. In our previous work, ''solid'' BaSO{sub 4} microspheres, mainly consisting of quasi-spherical nanoparticles, have been synthesized by precipitating Ba{sup 2+} ions with SO{sub 4}{sup 2-} ions, which were generated from the reduction of K{sub 2}S{sub 2}O{sub 8} in the presence of EDTA under N{sub 2} atmosphere by γ-irradiation.

Comparison of stainless and mild steel welding fumes in generation of reactive oxygen species

Directory of Open Access Journals (Sweden)

Frazer David

2010-11-01

Full Text Available Abstract Background Welding fumes consist of a wide range of complex metal oxide particles which can be deposited in all regions of the respiratory tract. The welding aerosol is not homogeneous and is generated mostly from the electrode/wire. Over 390,000 welders were reported in the U.S. in 2008 while over 1 million full-time welders were working worldwide. Many health effects are presently under investigation from exposure to welding fumes. Welding fume pulmonary effects have been associated with bronchitis, metal fume fever, cancer and functional changes in the lung. Our investigation focused on the generation of free radicals and reactive oxygen species from stainless and mild steel welding fumes generated by a gas metal arc robotic welder. An inhalation exposure chamber located at NIOSH was used to collect the welding fume particles. Results Our results show that hydroxyl radicals (.OH were generated from reactions with H2O2 and after exposure to cells. Catalase reduced the generation of .OH from exposed cells indicating the involvement of H2O2. The welding fume suspension also showed the ability to cause lipid peroxidation, effect O2 consumption, induce H2O2 generation in cells, and cause DNA damage. Conclusion Increase in oxidative damage observed in the cellular exposures correlated well with .OH generation in size and type of welding fumes, indicating the influence of metal type and transition state on radical production as well as associated damage. Our results demonstrate that both types of welding fumes are able to generate ROS and ROS-related damage over a range of particle sizes; however, the stainless steel fumes consistently showed a significantly higher reactivity and radical generation capacity. The chemical composition of the steel had a significant impact on the ROS generation capacity with the stainless steel containing Cr and Ni causing more damage than the mild steel. Our results suggest that welding fumes may cause acute

Interconnector capacity allocation in offshore grids with variable wind generation

DEFF Research Database (Denmark)

Schröder, Sascha Thorsten

2013-01-01

the interconnector capacity should be allocated for wind generation and for international power trading. The main difficulty arises from the stochastic nature of wind generation: in a case with radial connections to the national coast, the wind park owner has the possibility of aggregating the offshore wind park....... It is concluded that treating offshore generation as a single price zone within the interconnector reduces the wind operator’s ability to pool it with other generation. Furthermore, a single offshore price zone between two markets will always receive the lower spot market price of the neighbouring zones, although...

Roles of individual radicals generated by a submerged dielectric barrier discharge plasma reactor during Escherichia coli O157:H7 inactivation

Energy Technology Data Exchange (ETDEWEB)

Khan, Muhammad Saiful Islam [Department of Food Biotechnology, University of Science and Technology, Daejeon, 305-350 (Korea, Republic of); Lee, Eun-Jung [Food Safety Research Group, Korea Food Research Institute, Seongnam-si, Gyeonggi-Do (Korea, Republic of); Kim, Yun-Ji, E-mail: yunji@kfri.re.kr [Department of Food Biotechnology, University of Science and Technology, Daejeon, 305-350 (Korea, Republic of); Food Safety Research Group, Korea Food Research Institute, Seongnam-si, Gyeonggi-Do (Korea, Republic of)

2015-10-15

A submerged dielectric barrier discharge plasma reactor (underwater DBD) has been used on Escherichia coli O157:H7 (ATCC 35150). Plasma treatment was carried out using clean dry air gas to investigate the individual effects of the radicals produced by underwater DBD on an E. coli O157:H7 suspension (8.0 log CFU/ml). E. coli O157:H7 was reduced by 6.0 log CFU/ml for 2 min of underwater DBD plasma treatment. Optical Emission Spectra (OES) shows that OH and NO (α, β) radicals, generated by underwater DBD along with ozone gas. E. coli O157:H7 were reduced by 2.3 log CFU/ml for 10 min of underwater DBD plasma treatment with the terephthalic acid (TA) OH radical scavenger solution, which is significantly lower (3.7 log CFU/ml) than the result obtained without using the OH radical scavenger. A maximum of 1.5 ppm of ozone gas was produced during the discharge of underwater DBD, and the obtained reduction difference in E.coli O157:H7 in presence and in absence of ozone gas was 1.68 log CFU/ml. The remainder of the 0.62 log CFU/ml reduction might be due to the effect of the NO (α, β) radicals or due to the combined effect of all the radicals produced by underwater DBD. A small amount of hydrogen peroxide was also generated but does not play any role in E. coli O157:H7 inactivation.

Radical's view of sciences

International Nuclear Information System (INIS)

Mittal, J.P.

2004-01-01

Full text: General concept in radiation biology is that free radicals are highly reactive and they can damage vital cellular molecules leading to injurious effects. However, in this talk, evidence will be presented through the techniques of electron paramagnetic resonance ( EPR ) and pulse radiolysis that free radicals can be highly selective in their reaction with the target molecules. In addition, attempts will be made to present a brief account of emerging scenario of free radical generation, identification and their involvement in radiation damage mechanisms in chemical and biological systems

Interaction of radiation-generated radicals with myoglobin in aqueous solution

International Nuclear Information System (INIS)

Whitburn, K.D.; Hoffman, M.Z.

1985-01-01

The γ-radiolysis of aqueous solutions of ferrimyoglobin in the presence of N 2 O at pH 7.3 has been examined as a function of added catalase and oxygen. Changes in the nature of the heme group have been monitored by visible absorption spectrophotometry and analysed quantitatively by a multiple wavelength method based on Beer's Law. Simple chemical analyses have been used to confirm qualitative identification of the product derivatives. As observed previously, the ferriheme is reduced by indirect globin-mediated action initiated by radical OH/H radical. The yield of reduced product decreases as [O 2 ] derived from irradiated water and from protein-mediated processes in oxygenated solution, is eliminated by the presence of catalase. Formation of a hemichrome form of ferrimyoglobin is apparent at higher doses in the presence of O 2 . These results demonstrate that oxygen plays an important role in controlling the nature and extent of redox that manifests ultimately on the heme group of ferrimyoglobin as a result of the initial interaction of radical OH/H radical. (author)

Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

International Nuclear Information System (INIS)

Dzeba, I.; Mihaljevic, B.

2011-01-01

Complete text of publication follows. Plant derived resveratrol (trans-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties. Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis of competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1-octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. Tert-butoxyl radicals were generated directly by peroxide bond cleavage from di-tert-butyl peroxide in acetonitrile by light pulses of Nd:YAG at 355 nm, and ruby at 347 nm. Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions of resveratrol and other radicals generated by pulse radiolysis.

Radical scavenging propensity of Cu2 +, Fe3 + complexes of flavonoids and in-vivo radical scavenging by Fe3 +-primuletin

Science.gov (United States)

Jabeen, Erum; Janjua, Naveed Kausar; Ahmed, Safeer; Murtaza, Iram; Ali, Tahir; Hameed, Shahid

2017-01-01

Cu2 + and Fe3 + complexes of three flavonoids (morin or mo, quercetin or quer and primuletin or prim) were synthesized with the objective of improving antioxidant capacities of flavonoids. The radical scavenging activities of pure flavonoids and their metal complexes were assayed to monitor their tendencies towards sequestering of radicals at physiological conditions. The scavenger potencies of metal-flavonoid complexes were significantly higher than those of the parent flavonoids. Further, influence of the solvent polarity on the radical capturing by flavonoids and their metal complexes was in favor for the polar solvent. Fe3 +-prim displayed its radical scavenging ability via up gradation of CAT and SOD activities in in-vivo antioxidant assays.

Scavenging capacity of strawberry tree (Arbutus unedo L.) leaves on free radicals.

Science.gov (United States)

Oliveira, Ivo; Coelho, Valentim; Baltasar, Raquel; Pereira, José Alberto; Baptista, Paula

2009-07-01

Despite strawberry tree (Arbutus unedo L.) leaves had a long use in traditional medicine due to its antiseptic, diuretic, astringent and depurative properties, the potential of their antioxidant activity are still lacking. Our study goals to assess the antioxidant and free radical scavenging potential of water, ethanol, methanol and diethyl ether extracts of A. unedo leaves. Total phenols content was achieved spectrophotometrically using Folin-Ciocalteau reagent with gallic acid as standard. Antioxidant activity was evaluated using three different methods: reducing power of iron (III)/ferricyanide complex assay, scavenging effect on DPPH (2,2-diphenyl-1-picrylhydrazyl) radicals and scavenging effect on superoxide radicals by using the PMS-NADH-nitroblue tetrazolium system. Ethanol extracts of A. unedo leaves were the highest in reducing power (IC(50) 232.7 microg/mL) and DPPH scavenging effect (IC(50) 63.2 microg/mL) followed by water extracts (with IC(50) of 287.7 and 73.7 microg/mL, respectively); whereas diethyl ether extracts were the lowest. In the scavenging on superoxide radical assay, methanol extracts obtained the best results (IC(50) 6.9 microg/mL). For all the methods tested the antioxidant activity was concentration dependent. In accordance with antioxidant activity, highest total phenols content were found in ethanol, followed by water, methanol and diethyl ether extract. The results indicated that A. unedo leaves are a potential source of natural antioxidants.

Effect of early rehabilitation training on oxygen free radical generation and nerve injury in patients with cerebral hemorrhage

Directory of Open Access Journals (Sweden)

Zhao-Shu Liu

2017-08-01

Full Text Available Objective: To study the effect of early rehabilitation training combined with edaravone on oxygen free radical generation and nerve injury in patients with cerebral hemorrhage. Methods: A total of 56 patients with acute cerebral hemorrhage who were treated in Zigong Third People’s Hospital between July 2014 and March 2017 were selected and randomly divided into early rehabilitation group and routine rehabilitation group, the early rehabilitation group began the rehabilitation training 2 d after cerebral hemorrhage condition was stabilized, and routine rehabilitation group began the rehabilitation training 14 d after cerebral hemorrhage. Serum contents of oxygen free radicals, nerve injury markers and neurotrophic molecules were detected 28 d and 56 d after cerebral hemorrhage. Results: 28 d and 56 d after cerebral hemorrhage, serum MDA, AOPP, 8-OHdG, GFAP, NSE, Tf, Ft and S100B levels of early rehabilitation group were significantly lower than those of routine rehabilitation group while BDNF, NGF, NTF-α and IGF-I levels were significantly higher than those of routine rehabilitation group. Conclusion: Early rehabilitation training combined with edaravone for cerebral hemorrhage can inhibit the oxygen free radical generation, reduce the degree of nerve injury and improve the neurotrophic state.

Free radical scavenging capacity, anticandicidal effect of bioactive compounds from Sida Cordifolia L., in combination with nystatin and clotrimazole and their effect on specific immune response in rats

Directory of Open Access Journals (Sweden)

Ouédraogo Maurice

2012-12-01

Full Text Available Abstract Background Infectious diseases caused by fungi are still a major threat to public health, despite numerous efforts by researchers. Use of ethnopharmacological knowledge is one attractive way to reduce empiricism and enhance the probability of success in new drug-finding efforts. In this work, the total alkaloid compounds (AC from Sida cordifolia L. (Malvaceae have been investigated for their free radical scavenging capacity, antifungal and immunostimulatory properties. Method The antifungal activity was investigated against five candida strains using the microplate dilution method and the Fractional Inhibitory Concentration Index (FICI of compounds was evaluated. The antioxidant activity of the samples was evaluate using three separate methods, at last, the immunostimulatory effect on immunosuppressed wistar rats was performed. Results As for the antifungal activity, result varied according to microorganism. The results obtained in this antifungal activity were interesting and indicated a synergistic effect between alkaloid compounds and the antifungal references such as Nystatin and Clotrimazole. Antioxidant capacity noticed that the reduction capacity of DPPH radicals obtained the best result comparatively to the others methods of free radical scavenging. Our results showed a low immunostimulatory effect and this result could be explained by the lack of biologically active antioxidants such as polyphenol compounds lowly contained in the alkaloid compounds. Conclusion The results of this study showed that alkaloid compounds in combination with antifungal references (Nystatin and Clotrimazole exhibited antimicrobial effects against candida strains tested. The results supported the utilization of these plants in infectious diseases particularly in treatment of candida infections.

Structure and reactivity of the N-acetyl-cysteine radical cation and anion: does radical migration occur?

NARCIS (Netherlands)

Osburn, S.; Berden, G.; Oomens, J.; O'Hair, R.A.J.; Ryzhov, V.

2011-01-01

The structure and reactivity of the N-acetyl-cysteine radical cation and anion were studied using ion-molecule reactions, infrared multi-photon dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. The radical cation was generated by first nitrosylating the thiol of

Structure and Reactivity of the N-Acetyl-Cysteine Radical Cation and Anion: Does Radical Migration Occur?

NARCIS (Netherlands)

Osburn, S.; G. Berden,; Oomens, J.; O' Hair, R. A. J.; Ryzhov, V.

2011-01-01

The structure and reactivity of the N-acetyl-cysteine radical cation and anion were studied using ion-molecule reactions, infrared multi-photon dissociation (IRMPD) spectroscopy, and density functional theory (DFT) calculations. The radical cation was generated by first nitrosylating the thiol of

Preparation of high-capacity, weak anion-exchange membranes by surface-initiated atom transfer radical polymerization of poly(glycidyl methacrylate) and subsequent derivatization with diethylamine

International Nuclear Information System (INIS)

Qian, Xiaolei; Fan, Hua; Wang, Chaozhan; Wei, Yinmao

2013-01-01

Ion-exchange membrane is of importance for the development of membrane chromatography. In this work, a high-capacity anion-exchange membrane was prepared by grafting of glycidyl methacrylate (GMA) onto the surface of regenerated cellulose (RC) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequent derivatization with diethylamine. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize changes in the chemical functionality, surface topography and pore morphology of the modified membranes. The static capacity of the prepared anion-exchange membrane was evaluated with bovine serum albumin (BSA) as a model protein. The results indicated that the anion-exchange membrane which could reach a maximum capacity of 96 mg/mL for static adsorption possesses a higher adsorption capacity, and the adsorption capacity increases with the polymerization time. The effect of pH and salt concentration confirmed that the adsorption of BSA followed ion-exchange mechanism. The established method would have potential application in the preparation of anion-exchange membrane.

Leghemoglobin-derived radicals. Evidence for multiple protein-derived radicals and the initiation of peribacteroid membrane damage

DEFF Research Database (Denmark)

Moreau, S; Davies, Michael Jonathan; Mathieu, C

1996-01-01

, with the consequent generation of lipid-derived radicals. The formation of such radicals may result in the depletion of membrane antioxidants and the initiation of lipid peroxidation. This transfer of damage from the heme center via the protein surface to neighboring membranes may be of considerable biological......-derived phenoxyl radical present at Tyr-133 in the soybean protein and Tyr-138 in the lupin protein. To obtain further information on these protein radicals and their potential interaction with the physiologically important peribacteroid membrane (which surrounds the microsymbiont in vivo), EPR spin trapping......); these radicals may be side chain- or alpha-carbon-derived, their exact sites have not been determined. Some of these radicals are on the protein surface and may be key intermediates in the formation of protein dimers. These radicals have been shown to be capable of reacting with peribacteroid membrane fractions...

Antioxidant Capacity, Radical Scavenging Kinetics and Phenolic ...

African Journals Online (AJOL)

HP

Phenolic Profile of Methanol Extracts of Wild Plants of. Southern Sonora ... plant extracts. Phenolic compounds determination was carried out by high ... Determination of antioxidant capacity ..... In vitro antioxidant and antiproliferative activities ...

Structure and Reactivity of the Glutathione Radical Cation: Radical Rearrangement from the Cysteine Sulfur to the Glutamic Acid alpha-Carbon Atom

NARCIS (Netherlands)

Osburn, S.; Berden, G.; Oomens, J.; Gulyuz, K.; Polfer, N.C.; O'Hair, R.A.J.; Ryzhov, V.

2013-01-01

A gas-phase radical rearrangement through intramolecular hydrogen-atom transfer (HAT) was studied in the glutathione radical cation, [-ECG](+.), which was generated by a homolytic cleavage of the protonated S-nitrosoglutathione. Ion-molecule reactions suggested that the radical migrates from the

Comparative study of radical oxidation of DNA and its nucleosides by hydroxyl radicals and ferryl ions generated by the Fenton reaction

International Nuclear Information System (INIS)

Mouret, J.F.; Berger, M.; Anselmino, C.; Polverelli, M.; Cadet, J.

1991-01-01

A comparative study of the reaction of hydroxyl radicals and Fenton type oxidative species with DNA and 2'-deoxyribonucleosides was investigated. This study was based on the characterization of the diamagnetic products resulting from the chemical transformation of the transient radicals. Emphasis was placed on the radical oxidative reactions of the purine nucleosides. It is interesting to note that oxidative purine radicals can be reduced by reagents such as ascorbic acid or N,N,N',N'-tetramethyl-1, 4-p-phenylenediamine. The observed differences in the nature of the decomposition products resulting from the Fenton reaction are not consistent with the nature of the oxidative species (hydroxyl radicals or ferryl ions) involved, but due to the presence of ferrous sulfate [fr

Protection from radiation-induced enteropathy by elemental diet feeding: The role of free radicals

International Nuclear Information System (INIS)

McArdle, A.H.; Duong, M.N.

1991-01-01

Free radicals have been implicated in intestinal reperfusion injury following ischemia and in epithelial cell damage resulting from ionizing radiation. Elemental diets (ED) have been shown to afford significant prophylaxis to the intestine from these injuries. The purpose of the present study was to investigate whether ED alters the activity of the defense mechanisms necessary for free radical removal. Six female dogs, fed on normal dog chow, had a 30 cm resection of terminal ileum to form Thiry-Vella loops. The main intestine was biopsied and anastomosed. Two weeks later, biopsies were taken from the lips of the loops. Following this, the loops were fed daily with ED another 2 weeks and biopsied again. The dogs were then placed on ED for 3 days before and during 4 days of pelvic irradiation, and the loops also were fed ED daily; after which the animals were again anesthetized, and the loops and main intestine were biopsied. All biopsies were processed for histology, and assayed for xanthine oxidase (XO), superoxide dismutase (SOD), glutathione peroxidase (GSP) and catalase (CAT). The XO and SOD pathway of free oxygen radical generation and scavenging are not affected by radiation. However, ED lowers both XO and SOD activity and may result in a reduced production of peroxides. The significantly increased activity of GSP and CAT when ED is fed improves the scavenging capacity of the free hydroxyl radicals generated by the radiation, and is an important adjunct to an understanding of ED prophylaxis

Free radical scavenging window of infertile patients with polycystic ovary syndrome: correlation with embryo quality.

Science.gov (United States)

Huang, Bo; Li, Zhou; Ren, Xinling; Ai, Jihui; Zhu, Lixia; Jin, Lei

2017-06-01

The activity of free radicals in follicular fluid was related to ovarian responsiveness, in vitro fertilization (IVF), and embryo transfer success rate. However, studies analyzing the relationship between the free radical scavenging capacity and embryo quality of infertile women with polycystic ovarian syndrome (PCOS) were lacking. The aim of this study was to evaluate the relationship between the free radical scavenging window of women with PCOS and their embryo quality. The free radical scavenging capacity of follicular fluid from women with PCOS was determined by a,a-diphenyl-b-picrylhydrazyl (DPPH), 2,2-azinobis (3-ethylbenzthiazoline-6-sulphonic acid) assay, superoxide radical, and reactive oxygen species (ROS) assay. In the DPPH and ROS assays, the follicular fluid from grades I and II embryos was significantly higher than the follicular fluid from grades III and IVembryos. The lower control limit of DPPH radical scavenging capacity and upper control limit of ROS level were 13.2% and 109.0 cps, respectively. The calculated lower control limit and upper control limit were further confirmed in the follicular fluid of embryos of all grades. These cut-off values of free radical scavenging activity of follicular fluid could assist embryologists in choosing the development of embryos in PCOS patients undergoing IVF.

Confirmation of hydroxyl radicals ({sup •} OH) generated in the presence of TiO{sub 2} supported on AC under microwave irradiation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zhaohong, E-mail: lnuhjhx@163.com [School of Environmental Science, Liaoning University, Shenyang 110036 (China); Yu, Fengyang; Huang, Lirong; Jiatieli, Jianaerguli; Li, Yuanyuan; Song, Lijun [School of Environmental Science, Liaoning University, Shenyang 110036 (China); Yu, Ning [Experiment Center of Environmental Monitoring of Liaoning Province, Shenyang 110161 (China); Dionysiou, Dionysios D., E-mail: dionysios.d.dionysiou@uc.edu [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0012 (United States)

2014-08-15

Graphical abstract: - Highlights: • Generation of {sup •} OH in MW integrated with loaded TiO{sub 2}/AC system was confirmed. • Confirmation of {sup •} OH was conducted using radical scavenger such as BHT, MT and VC. • More {sup •} OH was formed using anatase TiO{sub 2}/AC than rutile TiO{sub 2}/AC under MW irradiation. • Effect of mass ratio, irradiation time, catalyst dose and DPCI on {sup •} OH was studied. - Abstract: In order to study the degradation mechanism of technology of microwave (MW) combined with TiO{sub 2} supported on activated carbon (TiO{sub 2}/AC), the reactive oxygen species (ROS) was explored through oxidation of 1,5-diphenyl carbazide (DPCI) to 1,5-diphenyl carbazone (DPCO). Furthermore, 2,6-di-tert-butyl-4-methylphenol (BHT), Mannitol (MT) and Vitamin C (VC) were used as radical scavengers to confirm the generation of the hydroxyl radicals ({sup •} OH). In addition, the influence of some parameters such as TiO{sub 2} mass ratio content, irradiation time, material dose, DPCI concentration and MW power on the determination of {sup •} OH were examined. The results showed that the {sup •} OH could be generated under MW combined with loaded TiO{sub 2}/AC. Also, anatase TiO{sub 2}/AC can generate more {sup •} OH radicals than rutile TiO{sub 2}/AC under MW irradiation. This work would provide new mechanistic insights on the enhanced degradation effect of organic pollutants in water using the supported TiO{sub 2}/AC coupled with MW technology.

Electric distribution systems and embedded generation capacity

International Nuclear Information System (INIS)

Calderaro, V.; Galdi, V.; Piccolo, A.; Siano, P.

2006-01-01

The main policy issues of European States are sustainable energy supply promotion and liberalization of energy markets, which introduced market competition in electricity production and created support mechanisms to encourage renewable electricity production and consumption. As a result of liberalization, any generator, including small-scale and renewable energy based units, can sell electricity on the free market. In order to meet future sustainability targets, connection of a higher number of Distributed Generation (DG) units to the electrical power system is expected, requiring changes in the design and operation of distribution electricity systems, as well as changes in electricity network regulation. In order to assist distribution system operators in planning and managing DG connections and in maximizing DG penetration and renewable sources exploitation, this paper proposed a reconfiguration methodology based on a Genetic Algorithm (GA), that was tested on a 70-bus system with DG units. The simulation results confirmed that the methodology represents a suitable tool for distribution system operators when dealing with DG capacity expansion and power loss issues, providing information regarding the potential penetration network-wide and allowing maximum exploitation of renewable generation. 35 refs., 4 tabs., 6 figs

In vitro antioxidant capacity and free radical scavenging evaluation of active metabolite constituents of Newbouldia laevis ethanolic leaf extract.

Science.gov (United States)

Habu, Josiah Bitrus; Ibeh, Bartholomew Okechukwu

2015-03-14

The aim of the present study was to evaluate the in vitro antioxidant and free radical scavenging capacity of bioactive metabolites present in Newbouldia laevis leaf extract. Chromatographic and spectrophotometric methods were used in the study and modified where necessary in the study. Bioactivity of the extract was determined at 10 μg/ml, 50 μg/ml, 100 μg/ml, 200 μg/ml and 400 μg/ml concentrations expressed in % inhibition. The yield of the ethanolic leaf extract of N.laevis was 30.3 g (9.93%). Evaluation of bioactive metabolic constituents gave high levels of ascorbic acid (515.53 ± 12 IU/100 g [25.7 mg/100 g]), vitamin E (26.46 ± 1.08 IU/100 g), saponins (6.2 ± 0.10), alkaloids (2.20 ± 0.03), cardiac glycosides(1.48 ± 0.22), amino acids and steroids (8.01 ± 0.04) measured in mg/100 g dry weight; moderate levels of vitamin A (188.28 ± 6.19 IU/100 g), tannins (0.09 ± 0.30), terpenoids (3.42 ± 0.67); low level of flavonoids (1.01 ± 0.34 mg/100 g) and absence of cyanogenic glycosides, carboxylic acids and aldehydes/ketones. The extracts percentage inhibition of DPPH, hydroxyl radical (OH.), superoxide anion (O2 .-), iron chelating, nitric oxide radical (NO), peroxynitrite (ONOO-), singlet oxygen (1O2), hypochlorous acid (HOCl), lipid peroxidation (LPO) and FRAP showed a concentration-dependent antioxidant activity with no significant difference with the controls. Though, IC50 of the extract showed significant difference only in singlet oxygen (1O2) and iron chelating activity when compared with the controls. The extract is a potential source of antioxidants/free radical scavengers having important metabolites which maybe linked to its ethno-medicinal use.

Status of thermal power generation in India-Perspectives on capacity, generation and carbon dioxide emissions

International Nuclear Information System (INIS)

Ghosh, Subhodip

2010-01-01

India's reliance on fossil-fuel based electricity generation has aggravated the problem of high carbon dioxide (CO 2 ) emissions from combustion of fossil fuels, primarily coal, in the country's energy sector. The objective of this paper is to analyze thermal power generation in India for a four-year period and determine the net generation from thermal power stations and the total and specific CO 2 emissions. The installed generating capacity, net generation and CO 2 emissions figures for the plants have been compared and large generators, large emitters, fuel types and also plant vintage have been identified. Specific emissions and dates of commissioning of plants have been taken into account for assessing whether specific plants need to be modernized. The focus is to find out areas and stations which are contributing more to the total emissions from all thermal power generating stations in the country and identify the overall trends that are emerging.

Managing nuclear predominant generating capacity

International Nuclear Information System (INIS)

Bouget, Y.H.; Carbonnier, D.

1999-01-01

The most common believe, associated with nuclear power plant, leads to the conclusion that it can only operate, as a base load plant. This observation can be reversed, by just looking at large generating capacity, using an important nuclear generation mix. Nuclear plants may certainly load follow and contribute to the grid frequency control. The French example illustrates these possibilities. The reactor control of French units has been customized to accommodate the grid requests. Managing such a large nuclear plant fleet requires to take various actions, ranging from a daily basis to a multi-annual prospective standpoint. The paper describes the various contributions leading to safe, reliable, well accepted and cost competitive nuclear plants in France. The combination of all aspects related to operations, maintenance scheduling, nuclear safety management, are presented. The use of PWR units carries considerable weight in economic terms, with several hundred million francs tied in with outage scheduling every year. This necessitates a global view of the entire generating system which can be mobilized to meet demand. There is considerable interaction between units as, on the one hand, they are competing to satisfy the same need, and, on the other hand, reducing maintenance costs means sharing the necessary resources, and thus a coordinated staggering of outages. In addition, nuclear fuel is an energy reserve which remains in the reactor for 3 or 4 years, with some of the fuel renewed each year. Due to the memory effect, the fuel retains a memory of past use, so that today's choices impact upon the future. A medium-term view of fuel management is also necessary. The coordination systems implemented by EDF aim to control these parameters for the benefit of electricity consumers. (author)

Radical chemistry of artemisinin

Energy Technology Data Exchange (ETDEWEB)

Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

2011-12-29

The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

Radical chemistry of artemisinin

Science.gov (United States)

Denisov, Evgenii T.; Solodova, S. L.; Denisova, Taisa G.

2010-12-01

The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

Radical chemistry of artemisinin

International Nuclear Information System (INIS)

Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G

2010-01-01

The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

Radical chemistry of artemisinin

Energy Technology Data Exchange (ETDEWEB)

Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

2010-12-29

The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

Antioxidant Capacity and Proanthocyanidin Composition of the Bark of Metasequoia glyptostroboides.

Science.gov (United States)

Chen, Fengyang; Zhang, Lin; Zong, Shuling; Xu, Shifang; Li, Xiaoyu; Ye, Yiping

2014-01-01

Metasequoia glyptostroboides Hu et Cheng is the only living species in the genus Metasequoia Miki ex Hu et Cheng (Taxodiaceae), which is well known as a "living fossil" species. In the Chinese folk medicine, the leaves and bark of M. glyptostroboides are used as antimicrobic, analgesic, and anti-inflammatory drug for dermatic diseases. This study is the first to report the free radical scavenging capacity, antioxidant activity, and proanthocyanidin composition of the bark of M. glyptostroboides. We observed total of six extracts and fractions, which were easily obtained by water-ethanol extraction and followed by a further separation with D101 resin column chromatography, had significant DPPH radical, superoxide anion radical, and hydroxyl radical scavenging capacity, total antioxidative capacity (T-AOC), lipid peroxidation inhibitory activity, and metal ions chelating capacity. The fraction MGEB, which was obtained by 60% ethanol extraction and followed by a further separation with D101 resin column chromatograph, possessed the highest proanthocyanidin content and the highest free radical scavenging and antioxidant activities. Furthermore, MGEB could significantly protect against CCl4 induced acute liver injury through inhibition of oxidative stress in mice. In addition, ten proanthocyanidins were isolated from MGEB, and six of them were firstly reported from this plant.

Antioxidant Capacity and Proanthocyanidin Composition of the Bark of Metasequoia glyptostroboides

Directory of Open Access Journals (Sweden)

Fengyang Chen

2014-01-01

Full Text Available Metasequoia glyptostroboides Hu et Cheng is the only living species in the genus Metasequoia Miki ex Hu et Cheng (Taxodiaceae, which is well known as a “living fossil” species. In the Chinese folk medicine, the leaves and bark of M. glyptostroboides are used as antimicrobic, analgesic, and anti-inflammatory drug for dermatic diseases. This study is the first to report the free radical scavenging capacity, antioxidant activity, and proanthocyanidin composition of the bark of M. glyptostroboides. We observed total of six extracts and fractions, which were easily obtained by water-ethanol extraction and followed by a further separation with D101 resin column chromatography, had significant DPPH radical, superoxide anion radical, and hydroxyl radical scavenging capacity, total antioxidative capacity (T-AOC, lipid peroxidation inhibitory activity, and metal ions chelating capacity. The fraction MGEB, which was obtained by 60% ethanol extraction and followed by a further separation with D101 resin column chromatograph, possessed the highest proanthocyanidin content and the highest free radical scavenging and antioxidant activities. Furthermore, MGEB could significantly protect against CCl4 induced acute liver injury through inhibition of oxidative stress in mice. In addition, ten proanthocyanidins were isolated from MGEB, and six of them were firstly reported from this plant.

EPR detection of hydroxyl radical generation and oxidative perturbations in lead-exposed earthworms (Eisenia fetida) in the presence of decabromodiphenyl ether.

Science.gov (United States)

Liu, Kou; Chen, Lin; Zhang, Wei; Lin, Kuangfei; Zhao, Li

2015-03-01

Lead (Pb) and decabromodiphenyl ether (BDE209) are the main contaminants at e-waste recycling sites, and their potential toxicological effects on terrestrial organisms have received extensive attention. However, the impacts on the oxidative perturbations and hydroxyl radical (·OH) generation in earthworms of exposure to the two chemicals remain almost unknown. Therefore, indoor incubation tests were performed on control and contaminated soil samples to determine the effects of Pb in earthworms Eisenia fetida in the presence of BDE209 through the use of several biomarkers in microcosms. The results have demonstrated that the addition of BDE209 (1 or 10 mg kg(-1)) decreased the enzymatic activities [superoxide dismutase, catalase (CAT), peroxidase] and total antioxidant capacity (T-AOC) compared with exposure to BDE209 alone (50, 250 or 500 mg kg(-1)). Electron paramagnetic resonance spectra indicated that ·OH radicals in earthworms were significantly induced by Pb in the presence of BDE209. The changing pattern of malondialdehyde (MDA) contents was accordant with that of ·OH intensity suggested that reactive oxygen species might lead to cellular lipid peroxidation. Furthermore, CAT exhibited more sensitive response to single Pb exposure than the other biomarkers, while T-AOC, ·OH and MDA might be three most sensitive biomarkers in earthworms after simultaneous exposure to Pb and BDE209. The results of these observations suggested that oxidative stress appeared in E. fetida, and it may play an important role in inducing the Pb and BDE209 toxicity to earthworms.

Thermochemical properties for isooctane and carbon radicals: computational study.

Science.gov (United States)

Snitsiriwat, Suarwee; Bozzelli, Joseph W

2013-01-17

Thermochemical properties for isooctane, its internal rotation conformers, and radicals with corresponding bond energies are determined by use of computational chemistry. Enthalpies of formation are determined using isodesmic reactions with B3LYP density function theory and composite CBS-QB3 methods. Application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations for the lowest energy conformer. Internal rotor potentials are determined for the isooctane parent and for the primary, secondary, and tertiary radicals in order to identify isomer energies. Intramolecular interactions are shown to have a significant effect on the enthalpy of formation of the isooctane parent and its radicals. The computed standard enthalpy of formation for the lowest energy conformers of isooctane from this study is -54.40 ± 1.60 kcal mol(-1), which is 0.8 kcal mol(-1) lower than the evaluated experimental value -53.54 ± 0.36 kcal mol(-1). The standard enthalpy of formation for the primary radical for a methyl on the quaternary carbon is -5.00 ± 1.69 kcal mol(-1), for the primary radical on the tertiary carbon is -5.18 ± 1.69 kcal mol(-1), for the secondary isooctane radical is -9.03 ± 1.84 kcal mol(-1), and for the tertiary isooctane radical is -12.30 ± 2.02 kcal mol(-1). Bond energy values for the isooctane radicals are 100.64 ± 1.73, 100.46 ± 1.73, 96.41 ± 1.88 and 93.14 ± 2.05 kcal mol(-1) for C3•CCCC2, C3CCCC2•, C3CC•CC2, and C3CCC•C2, respectively. Entropy and heat capacity values are reported for the lowest energy homologues.

Xanthine oxidase activity and free radical generation in patients with sepsis syndrome

DEFF Research Database (Denmark)

Galley, H F; Davies, Michael Jonathan; Webster, N R

1996-01-01

OBJECTIVE: To determine xanthine oxidase activity, free radical concentrations, and lipid peroxidation in patients with sepsis syndrome compared with noninfected critically ill patients. DESIGN: A prospective observational study. SETTING: A nine-bed intensive care unit in a university teaching......). CONCLUSIONS: Patients with sepsis have xanthine oxidase activation, high free-radical concentrations, and evidence of free radical damage. The finding that xanthine oxidase activity was lower in those patients who died, coupled with increased lactate concentrations implies more severe ischemia with incomplete...... to the Acute Physiology and Chronic Health Evaluation (APACHE) II score or to the presence of organ dysfunction. The mean ascorbyl radical concentration (arbitrary units) determined by electron paramagnetic resonance following spin trapping was increased in patients compared with healthy subjects (p

A modified method for studying behavioral paradox of antioxidants and their disproportionate competitive kinetic effect to scavenge the peroxyl radical formation.

Science.gov (United States)

Masood, Nusrat; Fatima, Kaneez; Luqman, Suaib

2014-01-01

We have described a modified method for evaluating inhibitor of peroxyl radicals, a well-recognized and -documented radical involved in cancer initiation and promotion as well as diseases related to oxidative stress and ageing. We are reporting hydrophilic and lipophilic as well as natural and synthetic forms of antioxidants revealing a diversified behaviour to peroxyl radical in a dose-dependent manner (1 nM-10 μM). A simple kinetic model for the competitive oxidation of an indicator molecule (ABTS) and a various antioxidant by a radical (ROO(•)) is described. The influences of both the concentration of antioxidant and duration of reaction (70 min) on the inhibition of the radical cation absorption are taken into account while determining the activity. The induction time of the reaction was also proposed as a parameter enabling determination of antioxidant content by optimizing and introducing other kinetic parameters in 96-well plate assays. The test evidently improves the original PRTC (peroxyl radical trapping capacity) assay in terms of the amount of chemical used, simultaneous tracking, that is, the generation of the radical taking place continually and the kinetic reduction technique (area under curve, peak value, slope, and Vmax).

Peroxyl radical reactions with carotenoids in microemulsions: Influence of microemulsion composition and the nature of peroxyl radical precursor.

Science.gov (United States)

El-Agamey, Ali; McGarvey, David J

2016-01-01

The reactions of acetylperoxyl radicals with different carotenoids (7,7'-dihydro-β-carotene and ζ-carotene) in SDS and CTAC microemulsions of different compositions were investigated using laser flash photolysis (LFP) coupled with kinetic absorption spectroscopy. The primary objective of this study was to explore the influence of microemulsion composition and the type of surfactant used on the yields and kinetics of various transients formed from the reaction of acetylperoxyl radicals with carotenoids. Also, the influence of the site (hydrocarbon phases or aqueous phase) of generation of the peroxyl radical precursor was examined by using 4-acetyl-4-phenylpiperidine hydrochloride (APPHCl) and 1,1-diphenylacetone (11DPA) as water-soluble and lipid-soluble peroxyl radical precursors, respectively. LFP of peroxyl radical precursors with 7,7'-dihydro-β-carotene (77DH) in different microemulsions gives rise to the formation of three distinct transients namely addition radical (λmax=460 nm), near infrared transient1 (NIR, λmax=700 nm) and 7,7'-dihydro-β-carotene radical cation (77DH(•+), λmax=770 nm). In addition, for ζ-carotene (ZETA) two transients (near infrared transient1 (NIR1, λmax=660 nm) and ζ-carotene radical cation (ZETA(•+), λmax=730-740 nm)) are generated following LFP of peroxyl radical precursors in the presence of ζ-carotene (ZETA) in different microemulsions. The results show that the composition of the microemulsion strongly influences the observed yield and kinetics of the transients formed from the reactions of peroxyl radicals (acetylperoxyl radicals) with carotenoids (77DH and ZETA). Also, the type of surfactant used in the microemulsions influences the yield of the transients formed. The dependence of the transient yields and kinetics on microemulsion composition (or the type of surfactant used in the microemulsion) can be attributed to the change of the polarity of the microenvironment of the carotenoid. Furthermore, the nature of

Chemical repair of trypsin-histidinyl radical

International Nuclear Information System (INIS)

Jovanovic, S.V.; Ruvarac, I.; Jankovic, I.; Josimovic, L.

1991-01-01

Oxyl radicals, such as hydroxyl, alkoxyl and peroxyl, react with biomolecules to produce bioradicals. Unless chemically repaired by suitable antioxidants, these bioradicals form stable products. This leads to loss of biological function of parent biomolecules with deleterious biological results, such as mutagenesis and cancer. Consequently, the understanding of the mechanisms of oxyl radical damage to biomolecules and chemical repair of such damage is crucial for the development of strategies for anticarcinogenesis and radioprotection. In this study the chemical repair of the histidinyl radical generated upon the trichloromethylperoxyl radical reaction with trypsin vas investigated by gamma radiolysis. The trypsin histidinyl radical is a resonance-stabilized heterocyclic free radical which was found to be unreactive with oxygen. The efficacy of the chemical repair of the trypsin-histidinyl radical by endogenous antioxidants which are electron donors (e.g. 5-hydroxytryptophan, uric acid) is compared to that of antioxidants which are H-atom donors (e. g. glutathione). 9 refs., 2 figs., 1 tab

Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

Energy Technology Data Exchange (ETDEWEB)

D’Ambro, Emma L.; Møller, Kristian H.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Liu, Jiumeng; Shilling, John E.; Lee, Ben Hwan; Kjaergaard, Henrik G.; Thornton, Joel A.

2017-04-11

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

Turning the wind into hydrogen: The long-run impact on electricity prices and generating capacity

International Nuclear Information System (INIS)

Green, Richard; Hu, Helen; Vasilakos, Nicholas

2011-01-01

Hydrogen production via electrolysis has been proposed as a way of absorbing the fluctuating electricity generated by wind power, potentially allowing the use of cheap electricity at times when it would otherwise be in surplus. We show that large-scale adoption of electrolysers would change the shape of the load-duration curve for electricity, affecting the optimal capacity mix. Nuclear power stations will replace gas-fired power stations, as they are able to run for longer periods of time. Changes in the electricity capacity mix will be much greater than changes to the pattern of prices. The long-run supply price of hydrogen will thus tend to be insensitive to the amount produced. - Research Highlights: → Hydrogen production from electrolysis may offset intermittent wind generation. → The generation capacity mix will change in response to changed demand patterns. → The long-run equilibrium supply curve for hydrogen will be quite flat. → The production cost will be very sensitive to fuel prices paid by generators.

Asymmetric Radical Cyclopropanation of Alkenes with In Situ-Generated Donor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis.

Science.gov (United States)

Wang, Yong; Wen, Xin; Cui, Xin; Wojtas, Lukasz; Zhang, X Peter

2017-01-25

Donor-substituted diazo reagents, generated in situ from sulfonyl hydrazones in the presence of base, can serve as suitable radical precursors for Co(II)-based metalloradical catalysis (MRC). The cobalt(II) complex of D 2 -symmetric chiral porphyrin [Co(3,5-Di t Bu-Xu(2'-Naph)Phyrin)] is an efficient metalloradical catalyst that is capable of activating different N-arylsulfonyl hydrazones for asymmetric radical cyclopropanation of a broad range of alkenes, affording the corresponding cyclopropanes in high yields with effective control of both diastereo- and enantioselectivity. This Co(II)-based metalloradical system represents the first catalytic protocol that can effectively utilize donor-type diazo reagents for asymmetric olefin cyclopropanation.

Generation of counter ion radical (Br2(•-)) and its reactions in water-in-oil (CTAB or CPB)/n-butanol/cyclohexane/water) microemulsion.

Science.gov (United States)

Guleria, Apurav; Singh, Ajay K; Sarkar, Sisir K; Mukherjee, Tulsi; Adhikari, Soumyakanti

2011-09-15

Herein we report the generation of counterion radicals and their reactions in quaternary water-in-oil microemulsion. Hydrated electrons in the microemulsion CTAB/H(2)O/n-butanol/cyclohexane have a remarkably short half-life (∼1 μs) and lower yield as compared to that in the pure water system. Electrons are solvated in two regions: one is the water core and other the interface; however, the electrons in the water core have a shorter half-life than those in the interface. The decay of the solvated electrons in the interface is found to be water content dependent and it has been interpreted in terms of increased interfacial fluidity with the increase in water content of the microemulsion. Interestingly another species, dibromide radical anion (Br(2)(•-)) in CTAB and CPB microemulsions have been observed after the electron beam irradiation. Assuming that the extinction coefficient of the radicals is the same as that in the aqueous solution, the yields of the radicals per 100 eV are 0.29 and 0.48 for the Br(2)(•-) radical in CTAB and CPB containing microemulsions (W(0) = 40), respectively, under N(2)O saturated conditions. Further, we intended to study electron transfer reactions, which occur at and through the interface. The reaction of the Br(2)(•-) radical anion with ABTS [2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)] has been studied to generate the ABTS radical in the water core, and further, its reaction has been investigated with the water-insoluble molecule vitamin E (tocopherol) and water-soluble vitamin C (ascorbic acid). In the present study, we were able to show that, even for molecules which are completely insoluble in water, ABTS scavenging assay is possible by pulse radiolysis technique. Furthermore, these results show that it is possible to follow the reaction of the hydrated inorganic radical with solutes dissolved in the organic phase in a microemulsion without use of a phase transfer catalyst. © 2011 American Chemical Society

Some reactions of oxidizing radicals with enzymes in aqueous solution

International Nuclear Information System (INIS)

Cundall, R.B.; Bisby, R.H.; Hoe, S.T.; Sims, H.E.; Anderson, R.F.

1979-01-01

A range of oxidizing radicals including some inorganic radical anions and the superoxide radical, can be generated by radiolysis of aqueous solutions. These radicals are more selective in their reactions with amino acids than the hydroxyl radical. Factors controlling the apparent reactivity of radical anions with proteins, such as free radical equilibria and ion-binding, are described. The superoxide radical inactivates papain by reaction with the cysteine residue. This reaction has been studied in solutions subjected to radiations of varying linear energy transfer. (Auth.)

Total aerobic destruction of azo contaminants with nanoscale zero-valent copper at neutral pH: promotion effect of in-situ generated carbon center radicals.

Science.gov (United States)

Dong, Guohui; Ai, Zhihui; Zhang, Lizhi

2014-12-01

In this study, nanoscale zero-valent copper (nZVC) was synthesized with a facile solvothermal method and used for the aerobic removal of azo contaminants at neutral pH for the first time. We found that both Cu(I) and OH generated during the nZVC induced molecular oxygen activation process accounted for the rapid total destruction of azo contaminants in the nZVC/Air system, where nZVC could activate molecular oxygen to produce H2O2, and also release Cu(I) to break the -NN- bond of azo contaminants via the sandmeyer reaction for the generation of carbon center radicals. The in-situ generated carbon center radicals would then react with OH produced by the Cu(I) catalyzed decomposition of H2O2, resulting in the generation of low molecular weight organic acids and their subsequent mineralization. The indispensible role of Cu(I) catalyzed sandmeyer reaction and the promotion effect of in-situ generated carbon center radicals on the rapid total destruction of azo contaminants in the nZVC/Air system were confirmed by gas chromatography-mass spectrometry analysis. This study can deepen our understanding on the degradation of organic pollutant with molecular oxygen activated by zero valent metal, and also provide a new method to remove azo contaminants at neutral pH. Copyright © 2014 Elsevier Ltd. All rights reserved.

A novel heterogeneous system for sulfate radical generation through sulfite activation on a CoFe2O4 nanocatalyst surface.

Science.gov (United States)

Liu, Zizheng; Yang, Shaojie; Yuan, Yanan; Xu, Jing; Zhu, Yifan; Li, Jinjun; Wu, Feng

2017-02-15

Heterogeneous catalytic activation is important for potential application of new sulfate-radical-based advanced oxidation process using sulfite as source of sulfate radical. We report herein a heterogeneous system for sulfite activation by CoFe 2 O 4 nanocatalyst for metoprolol removal. Factors that influence metoprolol removal were investigated, including pH and initial concentrations of components. The CoFe 2 O 4 nanocatalyst was characterized by X-ray diffractometry (XRD) and transmission electron microscopy (TEM), and the catalytic stability was tested by consecutive runs. Radicals generated in the CoFe 2 O 4 S(IV)O 2 system were identified through radical quenching experiments and by electron spin resonance (ESR). The catalytic mechanism was elucidated further by X-ray photoelectron spectroscopy (XPS). The catalytic process was dependent on initial pH, and more than 80% of the metoprolol can be removed at pH 10.0 following the Langmubir-Hinshelwood equation. The generation of Co-OH complexes on the CoFe 2 O 4 surface was crucial for sulfite activation. SO 4 - was verified to be the main oxidative species responsible for metoprolol degradation. Other organic pollutants, such as sulfanilamide, sulfasalazine, 2-nitroaniline, sulfapyridine, aniline, azo dye X-3B and 4-chloroaniline, could also be removed in this CoFe 2 O 4 S(IV)O 2 system. The results suggest that the CoFe 2 O 4 S(IV)O 2 system has good application prospects in alkaline organic wastewater treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

International Nuclear Information System (INIS)

Mandal, P.C.; Bardhan, D.K.; Bhattacharyya, S.N.

1992-01-01

Reactions of carbonate (CO 3 - radical) and bicarbonate (HCO 3 radical) radicals generated by photolysis of a carbonate or bicarbonate solution at pH 11.2 and 8.5, respectively, with Co(II) complexes of iminodiacetic acid (IDA) and ethylenediaminetetraacetic acid (EDTA) have been studied. The rate constants for the reactions were in the order of 10 6 -10 7 dm 3 mol -1 s -1 . From the time-resolved spectroscopy of the products formed after reaction of CO 3 - radical or HCO 3 radical, it is observed that CO 3 - radical or HCO 3 radical oxidize the metal center to its higher oxidation state. (author) 26 refs.; 2 figs.; 1 tab

The Rise of Radicals in Bioinorganic Chemistry

OpenAIRE

Gray, Harry B.; Winkler, Jay R.

2016-01-01

Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O_2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) a...

Engineering a horseradish peroxidase C stable to radical attacks by mutating multiple radical coupling sites.

Science.gov (United States)

Kim, Su Jin; Joo, Jeong Chan; Song, Bong Keun; Yoo, Young Je; Kim, Yong Hwan

2015-04-01

Peroxidases have great potential as industrial biocatalysts. In particular, the oxidative polymerization of phenolic compounds catalyzed by peroxidases has been extensively examined because of the advantage of this method over other conventional chemical methods. However, the industrial application of peroxidases is often limited because of their rapid inactivation by phenoxyl radicals during oxidative polymerization. In this work, we report a novel protein engineering approach to improve the radical stability of horseradish peroxidase isozyme C (HRPC). Phenylalanine residues that are vulnerable to modification by the phenoxyl radicals were identified using mass spectrometry analysis. UV-Vis and CD spectra showed that radical coupling did not change the secondary structure or the active site of HRPC. Four phenylalanine (Phe) residues (F68, F142, F143, and F179) were each mutated to alanine residues to generate single mutants to examine the role of these sites in radical coupling. Despite marginal improvement of radical stability, each single mutant still exhibited rapid radical inactivation. To further reduce inactivation by radical coupling, the four substitution mutations were combined in F68A/F142A/F143A/F179A. This mutant demonstrated dramatic enhancement of radical stability by retaining 41% of its initial activity compared to the wild-type, which was completely inactivated. Structure and sequence alignment revealed that radical-vulnerable Phe residues of HPRC are conserved in homologous peroxidases, which showed the same rapid inactivation tendency as HRPC. Based on our site-directed mutagenesis and biochemical characterization, we have shown that engineering radical-vulnerable residues to eliminate multiple radical coupling can be a good strategy to improve the stability of peroxidases against radical attack. © 2014 Wiley Periodicals, Inc.

The predictive value of the antioxidant capacity of structurally related flavonoids using the Trolox equivalent antioxidant capacity (TEAC) assay

NARCIS (Netherlands)

Berg, R. van den; Haenen, G.R.M.M.; Berg, H. van den; Vijgh, W. van der; Bast, A.

2000-01-01

The antioxidant capacity of a series of structurally related flavonoids is quantified by the amount of ABTS [2,2'-azinobis-(3-ethylbenzthiazoline-6-sulfonate)] radical anions (ABTS(.)-) that is able to react with the flavonoid and expressed as the Trolox equivalent antioxidant capacity (TEAC). To

Capacity factor prediction and planning in the wind power generation industry

Energy Technology Data Exchange (ETDEWEB)

Gurgur, Cigdem Z. [Department of Management and Marketing, Richard T. Doermer School of Business and Management Sciences, Indiana - Purdue University, 2101 Coliseum Blvd. East, Fort Wayne, IN 46805 (United States); Jones, Michael [Xcel Energy, Denver, CO 80223 (United States)

2010-12-15

The common practice to calculate wind generation capacity values relies more on heuristic approximations than true system estimations. In this paper we proposed a more accurate method. In the first part of our analysis, a Monte Carlo simulation was created based on Markov chains to provide an independent estimate of the true behavior of wind farm capacity value as a function of system penetration. With this curve as a baseline, a technique for using beta distributions to model the input variables was adopted. A final step to increase accuracy involved the use of numerical convolution within the program to eliminate summation estimates. (author)

EPR studies of the free radicals generated in gamma irradiated amino acid derivatives

Science.gov (United States)

Osmanoğlu, Y. Emre; Sütçü, Kerem

2017-10-01

Gamma irradiated powder forms of N-acetyl-DL-aspartic acid, N-carbamoyl-DL-aspartic acid and N-methyl-L-serine were investigated by electron paramagnetic resonance spectroscopy (EPR) at room temperature. In these compounds, the paramagnetic centers formed after irradiation were attributed to the HOOCCH2ĊHCOOH, COOHĊHCHNH and HOCH2ĊHCOOH radicals, respectively. The g values and the hyperfine coupling constants for the radical species are with values of g = 2.0038 ± 0.0005, aα = 2.15 mT, aβ(1) = 3.84 mT and aβ(2) = 2.15 for the first radical, g = 2.0039 ± 0.0005, aα = 1.7 mT, aß(1) = 0.62 mT, aß(2) = 0.54 mT, aγ = 0.53 mT for the second radical and g = 2.0039 ± 0.0005, aβ(1) = 2.40 mT, aβ(2) = 1.83 mT and aα = 1.83 mT for the third radical. The free radicals formed in three compounds were found to be stable for three months at room temperature. It was concluded that, spin density was concentrated predominantly in the 2pπ orbital of the carbon atom.

Analysis of Solar Energy Generation Capacity Using Hesitant Fuzzy Cognitive Maps

Directory of Open Access Journals (Sweden)

Veysel Coban

2017-01-01

Full Text Available Solar energy is an important and reliable source of energy. Better understanding the concepts and relationships of the factors that affect solar energy generation capacity can enhance the usage of solar energy. This understanding can lead investors and governors in their solar power investments. However, solar power generation process is complicated, and the relations among the factors are vague and hesitant. In this paper, a hesitant fuzzy cognitive map for solar energy generation is developed and used for modeling and analyzing the ambiguous relations. The concepts and the relationships among them are defined by using expertsr opinions. Different scenarios are formed and evaluated with the proposed model.

The Nuclear option for U.S. electrical generating capacity additions utilizing boiling water reactor technology

International Nuclear Information System (INIS)

Garrity, T.F.; Wilkins, D.R.

1993-01-01

The technology status of the Advanced Boiling Water (ABWR) and Simplified Boiling Water (SBWR) reactors are presented along with an analysis of the economic potential of advanced nuclear power generation systems based on BWR technology to meet the projected domestic electrical generating capacity need through 2005. The forecasted capacity needs are determined for each domestic North American Electric Reliability Council (NERC) region. Extensive data sets detailing each NERC region's specific generation and load characteristics, and capital and fuel cost parameters are utilized in the economic analysis of the optimal generation additions to meet this need by use of an expansion planning model. In addition to a reference case, several sensitivity cases are performed with regard to capital costs and fuel price escalation

EPR-Spin Trapping and Flow Cytometric Studies of Free Radicals Generated Using Cold Atmospheric Argon Plasma and X-Ray Irradiation in Aqueous Solutions and Intracellular Milieu.

Directory of Open Access Journals (Sweden)

Hidefumi Uchiyama

Full Text Available Electron paramagnetic resonance (EPR-spin trapping and flow cytometry were used to identify free radicals generated using argon-cold atmospheric plasma (Ar-CAP in aqueous solutions and intracellularly in comparison with those generated by X-irradiation. Ar-CAP was generated using a high-voltage power supply unit with low-frequency excitation. The characteristics of Ar-CAP were estimated by vacuum UV absorption and emission spectra measurements. Hydroxyl (·OH radicals and hydrogen (H atoms in aqueous solutions were identified with the spin traps 5,5-dimethyl-1-pyrroline N-oxide (DMPO, 3,3,5,5-tetramethyl-1-pyrroline-N-oxide (M4PO, and phenyl N-t-butylnitrone (PBN. The occurrence of Ar-CAP-induced pyrolysis was evaluated using the spin trap 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS in aqueous solutions of DNA constituents, sodium acetate, and L-alanine. Human lymphoma U937 cells were used to study intracellular oxidative stress using five fluorescent probes with different affinities to a number of reactive species. The analysis and quantification of EPR spectra revealed the formation of enormous amounts of ·OH radicals using Ar-CAP compared with that by X-irradiation. Very small amounts of H atoms were detected whereas nitric oxide was not found. The formation of ·OH radicals depended on the type of rare gas used and the yield correlated inversely with ionization energy in the order of krypton > argon = neon > helium. No pyrolysis radicals were detected in aqueous solutions exposed to Ar-CAP. Intracellularly, ·OH, H2O2, which is the recombination product of ·OH, and OCl- were the most likely formed reactive oxygen species after exposure to Ar-CAP. Intracellularly, there was no practical evidence for the formation of NO whereas very small amounts of superoxides were formed. Despite the superiority of Ar-CAP in forming ·OH radicals, the exposure to X-rays proved more lethal. The mechanism of free radical formation in aqueous solutions and

Synthesis of Environmentally Responsive Polymers by Atom Transfer Radical Polymerization: Generation of Reversible Hydrophilic and Hydrophobic Surfaces

Directory of Open Access Journals (Sweden)

Vikas Mittal

2010-05-01

Full Text Available Environmentally responsive poly(N-isopropylacrylamide brushes were grafted from the surface of polymer particles or flat surfaces in order to generate reversible hydrophilic and hydrophobic surfaces. The use of atom transfer radical polymerization was demonstrated for the grafting of polymer brushes as it allows efficient control on the amount of grafted polymer. The polymer particles were generated with or without surfactant in the emulsion polymerization and their surface could be modified with the atom transfer radical polymerization (ATRP initiator. The uniform functionalization of the surface with ATRP initiator was responsible for the uniform grafting of polymer brushes. The grafted brushes responded reversibly with changes in temperature indicating that the reversible responsive behavior could be translated to the particle surfaces. The particles were observed to adsorb and desorb protein and virus molecules by changing the temperatures below or higher than 32 °C. The initiator functionalized particles could also be adsorbed on the flat surfaces. The adsorption process also required optimization of the heat treatment conditions to form a uniform layer of the particles on the substrate. The grafted polymer brushes also responded to the changes in temperatures similar to the spherical particles studied through water droplets placed on the flat substrates.

OH radical induced depolymerization of poly(methacrylic acid)

Science.gov (United States)

Ulanski, Piotr; Bothe, Eberhard; von Sonntag, Clemens

1999-05-01

Hydroxyl radicals (generated pulse radiolytically in dilute N 2O-saturated aqueous solutions) react with poly(methacrylic acid) producing two kinds of radicals. The primary radical is converted into a secondary one by H-abstraction ( k=3.5 × 10 2 s -1) as monitored by changes in the UV spectrum. Subsequently, the secondary radicals undergo chain scission ( k=1.8 s -1 at pH 7-9). This process has been followed both by spectrophotometry as well as by conductometry. In competition with the bimolecular decay of the radicals the ensuing end-chain radicals undergo efficient depolymerization resulting in the release of monomer. Since the lifetime of the radicals is much longer at high pH, where the polymer attains a rod-like conformation, depolymerization is most efficient in basic solution.

Generation of Oxygen Free Radicals by Proflavine: Implication in Protein Degradation

Directory of Open Access Journals (Sweden)

Mansour K.M. Gatasheh

2017-07-01

Full Text Available Proflavine, an acridine dye, is a known DNA intercalating agent. In the present study, we show that proflavine alone on photoillumination can generate reactive oxygen species (ROS. These proflavine-derived ROS cause damage to proteins, and this effect is enhanced when the divalent metal ion Cu (II is included in the reaction. Bathocuproine, a specific Cu (I sequestering agent, when present in the reaction mixture containing Cu (II, was found to inhibit the protein degradation, showing that Cu (I is an essential intermediate in the reaction. The effect of several scavengers of ROS such as superoxide dismutase, sodium azide, potassium iodide, and thiourea were examined on the protein damaging reaction. Potassium iodide was found to be the most effective in inhibiting protein damage followed by sodium azide and thiourea. Our results indicate the involvement of superoxide, singlet oxygen, triplet oxygen, and hydroxyl radicals in proflavine-induced damage to proteins.

Dose and time effect of CdTe quantum dots on antioxidant capacities of the liver and kidneys in mice

Directory of Open Access Journals (Sweden)

Wang J

2017-09-01

Full Text Available Jilong Wang,1,2,* Hubo Sun,1,2,* Peijun Meng,1,2 Mengmeng Wang,1,2 Mi Tian,3 Yamin Xiong,1,2 Xueying Zhang,1,2 Peili Huang1,2 1School of Public Health, Capital Medical University, 2Beijing Key Laboratory of Environmental Toxicology, 3Medical Experiment and Test Center, Capital Medical University, Beijing, People’s Republic of China *These authors contributed equally to this work Abstract: Although quantum dot (QD-induced toxicity occurs due to free radicals, generation of oxidative stress mediated by reactive oxygen species (ROS formation is considered an important mechanism. However, free radical mechanisms are essentially difficult to elucidate at the molecular level because most biologically relevant free radicals are highly reactive and short-lived, making them difficult to directly detect, especially in vivo. Antioxidants play an important role in preventing or, in most cases, limiting the damage caused by ROS. Healthy people and animals possess many endogenous antioxidative substances that scavenge free radicals in vivo to maintain the redox balance and genome integrity. The antioxidant capacity of an organism is highly important but seldom studied. In this study, the dose and time effects of CdTe QDs on the antioxidant capacities of the liver and kidneys were investigated in mice using the electron paramagnetic resonance (EPR spin-trapping technique. We found that the liver and kidneys of healthy mice contain specific antioxidant capacities that scavenge ·OH and ·O2-. Furthermore, oxidative stress markers (superoxide dismutase [SOD], catalase [CAT], glutathione peroxidase [GPx], glutathione [GSH] and malondialdehyde [MDA] were examined. In dose course studies, the free radical scavenging efficiencies of the liver and kidneys were found to gradually decrease with increasing concentration of CdTe QD exposure. The activities and levels of SOD, CAT, GPx and MDA were observed to increase in treated groups, whereas those of GSH were reduced

A novel heterogeneous system for sulfate radical generation through sulfite activation on a CoFe{sub 2}O{sub 4} nanocatalyst surface

Energy Technology Data Exchange (ETDEWEB)

Liu, Zizheng [School of Civil Engineering, Wuhan University, Wuhan, 430072 (China); Yang, Shaojie; Yuan, Yanan; Xu, Jing; Zhu, Yifan [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China); Li, Jinjun, E-mail: ljj0410@163.com [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China); Wu, Feng, E-mail: fengwu@whu.edu.cn [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, Wuhan, 430079 (China)

2017-02-15

Highlights: • CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system is proposed as a new system of sulfate radical based AOPs. • Alkaline pH favors the activation of sulfite on CoFe{sub 2}O{sub 4} surface to produce oxysulfur radicals. • Generation of Co−OH complexes on the surface of CoFe{sub 2}O{sub 4} is the main factor for sulfite activation. • Degradation of organic contaminants by CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system were achieved. • Main intermediates and pathways for the degradation of metoprolol were identified. - Abstract: Heterogeneous catalytic activation is important for potential application of new sulfate-radical-based advanced oxidation process using sulfite as source of sulfate radical. We report herein a heterogeneous system for sulfite activation by CoFe{sub 2}O{sub 4} nanocatalyst for metoprolol removal. Factors that influence metoprolol removal were investigated, including pH and initial concentrations of components. The CoFe{sub 2}O{sub 4} nanocatalyst was characterized by X-ray diffractometry (XRD) and transmission electron microscopy (TEM), and the catalytic stability was tested by consecutive runs. Radicals generated in the CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system were identified through radical quenching experiments and by electron spin resonance (ESR). The catalytic mechanism was elucidated further by X-ray photoelectron spectroscopy (XPS). The catalytic process was dependent on initial pH, and more than 80% of the metoprolol can be removed at pH 10.0 following the Langmubir-Hinshelwood equation. The generation of Co-OH complexes on the CoFe{sub 2}O{sub 4} surface was crucial for sulfite activation. SO{sub 4}{sup ·−} was verified to be the main oxidative species responsible for metoprolol degradation. Other organic pollutants, such as sulfanilamide, sulfasalazine, 2-nitroaniline, sulfapyridine, aniline, azo dye X-3B and 4-chloroaniline, could also be removed in this CoFe{sub 2}O{sub 4}−S(IV)−O{sub 2} system. The

Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

International Nuclear Information System (INIS)

Williams, T.F.

1982-01-01

The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

Glutathione as a radical scavenger and the biological consequences of thiyl radical production

International Nuclear Information System (INIS)

Winterbourn, C.C.

1996-01-01

A large number of compounds that have toxic effects can be metabolised to free radicals and secondary reactive oxygen species. These may be directly damaging or affect cell function by altering regulatory mechanisms through changing redox status. Protection is provided by an integrated system of antioxidant defenses. This includes reduced glutathione (GSH), one of the functions of which is as a free radical scavenger. For GSH to be an effective radical scavenging antioxidant, therefore, it must act in concert with superoxide dismutase to remove the superoxide so generated. Superoxide is produced in a variety of metabolic processes. It is also a secondary product of radicals reacting with oxygen either directly or through GSH. The biological reactivity of superoxide has been the subject of much debate ever since the discovery of superoxide dismutase in 1968. It has more recently become apparent that its rapid reaction with nitric oxide to give peroxynitrite, and its ability to reversibly oxidise and inactivate iron sulphur enzymes, contribute to the toxicity of superoxide. Another mechanism that could be important involves addition reactions of superoxide with other radicals to give organic peroxides. This reaction, to form a tyrosine peroxide, has come to authors attention through the study of the scavenging of tyrosyl radicals by GSH. It is also shown that a tyrosine peroxide is a major product of the oxidation of tyrosine by neutrophils

Capacity payment impact on gas-fired generation investments under rising renewable feed-in — A real options analysis

International Nuclear Information System (INIS)

Hach, Daniel; Spinler, Stefan

2016-01-01

We assess the effect of capacity payments on investments in gas-fired power plants in the presence of different degrees of renewable energy technology (RET) penetration. Low variable cost renewables increasingly make investments in gas-fired generation unprofitable. At the same time, growing feed-in from intermittent RETs amplifies fluctuations in power generation, thus entailing the need for flexible buffer capacity—currently mostly gas-fired power plants. A real options approach is applied to evaluate investment decisions and timing of a single investor in gas-fired power generation. We investigate the necessity and effectiveness of capacity payments. Our model incorporates multiple uncertainties and assesses the effect of capacity payments under different degrees of RET penetration. In a numerical study, we implement stochastic processes for peak-load electricity prices and natural gas prices. We find that capacity payments are an effective measure to promote new gas-fired generation projects. Especially in times of high renewable feed-in, capacity payments are required to incentivize peak-load investments. - Highlights: • We assess capacity payments under the specific focus of the influence of different degrees of renewable feed-in. • We use a real options approach to analyze investment decision and timing. • Our model reflects stochastic gas prices and stochastic electricity prices. • The case study shows the value of capacity payments to investors especially under high renewable feed-in.

Crossed-beam studies of the dynamics of radical reactions

Energy Technology Data Exchange (ETDEWEB)

Liu, K. [Argonne National Laboratory, IL (United States)

1993-12-01

The objective of this program is to characterize the detailed dynamics of elementary radical reactions and to provide a better understanding of radical reactivity in general. The radical beam is typically generated by a laser photolysis method. After colliding with the reacting molecule in a crossed-beam apparatus, the reaction product state distribution is interrogated by laser spectroscopic techniques. Several radicals of combustion significance, such as O, CH, OH, CN and NCO have been successfully generated and their collisional behavior at the state-to-state integral cross section level of detail has been studied in this manner. During the past year, the detection system has been converted from LIF to REMPI schemes, and the emphasis of this program shifted to investigate the product angular distributions. Both inelastic and reactive processes have been studied.

Radical quenching by rosmarinic acid from Lavandula vera MM cell culture.

Science.gov (United States)

Kovacheva, Elena; Georgiev, Milen; Pashova, Svetlana; Angelova, Maria; Ilieva, Mladenka

2006-01-01

This study was conducted to evaluate the radical scavenging capacities of extracts and preparations from a Lavandula vera MM plant cell culture with different rosmarinic acid content and to compare them with pure rosmarinic and caffeic acids as well. The methods, which were used are superoxide anion and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt radicals scavenging assays. Results showed that extracts and preparations from Lavandula vera MM possess strong radical scavengers, as the best both radical scavengers appeared to be the fractions with enriched rosmarinic acid content, obtained after ethylacetate fractioning (47.7% inhibition of superoxide radicals and 14.2 microM 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid equivalents, respectively). These data reveal the possibilities for application of these preparations as antioxidants.

The impact of UV irradiation on the radical initiating capacity of dissolved dyes

International Nuclear Information System (INIS)

Vig, A.; Czilik, M.; Rusznak, I.

2002-01-01

Complete text of publication follows. Kinetics of photodecomposition of three model dyes dissolved in isopropanol-water mixture has been determined after exposure to UV radiation in the range from 360 through 400 nm and from 220 through 400 nm, respectively. It has been disclosed earlier that photodecomposition of the dissolved dyes was decelerated initially by the presence of the dissolved oxygen in the system. The presence of a radical initiator, AIBN was indispensable for arriving at the decomposition of the irradiated dye solution in the range from 360 through 400 nm. The equation of W i D = [O 2 ]/τ D was used for the calculation of radical initiating rate of the irradiated dye molecule on the isopropanol (W i D (mol/l x s)), where [O 2 ] (mol/l) is the dissolved oxygen concentration in the system and τ D (s) is duration of the induction period of the photodestruction of the dissolved dye. The equation is valid only for photodecomposition which are not chain reaction. The photodegradation of dissolved dyes was also other then chain reaction, consequently the above equation could be applied in the study too. The average radical initiating rate of the dyes applied in this study was in the order of magnitude equal to that of AIBN. The number of cycles between the first radical formation and the last regeneration of the dye molecule could be calculated in bath systems (in the presence and absence of oxygen, respectively): K = W i D /W D , where K is the number of cycles, W D (mol/l x s) is the initial rate of the decomposition of the dissolved dyed. The number of cycles in the oxygen containing systems significantly exceeded those obtained in the oxygen systems because W D was markedly higher in the latter system than in the former one

Free-radical scavenging capacity and antioxidant properties of some selected onions (Allium cepa L. and garlic (Allium sativum L. extracts

Directory of Open Access Journals (Sweden)

Noureddine Benkeblia

2005-09-01

Full Text Available The radical scavenging activity (RAS, chain-breaking activity, H2O2-scavenging, reducing capacity and total phenolics of four types of onions (Green onion, Yellow, Red and Purple and garlic were investigated. Total phenolics varied from 30 mg (green onion to 49 mg.100 g-1 fresh weight (garlic. Garlic extract showed the highest RAS, while green onion showed the lowest one. The chain-breaking activity of green onion extract was higher (0.48 than garlic extract (0.029. Chain-breaking activity of yellow, red and purple onion extracts was 0.19, 0.048 and 0.032 respectively. However, heating treatment (90 ºC, 3h caused an increase in this activity. Low ability of green onion extract to scavenge hydrogen peroxide was noted (35%, whereas high ability was noted in other onion and garlic extracts and ranged from 60 to 90%. The lowest reducing capacity was noted in green onion extract (18%, whereas the highest in garlic extract (196%. Statistically, high significant correlations were observed between total phenolics content and reducing power, scavenging of hydrogen peroxide and chain-breaking activity of extract

Identifying the distinct features of geometric structures for hole trapping to generate radicals on rutile TiO₂(110) in photooxidation using density functional theory calculations with hybrid functional.

Science.gov (United States)

Wang, Dong; Wang, Haifeng; Hu, P

2015-01-21

Using density functional theory calculations with HSE 06 functional, we obtained the structures of spin-polarized radicals on rutile TiO2(110), which is crucial to understand the photooxidation at the atomic level, and further calculate the thermodynamic stabilities of these radicals. By analyzing the results, we identify the structural features for hole trapping in the system, and reveal the mutual effects among the geometric structures, the energy levels of trapped hole states and their hole trapping capacities. Furthermore, the results from HSE 06 functional are compared to those from DFT + U and the stability trend of radicals against the number of slabs is tested. The effect of trapped holes on two important steps of the oxygen evolution reaction, i.e. water dissociation and the oxygen removal, is investigated and discussed.

Phenolic Compounds of Cereals and Their Antioxidant Capacity.

Science.gov (United States)

Van Hung, Pham

2016-01-01

Phenolic compounds play an important role in health benefits because of their highly antioxidant capacity. In this review, total phenolic contents (TPCs), phenolic acid profile and antioxidant capacity of the extracted from wheat, corn, rice, barley, sorghum, rye, oat, and millet, which have been recently reported, are summarized. The review shows clearly that cereals contain a number of phytochemicals including phenolics, flavonoids, anthocyanins, etc. The phytochemicals of cereals significantly exhibit antioxidant activity as measured by trolox equivalent antioxidant capacity (TEAC), 2,2-diphenyl-1-picrylhydrazyl radical scavenging, reducing power, oxygen radical absorbance capacity (ORAC), inhibition of oxidation of human low-density lipoprotein (LDL) cholesterol and DNA, Rancimat, inhibition of photochemilumenescence (PCL), and iron(II) chelation activity. Thus, the consumption of whole grains is considered to have significantly health benefits in prevention from chronic diseases such as cardiovascular disease, diabetes, and cancer because of the contribution of phenolic compounds existed. In addition, the extracts from cereal brans are considered to be used as a source of natural antioxidants.

Engineering radical polymer electrodes for electrochemical energy storage

Science.gov (United States)

Nevers, Douglas R.; Brushett, Fikile R.; Wheeler, Dean R.

2017-06-01

In principle a wide range of organic materials can store energy in the form of reversible redox conversions of stable radicals. Such chemistry holds great promise for energy storage applications due to high theoretical capacities, high rate capabilities, intrinsic structural tunability, and the possibility of low-cost "green" syntheses from renewable sources. There have been steady improvements in the design of organic radical polymers, in which radicals are incorporated into the backbone and/or as pendant groups. This review highlights opportunities for improved redox molecule and polymer design along with the key challenges (e.g., transport phenomena, solubility, and reaction mechanisms) to transitioning known organic radicals into high-performance electrodes. Ultimately, organic-based batteries are still a nascent field with many open questions. Further advances in molecular design, electrode engineering, and device architecture will be required for these systems to reach their full potential and meet the diverse and increasing demands for energy storage.

Radical-Mediated Enzymatic Polymerizations

Science.gov (United States)

Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

2016-01-01

Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

Effect of solid phase on the selectivity of alkyl radical formation by gamma-irradiation of branched alkanes

International Nuclear Information System (INIS)

Koizumi, Hitoshi; Hashino, Masatoshi; Ichikawa, Tsuneki; Yoshida, Hiroshi

1992-01-01

ESR and electron spin echo measurements of alkyl radicals generated by γ-irradiation of glassy and crystalline branched alkanes C 10 ∼ C 13 have been carried out to elucidate the effect of molecular structure and solid phase on the selectivity of alkyl radical formation. Alkyl radicals generated and stabilized at 77 K in the glassy alkanes are secondary penultimate radicals. Tertiary radicals and secondary radicals other than the penultimate one are not generated either by hydrogen abstraction or from ionized or excited molecules. In the crystalline alkanes, however, a small amount of secondary internal radicals are generated in addition to the predominant formation of the secondary penultimate radicals. It is concluded that the detachment of C-H hydrogen preferentially takes place at the location where the motion of carbon atoms assisting the detachment of the C-H hydrogen easily occurs. (author)

Level of hamstrings damage depending on force-generating capacity and creatine kinase activity

OpenAIRE

Carmona, Gerard; Alomar, Xavier; Mendiguchia, Jurdan; Serrano, David; Padullés, Josep Maria; Nescolarde Selva, Lexa Digna; Rodas Font, Gil; Cusso Calabuig, Roser; Guerrero, M.; Idoate, F.; Balius, Ramon; Cadefau, Joan

2014-01-01

The aim of the present study was to categorize the eccentric exercise-induced hamstrings damage by using easy measurable markers such as force-generating capacity and serum creatine kinase activity Peer Reviewed

Scavenging Capacities of Some Wines and Wine Phenolic Extracts

Directory of Open Access Journals (Sweden)

Ioannis G. Roussis

2005-01-01

Full Text Available The aim of this study was to assess the ability of different wines – a sweet red, a dry red, a sweet white, and a dry white – to scavenge the stable 1,1’-diphenyl-2-picryl-hydrazyl radical (DPPH. and to determine their phenolic composition. Both red wines contained, apart from anthocyanins, also higher concentration of total phenolics, tartaric esters, and flavonols than the two white wines. All wines exhibited scavenging activity analogous to their total phenolic content. However, their phenolics differed in antiradical potency, which was visible in their EC50 values. The dry red wine, Xinomavro, had a lower EC50 value, indicating the higher antiradical potency of its phenolics. The scavenging capacities of phenolic extracts from Xinomavro red wine on hydroxyl radicals, superoxide radicals, and singlet oxygen were also assessed. Wine total extract was fractionated by extraction, and each of the three fractions was then subfractionated by column chromatography into two subfractions. Wine total extract, and its fractions and subfractions exhibited scavenging capacity on hydroxyl radicals, superoxide radicals, and singlet oxygen, indicating the activity of many wine phenolics. The most active wine extracts towards hydroxyl radicals were characterized by the high peaks of flavanols, anthocyanins and flavonols in their HPLC-DAD chromatograms. The most active extract towards superoxide radicals was rich in flavanols and anthocyanins. The characteristic phenolics of the most active wine extracts towards singlet oxygen were flavanols, flavonols and phenolic acids. The ability of all red wine phenolic extracts to scavenge singlet oxygen, along with hydroxyl and superoxide radicals, emphasizes its health functionality.

Reactions of melatonin with radicals in deoxygenated aqueous solution

International Nuclear Information System (INIS)

Stasica, P.; Ulanski, P.; Rosiak, J.M.

1998-01-01

Reactions of melatonin (N-acetyl-5-methoxytryptamine) with radiolytically generated radicals were studied. Reaction of melatonin with OH radicals is diffusion-controlled (k=1.2 x 10 10 dm 3 mol -1 x s -1 ), the main (but not the only one) intermediate being the indolyl-type radical, while the rate constant for the reaction with hydrated electrons is k=4.3 x 10 8 dm 3 x mol -1 x s -1 . Melatonin is capable of scavenging tert-butanol radicals, while its reactivity towards polymer radicals of poly(acrylic acid) and poly(vinyl pyrrolidone) is very low. (author)

Environmental and economic appraisal of power generation capacity expansion plan in Nigeria

International Nuclear Information System (INIS)

Gujba, H.; Mulugetta, Y.; Azapagic, A.

2010-01-01

The power sector in Nigeria is undergoing structural reforms aimed at improving and expanding the current grid generation capacity and distribution network. The Government has injected huge funds into this sector while also granting licences to private companies for the provision of electricity. It is also aiming to increase electricity generation capacity to 25,000 MW by 2020 from the current installed capacity of 6500 MW while also pledging to connect 75% of the population to the grid from the current 40% by 2025. This paper sets out to analyse the implications of the energy policy in Nigeria and presents the life cycle environmental and economic analysis of the current and future electricity sector. The results show that all the life cycle impacts and economic costs increase significantly over the time-period (2003-2030), but at different rates depending on the types of technologies deployed. Renewables such as large hydro and solar proposed by the Government have a potential to reduce the overall life cycle environmental impacts from the electricity mix, considering their lower environmental impacts compared to fossil-fuels. However, this requires a five-fold increase in grid investments from the current US$1.7 billion per year to US$9.40 billion by 2030.

Radical fashion and radical fashion innovation

NARCIS (Netherlands)

Zhang, D.; Benedetto, Di A.C.

2010-01-01

This is a study of the related concepts of radical fashion and radical fashion innovation. Radical fashions are defined here as those that may never enter the market at all, and exist primarily on runway shows, in exhibitions and in publicity; by contrast, radical fashion innovations may be very

Generation of radicals in hard biological tissues under the action of laser radiation

Science.gov (United States)

Sviridov, Alexander P.; Bagratashvili, Victor N.; Sobol, Emil N.; Omelchenko, Alexander I.; Lunina, Elena V.; Zhitnev, Yurii N.; Markaryan, Galina L.; Lunin, Valerii V.

2002-07-01

The formation of radicals upon UV and IR laser irradiation of some biological tissues and their components was studied by the EPR technique. The radical decay kinetics in body tissue specimens after their irradiation with UV light were described by various models. By the spin trapping technique, it was shown that radicals were not produced during IR laser irradiation of cartilaginous tissue. A change in optical absorption spectra and the dynamics of optical density of cartilaginous tissue, fish scale, and a collagen film under exposure to laser radiation in an air, oxygen, and nitrogen atmosphere was studied.

Distribution System Augmented by DC Links for Increasing the Hosting Capacity of PV Generation

DEFF Research Database (Denmark)

Chaudhary, Sanjay; Demirok, Erhan; Teodorescu, Remus

2012-01-01

This paper presents a concept of enhancing the photovoltaic (PV) power generation hosting capacity of distribution networks. Distribution network serving electrical energy to farm settlements was selected as an example for their large roof area available for PV installation. Further, they are cha......This paper presents a concept of enhancing the photovoltaic (PV) power generation hosting capacity of distribution networks. Distribution network serving electrical energy to farm settlements was selected as an example for their large roof area available for PV installation. Further......, they are characterized by long radial feeders. Such feeders suffer from voltage rise and transformer overloading problems as the total number and capacity of the PV installations increase. The distribution network can be augmented by dc distribution links with power electronic converter interfaces to the traditional ac...... distribution systems. It is shown here that the dc links can be used to interconnect the different radial feeders and the excess power thus could be transferred to the nearby industrial load-center....

8760-Based Method for Representing Variable Generation Capacity Value in Capacity Expansion Models

Energy Technology Data Exchange (ETDEWEB)

Frew, Bethany A [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2017-08-03

Capacity expansion models (CEMs) are widely used to evaluate the least-cost portfolio of electricity generators, transmission, and storage needed to reliably serve load over many years or decades. CEMs can be computationally complex and are often forced to estimate key parameters using simplified methods to achieve acceptable solve times or for other reasons. In this paper, we discuss one of these parameters -- capacity value (CV). We first provide a high-level motivation for and overview of CV. We next describe existing modeling simplifications and an alternate approach for estimating CV that utilizes hourly '8760' data of load and VG resources. We then apply this 8760 method to an established CEM, the National Renewable Energy Laboratory's (NREL's) Regional Energy Deployment System (ReEDS) model (Eurek et al. 2016). While this alternative approach for CV is not itself novel, it contributes to the broader CEM community by (1) demonstrating how a simplified 8760 hourly method, which can be easily implemented in other power sector models when data is available, more accurately captures CV trends than a statistical method within the ReEDS CEM, and (2) providing a flexible modeling framework from which other 8760-based system elements (e.g., demand response, storage, and transmission) can be added to further capture important dynamic interactions, such as curtailment.

Oxidation of myosin by haem proteins generates myosin radicals and protein cross-links

DEFF Research Database (Denmark)

Lametsch, Marianne Lund; Luxford, Catherine; Skibsted, Leif Horsfelt

2008-01-01

of thiyl and tyrosyl radicals is consistent with the observed consumption of cysteine and tyrosine residues, the detection of di-tyrosine by HPLC and the detection of both reducible (disulfide bond) and non-reducible cross-links between myosin molecules by SDS/PAGE. The time course of radical formation...

The herbicide 2,4-dichlorophenoxyacetic acid induces the generation of free-radicals and associated oxidative stress responses in yeast

International Nuclear Information System (INIS)

Teixeira, Miguel C.; Telo, Joao P.; Duarte, Nuno F.; Sa-Correia, Isabel

2004-01-01

The pro-oxidant action of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) is demonstrated in this study using Saccharomyces cerevisiae as a eukaryotic experimental model. Evidence is presented for the generation of hydroxyl-radicals, in yeast cells suddenly exposed to 2,4-D, detected by in vivo electron paramagnetic resonance (EPR) spectroscopy using 5,5'-dimethyl-1-pyrroline N-oxide and 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide as spin-traps. The intensity of the EPR spectra was dependent on the concentration of herbicide tested and was consistently higher in a mutant (Δsod1) devoid of the cytosolic CuZn-superoxide dismutase. A time-course-dependent variation of the level of free-radical adducts was registered upon sudden exposure of an yeast cell population to concentrations of 2,4-D that lead to an initial period of viability loss, before resumption of inhibited growth by the viable adapted population. The variation pattern of the level of hydroxyl-radical adducts correlated with the one determined for the activity of Sod1p, cytosolic catalase Ctt1p, and the dithiol glutaredoxins Grx1p and Grx2p

Generation Capacity Investments and High Levels of Renewables. The Impact of a German Capacity Market on Northwest Europe. Discussion paper

Energy Technology Data Exchange (ETDEWEB)

Ozdemir, O.; De Joode, J.; Koutstaal, P.R.; Van Hout, M. [ECN Policy Studies, Amsterdam (Netherlands)

2013-05-15

Presently, Northwest European centralised electricity markets are designed as 'energy-only' markets. In an energy-only market, the price received for electricity produced is set by the marginal generation unit. Potentially, the designs of these markets could leave the owners of these units with 'missing money': i.e. money that is required to recover investment cost. Further, increasing penetration of renewables could exacerbate this problem. Of all the different options available to tackle the 'missing money' problem, capacity mechanisms have attracted most of the attention in recent policy debates in Europe. This paper contributes to ongoing policy discussions by providing a quantitative analysis of the phenomena of 'missing money' and capacity mechanisms in Northwest Europe. Our analysis shows that in the case of energy-only markets with a much higher penetration of intermittent electricity sources such as wind and solar PV, the 'missing money' problem may be aggravated, because operating hours for peak and mid-merit order capacity will be considerably reduced. Furthermore, unilateral introduction of capacity mechanisms in integrated electricity markets can have considerable impacts on cross-border electricity flows and investment decisions. Stand-alone introduction of a capacity market in Germany will likely result in higher investments in Germany at the expense of lower investments outside Germany and an increase in net exports from Germany. A possible advantage of a unilateral capacity mechanism in Germany may be a reduction in super-peak prices in the larger market area. Thus, neighbouring countries may have the possibility to free ride on the increase in flexible capacity in Germany. However, this advantage is conditional and depends on sufficient availability of interconnection capacity necessary to be able to use this reserve capacity. Otherwise, security of supply might be more at risk if the German

Why Nature Uses Radical SAM Enzymes so Widely: Electron Nuclear Double Resonance Studies of Lysine 2,3-Aminomutase Show the 5'-dAdo• "Free Radical" Is Never Free.

Science.gov (United States)

Horitani, Masaki; Byer, Amanda S; Shisler, Krista A; Chandra, Tilak; Broderick, Joan B; Hoffman, Brian M

2015-06-10

Lysine 2,3-aminomutase (LAM) is a radical S-adenosyl-L-methionine (SAM) enzyme and, like other members of this superfamily, LAM utilizes radical-generating machinery comprising SAM anchored to the unique Fe of a [4Fe-4S] cluster via a classical five-membered N,O chelate ring. Catalysis is initiated by reductive cleavage of the SAM S-C5' bond, which creates the highly reactive 5'-deoxyadenosyl radical (5'-dAdo•), the same radical generated by homolytic Co-C bond cleavage in B12 radical enzymes. The SAM surrogate S-3',4'-anhydroadenosyl-L-methionine (anSAM) can replace SAM as a cofactor in the isomerization of L-α-lysine to L-β-lysine by LAM, via the stable allylic anhydroadenosyl radical (anAdo•). Here electron nuclear double resonance (ENDOR) spectroscopy of the anAdo• radical in the presence of (13)C, (2)H, and (15)N-labeled lysine completes the picture of how the active site of LAM from Clostridium subterminale SB4 "tames" the 5'-dAdo• radical, preventing it from carrying out harmful side reactions: this "free radical" in LAM is never free. The low steric demands of the radical-generating [4Fe-4S]/SAM construct allow the substrate target to bind adjacent to the S-C5' bond, thereby enabling the 5'-dAdo• radical created by cleavage of this bond to react with its partners by undergoing small motions, ∼0.6 Å toward the target and ∼1.5 Å overall, that are controlled by tight van der Waals contact with its partners. We suggest that the accessibility to substrate and ready control of the reactive C5' radical, with "van der Waals control" of small motions throughout the catalytic cycle, is common within the radical SAM enzyme superfamily and is a major reason why these enzymes are the preferred means of initiating radical reactions in nature.

Hypochlorite- and hypobromite-mediated radical formation and its role in cell lysis

DEFF Research Database (Denmark)

Hawkins, C L; Brown, B E; Davies, Michael Jonathan

2001-01-01

. In this study it is shown that HOBr induces red blood cell lysis at approximately 10-fold lower concentrations than HOCl, whereas with monocyte (THP1) and macrophage (J774) cells HOCl and HOBr induce lysis at similar concentrations. The role of radical formation during lysis has been investigated by EPR spin...... trapping, and it is shown that reaction of both oxidants with each cell type generates cell-derived radicals. Red blood cells exposed to nonlytic doses of HOCl generate novel nitrogen-centered radicals whose formation is GSH dependent. In contrast, HOBr gives rise to nitrogen-centered, membrane......-derived protein radicals. With lytic doses of either oxidant, protein (probably hemoglobin)-derived, nitrogen-centered radicals are observed. Unlike the red blood cells, treatment of monocytes and macrophages with HOCl gives significant radical formation only under conditions where cell lysis occurs concurrently...

Electron spin resonance of spin-trapped radicals of amines and polyamines. Hydroxyl radical reactions in aqueous solutions and. gamma. radiolysis in the solid state

Energy Technology Data Exchange (ETDEWEB)

Mossoba, M.M.; Rosenthal, I.; Riesz, P. (National Cancer Inst., Bethesda, MD (USA))

1982-06-15

The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H/sub 2/O/sub 2/ and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ..gamma..-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the ..cap alpha..-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H/sub 2/O/sub 2/ in the dark. ..gamma..-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the ..cap alpha..-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine.

Radical-induced oxidation of RAFT agents : a kinetic study

NARCIS (Netherlands)

Li, Changxi; He, Junpo; Zhou, Yanwu; Gu, Yuankai; Yang, Yuliang

2011-01-01

Radical-induced oxidn. of reversible addn.-fragmentation chain transfer (RAFT) agents is studied with respect to the effect of mol. structure on oxidn. rate. The radicals are generated by homolysis of either azobisisobutyronitrile or alkoxyamine and transformed in situ immediately into peroxy

Isoflurane preconditions myocardium against infarction via release of free radicals

NARCIS (Netherlands)

Müllenheim, Jost; Ebel, Dirk; Frässdorf, Jan; Preckel, Benedikt; Thämer, Volker; Schlack, Wolfgang

2002-01-01

BACKGROUND: Isoflurane exerts cardioprotective effects that mimic the ischemic preconditioning phenomenon. Generation of free radicals is implicated in ischemic preconditioning. The authors investigated whether isoflurane-induced preconditioning may involve release of free radicals. METHODS:

Enantioselective cyclizations and cyclization cascades of samarium ketyl radicals

Science.gov (United States)

Kern, Nicolas; Plesniak, Mateusz P.; McDouall, Joseph J. W.; Procter, David J.

2017-12-01

The rapid generation of molecular complexity from simple starting materials is a key challenge in synthesis. Enantioselective radical cyclization cascades have the potential to deliver complex, densely packed, polycyclic architectures, with control of three-dimensional shape, in one step. Unfortunately, carrying out reactions with radicals in an enantiocontrolled fashion remains challenging due to their high reactivity. This is particularly the case for reactions of radicals generated using the classical reagent, SmI2. Here, we demonstrate that enantioselective SmI2-mediated radical cyclizations and cascades that exploit a simple, recyclable chiral ligand can convert symmetrical ketoesters to complex carbocyclic products bearing multiple stereocentres with high enantio- and diastereocontrol. A computational study has been used to probe the origin of the enantioselectivity. Our studies suggest that many processes that rely on SmI2 can be rendered enantioselective by the design of suitable ligands.

Effects of oxygen radical scavengers on the inactivation of SS phi X174 DNA by the semi-quinone free radical of the antitumor agent etoposide

NARCIS (Netherlands)

van Maanen, M.J.; Mans, D.R.A.; Lafleur, M.V.M.; Van Schaik, M A; de Vries, J; Vermeulen, N P; Retèl, J.; Lankelma, J

1990-01-01

We have studied the effects of oxygen radical scavengers on the inactivation of ss phi X174 DNA by the semi-quinone free radical of the antitumor agent etoposide (VP 16-213), which was generated from the ortho-quinone of etoposide at pH greater than or equal to 7.4. A semi-quinone free radical of

Antioxidant capacity and physical exercise

Directory of Open Access Journals (Sweden)

A Marciniak

2009-09-01

Full Text Available The aim of this article is a presentation of current knowledge regarding the changes of plasma antioxidant capacity observed in response to physical exercise. Human body created the enzymatic and non-enzymatic systems, which play a protective role in the harmful impact of free radicals. Those two systems constitute what is known as the plasma total antioxidant capacity. The amount of reactive oxygen species (ROS and reactive nitrogen species (NOS in combination with oxidation processes increases in some tissues during physiological response to physical exercise. These changes are observed after single bout of exercise as well as after regular training. The response of human body to physical exercise can be analysed using various models of exercise test. Application of repeated type of exhaustion allows for characterizing the ability of human body to adjust to the increased energy loss and increased oxygen consumption. This article presents the characteristics of components of plasma antioxidant capacity, the mechanisms of free radicals production and their role in human body. It discusses also the currently used methods of detecting changes in total antioxidant capacity and its individual elements in response to single bout of exercise and regular training. It presents the review of literature about research performed in groups of both regularly training and low exercise activity individuals as well as in group of healthy subjects and patients with circulation diseases.

Generation and detection of the peroxyacetyl radical in the pyrolysis of peroxyacetyl nitrate in a supersonic expansion.

Science.gov (United States)

Hu, Y J; Fu, H B; Bernstein, E R

2006-03-02

The peroxyacetyl radical (PA, CH3C(O)OO) is generated by flash pyrolysis of peroxyacetyl nitrate (PAN, CH3C(O)OONO2) in a supersonic jet. The 0(0)(0) A2A' CH3CO mass channel. Rotational envelope simulation results find that the rotational temperature for PA in its ground electronic and vibrational state is ca. 55 K. At ca. 330 degrees C, the thermal decomposition of PAN by flash pyrolysis in a heated nozzle with supersonic expansion is mainly by formation of PA and NO2. The maximum yield of PA is obtained at this temperature. At higher temperatures (300-550 degrees C), an intense signal in the CH2CO+ mass channel is observed, generated by the decomposition of PA.

A stochastic dynamic model for optimal timing of investments in new generation capacity in restructured power systems

International Nuclear Information System (INIS)

Botterud, Audun; Korpaas, Magnus

2007-01-01

In this paper we formulate the power generation investment problem for a decentralised and profit-maximising investor operating in a restructured and competitive power system. In particular, we look at how uncertainty influences the optimal timing of investments in new power generation capacity. A real options approach is used to take long-term uncertainty in load growth, and its influence on future electricity prices, into account in the investment optimisation. In order to value the operational flexibility of a new power plant we use an electricity price model, where the spot price is a function of load level and installed generation capacity, in addition to short-term uncertainties and temporal fluctuations in the market. The investor's income from a capacity payment, which also can depend on the system's total capacity balance, can also be represented. Hence, with the optimisation model we can analyse power plant profitability and optimal timing of new investments under different market designs. In a case study from the Nordic electricity market we analyse the effect of uncertainty on optimal investment timing. We also examine how a fixed or variable capacity payment would influence the investment decision, and discuss the system consequences of the resulting investment strategies. (author)

In vitro free radical scavenging activity of platinum nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Watanabe, Aki; Kajita, Masashi; Kim, Juewon; Kanayama, Atsuhiro; Miyamoto, Yusei [Department of Integrated Biosciences, Graduate School of Frontier Sciences, University of Tokyo, Bioscience Building 402, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8562 (Japan); Takahashi, Kyoko; Mashino, Tadahiko, E-mail: yusei74@k.u-tokyo.ac.j [Department of Pharmaceutical Sciences, Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato, Tokyo 105-8512 (Japan)

2009-11-11

A polyacrylic acid (PAA)-protected platinum nanoparticle species (PAA-Pt) was prepared by alcohol reduction of hexachloroplatinate. The PAA-Pt nanoparticles were well dispersed and homogeneous in size with an average diameter of 2.0 {+-} 0.4 nm (n = 200). We used electron spin resonance to quantify the residual peroxyl radical AOO. generated from 2,2-azobis (2-aminopropane) dihydrochloride (AAPH) by thermal decomposition in the presence of O{sub 2} and a spectrophotometric method to quantify the residual 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. PAA-Pt scavenged these two radicals in a dose-dependent manner. Platinum was the functional component. PAA-Pt reduced the rate of oxygen consumption required for linoleic acid peroxidation initiated by AOO. generated from AAPH, indicating inhibition of the propagation of linolate peroxidation. A thiobarbituric acid test also revealed dose-dependent inhibition of the linolate peroxidation by PAA-Pt. Fifty micromolar platinum, as PAA-Pt, completely quenched 250 {mu}M DPPH radical for 5 min. Even when twice diluted in half, the PAA-Pt still quenched 100% of the 250 {mu}M DPPH radical. The scavenging activity of PAA-Pt is durable. These observations suggest that PAA-Pt is an efficient scavenger of free radicals.

Missing Peroxy Radical Sources Within a Rural Forest Canopy

Science.gov (United States)

Wolfe, G. M.; Cantrell, C.; Kim, S.; Mauldin, R. L., III; Karl, T.; Harley, P.; Turnipseed, A.; Zheng, W.; Flocke, F.; Apel, E. C.;

Radical-induced generation of small silver particles in SPEEK/PVA polymer films and solutions: UV-Vis, EPR, and FT-IR studies.

Science.gov (United States)

Korchev, A S; Konovalova, T; Cammarata, V; Kispert, L; Slaten, L; Mills, G

2006-01-03

The present study is centered on the processes involved in the photochemical generation of nanometer-sized Ag particles via illumination at 350 nm of aqueous solutions and cross linked films containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol). Optical and electron paramagnetic resonance experiments, including electron nuclear double resonance data, proved conclusively that the photogenerated chromophore exhibiting a band with lambda(max) = 565 nm is an alpha-hydroxy aromatic (ketyl) radical of the polymeric ketone. This reducing species was produced by illumination of either solutions or films, but the radical lifetime extended from minutes in the fluid phase to hours in the solid. Direct evidence is presented that this long-lived chromophore reduces Ag(I), Cu(II), and Au(III) ions in solution. A rate constant of k = 1.4 x 10(3) M(-)(1) s(-)(1) was obtained for the reduction of Ag(+) by the ketyl radical from the post-irradiation formation of Ag crystallites. FTIR results confirmed that the photoprocess yielding polymeric ketyl radicals involves a reaction between the macromolecules. The photochemical oxidation of the polymeric alcohol, as well as the formation of light-absorbing macromolecular products and polyols, indicates that the sulfonated polyketone experienced transformations similar to those encountered during illumination of the benzophenone/2-propanol system.

Pulse radiolysis of alkanes: a time-resolved EPR study - Part I. Alkyl radicals

International Nuclear Information System (INIS)

Shkrob, I.A.; Trifunac, A.D.

1995-01-01

Time-resolved EPR was applied to detect short-lived alkyl radicals in pulse radiolysis of liquid alkanes. Two problems were addressed: (i) the mechanism of radical formation and (ii) the mechanism of chemically-induced spin polarization in these radicals. (i) The ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation was found to be ≅ 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the proton transfer reaction involving excited radical cations must be a prevailing route of radical generation. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. (ii) The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals gain the emissive polarization in spur reactions. This initial polarization increases with shortening of the aliphatic chain. We suggest that the origin of this polarization is the ST mechanism operating in the pairs of alkyl radicals and hydrogen atoms generated in dissociation of excited alkane molecules. It is also found that a long-chain structure of alkyl radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate (up to 30 times). That suggests prominent steric effects in recombination or the occurrence of through-chain electron exchange. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. (Author)

Antioxidant and Nitrite-Scavenging Capacities of Phenolic Compounds from Sugarcane (Saccharum officinarum L. Tops

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Jian Sun

2014-08-01

Full Text Available Sugarcane tops were extracted with 50% ethanol and fractionated by petroleum ether, ethyl acetate (EtOAc, and n-butyl alcohol successively. Eight phenolic compounds in EtOAc extracts were purified through silica gel and Sephadex LH-20 column chromatographies, and then identified by nuclear magnetic resonance and electrospray ionization mass spectra. The results showed that eight phenolic compounds from EtOAc extracts were identified as caffeic acid, cis-p-hydroxycinnamic acid, quercetin, apigenin, albanin A, australone A, moracin M, and 5'-geranyl-5,7,2',4'-tetrahydroxyflavone. The antioxidant and nitrite-scavenging capacities of different solvent extracts correlated positively with their total phenolic (TP contents. Amongst various extracts, EtOAc extracts possessed the highest TP content and presented the strongest oxygen radical absorbance capacity (ORAC, 1,1'-diphenyl-2-picrylhydrazyl (DPPH radical-scavenging capacity, 2,2'-azobis-3-ethylbenthiaazoline-6-sulfonic acid (ABTS radical-scavenging capacity, ferric reducing antioxidant power (FRAP and nitrite-scavenging capacity. Thus, sugarcane tops could be promoted as a source of natural antioxidant.

International Radical Cystectomy Consortium: A way forward

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Syed Johar Raza

2014-01-01

Full Text Available Robot-assisted radical cystectomy (RARC is an emerging operative alternative to open surgery for the management of invasive bladder cancer. Studies from single institutions provide limited data due to the small number of patients. In order to better understand the related outcomes, a world-wide consortium was established in 2006 of patients undergoing RARC, called the International Robotic Cystectomy Consortium (IRCC. Thus far, the IRCC has reported its findings on various areas of operative interest and continues to expand its capacity to include other operative modalities and transform it into the International Radical Cystectomy Consortium. This article summarizes the findings of the IRCC and highlights the future direction of the consortium.

Inhibition of radiation-induced DNA strand breaks by hoechst 33258: OH-radical scavenging and DNA radical quenching

International Nuclear Information System (INIS)

Adhikary, A.; Bothe, E.; Von Sonntag, C.; Adhikary, A.

1997-01-01

The minor-groove-binding dye Hoechst 33258 has been found to protect pBR322 DNA in aqueous solution against radiation-induced single-strand breaks (ssb). This protective effect has been assumed to be largely due to the scavenging of the strand-break-generating OH radicals by Hoechst. From D 37 values for ssb at different Hoechst concentrations the value of the OH radical scavenging constant of DNA-bound Hoechst has been estimated at k Ho/DNA = 2.7 * 10 11 dm 3 mol -1 . This unexpectedly high value has led us to study the reactions of OH radicals with Hoechst in the absence and in the presence of double-stranded calf thymus DNA (ds DNA) by pulse radiolysis, and the formation of radiation-induced ssb by low angle laser light scattering. The D 37 /D 37 0 values at different Hoechst concentrations agree with the values obtained by Martin and al. and demonstrate the protection. However, this protection cannot be explained on the basis of OH radical scavenging alone using the above rate constants. There must, in addition, be some quenching of DNA radicals. Hoechst radicals are formed in the later ms time range, i.e a long time after the disappearance of the OH radicals. This delayed Hoechst radical formation has been assigned to a a reaction of DNA radicals with Hoechst, thereby inhibiting strand breakage. In confirmation, pulse radiolysis of aqueous solution of nucleotides in the presence of Hoechst yields a similar delayed Hoechst radical formation. The data indicate that in DNA the cross-section of this quenching has a diameter of 3 to 4 base pairs per Hoechst molecule. (N.C.)

Radicals derived from histone hydroperoxides damage nucleobases in RNA and DNA

DEFF Research Database (Denmark)

Luxford, C; Dean, R T; Davies, Michael Jonathan

2000-01-01

Exposure of individual histone proteins (H1, H2A, H2B, H3, or H4) and histone octamers (consisting of two molecules each of H2A, H2B, H3, and H4) to hydroxyl radicals, generated by gamma-irradiation, in the presence of O(2) generates protein-bound hydroperoxides in a dose-dependent fashion......; this is in accord with previous studies with other proteins. These histone hydroperoxides are stable in the absence of exogenous catalysts (e.g., heat, light, and transition metal ions), but in the presence of these agents decompose rapidly to give a variety of radicals which have been identified by EPR spin...... trapping. Histone hydroperoxide-derived radicals generated on decomposition of the hydroperoxides with Cu(+) react with both pyrimidine and purine nucleobases. Thus, with uridine the histone hydroperoxide-derived radicals undergo addition across the C(5)-C(6) double bond of the pyrimidine ring to give...

Reactions of inorganic free radicals with liver protecting drugs

International Nuclear Information System (INIS)

Gyoergy, I.; Foeldiak, G.; Blazovics, A.; Feher, J.

1990-01-01

Liver protecting drugs, silibinin, a flavonolignane, and the dihydroquinoline derivatives, CH 402 and MTDQ-DA, were shown to inhibit processes in which enzymatically or non-enzymatically generated free radicals were involved. Inorganic free radicals (N 3 , (SCN) 2 - , OH, Trp, CO 2 - , O 2 - ) produced by pulse radiolysis readily react with the compounds, which transform into exceptionally long-lived, unreactive transients. Time evolution of the UV and visible spectra indicate that oxidising radicals form a phenoxyl type radical from silibinin, while OH forms an adduct by attacking, simultaneously, at various sites of the molecule. Superoxide radicals reduce silibinin and oxidise CH 402 and MTDQ-DA. It is concluded that the drugs might exhibit antioxidant behavior in living systems. (author)

Measurement of antioxidant activity with trifluoperazine dihydrochloride radical cation

Directory of Open Access Journals (Sweden)

M.N. Asghar

2008-06-01

Full Text Available A novel, rapid and cost-effective trifluoperazine dihydrochloride (TFPH decolorization assay is described for the screening of antioxidant activity. A chromogenic reaction between TFPH and potassium persulfate at low pH produces an orange-red radical cation with maximum absorption at 502 nm in its first-order derivative spectrum. TFPH was dissolved in distilled water to give a 100 mM solution. The TFPH radical cation solution was made by reacting 0.5 mL of the solution with K2S2O8 (final concentration: 0.1 mM and diluting to 100 mL with 4 M H2SO4 solution. A linear inhibition of color production was observed with linearly increasing amounts of antioxidants, with correlation coefficients (R² ranging from 0.999 to 0.983. The antioxidant capacity of standard solutions of an antioxidant was evaluated by comparing with the inhibition curve using Trolox as the standard. Comparison of antioxidant capacity determined with this newly developed TFPH assay and with the well-known 2,2'-azinobis-[3-ethylbenzthiazoline-6-sulfonic acid] (ABTS-persulfate decolorization assay indicated the efficacy and sensitivity of the procedure. The proposed assay is less expensive (costs about US$4 per 100 assays and requires only 20 min for preparation of radical cation solution in comparison with ABTS assay, in which almost 12-16 h are required for preparation of a stable ABTS radical cation solution. The present assay has the advantage over ABTS assay that it can be used to measure the antioxidant activity of the samples, which are naturally found at a pH as low as 1, because the radical cation itself has been stabilized at low pH.

Degradation and intermediates of diclofenac as instructive example for decomposition of recalcitrant pharmaceuticals by hydroxyl radicals generated with pulsed corona plasma in water.

Science.gov (United States)

Banaschik, Robert; Jablonowski, Helena; Bednarski, Patrick J; Kolb, Juergen F

2018-01-15

Seven recalcitrant pharmaceutical residues (diclofenac, 17α-ethinylestradiol, carbamazepine, ibuprofen, trimethoprim, diazepam, diatrizoate) were decomposed by pulsed corona plasma generated directly in water. The detailed degradation pathway was investigated for diclofenac and 21 intermediates could be identified in the degradation cascade. Hydroxyl radicals have been found primarily responsible for decomposition steps. By spin trap enhanced electron paramagnetic resonance spectroscopy (EPR), OH-adducts and superoxide anion radical adducts were detected and could be distinguished applying BMPO as a spin trap. The increase of concentrations of adducts follows qualitatively the increase of hydrogen peroxide concentrations. Hydrogen peroxide is eventually consumed in Fenton-like processes but the concentration is continuously increasing to about 2mM for a plasma treatment of 70min. Degradation of diclofenac is inversely following hydrogen peroxide concentrations. No qualitative differences between byproducts formed during plasma treatment or due to degradation via Fenton-induced processes were observed. Findings on degradation kinetics of diclofenac provide an instructive understanding of decomposition rates for recalcitrant pharmaceuticals with respect to their chemical structure. Accordingly, conclusions can be drawn for further development and a first risk assessment of the method which can also be applied towards other AOPs that rely on the generation of hydroxyl radicals. Copyright © 2017 Elsevier B.V. All rights reserved.

Rubidium uptake by mouse pancreatic islets exposed to 6-hydroxydopamine, ninhydrin, or other generators of hydroxyl radicals

Energy Technology Data Exchange (ETDEWEB)

Grankvist, K.; Sehlin, J.; Taeljedal, I.-B.

1986-01-01

The purpose was to study the toxicity of drugs known to generate free radicals on isolated pancreatic islets. The accumulation of /sup 86/Rb/sup +/ by mouse pancreatic islets was measured in vitro. Exposing the islets to 6-hydroxydopamine, minhydrin, or phenazine methosulphate + NADH inhibited the Rb/sup +/ uptake, whereas paraquat or acetylphenylhydrazine had no effect. This effect of 6-hydroxydopamine was prevented by either of the hydroxyl radical scavengers, sodium benzoate and mannitol, but not by the non-scavenger urea; ninhydrin was partially protected against by mannitol but not by benzoate. Protection against 6-hydroxydopamine was also afforded by D-glucose but not by L-glucose or 3-O-methyl-D-glucose; none of the sugars protected against ninhydrin. In damaging islet beta-cells and in being protected against by D-glucose, 6-hydroxydopamine closely resembles the diabetogenic drug, alloxan. It is suggested that protection against alloxan may involve both glucose metabolism and the interaction of glucose with its membrane-located carrier, while protection against 6-hydroxydopamine appears to be unrelated to the hexose carrier mechanism.

In vitro free radical scavenging activity of Ixora coccinea L

Directory of Open Access Journals (Sweden)

Moni Rani Saha

2008-06-01

Full Text Available Antioxidant activity of the methanol extract of Ixora coccinea L. was determined by DPPH free radical scavenging assay, reducing power and total antioxidant capacity using phosphomolybdenum method. Preliminary phytochemical screening revealed that the extract of the flower of I. coccinea possesses flavonoids, steroids and tannin materials. The extract showed significant activities in all antioxidant assays compared to the standard antioxidant in a dose dependent manner and remarkable activities to scavenge reactive oxygen species (ROS may be attributed to the high amount of hydrophilic phenolics. In DPPH radical scavenging assay the IC50 value of the extract was found to be 100.53 μg/mL while ascorbic acid had the IC50 value 58.92 μg/mL. Moreover, I. coccinea extract showed strong reducing power and total antioxidant capacity.

Radical polarization in double switching of external magnetic field

International Nuclear Information System (INIS)

Lukzen, N.N.; Morozov, V.A.; Sagdeev, R.Z.

1999-01-01

Theoretical treatment of radical spin evolution under the action of double switching of external magnetic field is proposed. Account is taken of evolution of the radical spin state during laser pulse which generates paramagnetic particles. It is shown that the most effective beats in the nuclear magnetization of diamagnetic products of recombination occur upon the jump into zero magnetic field after laser pulse. The phase of observed beats bears information about the type of the initial radical polarization. The frequency of the beats is determined by radical hyperfine structure. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

The research progress of several kinds of free radical scavengers

International Nuclear Information System (INIS)

Qian Liren; Huang Yuecheng; Cai Jianming

2009-01-01

Ionization radiation can generate free radicals in biological system, which could induce lipid peroxi-dation, biomacromolecule and biomembrane damage, lost of cell function, cell cycle disturbance, genetic mutation and so on. The scavenging free radicals can protect organism from radiation damage. Many radio-protective agents, such as amylase, hydroxyl-benzene derivatives, hormone, vitamin, have great abilities to protect organism from radiation via scavenging free radicals. In this paper, we mainly review the free radical scavenging effects of several kinds of radio-protective agents. (authors)

Free Radical Scavenging Properties of Annona squamosa

Science.gov (United States)

Vikas, Biba; Akhil B, S; P, Remani; Sujathan, K

2017-10-26

Annona squamosa has extensively been used in the traditional and folkloric medicine and found to possess many biological activities. Different solvents, petroleum ether, chloroform, ethyl acetate and methanol extracts of Annona squamosa seeds (ASPE, ASCH, ASEA, ASME) have been used to prepare plant extracts. The present investigations dealt with the free radical scavenging activity of four extracts using various techniques such as total reducing power estimation, total phenolic count, 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging effect, evaluation of ABTS cation decolorisation capacity, FRAP assay, hdroxyl radical scavenging assay, super oxide assay and Nitric oxide radical scavenging assay of the extracts. The results showed that the four extracts of Annona squamosa showed significant reducing power in four extracts. The total phenolic contents in petroleum ether, chloroform, ethyl acetate, methanol extracts and positive control were 0.64±0.17, 0.54±0.27, 0.49±0.24, 0.57±0.22 and 0.66±0.33. The antioxidant capacity by ABTS assay of ASPE, ASCH, ASEA, ASME and positive control, trolox showed 77.75±0.5,73.25±1.7,78.5± 1.2 , 80 ± 0.8 μg/ml and 94.2 ± 0.9 respectively. The (50 % scavenging activity) SA50 of ASPE and ASCH, ASEA and ASME was found to be 34.4 μg/ml, 43.8 μg/ml 34.7 μg/m and 28.8 μg/ml respectively by DPPH assay. The percentage of hydroxyl radical scavenging increased with the increasing concentration of the extracts. ASPE, ASCH, ASEA and ASME showed superoxide radical scavenging activity, as indicated by their values 66 ± 0.5, 68 ± 1 ,63 ± 1 and 70 ± 0.5 μg/ml respectively compared to gallic acid which was 97 ± 0.5 μg/ml. The values for scavenging of nitric oxide for ASPE, ASCH, ASEA and ASME were 91.0 ± 1.0, 66.75 ± 0.5, 71.75 ± 1.1 and 75.75 ± 1.15 μg/ml while value for standard ascorbic acid was 91.0 ± 1.0 μg/ml. The results revealed strong antioxidants in four extracts may lead to the development of potent

Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study

International Nuclear Information System (INIS)

Erben-Russ, Michael; Bors, Wolf; Saran, Manfred

1987-01-01

Linoleic acid peroxyl radicals (LOO) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N 2 O/O 2 -saturated solutions leads to a mixture of peroxyl radical isomers; reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N 2 O-saturated solution produces 13-LOO radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO). The same aroxyl radicals were generated by OH and N 3 with rate constants exceeding 10 9 dm 3 mol -1 s -1 . Applying a reaction scheme that includes competing generation and decay reactions of both LOO and ArO radicals, individual rate constants were derived for LOO reactions with the phenols (> 10 7 dm 3 mol -1 s-? 1 ), with aroxyl radicals to form covalent adducts (> 10 8 dm 3 mol -1 s -1 ), as well as for their bimilecular decay (3.0 x 10 8 dm 3 mol -1 s -1 ). These results demonstrate high reactivity of fatty acid peroxyl radicals and flavone antioxidants in aqueous solution. (author)

Superoxide radicals can act synergistically with hypochlorite to induce damage to proteins

DEFF Research Database (Denmark)

Hawkins, Clare Louise; Rees, Martin D; Davies, Michael Jonathan

2002-01-01

Activated phagocytes generate both superoxide radicals via a respiratory burst, and HOCl via the concurrent release of the haem enzyme myeloperoxidase. Amine and amide functions on proteins and carbohydrates are major targets for HOCl, generating chloramines (RNHCl) and chloramides (RC(O)NClR'), ......Activated phagocytes generate both superoxide radicals via a respiratory burst, and HOCl via the concurrent release of the haem enzyme myeloperoxidase. Amine and amide functions on proteins and carbohydrates are major targets for HOCl, generating chloramines (RNHCl) and chloramides (RC...

Mechanism of free radical generation in platelets and primary hepatocytes: A novel electron spin resonance study.

Science.gov (United States)

Wang, Chiun-Lang; Yang, Po-Sheng; Tsao, Jeng-Ting; Jayakumar, Thanasekaran; Wang, Meng-Jiy; Sheu, Joen-Rong; Chou, Duen-Suey

2018-01-01

Oxygen free radicals have been implicated in the pathogenesis of toxic liver injury and are thought to be involved in cardiac dysfunction in the cirrhotic heart. Therefore, direct evidence for the electron spin resonance (ESR) detection of how D‑galactosamine (GalN), an established experimental hepatotoxic substance, induced free radicals formation in platelets and primary hepatocytes is presented in the present study. ESR results demonstrated that GalN induced hydroxyl radicals (OH•) in a resting human platelet suspension; however, radicals were not produced in a cell free Fenton reaction system. The GalN‑induced OH• formation was significantly inhibited by the cyclooxygenase (COX) inhibitor indomethasin, though it was not affected by the lipoxygenase (LOX) or cytochrome P450 inhibitors, AA861 and 1‑aminobenzotriazole (ABT), in platelets. In addition, the present study demonstrated that baicalein induced semiquinone free radicals in platelets, which were significantly reduced by the COX inhibitor without affecting the formed OH•. In the mouse primary hepatocytes, the formation of arachidonic acid (AA) induced carbon‑centered radicals that were concentration dependently enhanced by GalN. These radicals were inhibited by AA861, though not affected by indomethasin or ABT. In addition, GalN did not induce platelet aggregation prior to or following collagen pretreatment in human platelets. The results of the present study indicated that GalN and baicalein may induce OH• by COX and LOX in human platelets. GalN also potentiated AA induced carbon‑centered radicals in hepatocytes via cytochrome P450. The present study presented the role of free radicals in the pathophysiological association between platelets and hepatocytes.

Fast beam studies of free radical photodissociation

Energy Technology Data Exchange (ETDEWEB)

Neumark, D.M. [Lawrence Berkeley Laboratory, CA (United States)

1993-12-01

The authors have developed a novel technique for studying the photodissociation spectroscopy and dynamics of free radicals. In these experiments, radicals are generated by laser photodetachment of a fast (6-8 keV) mass-selected negative ion beam. The resulting radicals are photodissociated with a second laser, and the photofragments are collected and detected with high efficiency using a microchannel plate detector. The overall process is: ABC{sup -} {yields} ABC + e{sup -} {yields} A + BC, AB + C. Two types of fragment detection schemes are used. To map out the photodissociation cross-section of the radical, the photodissociation laser is scanned and the total photofragment yield is measured as a function of wavelength. In other experiments, the photodissociation frequency is fixed and the photofragment masses, kinetic energy release, and scattering angle is determined for each photodissociation event.

On the ergodic capacity of legacy systems in the presence of next generation interference

KAUST Repository

Mahmood, Nurul Huda

2011-11-01

Next generation wireless systems facilitating better utilization of the scarce radio spectrum have emerged as a response to inefficient rigid spectrum assignment policies. These are comprised of intelligent radio nodes that opportunistically operate in the radio spectrum of existing legacy systems; yet unwanted interference at the legacy receivers is unavoidable. In order to design efficient next generation systems and to minimize their harmful consequences, it is necessary to realize their impact on the performance of legacy systems. In this work, a generalized framework for the ergodic capacity analysis of such legacy systems in the presence of interference from next generation systems is presented. The analysis is built around a model developed for the statistical representation of the interference at the legacy receivers, which is then used to evaluate the ergodic capacity of the legacy system. Moreover, this analysis is not limited to the context of legacy systems, and is in fact applicaple to any interference limited system. Findings of analytical performance analyses are confirmed through selected computer-based Monte-Carlo simulations. © 2011 IEEE.

Effect of Rubia cordifolia, Fagonia cretica linn, and Tinospora cordifolia on free radical generation and lipid peroxidation during oxygen-glucose deprivation in rat hippocampal slices

International Nuclear Information System (INIS)

Rawal, Avinash; Muddeshwar, Manohar; Biswas, Saibal

2004-01-01

The major damaging factor during and after the ischemic/hypoxic insult is the generation of free radicals, which leads to apoptosis, necrosis, and ultimately cell death. Rubia cordifolia (RC), Fagonia cretica linn (FC), and Tinospora cordifolia (TC) have been reported to contain a wide variety of antioxidants and have been in use in the eastern system of medicine for various disorders. Hippocampal slices were subjected to oxygen-glucose deprivation (OGD) and divided into three groups, control, OGD, and OGD+drug treated. Cytosolic reduced glutathione (GSH), nitric oxide [NO, measured as nitrite (NO 2 )]. EPR was used to establish the antioxidant effect of RC, FC, and TC with respect to superoxide anion (O2-), hydroxyl radicals (OH), nitric oxide (NO) radical, and peroxynitrite anion (ONOO - ) generated from pyrogallol, menadione, DETA-NO, and Sin-1, respectively. RT-PCR was performed for the three herbs to assess their effect on the expression of γ-glutamylcysteine ligase (GCLC), iNOS, and GAPDH gene expression. All the three herbs were effective in elevating the GSH levels and expression of the GCLC. The herbs also exhibited strong free radical scavenging properties against reactive oxygen and nitrogen species as revealed by electron paramagnetic resonance spectroscopy, diminishing the expression of iNOS gene. RC, FC, and TC therefore attenuate oxidative stress mediated cell injury during OGD and exert the above effects at both the cytosolic as well as at gene expression levels and may be effective therapeutic tool against ischemic brain damage

Abstracts of 2. symposium on free radicals in biology and medicine

Energy Technology Data Exchange (ETDEWEB)

NONE

1994-12-31

The abstracts presented in the booklet concern influence of free radicals (frequently generated by ionizing radiation) on DNA, proteins, lipids and chromatin of various living organisms. Works show, that free radicals cause serious damages in biological systems leading to carcinogenesis and many genetic diseases. Thus understanding of mechanisms of free radical action is important issue in medicine and life sciences.

Abstracts of 2. symposium on free radicals in biology and medicine

International Nuclear Information System (INIS)

1994-01-01

The abstracts presented in the booklet concern influence of free radicals (frequently generated by ionizing radiation) on DNA, proteins, lipids and chromatin of various living organisms. Works show, that free radicals cause serious damages in biological systems leading to carcinogenesis and many genetic diseases. Thus understanding of mechanisms of free radical action is important issue in medicine and life sciences

Reaction kinetics of resveratrol with tert-butoxyl radicals

International Nuclear Information System (INIS)

Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

2012-01-01

The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×10 8 M −1 s −1 . This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol. - Highlights: ► tert-butoxyl radicals were generated directly using laser flash photolysis. ► Rate constant was determined by the phenoxyl radical formation rate in acetonitrile. ► Rate constant was determined to be 6.5×10 8 M −1 s −1 .

Distributed generation, storage, demand response and energy efficiency as alternatives to grid capacity enhancement

International Nuclear Information System (INIS)

Poudineh, Rahmatallah; Jamasb, Tooraj

2014-01-01

The need for investment in capital intensive electricity networks is on the rise in many countries. A major advantage of distributed resources is their potential for deferring investments in distribution network capacity. However, utilizing the full benefits of these resources requires addressing several technical, economic and regulatory challenges. A significant barrier pertains to the lack of an efficient market mechanism that enables this concept and also is consistent with business model of distribution companies under an unbundled power sector paradigm. This paper proposes a market-oriented approach termed as “contract for deferral scheme” (CDS). The scheme outlines how an economically efficient portfolio of distributed generation, storage, demand response and energy efficiency can be integrated as network resources to reduce the need for grid capacity and defer demand driven network investments. - Highlights: • The paper explores a practical framework for smart electricity distribution grids. • The aim is to defer large capital investments in the network by utilizing and incentivising distributed generation, demand response, energy efficiency and storage as network resources. • The paper discusses a possible new market model that enables integration of distributed resources as alternative to grid capacity enhancement

Electron spin resonance of spin-trapped radicals of amines and polyamines

International Nuclear Information System (INIS)

Mossoba, M.M.; Rosenthal, Ionel; Riesz, Peter

1982-01-01

The reactions of hydroxyl radicals with methylamine, dimethylamine, trimethylamine, diethylamine, sec-butylamine, ethylene-diamine, 1,3-diaminopropane, putrescine, cadaverine, 1,7-diaminoheptane, ornithine, spermidine, spermine, agmatine, and arcaine in aqueous solutions have been investigated by spin-trapping and esr. Hydroxyl radicals were generated by the uv photolysis of H 2 O 2 and 2-methyl-2-nitrosopropane (MNP) was used as the spin-trap. The effects of ionizing radiation on the same polyamines in the polycrystalline state were also investigated. The free radicals produced by ν-radiolysis of these solids at room temperature in the absence of air were identified by dissolution in aqueous solutions of MNP. The predominant reaction of OH radicals with amines and polyamines below pH 7 was the abstraction of hydrogen atoms from a carbon that is not adjacent to the protonated amino group. For agmatine and arcaine which contain guanidinium groups abstraction occurred from the α-CH. Dimethylamine was oxidized to the dimethylnitroxyl radical by H 2 O 2 in the dark. ν-Radiolysis of polyamines in the polycrystalline state generated radicals due to H-abstraction from either the α-Ch or from a carbon atom in the middle of the alkyl chain. The deamination radical was obtained from ornithine

Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Erben-Russ, M.; Bors, W.; Saran, M.

1987-09-01

Linoleic acid peroxyl radicals (LOO) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N/sub 2/O/O/sub 2/-saturated solutions leads to a mixture of peroxyl radical isomers; reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N/sub 2/O-saturated solution produces 13-LOO radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO). The same aroxyl radicals were generated by OH and N/sub 3/ with rate constants exceeding 10/sup 9/ dm/sup 3/ mol/sup -1/ s/sup -1/. Applying a reaction scheme that includes competing generation and decay reactions of both LOO and ArO radicals, individual rate constants were derived for LOO reactions with the phenols (> 10/sup 7/ dm/sup 3/ mol/sup -1/ s-./sup 1/), with aroxyl radicals to form covalent adducts (> 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/), as well as for their bimilecular decay (3.0 x 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/). These results demonstrate high reactivity of fatty acid peroxyl radicals and flavone antioxidants in aqueous solution.

Evidence of radicals created by plasma in bacteria in water

International Nuclear Information System (INIS)

Lee, Chae Bok; Na, Young Ho; Hong, Tae-Eun; Choi, Eun Ha; Uhm, Han S.; Baik, Ku Youn; Kwon, Gichung

2014-01-01

Heavy water (D 2 O) was introduced into a non-thermal plasma-jet (NTPJ) device to generate deuterium monoxide (OD) radicals at room temperature. Owing to the similar reactivity and low prevalence of deuterium in nature, OD radicals can be utilized to visualize the OH radical interactions with water and living cells. Escherichia coli in water were treated with OD radicals, and D atom incorporation into cells was visualized using time-of-flight SIMS and Nano-SIMS. The results show that D atoms from NTPJ reach the cytoplasm of E. coli in H 2 O, indicating the usefulness of this OD-tracking method for the study of radical interactions with living cells.

Ethylbenzene induces microsomal oxygen free radical generation: antibody-directed characterization of the responsible cytochrome P450 enzymes.

Science.gov (United States)

Serron, S C; Dwivedi, N; Backes, W L

2000-05-01

influence free radical production and that the increase in free radical production in EB treated rats is consistent with the EB-mediated elevation of CYP2B, CYP 2E1, and CYP3A2. Such alterations in free radical generation in response to hydrocarbon treatment may contribute to the toxicity of these compounds. Copyright 2000 Academic Press.

Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

Science.gov (United States)

Wink, David A.; Desrosiers, Marc F.

The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant ( .Br -2). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive intermediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide radical. Unexpectedly, addition of DBNBS to a solution containing dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented.

Generation and reactivity of ketyl radicals with lignin related structures. On the importance of the ketyl pathway in the photoyellowing of lignin containing pulps and papers.

Science.gov (United States)

Fabbri, Claudia; Bietti, Massimo; Lanzalunga, Osvaldo

2005-04-01

[reaction: see text] Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pKa = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k2 = 1.8-2.7 x 10(9) M(-1) s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation of the reduced acceptor (methyl viologen radical cation, MV+*), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2*))(OH)CH2(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled

Cation radicals of xanthophylls.

Science.gov (United States)

Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

2007-10-01

Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

Intramolecular addition of benzylic radicals onto ketenimines. Synthesis of 2-alkylindoles.

Science.gov (United States)

Alajarín, Mateo; Vidal, Angel; Ortín, María-Mar

2003-12-07

The inter- and intramolecular addition of free radicals onto ketenimines is studied. All the attempts to add intermolecularly several silicon, oxygen or carbon centered radicals to N-(4-methylphenyl)-C,C-diphenyl ketenimine were unsuccessful. In contrast, the intramolecular addition of benzylic radicals, generated from xanthates, onto the central carbon of a ketenimine function with its N atom linked to the ortho position of the aromatic ring occurred under a variety of reaction conditions. These intramolecular cyclizations provide a novel radical-mediated synthesis of 2-alkylindoles.

p53 Mutagenesis by Benzo[a]pyrene derived Radical Cations

Science.gov (United States)

Sen, Sushmita; Bhojnagarwala, Pratik; Francey, Lauren; Lu, Ding; Jeffrey Field, Trevor M. Penning

2013-01-01

Benzo[a]pyrene (B[a]P), a major human carcinogen in combustion products such as cigarette smoke and diesel exhaust, is metabolically activated into DNA-reactive metabolites via three different enzymatic pathways. The pathways are the anti-(+)-benzo[a]pyrene 7,8-diol 9, 10-epoxide pathway (P450/ epoxide hydrolase catalyzed) (B[a]PDE), the benzo[a]pyrene o-quinone pathway (aldo ketose reductase (AKR) catalyzed) and the B[a]P radical cation pathway (P450 peroxidase catalyzed). We used a yeast p53 mutagenesis system to assess mutagenesis by B[a]P radical cations. Because radical cations are short-lived, they were generated in situ by reacting B[a]P with cumene hydroperoxide (CuOOH) and horse radish peroxidase (HRP) and then monitoring the generation of the more stable downstream products, B[a]P-1,6-dione and B[a]P-3,6-dione. Based on the B[a]P-1,6 and 3,6-dione formation, approximately 4µM of radical cation was generated. In the mutagenesis assays, the radical cations produced in situ showed a dose-dependent increase in mutagenicity from 0.25 µM to 10 µM B[a]P with no significant increase seen with further escalation to 50 µM B[a]P. However, mutagenesis was 200-fold less than with the AKR pathway derived B[a]P, 7–8 dione. Mutant p53 plasmids, which yield red colonies, were recovered from the yeast to study the pattern and spectrum of mutations. The mutation pattern observed was G to T (31%) > G to C (29%) > G to A (14%). The frequency of codons mutated by the B[a]P radical cations was essentially random and not enriched at known cancer hotspots. The quinone products of radical cations, B[a]P-1,6-dione and B[a]P-3,6-dione were more mutagenic than the radical cation reactions, but still less mutagenic than AKR derived B[a]P-7,8-dione. We conclude that B[a]P radical cations and their quinone products are weakly mutagenic in this yeast-based system compared to redox cycling PAH o-quinones. PMID:22768918

Photoredox Generated Radicals in Csp2-Csp3 Bond Construction

Science.gov (United States)

Primer, David Neal

The routine application of Csp3-hybridized nucleophiles in cross-coupling has been an ongoing pursuit in the agrochemical, pharmaceutical, and materials science industries for over 40 years. Unfortunately, despite numerous attempts to circumvent the problems associated with alkyl nucleophiles, application of these reagents in transition metal-catalyzed C-C bond-forming reactions has remained largely restricted. In recent years, many chemists have noted the lack of reliable, turnkey reactions that exist for the installation of Csp3-hybridized centers--reactions that would be useful for delivering molecules with enhanced three-dimensional topology and altered chemical properties. As such, a general method for alkyl nucleophile activation in cross-coupling would offer access to a host of compounds inaccessible by other means. From a mechanistic standpoint, the continued failure of alkylmetallics is inherent to the high energy intermediates associated with a traditional transmetalation. To overcome this problem, we have pioneered an alternate, single-electron pathway involving 1) initial oxidation of an alkylmetallic reagent, 2) oxidative alkyl radical capture at a metal center, and 3) subsequent reduction of the metal center to return its initial oxidation state. This series of steps constitutes a formal transmetalation that avoids the energy-demanding steps that plague a traditional anionic approach. Under this enabling paradigm, a host of alkyl precursors (alkyl-trifluoroborates and -silicates) have been generally used in cross-coupling for the first time. In summary, the synergistic use of an Ir photoredox catalyst and a Ni cross-coupling catalyst to mediate the cross-coupling of (hetero)aryl bromides with diverse alkyl radical precursors will be discussed. Methods for coupling various trifluoroborate classes (alpha-alkoxy, alpha-trifluoromethyl, secondary and tertiary alkyl) will be covered, focusing on their complementarity to traditional protocols. Finally, a

Capacity competition in electricity markets

International Nuclear Information System (INIS)

Crampes, Claude; Creti, Anna

2005-01-01

The article analyzed a two-stage game where capacity constrained electricity generators first choose how much capacity they make available and then compete in a uniform-rice auction. It is studied how capacity withholding can be used strategically to enforce market power and how uniform auctions in the price game change the results of capacity constrained competition models. The uniform auction procedure gives strong incentives to capacity restriction. At equilibrium, however, power shortage never occurs. Though auctions in electricity markets have already been studied by several economists, yet an important feature of spot trading is the capacity availability decision. In fact, for technical reasons, such as equipment maintenance or failures, the installed capacity may not work at maximum operating level and the spot market rules oblige generators to announce which plants they are willing to use and simultaneously their offer prices. Beside technical reasons, the so-called 'capacity declarations' also offer a strategic instrument for firms: by restricting capacity, operators can benefit from scarcity rents. Assessing whether generators withhold capacity is an intriguing issue for real electricity markets, though proving it is a difficult task. Several theoretical papers show that generators are able to keep wholesale prices high as compared to their generation costs. In our model, a generator is not obliged to declare all installed capacity as available, but decides on the amount of MW of electricity that is available. Hence the available capacity is an endogenous variable while the installed one is exogenous. The distinction between installed capacities and 'available' capacities allows to explain clearly whether generators exert market power by declaring unavailable some production units. Although we find multiple sub game perfect equilibria that cannot be eliminated by Pareto-dominance, all the outcomes are characterized by market price at the highest

Antioxidant capacity of Macaronesian traditional medicinal plants.

Science.gov (United States)

Tavares, Lucélia; Carrilho, Dina; Tyagi, Meenu; Barata, David; Serra, Ana Teresa; Duarte, Catarina Maria Martins; Duarte, Rui Oliveira; Feliciano, Rodrigo Pedro; Bronze, Maria Rosário; Chicau, Paula; Espírito-Santo, Maria Dalila; Ferreira, Ricardo Boavida; dos Santos, Cláudia Nunes

2010-04-12

The use of many traditional medicinal plants is often hampered by the absence of a proper biochemical characterization, essential to identify the bioactive compounds present. The leaves from five species endemic to the Macaronesian islands with recognized ethnobotanical applications were analysed: Apollonias barbujana (Cav.) Bornm., Ocotea foetens (Ainton) Baill, Prunus azorica (Mouill.) Rivas-Mart., Lousã, Fern. Prieto, E. Días, J.C. Costa & C. Aguiar, Rumex maderensis Lowe and Plantago arborescens Poir. subsp. maderensis (Dcne.) A. Hans. et Kunk.. Since oxidative stress is a common feature of most diseases traditionally treated by these plants, it is important to assess their antioxidant capacity and determine the molecules responsible for this capacity. In this study, the antioxidant capacity of these plants against two of the most important reactive species in human body (hydroxyl and peroxyl radicals) was determined. To trace the antioxidant origin total phenol and flavonoid contents as well as the polyphenolic profile and the amount of trace elements were determined. There was a wide variation among the species analysed in what concerns their total leaf phenol and flavonoid contents. From the High Performance Liquid Chromatography (HPLC) electrochemically detected peaks it was possible to attribute to flavonoids the antioxidant capacity detected in A. barbujana, O. foetens, R. maderensis and P. azorica extracts. These potential reactive flavonoids were identified for A. barbujana, R. maderensis and P. azorica. For R. maderensis a high content (7 mg g-1 dry weight) of L-ascorbic acid, an already described antioxidant phytomolecule, was found. A high content in selenomethionine (414.35 microg g-1 dry weight) was obtained for P. arborescens subsp. maderensis extract. This selenocompound is already described as a hydroxyl radical scavenger is reported in this work as also possessing peroxyl radical scavenging capacity. This work is a good illustration of

Generation and photosensitization properties of the oxidized radical of riboflavin: a laser flash photolysis study

International Nuclear Information System (INIS)

Han Zhenhui; Lu Changyuan; Wang Wenfeng; Lin Weizhen; Yao Side; Lin Nianyun

2000-01-01

Direct excitation of riboflavin with 248 nm laser gives rise to a transient absorption spectrum with contributions from (1) oxidized radical, (2) hydrated electron, (3) triplet state and reduced radical, and distinction between the transient species below 360 nm is difficult for the absorption overlapped. The RF ·+ or RF(-H) · has been clearly produced via direct photoionization by 248 nm laser in aqueous solution, which has been unambiguously identified by SO 4 ·- radical oxidation, although its transient absorption can not be observed clearly for both lower absorption coefficient (ε = 2000 dm 3 mol -1 cm -1 at 640 nm at pH 7.1) and overlap from others. In the present paper, electron transfer from purine and pyrimidine nucleotides to one-electron oxidized radical of riboflavin were observed for the first time in aqueous solution, and the reaction rate constants were determined respectively, which would obviously be of considerable significance in vivo and in vitro. The results clearly demonstrate the importance of oxidized radical of riboflavin in flavin photochemistry and photobiology. These reaction paths are important for the elucidation of the interaction between riboflavin and DNA nucleotides under photoexcitation. When riboflavin was excited, triplet state and oxidized radical can be formed directly or by sequence reactions of triplet state. In the presence of DNA, electron transfer can take place to form a base radical cation, then hole migration to GG step along base-stacking of DNA leads to DNA strand scission, which has been verified by many steady product analysis. This selective cleavage of DNA shows the potential application of riboflavin as a site-specify photonuclease, which has become a highlight' in the currently photochemistry, photomedicine and photobiology areas. The mechanism implies that riboflavin can be applied potentially to photosensitization of oxygen deficient or under high intensity pulsed laser irradiation. (author)

Alkylperoxyl radical scavenging activity of red leaf lettuce (Lactuca sativa L.) phenolics.

Science.gov (United States)

Caldwell, Charles R

2003-07-30

Although lettuce may provide relatively low levels of antioxidative phytochemicals which may contribute to human health, lettuce leaf extracts in fact contained compounds with high specific peroxyl radical scavenging activities. After determining the extraction conditions that minimized phenolic oxidation and produced the highest oxygen radical absorbance capacity (ORAC) values, the phenolic compounds from red leaf lettuce were separated by reverse-phase high-performance liquid chromatography (HPLC). The primary phenolic compounds in the leaf tissue extracts were mono- and dicaffeoyltartaric acid (CTA and DCTA), mono- and dicaffeoylquinic acid (CQA and DCQA), quercetin 3-malonylglucoside (QMG), quercetin 3-glucoside (QG), cyanidin 3-malonylglucoside (CMG), and an unknown phenolic ester (UPE). Significant levels of DCQA were only found after wounding. Using the new fluorescein-based ORAC assay procedures, fractions from the HPLC analyses were assayed for peroxyl radical absorbance capacity. Using absorbance to estimate concentration, the decreasing order of contribution to the total ORAC value of an extract from wounded tissue was QMG > DCQA > CMG > DCTA > UPE > QG > CTA. The decreasing order of the specific peroxyl radical scavenging activities was CMG > QG > DCTA > DCQA > QMG > UPE > CQA > CTA. Since the concentrations of plant flavonoid and phenolic acid esters are sensitive to environmental factors, this information may be used to develop pre- and postharvest conditions which increase the dietary benefits of leaf lettuce.

Airborne measurement of peroxy radicals in the lower troposphere

Science.gov (United States)

Andrés Hernández, Maria Dolores; Horstjann, Markus; Kartal, Deniz; Krebsbach, Marc; Linke, Christian; Lichtenstern, Michael; Andrey, Javier; Burrows, John P.

2013-04-01

The importance of peroxy radicals in the tropospheric chemistry is well recognized in the scientific literature. Hydroxy- and organic peroxy radicals (HO2 and RO2, R being an organic chain) are key intermediates in the OH radical initiated oxidation of CO and SO2, of volatile organic compounds (VOC), in the ozonolysis of alkenes and photo-oxidation of carbonyl species. Peroxy radicals are responsible for the ozone production in the troposphere, the formation of peroxides and other oxidants. Although radical chemistry in the troposphere has been subject of intensive research in the past three decades, it is still very few known about the vertical distribution of peroxy radicals. Airborne observations are scarce in spite of their particular importance to improve the understanding of the tropospheric chemistry and the oxidising capacity of the atmosphere at different altitudes. In situ trace gas measurements were carried out in summer 2010 on board of the INTA (Instituto Nacional de Técnicas Aeroespaciales) C212 aircraft over Spain in the frame of the EUFAR project VERDRILLT (VERtical Distribution of Radicals In the Lower Layers of the Troposphere), and in cooperation with the DLR (Deutsches Zentrum für Luft- und Raumfahrt), the University of Wuppertal, the CEAM (Centro de Estudios Ambientales del Mediterráneo) and the UPV-EHU University in Bilbao. VERDRILLT aimed at getting a deeper understanding of the vertical distribution of peroxy radicals in the lower layers of the troposphere. Measurements were taken over urban areas and extensions of different vegetation under meteorological conditions favouring active photochemistry and convection from the ground into close atmospheric layers. Results and main findings will be presented and discussed.

Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited.

Science.gov (United States)

Assaf, Emmanuel; Song, Bo; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

2016-11-17

The reaction between CH 3 O 2 and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH 4 and H 2 O for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF 2 . An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CH 3 O 2 was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF. To remove dubiety from the quantification of CH 3 O 2 by cw-CRDS in the near-infrared, its absorption cross section has been determined at 7489.16 cm -1 using two different methods. A rate constant of k 1 = (1.60 ± 0.4) × 10 -10 cm 3 s -1 has been determined at 295 K, nearly a factor of 2 lower than an earlier determination from our group ((2.8 ± 1.4) × 10 -10 cm 3 s -1 ) using CH 3 I photolysis as a precursor. Quenching of electronically excited I atoms (from CH 3 I photolysis) in collision with OH(v = 0) is suspected to be responsible for a bias in the earlier, fast rate constant.

Computational studies of free radical-scavenging properties of phenolic compounds.

Science.gov (United States)

Alov, Petko; Tsakovska, Ivanka; Pajeva, Ilza

2015-01-01

For more than half a century free radical-induced alterations at cellular and organ levels have been investigated as a probable underlying mechanism of a number of adverse health conditions. Consequently, significant research efforts have been spent for discovering more effective and potent antioxidants / free radical scavengers for treatment of these adverse conditions. Being by far the most used antioxidants among natural and synthetic compounds, mono- and polyphenols have been the focus of both experimental and computational research on mechanisms of free radical scavenging. Quantum chemical studies have provided a significant amount of data on mechanisms of reactions between phenolic compounds and free radicals outlining a number of properties with a key role for the radical scavenging activity and capacity of phenolics. The obtained quantum chemical parameters together with other molecular descriptors have been used in quantitative structure-activity relationship (QSAR) analyses for the design of new more effective phenolic antioxidants and for identification of the most useful natural antioxidant phenolics. This review aims at presenting the state of the art in quantum chemical and QSAR studies of phenolic antioxidants and at analysing the trends observed in the field in the last decade.

Formation of radical cations of diaryloxadiazoles

International Nuclear Information System (INIS)

Helmstreit, W.

1988-01-01

The nature of the formation of the radical cation of the 2,5-bis-(p-diethylaminophenyl)-1,3,4-oxadiazole (PC) in liquid n-butyl chloride and acetonitrile has been investigated by observing excited state fluorescence and transient absorption using nanosecond pulse radiolysis and laser flash photolysis. The formation of solute oxonium ions has also been observed. At concentrations -4 mol dm -3 the growth time at which the transient absorption of the radical cation reaches the maximum follows the rise time of the electron pulse ( 2 laser yields the solute radical cation in an acetonitrile solution of 2 x 10 -4 mol dm -3 PC via an electronically excited state. Here, the generation time was smaller than 5 ns. The yield of the cation is increased by addition of CCl 4 . A reaction mechanism is proposed that explains the fast cation formation in terms of an exciplex formed by interaction between an electronically excited state of diaryloxadiazole and the ground state of the solvent. This exciplex yields the solute radical cation. (author)

Some biological compounds, radical scavenging capacities and antimicrobial activities in the seeds of Nepeta italica L. and Sideritis montana L. sub sp. montana from Turkey

Energy Technology Data Exchange (ETDEWEB)

Emre, I.; Kursat, M.; Yilmaz, O.; Erecevit, P.

2011-07-01

This study determined some biological compounds (fatty acid compositions, lipid-soluble vitamins, sterols, flavonoids), radical scavenging capacities and antimicrobial activities in the seeds of Nepeta italica L. and Sideritis montana L. subsp. montana. It was found that palmitic acid (C16:0; 8.54+-0.13-3.05+-0.04%), oleic acid (C18:1 n9, 22.41+-0.8-18.83+-0.1%) and a-inolenic acid were the dominant fatty acids in both Nepeta italica L. and Sideritis montana L. subsp. montana. It was concluded that both Nepeta italica L. and Sideritis montana L. subsp. montana contained stigmasterol and ergosterol as well as beta-sitosterol. The present findings show that Nepeta italica L. contains morin, catechin, naringin and Sideritis montana L. subsp. montana contains morin, naringenin as major flavonoids. It was also determined that methanol extracts of Nepeta italica L. and Sideritis montana L. subsp. montana were most effective against DPPH radicals. The results of the present study show that the vitamins, flavonoids and fatty acid extracts in the seeds of N. italica L. and S. montana L. subsp. montana prevented the growth of the microorganisms used in the tests at different ratios. (Author).

Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

Energy Technology Data Exchange (ETDEWEB)

Wink, D A [National Cancer Inst., Frederick, MD (United States); Desrosiers, M F [National Inst. of Standards and Technology, Gaithersburg, MD (United States)

1991-01-01

The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3.5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant (BR{sub 2}{sup -}). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive inter-mediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented. (author).

Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

International Nuclear Information System (INIS)

Wink, D.A.; Desrosiers, M.F.

1991-01-01

The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3.5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant (BR 2 - ). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive inter-mediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented. (author)

Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions

Science.gov (United States)

Nguyen, John D.; D'Amato, Erica M.; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

2012-10-01

Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

Free radicals. High-resolution spectroscopy and molecular structure

International Nuclear Information System (INIS)

Hirota, E.

1983-01-01

High-resolution, high-sensitivity spectroscopy using CW laser and microwave sources has been applied to free radicals and transient molecules to establish their existence and to explore their properties in detail. The radicals studied were mainly generated by discharge-induced reactions. A few molecules are used as typical examples to illustrate the results so far obtained. The molecular and electronic structures of free radicals, intramolecular motions of large amplitudes in some labile molecules, and metastable electronic states of carbenes are given special emphasis. The significance of the present spectroscopic results in other related fields such as astronomy and atmospheric chemistry is stressed. 4 figures, 3 tables

Free radical generation induced by ultrasound in red wine and model wine: An EPR spin-trapping study

OpenAIRE

Zhang, Quing An; Shen, Yuan; Fan, Xue-Hui; García-Martín, Juan Francisco; Wang, Xi; Song, Yun

2015-01-01

© 2015 Published by Elsevier B.V. Direct evidence for the formation of 1-hydroxylethyl radicals by ultrasound in red wine and air-saturated model wine is presented in this paper. Free radicals are thought to be the key intermediates in the ultrasound processing of wine, but their nature has not been established yet. Electron paramagnetic resonance (EPR) spin trapping with 5,5-dimethyl-l-pyrrolin N-oxide (DMPO) was used for the detection of hydroxyl free radicals and 1-hydroxylethyl free radic...

Resveratrol products resulting by free radical attack

Energy Technology Data Exchange (ETDEWEB)

Bader, Yvonne; Quint, R.M. [Section Radiation Biology, Department of Nutritional Sciences, Faculty of Life Sciences, University of Vienna, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Getoff, Nikola [Section Radiation Biology, Department of Nutritional Sciences, Faculty of Life Sciences, University of Vienna, UZAII, Althanstrasse 14, A-1090 Vienna (Austria)], E-mail: nikola.getoff@univie.ac.at

2008-06-15

Trans-resveratrol (trans-3,4',5-trihydroxystilbene; RES), which is contained in red wine and many plants, is one of the most relevant and extensively investigated stilbenes with a broad spectrum of biological activities. Among other duties, RES has been reported to have anti-carcinogenetic activities, which could be attributed to its antioxidant properties. The degradation of RES was studied under various conditions. The products (aldehydes, carboxylic acids, etc.) generated from RES by the attack of free radicals were registered as a function of the radical concentration (absorbed radiation dose). Based on the obtained data it appears that the OH radicals are initiating the rather complicated process, which involves of the numerous consecutive reactions. A possible starting reaction mechanism is presented.

In vitro anti-inflammatory and free radical scavenging activities of ...

African Journals Online (AJOL)

Methods: In vitro antioxidant activity was determined using free radical scavenging assays such as DPPH, ABTS and NO2. The antiinflammatory potential was carried out using inhibition of protein denaturation of egg albumin as a model of anti-inflammatory capacity. Results: Both the crude methanolic extract and saponins ...

OH radicals distribution in an Ar-H2O atmospheric plasma jet

Science.gov (United States)

Li, L.; Nikiforov, A.; Xiong, Q.; Britun, N.; Snyders, R.; Lu, X.; Leys, C.

2013-09-01

Recently, plasma jet systems found numerous applications in the field of biomedicine and treatment of temperature-sensitive materials. OH radicals are one of the main active species produced by these plasmas. Present study deals with the investigation of RF atmospheric pressure plasma jet in terms of OH radicals production by admixture of H2O into argon used as a feed gas. Generation of OH radicals is studied by laser-induced fluorescence spectroscopy. The excitation dynamics of OH radicals induced by the laser photons is studied by time-resolved spectroscopy. It is shown that vibrational and rotational energy transfer processes, which are sensitive to the surrounding species, can lead to the complication in the OH radicals diagnostics at high pressure and have to be considered during experiments. The axial and radial 2D maps of absolute densities of hydroxyl radicals at different water contents are obtained. The highest density of 1.15 × 1020 m-3 is measured in the plasma core for the case of 0.3% H2O. In the x-y-plane, the OH density steeply decreases within a range of ±2 mm from its maximum value down to 1018 m-3. The effect of H2O addition on the generation of OH radicals is investigated and discussed.

Photoactivation of isoflavonoid phytoalexins: involvement of free radicals

International Nuclear Information System (INIS)

Bakker, J.; Gommers, F.J.; Smits, L.; Fuchs, A.; Vries, F.W. de

1983-01-01

Ultraviolet irradiation of isoflavonoid phytoalexins phaseollin, 3.6a. 9-trihydroxypterocarpan, glyceollin, tuberosin and pisatin, but not medicarpin, brought about inactivation of glucose-6-phosphate dehydrogenase in an in vitro assay system. Photoinactivation of the enzyme by photoactivated pisatin in air-saturated solutions was hardly affected by singlet oxygen quenchers such as NaN 3 , bovine serum albumin, histidine or methionine. Neither addition of the hydroxyl radical scavengers mannitol, Na-benzoate and ethanol nor the presence of catalase or superoxide dismutase protected the enzyme against photoinactivation, suggesting that OHradical, H 2 O 2 and O 2 radical are not the reactive oxygen species involved. However, the free radical scavenger S-(2-amino-ethyl)isothiouronium bromide hydrobromide (AET) protected the enzyme against inactivation by photoactivated pisatin. Direct evidence for the generation of free radicals was obtained by ESR measurements of solutions of phaseollin, pisatin and medicarpin in hexane irradiated with ultraviolet light in the presence or absence of O 2 . Phaseollin produced the most stable free radicals, whereas medicarpin hardly gave rise to free radical formation; pisatin took a somewhat intermediate position by producing a strong ESR signal which, however, decayed rather quickly. These results indicate free radical formation as the cause for photoinactivation of enzymes by photoactivated isoflavonoid phytoalexins. (author)

Ca2+ and Mg2+-enhanced reduction of arsenazo III to its anion free radical metabolite and generation of superoxide anion by an outer mitochondrial membrane azoreductase.

Science.gov (United States)

Moreno, S N; Mason, R P; Docampo, R

1984-12-10

At the concentrations usually employed as a Ca2+ indicator, arsenazo III underwent a one-electron reduction by rat liver mitochondria to produce an azo anion radical as demonstrated by electron-spin resonance spectroscopy. Either NADH or NADPH could serve as a source of reducing equivalents for the production of this free radical by intact rat liver mitochondria. Under aerobic conditions, addition of arsenazo III to rat liver mitochondria produced an increase in electron flow from NAD(P)H to molecular oxygen, generating superoxide anion. NAD(P)H generated from endogenous mitochondrial NAD(P)+ by intramitochondrial reactions could not be used for the NAD(P)H azoreductase reaction unless the mitochondria were solubilized by detergent or anaerobiosis. In addition, NAD(P)H azoreductase activity was higher in the crude outer mitochondrial membrane fraction than in mitoplasts and intact mitochondria. The steady-state concentration of the azo anion radical and the arsenazo III-stimulated cyanide-insensitive oxygen consumption were enhanced by calcium and magnesium, suggesting that, in addition to an enhanced azo anion radical-stabilization by complexation with the metal ions, enhanced reduction of arsenazo III also occurred. Accordingly, addition of cations to crude outer mitochondrial membrane preparations increased arsenazo III-stimulated cyanide-insensitive O2 consumption, H2O2 formation, and NAD(P)H oxidation. Antipyrylazo III was much less effective than arsenazo III in increasing superoxide anion formation by rat liver mitochondria and gave a much weaker electron spin resonance spectrum of an azo anion radical. These results provide direct evidence of an azoreductase activity associated with the outer mitochondrial membrane and of a stimulation of arsenazo III reduction by cations.

Interaction of radiation-generated radicals with myoglobin in aqueous solution

International Nuclear Information System (INIS)

Whitburn, K.D.; Hoffman, M.Z.

1984-01-01

The interaction of radiation-generated OH/H with oxymyoglobin (MbO 2 ) has been studied in the presence of catalase at pH 7.3 over the range of 5 to 510 μM O 2 . The conversion of MbO 2 to heme-modified products has been examined under conditions where depletion of O 2 in irradiated solutions both can and cannot be compensated by O 2 -transfer across the solution phase boundary. In the theoretical limit of [O 2 ] -> 0 in bulk solution, MbO 2 is converted stoichiometrically to ferri- and ferromyoglobin with G(-MbO 2 ) approx.= 6.0, G(ferroMb) approx.3.0, and G(ferriMb) approx.= 3.0. An increase in [O 2 ] in bulk solution beyond the zero-limit progressively suppresses the conversion of MbO 2 to the heme-modified derivatives. At [O 2 ] >300 μM, an O 2 -independent path of ferriMb formation with G approx.= 0.6 is evident. Two sources of ferriMb induced by OH/H are proposed: an O 2 -independent path involving direct oxidative attack of OH at the oxyferroheme, and O 2 -dependent paths of production of ferriMb and ferroMb involving the mediation of O 2 -scavengeable secondary hemeprotein radicals. It is suggested that the modifications of the heme group in the absence of O 2 are accompanied by redox modifications on the globin moiety. (author)

Selenium and Zinc content and radical scavenging capacity of edible mushrooms Armilaria mellea and Lycoperdon saccatum

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Z. Zeković

2010-01-01

Full Text Available Armillaria mellea and Lycoperdon saccatum are two delicious mushrooms growing widely trough all Balkan region. Investigation of A. mellea and L. saccatum antioxidant properties includes preparation of mushrooms extracts, determination of Selenium and Zinc content and evaluation of theirs antioxidant activity involving scavenging activity of ˙O2- radicals, DPPH and reducing power assay. Higher extraction yield of 24.48 % has been achieved for L. saccatum, but higher content of Selenium and Zinc was determined in A. mallea extract, 2.359 mg/kg and 50.380 mg/kg, respectively. The radical scavenging activity was found to exhibit 50 % of inhibition value (IC50 value at the extracts concentration of 0.0161±0.0001 mg/ml for the L. saccatum extract and 0.0108±0.0002 mg/ml for A. mallea extract. The determined relative inhibition of ˙O2- radicals for L. sacatum extract is lower than for A. malea. It was determined that both mushrooms extract posses’ reductive capabilities and thus were capable of reducing iron (III.

Phytochemicals and Antioxidant Capacity from Nypa fruticans Wurmb. Fruit

Science.gov (United States)

Prasad, Nagendra; Yang, Bao; Kong, Kin Weng; Khoo, Hock Eng; Sun, Jian; Azlan, Azrina; Ismail, Amin; Romli, Zulfiki Bin

2013-01-01

Nypa fruticans Wurmb. is one of the important underutilized fruit of Malaysia, which lacks scientific attention. Total phenolics, flavonoid content, and antioxidant capacities from endosperm extracts of Nypa fruticans (unripe and ripe fruits) were evaluated. Endosperm extract of unripe fruits (EEU) exhibited the highest phenolics (135.6 ± 4.5 mg GAE/g), flavonoid content (68.6 ± 3.1 RE/g), and antioxidant capacity. Free radical scavenging capacity of EEU as assessed by 2-2′-azino-bis (3-ethylbenz-thiazoline-6-sulfonic acid (ABTS) and 1,1-diphenyl-2-picryl hydrazyl (DPPH) radicals showed inhibitory activity of 78 ± 1.2% and 85 ± 2.6%, respectively. Beta carotene bleaching coefficient of EEU was higher (2550 ± 123), when compared to endosperm extract of ripe fruits (1729 ± 172). Additionally, EEU exhibited high antioxidant capacity by phosphomolybdenum method and ferric reducing antioxidant power values. Eight phenolic compounds from Nypa fruticans endosperm extracts were identified and quantified by ultra-high-performance liquid chromatography. Chlorogenic acid, protocatechuic acid, and kaempferol were the major phenolic compounds. Thus this fruit could be used as a potential source of natural antioxidant. PMID:23710209

Optimizing Geographic Allotment of Photovoltaic Capacity in a Distributed Generation Setting: Preprint

Energy Technology Data Exchange (ETDEWEB)

Urquhart, B.; Sengupta, M.; Keller, J.

2012-09-01

A multi-objective optimization was performed to allocate 2MW of PV among four candidate sites on the island of Lanai such that energy was maximized and variability in the form of ramp rates was minimized. This resulted in an optimal solution set which provides a range of geographic allotment alternatives for the fixed PV capacity. Within the optimal set, a tradeoff between energy produced and variability experienced was found, whereby a decrease in variability always necessitates a simultaneous decrease in energy. A design point within the optimal set was selected for study which decreased extreme ramp rates by over 50% while only decreasing annual energy generation by 3% over the maximum generation allocation. To quantify the allotment mix selected, a metric was developed, called the ramp ratio, which compares ramping magnitude when all capacity is allotted to a single location to the aggregate ramping magnitude in a distributed scenario. The ramp ratio quantifies simultaneously how much smoothing a distributed scenario would experience over single site allotment and how much a single site is being under-utilized for its ability to reduce aggregate variability. This paper creates a framework for use by cities and municipal utilities to reduce variability impacts while planning for high penetration of PV on the distribution grid.

EPR detection of hydroxyl radical generation and its interaction with antioxidant system in Carassius auratus exposed to pentachlorophenol

Energy Technology Data Exchange (ETDEWEB)

Luo Yi [Key Laboratory of Pollution Processes and Environmental Criteria (Nankai University), Ministry of Education, College of Environmental Sciences and Engineering, Nankai University, Tianjin 300071 (China); Wang Xiaorong, E-mail: yiyluo@gmail.com [State Key Laboratory of Pollution Control and Resources Reuse, School of Environment, Nanjing University, Nanjing 210093 (China); Ji Liangliang; Su Yan [State Key Laboratory of Pollution Control and Resources Reuse, School of Environment, Nanjing University, Nanjing 210093 (China)

2009-11-15

In the present study, direct evidence of hydroxyl radical production in livers of Carassius auratus exposed to pentachlorophenol (PCP) was provided using electron paramagnetic resonance (EPR) with spin-trapping. A dose-effect relationship was obtained between hydroxyl radical intensities and PCP exposure. It was observed that hydroxyl radical was significantly induced by 0.001 mg l{sup -1} (below the criteria for Chinese fishery water quality) of PCP exposure. A strong positive correlation (r = 0.9581, p < 0.001) was observed between PCP liver concentrations and hydroxyl radical intensities within 7 d of PCP exposure, which suggests that hydroxyl radical are mainly produced from PCP itself. However, no correlation was observed between PCP liver concentrations and hydroxyl radical intensities after 7 d, and a higher intensity of hydroxyl radical could still be observed when the PCP liver concentrations decreased to a lower level, which suggests that other mechanisms may possibly contribute to hydroxyl radical production after 7 d. The glutathione/oxidized glutathione (GSH/GSSG) ratio decreased below that of the control level during the entire period of PCP exposure (0.05 mg l{sup -1}), which suggested oxidative stress occurred.

Measurement of the energy flow at large pseudorapidities for {radical}(s)=0.9 TeV and {radical}(s)=7 TeV at the large hadron collider using the compact muon solenoid

Energy Technology Data Exchange (ETDEWEB)

Sen, Niladri

2011-11-15

Energy flow, dE/d{eta}, has been measured in proton-proton collisions at the lhc, for two centre-of-mass energies, {radical}(s)=0.9 TeV and 7 TeV, using an integrated luminosity of 239 {mu}b{sup -1} and 206 {mu}b{sup -1} respectively. The measurements were made in a previously unexplored phase space (3.15 < vertical stroke {eta} vertical stroke < 4.9) using the CMS detector for two separate event topologies: minimum bias events and events with a hard scale set by the transverse momentum of the jets in a di-jet system. Data from each of the measurements have been compared to leading order Monte Carlo pp-collision event generators that use k{sub T}{sup 2}-, Q{sup 2}- and angular-ordered parton showers. The forward energy ow measurements are shown to be sensitive to the models and tuning parameters in both their shape and magnitude. The necessity of underlying event models in order to describe data will be demonstrated. In addition, predictions from cosmic-ray event generators are shown to describe data consistently well for each of the measurements. (orig.)

Understanding the generative capacity of analogies as a tool for explanation

Science.gov (United States)

Wong, E. David

1993-12-01

Psychological studies have typically portrayed analogical reasoning as a process of schema transfer from a familiar domain of understanding to a problem situation. These studies have usually examined analogical reasoning in contexts where (a) individuals possess or have been provided with appropriate, problem-specific schema, (b) the nature of the problem and/or solution is fairly well defined, and (c) ideal analogies are provided or suggested by an outside source. This study examines analogical reasoning in contexts where understanding is generated from loosely organized, incomplete prior knowledge rather than transferred from a well-structured domain of understanding. In addition, participants were asked to create, apply, and modify their own analogies - as opposed to applying a given analogy - as a heuristic for constructing, evaluating, and modifying their explanations for a particular scientific phenomena. The results provide empirical support for the generative properties of analogies; that is, analogies can stimulate new inferences and insight. Furthermore, under specific conditions, individuals can productively harness the generative capacity of their own analogies to advance their conceptual understanding of scientific phenomena.

Cheaper power generation from surplus steam generating capacities

International Nuclear Information System (INIS)

Gupta, K.

1996-01-01

Prior to independence most industries had their own captive power generation. Steam was generated in own medium/low pressure boilers and passed through extraction condensing turbines for power generation. Extraction steam was used for process. With cheaper power made available in Nehru era by undertaking large hydro power schemes, captive power generation in industries was almost abandoned except in sugar and large paper factories, which were high consumers of steam. (author)

The determination of the radical power - an in vitro test for the evaluation of cosmetic products.

Science.gov (United States)

Herrling, T; Seifert, M; Sandig, G; Jung, K

2016-06-01

Cosmetic formulations are influenced by environmental impacts and ageing, resulting in rancidity and change of colour and structure. These changes are caused by free radicals (FRs). The sensitivity of cosmetics generating FRs is a metric for its quality and should be determined. Electron spin resonance spectroscopy in combination with UV irradiation tested cosmetics such as creams, milks, lotions and fragrances. The probes were directly measured without expensive preparation. Nine formulations are tested for its radical generation and ranked corresponding to the radical power. The transformation of the FR properties of three formulations to skin is measured by the radical skin status factor (RSF) method. It shows that the higher the radical power (RP) is, the lower the radical status RSF of skin will be. The knowledge of the sensitivity of cosmetics to generate FRs is necessary for its stabilization and prevention of potential damages to skin. It is a new way in development of cosmetics which has to be considered. © 2015 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

Battery designs with high capacity anode materials and cathode materials

Energy Technology Data Exchange (ETDEWEB)

Masarapu, Charan; Anguchamy, Yogesh Kumar; Han, Yongbong; Deng, Haixia; Kumar, Sujeet; Lopez, Herman A.

2017-10-03

Improved high energy capacity designs for lithium ion batteries are described that take advantage of the properties of high specific capacity anode active compositions and high specific capacity cathode active compositions. In particular, specific electrode designs provide for achieving very high energy densities. Furthermore, the complex behavior of the active materials is used advantageously in a radical electrode balancing design that significantly reduced wasted electrode capacity in either electrode when cycling under realistic conditions of moderate to high discharge rates and/or over a reduced depth of discharge.

Potential of EPR spin-trapping to investigate in situ free radicals generation from skin allergens in reconstructed human epidermis: cumene hydroperoxide as proof of concept.

Science.gov (United States)

Kuresepi, Salen; Vileno, Bertrand; Turek, Philippe; Lepoittevin, Jean-Pierre; Giménez-Arnau, Elena

2018-02-01

The first step in the development of skin sensitisation to a chemical, and in the elicitation of further allergic contact dermatitis (ACD), is the binding of the allergen to skin proteins after penetrating into the epidermis. The so-formed antigenic adduct is then recognised by the immune system as foreign to the body. Sensitising organic hydroperoxides derived from autoxidation of natural terpenes are believed to form antigens through radical-mediated mechanisms, although this has not yet been established. So far, in vitro investigations on reactive radical intermediates derived from these skin sensitisers have been conducted in solution, yet with experimental conditions being far away from real-life sensitisation. Herein, we report for the first time, the potential use of EPR spin-trapping to study the in situ generation of free radicals derived from cumene hydroperoxide CumOOH in a 3D reconstructed human epidermis (RHE) model, thus much closer to what may happen in vivo. Among the undesirable effects associated with dermal exposure to CumOOH, it is described to cause allergic and irritant dermatitis, being reported as a significant sensitiser. We considered exploiting the usage of spin-trap DEPMPO as an extensive view of all sort of radicals derived from CumOOH were observed all at once in solution. We showed that in the Episkin TM RHE model, both by incubating in the assay medium and by topical application, carbon radicals are mainly formed by redox reactions suggesting the key role of CumOOH-derived carbon radicals in the antigen formation process.

Biological activity of clovers - free radical scavenging ability and antioxidant action of six Trifolium species.

Science.gov (United States)

Kolodziejczyk-Czepas, Joanna; Nowak, Pawel; Kowalska, Iwona; Stochmal, Anna

2014-10-01

Clovers were chosen on the basis of traditional medicine recommendations, agricultural value, or available information on their promising chemical profiles. This study evaluates and compares free radical scavenging and antioxidant properties of six clover species: Trifolium alexandrinum L. (Leguminosae), Trifolium fragiferum L., Trifolium hybridum L., Trifolium incarnatum L., Trifolium resupinatum var. majus Boiss., and Trifolium resupinatum var. resupinatum L. Free radical scavenging activity of the extracts (1.5-50 µg/ml) was estimated by reduction of 1,1-diphenyl-2-picrylhydrazyl (DPPH(•)) and 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonic) acid (ABTS(•)) radicals. The Trifolium extract effects on total antioxidant capacity of blood plasma were determined by the reduction of ABTS(•+) and DPPH(•) radicals, as well as with the use of the ferric reducing ability of plasma (FRAP) assay. The UPLC analysis of chemical profiles of the examined extracts showed the presence of three or four groups of phenolic substances, including phenolic acids, clovamides, isoflavones, and other flavonoids. The measurements of free radical scavenging and ferric reducing ability of the examined clover extracts revealed the strongest effect for T. alexandrinum. Furthermore, antioxidant activity assays in human plasma have shown protective effects of all extracts against peroxynitrite-induced reduction of total antioxidant capacity. Trifolium plants may be a rich source of bioactive substances with antioxidant properties. The examined extracts displayed free radical scavenging action and partly protected blood plasma against peroxynitrite-induced oxidative stress; however, the beneficial effects of T. alexandrinum and T. incarnatum seem to be slightly higher.

A multiple free-radical scavenging (MULTIS) study on the antioxidant capacity of a neuroprotective drug, edaravone as compared with uric acid, glutathione, and trolox.

Science.gov (United States)

Kamogawa, Erisa; Sueishi, Yoshimi

2014-03-01

Edaravone (3-methyl-1-phenyl-2-pyrazoline-5-one) is a neuroprotective drug that has been used for brain ischemia injury treatment. Because its activity is speculated to be due to free radical scavenging activity, we carried out a quantitative determination of edaravone's free radical scavenging activity against multiple free radical species. Electron spin resonance (ESR) spin trapping-based multiple free-radical scavenging (MULTIS) method was employed, where target free radicals were hydroxyl radical, superoxide anion, alkoxyl radical, alkylperoxyl radical, methyl radical, and singlet oxygen. Edaravone showed relatively high scavenging abilities against hydroxyl radical (scavenging rate constant k=2.98×10(11) M(-1) s(-1)), singlet oxygen (k=2.75×10(7) M(-1) s(-1)), and methyl radical (k=3.00×10(7) M(-1) s(-1)). Overall, edaravone's scavenging activity against multiple free radical species is as robust as other known potent antioxidant such as uric acid, glutathione, and trolox. A radar chart illustration of the MULTIS activity relative to uric acid, glutathione, and trolox indicates that edaravone has a high and balanced antioxidant activity with low specificity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Cholesterol Hydroperoxide Generation, Translocation, and Reductive Turnover in Biological Systems.

Science.gov (United States)

Girotti, Albert W; Korytowski, Witold

2017-12-01

Cholesterol is like other unsaturated lipids in being susceptible to peroxidative degradation upon exposure to strong oxidants like hydroxyl radical or peroxynitrite generated under conditions of oxidative stress. In the eukaryotic cell plasma membrane, where most of the cellular cholesterol resides, peroxidation leads to membrane structural and functional damage from which pathological states may arise. In low density lipoprotein, cholesterol and phospholipid peroxidation have long been associated with atherogenesis. Among the many intermediates/products of cholesterol oxidation, hydroperoxide species (ChOOHs) have a number of different fates and deserve special attention. These fates include (a) damage-enhancement via iron-catalyzed one-electron reduction, (b) damage containment via two-electron reduction, and (c) inter-membrane, inter-lipoprotein, and membrane-lipoprotein translocation, which allows dissemination of one-electron damage or off-site suppression thereof depending on antioxidant location and capacity. In addition, ChOOHs can serve as reliable and conveniently detected mechanistic reporters of free radical-mediated reactions vs. non-radical (e.g., singlet oxygen)-mediated reactions. Iron-stimulated peroxidation of cholesterol and other lipids underlies a newly discovered form of regulated cell death called ferroptosis. These and other deleterious consequences of radical-mediated lipid peroxidation will be discussed in this review.

Observation of OH radicals produced by pulsed discharges on the surface of a liquid

Science.gov (United States)

Kanazawa, Seiji; Kawano, Hirokazu; Watanabe, Satoshi; Furuki, Takashi; Akamine, Shuichi; Ichiki, Ryuta; Ohkubo, Toshikazu; Kocik, Marek; Mizeraczyk, Jerzy

2011-06-01

The hydroxyl radical (OH) plays an important role in plasma chemistry at atmospheric pressure. OH radicals have a higher oxidation potential compared with other oxidative species such as free radical O, atomic oxygen, hydroperoxyl radical (HO2), hydrogen peroxide(H2O2) and ozone. In this study, surface discharges on liquids (water and its solutions) were investigated experimentally. A pulsed streamer discharge was generated on the liquid surface using a point-to-plane electrode geometry. The primary generation process of OH radicals is closely related to the streamer propagation, and the subsequent secondary process after the discharge has an influence on the chemical reaction. Taking into account the timescale of these processes, we investigated the behavior of OH radicals using two different diagnostic methods. Time evolution of the ground-state OH radicals above the liquid surface after the discharge was observed by a laser-induced fluorescence (LIF) technique. In order to observe the ground-state OH, an OH [A 2∑+(v' = 1) <-- X 2Π(v'' = 0)] system at 282 nm was used. As the secondary process, a portion of OH radicals diffused from gas phase to the liquid surface and dissolved in the liquid. These dissolved OH radicals were measured by a chemical probe method. Terephthalic acid was used as an OH radical trap and fluorescence of the resulting 2-hydroxyterephthalic acid was measured. This paper directly presents visualization of OH radicals over the liquid surface by means of LIF, and indirectly describes OH radicals dissolved in water by means of a chemical method.

Radical Addition to Iminium Ions and Cationic Heterocycles

Directory of Open Access Journals (Sweden)

Johannes Tauber

2014-10-01

Full Text Available Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta reaction, and the Knabe rearrangement will be discussed along with transition metal and photoredox catalysis or electrochemical methods to generate the odd-electron species.

Electrochemical study of the increased antioxidant capacity of flavonoids through complexation with iron(II) ions

International Nuclear Information System (INIS)

Porfírio, Demóstenes Amorim; Ferreira, Rafael de Queiroz; Malagutti, Andréa Renata; Valle, Eliana Maíra Agostini

2014-01-01

Highlights: • Metal-Flavonoid complexes exhibit greater antioxidant capacity than the free flavonoid;. • Voltammetric profile is an additional information for determining antioxidant capacity;. • Pyrogallol group is a stronger complex-forming group than the catechol;. • Morin, quercetin and fisetin increased their antioxidant capacity in 15%, 32% and 28%, respectively. - Abstract: Flavonoids are polyphenolic compounds that act as natural antioxidants in the human body through various mechanisms, with an emphasis on suppressing reactive oxygen species (ROS) formation by inhibiting enzymes, the direct capture of ROS, and the regulation/protection of antioxidant defenses. Additionally, flavonoids can coordinate with transition metals to catalyze electron transport and promote free radical capture. Recently, metal ion chelation mechanisms have generated considerable interest, as experimental data show that flavonoids in metal complexes exhibit greater antioxidant activity than free flavonoids. However, few studies have correlated the complexing properties of flavonoids with their antioxidant capacity. Thus, the aim of this study was to use the CRAC (Ceric Reducing Antioxidant Capacity) electrochemical assay to measure the antioxidant capacity of five free flavonoids and Fe 2+ -flavonoid complexes. In addition, the interactions between the flavonoids and Fe 2+ were analyzed based on the oxidation peaks formed in their cyclic voltammograms

Free radical scavenging capacity and antioxidant activity of methanolic and ethanolic extracts of plum (Prunus domestica L. in both fresh and dried samples

Directory of Open Access Journals (Sweden)

Amin Morabbi Najafabad

2014-09-01

Full Text Available Objectives: Consumption of fruits, such as plums and prunes, is useful in treating blood circulation disorder, measles, digestive disorder, and prevention of cancer, diabetes, and obesity. The paper presents a description of antioxidant and antiradical capacity of plum (Prunus domestica L. in both fresh and dried samples. Materials and Methods: Samples were mixed with methanol and ethanol (as solvents and were extracted on magnetic shaker, separately. The experiments were carried out to measure the Total Phenolic Content (TPC, Total Flavonoid Content (TFC, Total Antioxidant Capacity (TAC, Reducing Power Assay (RPA, Chain Breaking Activity (CBA, and quantity of Malondialdehyde (MDA, 2,2-Diphenyl-1-Picrylhydrazyl (DPPH,Nitric Oxide (NO,Hydrogen peroxide (H2O2 and superoxide(O2- radicals inhibition. Results: The results showed that the highest values for the TPC, TFC,TAC, RPA, CBA, DPPH, and NO were related to ethanolic extractsof dried sample which showed statistically significant differences (p2O2 and O2-were related to ethanolic extracts of fresh sample. The correlations data were analyzed among all parameters and the TPC and TFC had a significant correlation (r2=0.977. Moreover, it was found that methanol was more successful in extraction procedure than ethanol (p

Hydroxyl-radical-induced oxidation of cyclic dipeptides: Reactions of free peptide radicals and their peroxyl radicals

International Nuclear Information System (INIS)

Mieden, O.J.

1989-01-01

In the course of this study investigations were carried out into the reactions of hydroxyl radicals and hydrogen atoms with cyclic dipeptides as well as the subsequent reactions of peptide radicals and their peroxyl radicals in aqueous solution. The radiolysis products formed in the absence and presence of oxygen or transient metal complexes were characterized and determined on a quantitative basis. The linking of information from product analyses to the kinetic data for transient species obtained by time-resolving UV/VIS and conductivity measurements (pulse radiolysis) as well as computer-assisted simulations of individual events during the reaction permitted an evaluation of the mechanisms underlying the various processes and an identification of interim products with short life-times, which did or did not belong to the group of radicals. Through the characterization of key reactions of radicals and peroxyl radicals of this substance class a major advance has been made towards a better understanding of the role of radicals in the peptide compound and the mechanisms involved in indirect radiation effects on long-chain peptides and proteins. (orig.) [de

Free-Radical-Scavenging, Antityrosinase, and Cellular Melanogenesis Inhibitory Activities of Synthetic Isoflavones.

Science.gov (United States)

Lu, Tzy-Ming; Ko, Horng-Huey; Ng, Lean-Teik; Hsieh, Yen-Pin

2015-06-01

In this study, we examined the potential of synthetic isoflavones for application in cosmeceuticals. Twenty-five isoflavones were synthesized and their capacities of free-radical-scavenging and mushroom tyrosinase inhibition, as well as their impact on cell viability of B16F10 murine melanoma cells and HaCaT human keratinocytes were evaluated. Isoflavones that showed significant mushroom tyrosinase inhibitory activities were further studied on reduction of cellular melanin formation and antityrosinase activities in B16F10 melanocytes in vitro. Among the isoflavones tested, 6-hydroxydaidzein (2) was the strongest scavenger of both ABTS(.+) and DPPH(.) radicals with SC50 values of 11.3 ± 0.3 and 9.4 ± 0.1 μM, respectively. Texasin (20) exhibited the most potent inhibition of mushroom tyrosinase (IC50 14.9 ± 4.5 μM), whereas retusin (17) showed the most efficient inhibition both of cellular melanin formation and antityrosinase activity in B16F10 melanocytes, respectively. In summary, both retusin (17) and texasin (20) exhibited potent free-radical-scavenging capacities as well as efficient inhibition of cellular melanogenesis, suggesting that they are valuable hit compounds with potential for advanced cosmeceutical development. Copyright © 2015 Verlag Helvetica Chimica Acta AG, Zürich.

A radical approach to radical innovation

NARCIS (Netherlands)

D. Deichmann (Dirk); J.C.M. van den Ende (Jan)

2014-01-01

textabstractInnovation pays. Amazon, Apple, Facebook, Google – nearly every one of today’s most successful companies has a talent for developing radical new ideas. But how best to encourage radical initiative taking from employees, and does their previous success or failure at it play a role?

Free radical scavenging injectable hydrogels for regenerative therapy.

Science.gov (United States)

Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

2017-02-01

Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Rankine cycle generators using geothermal fluids. Final progress report

Energy Technology Data Exchange (ETDEWEB)

1981-01-01

The Rankine Cycle generator was delivered and installed at Gila Hot Springs. Trial runs were made at that time, using Freon 12 as the expansion fluid. These tests showed that the boiler capacity was inadequate. It could not extract enough heat to generate sufficient volumes of Freon gas at the heat and pressure necessary to operate the system at an acceptable level. Increasing and decreasing the flow of hot water had a direct influence on efficiency, but it was not a linear relationship. Added amounts of hot water increased the power very little, but raised the water temperature at the discharge point. This implied that the heat exchange capacity of the boiler was saturated. The reverse was found in the condenser system. There was little increase in pressure of the condenser when we switched from static to run mode. Efficiency was maintained even when the cold water flow was reduced as much as 40%. The tests using Freon 12 resulted in the conclusion that the boiler volume needs to be increased and/or the configuration changed to radically increase its efficiency.

Observation of OH radicals produced by pulsed discharges on the surface of a liquid

Energy Technology Data Exchange (ETDEWEB)

Kanazawa, Seiji; Kawano, Hirokazu; Watanabe, Satoshi; Furuki, Takashi; Akamine, Shuichi; Ichiki, Ryuta; Ohkubo, Toshikazu [Department of Electrical and Electronic Engineering, Oita University, 700 Dannoharu, Oita 870-1192 (Japan); Kocik, Marek; Mizeraczyk, Jerzy, E-mail: skana@cc.oita-u.ac.jp [Szewalski Institute of Fluid Flow Machinery, Polish Academy of Sciences Fiszera 14, 80-952, Gdansk (Poland)

2011-06-15

The hydroxyl radical (OH) plays an important role in plasma chemistry at atmospheric pressure. OH radicals have a higher oxidation potential compared with other oxidative species such as free radical O, atomic oxygen, hydroperoxyl radical (HO{sub 2}), hydrogen peroxide(H{sub 2}O{sub 2}) and ozone. In this study, surface discharges on liquids (water and its solutions) were investigated experimentally. A pulsed streamer discharge was generated on the liquid surface using a point-to-plane electrode geometry. The primary generation process of OH radicals is closely related to the streamer propagation, and the subsequent secondary process after the discharge has an influence on the chemical reaction. Taking into account the timescale of these processes, we investigated the behavior of OH radicals using two different diagnostic methods. Time evolution of the ground-state OH radicals above the liquid surface after the discharge was observed by a laser-induced fluorescence (LIF) technique. In order to observe the ground-state OH, an OH [A {sup 2}{Sigma}{sup +}(v' = 1) <- X {sup 2}{Pi}(v'' = 0)] system at 282 nm was used. As the secondary process, a portion of OH radicals diffused from gas phase to the liquid surface and dissolved in the liquid. These dissolved OH radicals were measured by a chemical probe method. Terephthalic acid was used as an OH radical trap and fluorescence of the resulting 2-hydroxyterephthalic acid was measured. This paper directly presents visualization of OH radicals over the liquid surface by means of LIF, and indirectly describes OH radicals dissolved in water by means of a chemical method.

Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

Directory of Open Access Journals (Sweden)

Bahir ahmad

2015-08-01

Full Text Available ABSTRACT It is pertinent to mention that radicalism is not intrinsic to Islam and radical interpretations of the religion or for that matter may occur within any way of life and religion Saikal 2003 and yet the question remains as to why Muslims in certain geographical regions have more radical approaches towards their religion and also that what are the causes of such radicalization. Becoming a radical Muslim is not even a matter of a day nor is it a sudden process. There are several reasons behind making a person radical peaceful angry smiling or tolerant. For knowing the reason behind radicalization or radicals persons one has to understand the causes. Tracing these causes is one of the ways to eliminate such behavior. The first step in the elimination of the radical sentiments in a person is to develop peace in his personality Fair Malhotra amp Shapiro 2010. The chapter which has been addressed here is going to shed light on the roots and symptoms of the radicalism. There will be a brief discussion on how the roots of radicalism can be traced and can be eliminated. The assessment and discussion will be conducted on the parameters of the economy media politics and theology from social cultural point of view. According to the analysis of Ahrari 2000 political factor is one of the major and direct factors which have resulted in causing of the radicalism. These factors however intertwine with one another. Radical actions cannot take place only because of the political factors.

Neutrophil superoxide-anion generating capacity in chronic smoking: effect of long-term alpha-tocopherol therapy

NARCIS (Netherlands)

Tits, van L.; Waart, de F.; Hak-Lemmers, H.L.M.; Graaf, de J.; Demacker, P.N.; Stalenhoef, A.F.

2003-01-01

We investigated whether long-term alpha-tocopherol therapy in chronic smoking affects superoxide generating capacity of neutrophils ex vivo. To this purpose, we randomly assigned 128 male chronic smokers (37 21 pack years of smoking) to treatment with placebo (n = 64) or alpha-tocopherol (400 IU

Nitroxide radicals formed in situ as polymer chain growth regulators

International Nuclear Information System (INIS)

Kolyakina, Elena V; Grishin, Dmitry F

2009-01-01

Published data on controlled synthesis of macromolecules using nitroxide radicals, formed in situ during polymerization, as polymer chain growth regulators are systematized and generalized. The attention is focused on the mechanism of polymer chain growth control during reversibly inhibited radical homopolymerization and the effect of structure of precursors and regulating additives on the polymerization kinetics of monomers of different nature and the molecular-mass characteristics of the polymers thus formed. The key methods for generation of nitroxide radicals directly during polymerization are considered. The prospects for development and practical use of these approaches for the synthesis of new polymeric materials are evaluated.

Antiradical capacity and reducing power of different extraction ...

African Journals Online (AJOL)

Areca catechu is a common traditional Chinese medicinal plant used to treat dyspepsia, constipation, beriberi and oedema. The antiradical capacities of different extraction method of A. catechu extracts were evaluated by scavenging activity on 1,1-diphenyl-2-picrylhydrazyl (DPPH) and superoxide radicals. Reducing power ...

Antioxidant Capacity and Metal Content of Physalis Peruviana L. Fruit Sold in Markets

Directory of Open Access Journals (Sweden)

Ayse Eken

2014-12-01

Full Text Available Aim: The dietary intake of medicinal food with antioxidant activity and required amounts of trace elements is important to pursue good healthy life. In our study, we aimed to determine the antioxidant capacity and metal content of goldenberry (Physalis peruviana L. fruit sold in markets in Kayseri. Material and Method: The antioxidant capacity of P. peruviana fruit was determined by the 2,2-diphenyl-1-picrylhydrazyl (DPPH free radical scavenging assay. The DPPH radical scavenger capacity of the methanol extract of fruit was compared with known antioxidants such as ascorbic acid, gallic acid, and butylated hydroxytoluene (BHT as references. The metal content of P. peruviana fruit was measured by using atomic absorption spectrometer (AAS. Results: The fruit of P. peruviana was found to possess DPPH free radical scavenging activity but the antioxidant capacity was lower than the standard substances. Inhibitory concentration 50% (IC50 values of P. peruviana, ascorbic acid, gallic acid, and BHT were determined as 32 mg/ml, 3.8 mg/ml, 3.51 mg/ml, and 1.21 mg/ml, respectively. As a result of the analysis by AAS, it was observed that P. peruviana fruit contented plentiful trace elements and the content of heavy metal was small amount or not detected. Discussion: These observations suggest that the fruit of P. peruviana has a potential source of antioxidant and trace elements of natural origin.

Influence of Free Radicals on the Intrinsic MRI Relaxation Properties.

Science.gov (United States)

Tain, Rong-Wen; Scotti, Alessandro M; Li, Weiguo; Zhou, Xiaohong Joe; Cai, Kejia

2017-01-01

Free radicals are critical contributors in various conditions including normal aging, Alzheimer's disease, cancer, and diabetes. Currently there is no non-invasive approach to image tissue free radicals based on endogenous contrast due to their extremely short lifetimes and low in vivo concentrations. In this study we aim at characterizing the influence of free radicals on the MRI relaxation properties. Phantoms containing free radicals were created by treating egg white with various H 2 O 2 concentrations and scanned on a 9.4 T MRI scanner at room temperature. T 1 and T 2 relaxation maps were generated from data acquired with an inversion recovery sequence with varied inversion times and a multi-echo spin echo sequence with varied echo times (TEs), respectively. Results demonstrated that free radicals express a strong shortening effect on T 1 , which was proportional to the H 2 O 2 concentration, and a relatively small reduction in T 2 (free radicals was estimated to be in the pM range that is within the physiological range of in vivo free radical expression. In conclusion, the free radicals show a strong paramagnetic effect that may be utilized as an endogenous MRI contrast for its non-invasive in vivo imaging.

Investigation the foam dynamics capacity of SDS in foam generator by affecting the presence of organic and inorganic contaminant

Science.gov (United States)

Haryanto, Bode; Siswarni, M. Z.; Sianipar, Yosef C. H.; Sinaga, Tongam M. A.; Bestari, Imam

2017-05-01

The effect of negative charge SDS monomer on its foam capacity with the presence of contaminants was investigated in foam generator. Generally, surfactant with higher concentration has higher foam capacity. The higher concentration will increase the number of monomer then increase the micelles in liquid phase. Increasing the number of monomer with the negative charge is a potential to increase interaction with metal ion with positive charge in solution. The presence of inorganic compound as metal ion with positive charge and organic compound (colloid) as particle of coffee impacting to generate the foam lamella with monomer is evaluated. Foam dynamic capacity of only SDS with variation of CMC, 1 x; 2 x; 3 x have the height 7.5, 8.0 and 8.3 cm respectively with the different range time were investigated. The Height of foam dynamic capacity with the presence of 20 ppm Cd2+ ion contaminant was 8.0, 8.3 and 8.4 cm at the same CMC variation of SDS. The presence of metal ion contaminant within the foam was confirmed by AAS. The black coffee particles and oil as contaminant decreased the foam capacity significantly in comparing to metal ions.

Free radical scavenging injectable hydrogels for regenerative therapy

Energy Technology Data Exchange (ETDEWEB)

Komeri, Remya [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India); Thankam, Finosh Gnanaprakasam [Dept. of Biomedical Sciences, Creighton University, 2500 California Plaza, Omaha NE68178 (United States); Muthu, Jayabalan, E-mail: mjayabalan52@gmail.com [Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Science Division, BMT Wing, Thiruvananthapuram 695 012, Kerala State (India)

2017-02-01

Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

Free radical scavenging injectable hydrogels for regenerative therapy

International Nuclear Information System (INIS)

Komeri, Remya; Thankam, Finosh Gnanaprakasam; Muthu, Jayabalan

2017-01-01

Pathological free radicals generated from inflamed and infarcted cardiac tissues interferes natural tissue repair mechanisms. Hypoxic microenvironment at the injured zone of non-regenerating cardiac tissues hinders the therapeutic attempts including cell therapy. Here we report an injectable, cytocompatible, free radical scavenging synthetic hydrogel formulation for regenerative therapy. New hydrogel (PEAX-P) is prepared with D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer (PEAX) and PEGDiacrylate. PEAX-P hydrogel swells 4.9 times the initial weight and retains 100.07 kPa Young modulus at equilibrium swelling, which is suitable for cardiac applications. PEAX-P hydrogel retains elastic nature even at 60% compressive strain, which is favorable to fit with the dynamic and elastic natural tissue counterparts. PEAX-P hydrogel scavenges 51% DPPH radical, 40% hydroxyl radicals 41% nitrate radicals with 31% reducing power. The presence of hydrogel protects 62% cardiomyoblast cells treated with stress inducing media at LD 50 concentration. The free hydroxyl groups in sugar alcohols of the comacromer influence the free radical scavenging. Comparatively, PEAX-P hydrogel based on xylitol evinces slightly lower scavenging characteristics than with previously reported PEAM-P hydrogel containing mannitol having more hydroxyl groups. The possible free radical scavenging mechanism of the present hydrogel relies on the free π electrons associated with uncrosslinked fumarate bonds, hydrogen atoms associated with sugar alcohols/PEG and radical dilution by free water in the matrix. Briefly, the present PEAX-P hydrogel is a potential injectable system for combined antioxidant and regenerative therapy. - Graphical abstract: Injectable hydrogel with inherent free radical scavenging property for regenerative tissue engineering application. - Highlights: • Novel injectable hydrogel (PEAX-P) is prepared using D-xylitol-co-fumarate-co-poly ethylene adipate-co-PEG comaromer

OH radicals distribution in an Ar-H{sub 2}O atmospheric plasma jet

Energy Technology Data Exchange (ETDEWEB)

Li, L.; Leys, C. [Department of Applied Physics, Research Unit Plasma Technology, Ghent University, Sint-Pietersnieuwstraat 41, Ghent B-9000 (Belgium); Nikiforov, A. [Department of Applied Physics, Research Unit Plasma Technology, Ghent University, Sint-Pietersnieuwstraat 41, Ghent B-9000 (Belgium); Institute of Solution Chemistry of the Russian Academy of Sciences, Academicheskaya St., 1, Ivanono, 153045 (Russian Federation); Xiong, Q. [Department of Applied Physics, Research Unit Plasma Technology, Ghent University, Sint-Pietersnieuwstraat 41, Ghent B-9000 (Belgium); College of Electrical and Electronic Engineering, HuaZhong University of Science and Technology, WuHan, Hubei 430074 (China); Britun, N. [Chimie des Interactions Plasma-Surface (ChIPS), CIRMAP, Universite de Mons, 20 Place du Parc, B-7000 Mons (Belgium); Snyders, R. [Chimie des Interactions Plasma-Surface (ChIPS), CIRMAP, Universite de Mons, 20 Place du Parc, B-7000 Mons (Belgium); Materia Nova Research Centre, Parc Initialis, B-7000 Mons (Belgium); Lu, X. [College of Electrical and Electronic Engineering, HuaZhong University of Science and Technology, WuHan, Hubei 430074 (China)

2013-09-15

Recently, plasma jet systems found numerous applications in the field of biomedicine and treatment of temperature-sensitive materials. OH radicals are one of the main active species produced by these plasmas. Present study deals with the investigation of RF atmospheric pressure plasma jet in terms of OH radicals production by admixture of H{sub 2}O into argon used as a feed gas. Generation of OH radicals is studied by laser-induced fluorescence spectroscopy. The excitation dynamics of OH radicals induced by the laser photons is studied by time-resolved spectroscopy. It is shown that vibrational and rotational energy transfer processes, which are sensitive to the surrounding species, can lead to the complication in the OH radicals diagnostics at high pressure and have to be considered during experiments. The axial and radial 2D maps of absolute densities of hydroxyl radicals at different water contents are obtained. The highest density of 1.15 × 10{sup 20} m{sup −3} is measured in the plasma core for the case of 0.3% H{sub 2}O. In the x–y-plane, the OH density steeply decreases within a range of ±2 mm from its maximum value down to 10{sup 18} m{sup −3}. The effect of H{sub 2}O addition on the generation of OH radicals is investigated and discussed.

Effect of metal complexation to anti-inflammatory over the action against oxidative and free radicals: ketoprofen action

International Nuclear Information System (INIS)

Manente, Francine Alessandra; Mello, Lucas Rosolen de Almeida; Vellosa, Jose Carlos Rebuglio; Khalil, Omar Arafat Kdudsi; Carvalho, Claudio Teodoro de; Bannach, Gilbert

2011-01-01

Free radicals are highly reactive species generated in living organisms for the purpose of protection. However, in some circumstances, they are responsible for the occurrence or aggravation of tissue damage. Many anti-inflammatory drugs have a direct effect on free radicals and not radical reactive species, which contributes to its actions against inflammation. Ketoprofen is a nonsteroidal anti-inflammatory agent that generates free radicals by photo irradiation and has an important hemolytic effect with that. The complexation of metals to different drugs has been used as a strategy to improve the pharmacological action of different molecules and reduce their side effects. This paper presents the results of ketoprofen and their metallic complexes action on erythrocytes and free radicals. It was observed that the cerium enhances the scavenger properties of ketoprofen on free radicals, while copper enhances its action over non-radical oxidants. Copper also reduced the hemolytic effect presented by ketoprofen meanwhile its cerium derivative maintained it. (author)

Total Phenolic, Flavonoids and Antioxidant Capacity of Some Medicinal and Aromatic Plants

Directory of Open Access Journals (Sweden)

Melinda Nagy

2014-11-01

Full Text Available Abstract: Antioxidants are substances that protect cells from the induced oxidative stress damage caused by unstable molecules known as free radicals that. Antioxidants neutralize free radicals as a natural by-product of normal cell processes. In the present study,were evaluated  the phenolic and flavonoids contents as well as the antioxidant capacity of seeds from  the Lamiaceae and Apiaceae family: fennel  (Foeniculum vulgare, dill (Anethum graveolens and rosemary (Rosmarinus officinalis . (Sreemoyee Ch. et. al., 2012 The main objective of the study was the comparative assessment of the phenolic and flavonoid compounds from dill, rosemary and fennel methanolic extracts correlated with their  antioxidant activity. Both total phenolic content and flavonoids content of the seeds samples were measured spectrophotometrically using the Folin-Ciocalteu assay and a chromogenic system of NaNO2–Al(NO33–NaOH, respectively.. Antioxidant capacity was determined by 2,2-DPPH method. Results strongly showed that Rosmarinus officinalis extract has the most effective antioxidant capacity in scavenging DPPH radicals, while Foeniculum vulgare and Anethum graveolens were less active. The total phenolic content was within 773,14 and 3367,24mg GAE/ 100g while the concentration in flavonoids was between 231,84 and 1325,53 QEg/100g dry seeds.  

Resonance Raman and quantum chemical studies of short polyene radical cations

DEFF Research Database (Denmark)

Keszthelyi, T.; Wilbrandt, R.; Bally, T.

1997-01-01

,3,5-hexatriene have been studied. The radical cations were generated radiolytically in a glassy Freon matrix and investigated by optical absorption and resonance Raman spectroscopy. Ab initio and density functional molecular-orbital calculations have been carried out to predict equilibrium structures...... and to assist assignment of the resonance Raman spectra. A new and improved scaled quantum mechanical force field for the butadiene radical cation was also determined. The presence of more than one rotamer was observed in all the polyene radical cations we investigated. (C) 1997 Elsevier Science B.V....

Variable capacity utilization, ambient temperature shocks and generation asset valuation

Energy Technology Data Exchange (ETDEWEB)

Tseng, Chung-Li; Dmitriev, Alexandre [Australian School of Business, University of New South Wales, Sydney NSW 2052 (Australia); Zhu, Wei [Optim Energy, 225 E. John Carpenter Freeway, Irving, TX 75062 (United States)

2009-11-15

This paper discusses generation asset valuation in a framework where capital utilization decisions are endogenous. We use real options approach for valuation of natural gas fueled turbines. Capital utilization choices that we explore include turning on/off the unit, operating the unit at increased firing temperatures (overfiring), and conducting preventive maintenance. Overfiring provides capacity enhancement which comes at the expense of reduced maintenance interval and increased costs of part replacement. We consider the costs and benefits of overfiring in attempt to maximize the asset value by optimally exercising the overfire option. In addition to stochastic processes governing prices, we incorporate an exogenous productivity shock: ambient temperature. We consider how variation in ambient temperature affects the asset value through its effect on gas turbine's productivity. (author)

A new face of phenalenyl-based radicals in the transition metal-free C-H arylation of heteroarenes at room temperature: trapping the radical initiator via C-C σ-bond formation.

Science.gov (United States)

Ahmed, Jasimuddin; P, Sreejyothi; Vijaykumar, Gonela; Jose, Anex; Raj, Manthan; Mandal, Swadhin K

2017-11-01

The radical-mediated transition metal-free approach for the direct C-H bond functionalization of arenes is considered as a cost effective alternative to transition metal-based catalysis. An organic ligand-based radical plays a key role by generating an aryl radical which undergoes a subsequent functionalization process. The design principle of the present study takes advantage of a relatively stable odd alternant hydrocarbon-based phenalenyl (PLY) radical. In this study, the first transition metal-free catalyzed direct C-H arylation of a variety of heteroarenes such as azoles, furan, thiophene and pyridine at room temperature has been reported using a phenalenyl-based radical without employing any photoactivation step. This protocol has been successfully applied to the gram scale synthesis of core moieties of bioactive molecules. The phenalenyl-based radical initiator has been characterized crystallographically by trapping it via the formation of a C-C σ-bond between the phenalenyl radical and solvent-based radical species.

Central diffraction in proton-proton collisions at {radical}(s) = 7TeV with ALICE at LHC

Energy Technology Data Exchange (ETDEWEB)

Reidt, Felix [Physikalisches Institut, Im Neuenheimer Feld 226, 69120 Heidelberg (Germany); Collaboration: ALICE Collaboration

2013-04-15

A double-gap topology is used for filtering central-diffractive events from a protonproton minimum-bias data sample at a centre-of-mass energy Central diffraction in proton-proton collisions at {radical}(s) = 7TeV. This topology is defined by particle activity in the ALICE central barrel and absence of particle activity outside. The fraction of events satisfying the double-gap requirement R{sub DG} is found to be 7.63{+-}0.02(st at.){+-}0.87(syst.) Multiplication-Sign 10{sup -4}. The background of this double-gap fraction is estimated by studying the contributions of non-diffractive, single-and double-diffractive dissociation processes as modelled by Monte Carlo event generators, and is found to be about 10%.

Reductive Umpolung of Carbonyl Derivatives with Visible-Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α-Amino Radicals and Ketyl Radicals

KAUST Repository

Fava, Eleonora; Millet, Anthony; Nakajima, Masaki; Loescher, Sebastian; Rueping, Magnus

2016-01-01

Visible-light-mediated photoredox-catalyzed aldimine-aniline and aldehyde-aniline couplings have been realized. The reductive single electron transfer (SET) umpolung of various carbonyl derivatives enabled the generation of intermediary ketyl and α-amino radical anions, which were utilized for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols. Anilines can be coupled with aldimines or aldehydes in a visible-light-mediated photoredox-catalyzed process. Reductive single electron transfer (SET) umpolung of the carbonyl derivatives leads to the generation of intermediary ketyl and α-amino radical anions, which were used for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols.

Reductive Umpolung of Carbonyl Derivatives with Visible-Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α-Amino Radicals and Ketyl Radicals

KAUST Repository

Fava, Eleonora

2016-05-02

Visible-light-mediated photoredox-catalyzed aldimine-aniline and aldehyde-aniline couplings have been realized. The reductive single electron transfer (SET) umpolung of various carbonyl derivatives enabled the generation of intermediary ketyl and α-amino radical anions, which were utilized for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols. Anilines can be coupled with aldimines or aldehydes in a visible-light-mediated photoredox-catalyzed process. Reductive single electron transfer (SET) umpolung of the carbonyl derivatives leads to the generation of intermediary ketyl and α-amino radical anions, which were used for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols.

Influence of Laccase and Tyrosinase on the Antioxidant Capacity of Selected Phenolic Compounds on Human Cell Lines

Directory of Open Access Journals (Sweden)

Matthias Riebel

2015-09-01

Full Text Available Polyphenolic compounds affect the color, odor and taste of numerous food products of plant origin. In addition to the visual and gustatory properties, they serve as radical scavengers and have antioxidant effects. Polyphenols, especially resveratrol in red wine, have gained increasing scientific and public interest due to their presumptive beneficial impact on human health. Enzymatic oxidation of phenolic compounds takes place under the influence of polyphenol oxidases (PPO, including tyrosinase and laccase. Several studies have demonstrated the radical scavenger effect of plants, food products and individual polyphenols in vitro, but, apart from resveratrol, such impact has not been proved in physiological test systems. Furthermore, only a few data exist on the antioxidant capacities of the enzymatic oxidation products of phenolic compounds generated by PPO. We report here first results about the antioxidant effects of phenolic substances, before and after oxidation by fungal model tyrosinase and laccase. In general, the common chemical 2,2-diphenyl-1-picrylhydrazyl assay and the biological tests using two different types of cell cultures (monocytes and endothelial cells delivered similar results. The phenols tested showed significant differences with respect to their antioxidant activity in all test systems. Their antioxidant capacities after enzymatic conversion decreased or increased depending on the individual PPO used.

Role of catechins in the antioxidant capacity of an active film containing green tea, green coffee, and grapefruit extracts.

Science.gov (United States)

Colon, M; Nerin, C

2012-10-03

The oxygen radical absorbance capacity (ORAC) method was used to characterize the antioxidant capacity of natural extracts of green tea, green coffee, and grapefruit. These natural extracts were incorporated into a plastic film layer, which was subsequently subjected to a free radical gas stream in order to determine the antioxidant capacity directly in the active film. The green tea extract (GTE) afforded the strongest antioxidant activity. To identify the active compounds in the extract, concentration of the diverse catechins in samples were determined by HPLC-UV analysis. The results showed that the content of catechins in the GTE is around 77% (w/w), the major components being (-)-epigallocatechin gallate, (-)-epicatechin gallate, and (-)-epicatechin. A variation in the concentration profile of catechins was detected during the oxidation process. The chromatographic study demonstrated that (-)-gallocatechin, (-)- epigallocatechin, (+)-catechin, and (-)-catechin gallate exhibited the most radical scavenging.

Antioxidant capacity and polyphenolic content of blueberry (Vaccinium corymbosum L.) leaf infusions.

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Piljac-Zegarac, J; Belscak, A; Piljac, A

2009-06-01

Antioxidant capacity and polyphenolic content of leaf infusions prepared from six highbush blueberry cultivars (Vaccinium corymbosum L.), one wild lowbush blueberry cultivar (Vaccinium myrtillus L.), and one commercially available mix of genotypes were determined. In order to simulate household tea preparation conditions, infusions were prepared in water heated to 95 degrees C. The dynamics of extraction of polyphenolic antioxidants were monitored over the course of 30 minutes. Extraction efficiency, quantified in terms of the total phenol (TP) content, and antioxidant capacity of infusions, evaluated by the ferric reducing antioxidant power (FRAP) and 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging assays, were compared with cultivar type and extraction time. The 30-minute infusions exhibited the highest TP content and antioxidant capacity according to all three assays. Wild blueberry infusion had the highest TP content (1,879 mg/L gallic acid equivalents [GAE]) and FRAP values (20,050 microM). The range of TP values for 30-minute infusions was 394-1,879 mg/L GAE with a mean of 986 mg/L GAE across cultivars; FRAP values fell between 3,015 and 20,050 microM with a mean of 11,234 microM across cultivars. All 30-minute infusions exhibited significant scavenging capacity for DPPH(*) and ABTS(*+) radicals, comparable to different concentrations of catechin, gallic acid, and 6-hydroxy-2,5,7,8-tetramethylchromane-2-carboxylic acid. Overall, tested infusions showed significant reducing capacity as well as radical scavenging potential, which places blueberry leaf tea high on the list of dietary sources of antioxidants.

A Study on Grid-Square Statistics Based Estimation of Regional Electricity Demand and Regional Potential Capacity of Distributed Generators

Science.gov (United States)

Kato, Takeyoshi; Sugimoto, Hiroyuki; Suzuoki, Yasuo

We established a procedure for estimating regional electricity demand and regional potential capacity of distributed generators (DGs) by using a grid square statistics data set. A photovoltaic power system (PV system) for residential use and a co-generation system (CGS) for both residential and commercial use were taken into account. As an example, the result regarding Aichi prefecture was presented in this paper. The statistical data of the number of households by family-type and the number of employees by business category for about 4000 grid-square with 1km × 1km area was used to estimate the floor space or the electricity demand distribution. The rooftop area available for installing PV systems was also estimated with the grid-square statistics data set. Considering the relation between a capacity of existing CGS and a scale-index of building where CGS is installed, the potential capacity of CGS was estimated for three business categories, i.e. hotel, hospital, store. In some regions, the potential capacity of PV systems was estimated to be about 10,000kW/km2, which corresponds to the density of the existing area with intensive installation of PV systems. Finally, we discussed the ratio of regional potential capacity of DGs to regional maximum electricity demand for deducing the appropriate capacity of DGs in the model of future electricity distribution system.

Free radical inactivation of trypsin

International Nuclear Information System (INIS)

Cudina, Ivana; Jovanovic, S.V.

1988-01-01

Reactivities of free radical oxidants, radical OH, Br2-anion radical and Cl 3 COO radical and a reductant, CO2-anion radical, with trypsin and reactive protein components were determined by pulse radiolysis of aqueous solutions at pH 7, 20 0 C. Highly reactive free radicals, radical OH, Br2-anion radical and CO2-anion radical, react with trypsin at diffusion controlled rates. Moderately reactive trichloroperoxy radical, k(Cl 3 COO radical + trypsin) preferentially oxidizes histidine residues. The efficiency of inactivation of trypsin by free radicals is inversely proportional to their reactivity. The yields of inactivation of trypsin by radical OH, Br2-anion radical and CO2-anion radical are low, G(inactivation) = 0.6-0.8, which corresponds to ∼ 10% of the initially produced radicals. In contrast, Cl 3 COO radical inactivates trypsin with ∼ 50% efficiency, i.e. G(inactivation) = 3.2. (author)

The mitochondrial free radical theory of aging.

Science.gov (United States)

Barja, Gustavo

2014-01-01

The mitochondrial free radical theory of aging is reviewed. Only two parameters currently correlate with species longevity in the right sense: the mitochondrial rate of reactive oxygen species (mitROS) production and the degree of fatty acid unsaturation of tissue membranes. Both are low in long-lived animals. In addition, the best-known manipulation that extends longevity, dietary restriction, also decreases the rate of mitROS production and oxidative damage to mtDNA. The same occurs during protein restriction as well as during methionine restriction. These two manipulations also increase maximum longevity in rodents. The decrease in mitROS generation and oxidative stress that takes place in caloric restriction seems to be due to restriction of a single dietary substance: methionine. The information available supports a mitochondrial free radical theory of aging focused on low generation of endogenous damage and low sensitivity of membranes to oxidation in long-lived animals. © 2014 Elsevier Inc. All rights reserved.

A Derivative Method with Free Radical Oxidation to Predict Resveratrol Metabolites by Tandem Mass Spectrometry.

Science.gov (United States)

Liu, Wangta; Shiue, Yow-Ling; Lin, Yi-Reng; Lin, Hugo You-Hsien; Liang, Shih-Shin

2015-10-01

In this study, we demonstrated an oxidative method with free radical to generate 3,5,4'-trihydroxy- trans -stilbene ( trans -resveratrol) metabolites and detect sequentially by an autosampler coupling with liquid chromatography electrospray ionization tandem mass spectrometer (LC-ESI-MS/MS). In this oxidative method, the free radical initiator, ammonium persulfate (APS), was placed in a sample bottle containing resveratrol to produce oxidative derivatives, and the reaction progress was tracked by autosampler sequencing. Resveratrol, a natural product with purported cancer preventative qualities, produces metabolites including dihydroresveratrol, 3,4'-dihydroxy- trans -stilbene, lunularin, resveratrol monosulfate, and dihydroresveratrol monosulfate by free radical oxidation. Using APS free radical, the concentrations of resveratrol derivatives differ as a function of time. Besides simple, convenient and time- and labor saving, the advantages of free radical oxidative method of its in situ generation of oxidative derivatives followed by LC-ESI-MS/MS can be utilized to evaluate different metabolites in various conditions.

In vitro antioxidant and free radical scavenging activity of different parts of Tabebuia pallida growing in Bangladesh.

Science.gov (United States)

Rahman, Md Mahbubur; Islam, Md Badrul; Biswas, Mohitosh; Khurshid Alam, A H M

2015-10-30

In humans, many diseases are associated with the accumulation of free radicals. Antioxidants can scavenge free radicals and minimize their impact. Therefore, the search for naturally occurring antioxidants of plant origin is imperative. Here, we aimed to investigate the antioxidant and free radical scavenging properties of methanolic extracts from Tabebuia pallida (T. pallida) stem bark (TPSB), root bark (TPRB), leaves (TPL), and flowers (TPF). The antioxidant and free radical scavenging activity were determined by several standard methods using spectrophotomer. Total phenolic and flavonoid contents were estimated using Folin-Ciocalteu reagent and aluminum chloride colorimetric assay methods, respectively. Among the extracts, TPL showed the highest total antioxidant capacity followed by TPRB, TPF, and TPSB. Based on DPPH and hydroxyl radical scavenging activity, TPL showed strong scavenging activity (91.05 ± 1.10 and 62.00 ± 0.57) with IC50 of 9.20 ± 0.28 and 46.00 ± 2.84 μg/mL, respectively when compared with standard BHT (IC50 of 7.00 ± 0.25 μg/mL) and CA (75.00 ± 0.14 μg/mL). These results suggest that TPL had the highest radical scavenging activity among the extractives that closely resembled the standard's. In lipid peroxidation inhibition assay, TPL exhibited the most potent inhibitory activity (83.18 ± 2.12 %) with IC50 of 12.00 ± 2.12 μg/mL, which closely resembled standard CA (IC50 of 10.50 ± 0.28 μg/mL). Also, the reducing capacity on ferrous ion was in the following order: TPL > TPRB > TF > TPSB. The phenolic and flavonoid contents of TPL were higher than other extractives. A positive correlation (p value free radical (DPPH(·) and (·)OH) scavenging efficiencies and lipid peroxidation inhibition activity. Methanolic extract of T. pallida leaf is a potential source of natural antioxidants and serves as an effective free radical scavenger and/or inhibitor. Hence, T. pallida might be a good plant-based pharmaceutical product for several

Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

Energy Technology Data Exchange (ETDEWEB)

Neti, Venkata S. [Chemical; Das, Sadananda [Chemical; Brown, Suree [Department; Janke, Christopher J. [Materials; Kuo, Li-Jung [Marine; Gill, Gary A. [Marine; Dai, Sheng [Chemical; Department; Mayes, Richard T. [Chemical

2017-09-14

Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screening tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).

Radical SAM, A Novel Protein Superfamily Linking Unresolved Steps in Familiar Biosynthetic Pathways with Radical Mechanisms: Functional Characterization Using New Analysis and Information Visualization Methods

Energy Technology Data Exchange (ETDEWEB)

Sofia, Heidi J.; Chen, Guang; Hetzler, Elizabeth G.; Reyes Spindola, Jorge F.; Miller, Nancy E.

2001-03-01

A large protein superfamily with over 500 members has been discovered and analyzed using powerful new bioinformatics and information visualization methods. Evidence exists that these proteins generate a 5?-deoxyadenosyl radical by reductive cleavage of S-adenosylmethionine (SAM) through an unusual Fe-S center. Radical SAM superfamily proteins function in DNA precursor, vitamin, cofactor, antibiotic, and herbicide biosynthesis in a collection of basic and familiar pathways. One of the members is interferon-inducible and is considered a candidate drug target for osteoporosis. The identification of this superfamily suggests that radical-based catalysis is important in a number of previously well-studied but unresolved biochemical pathways.

Atmospheric hydroxyl radical production from electronically excited NO2 and H2O.

Science.gov (United States)

Li, Shuping; Matthews, Jamie; Sinha, Amitabha

2008-03-21

Hydroxyl radicals are often called the "detergent" of the atmosphere because they control the atmosphere's capacity to cleanse itself of pollutants. Here, we show that the reaction of electronically excited nitrogen dioxide with water can be an important source of tropospheric hydroxyl radicals. Using measured rate data, along with available solar flux and atmospheric mixing ratios, we demonstrate that the tropospheric hydroxyl contribution from this source can be a substantial fraction (50%) of that from the traditional O(1D) + H2O reaction in the boundary-layer region for high solar zenith angles. Inclusion of this chemistry is expected to affect modeling of urban air quality, where the interactions of sunlight with emitted NOx species, volatile organic compounds, and hydroxyl radicals are central in determining the rate of ozone formation.

Sulfate radical-based degradation of polychlorinated biphenyls: Effects of chloride ion and reaction kinetics

Energy Technology Data Exchange (ETDEWEB)

Fang, Guo-Dong [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Dionysiou, Dionysios D. [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0071 (United States); Wang, Yu [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Al-Abed, Souhail R. [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States); Zhou, Dong-Mei, E-mail: dmzhou@issas.ac.cn [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China)

2012-08-15

Highlights: Black-Right-Pointing-Pointer A kinetic model was used to predict the radical species and their distributions. Black-Right-Pointing-Pointer The generated radical species were identified by EPR. Black-Right-Pointing-Pointer The second-order rate constants of sulfate radical with PCBs were determined. - Abstract: Advanced oxidation processes (AOPs) based on sulfate radical (SO{sub 4}{center_dot}{sup -}) have been recently used for soil and groundwater remediation. The presence of chloride ion in natural or wastewater decreases the reactivity of sulfate radical system, but explanations for this behavior were inconsistent, and the mechanisms are poorly understood. Therefore, in this paper we investigated the effect of chloride ion on the degradation of 2,4,4 Prime -CB (PCB28) and biphenyl (BP) by persulfate, based on the produced SO{sub 4}{center_dot}{sup -}. The results showed that the presence of chloride ion greatly inhibited the transformation of PCB28 and BP. Transformation intermediates of BP were monitored, suggesting that the chloride ion can react with SO{sub 4}{center_dot}{sup -} to produce chlorine radical, which reacts with BP to generate chlorinated compounds. To better understand the underlying mechanisms of these processes, a kinetic model was developed for predicting the effect of chloride ion on the types of radical species and their distributions. The results showed that chloride ion could influence the selectivity of radical species and their distribution, and increase the concentration of the sum of radical species. In addition, the second-order rate constants of sulfate radical with PCBs were determined, and quantum-chemical descriptors were introduced to predict the rate constants of other PCBs based on our experimental data.

Comparison of fluorescence-based techniques for the quantification of particle-induced hydroxyl radicals

Directory of Open Access Journals (Sweden)

Cohn Corey A

2008-02-01

Full Text Available Abstract Background Reactive oxygen species including hydroxyl radicals can cause oxidative stress and mutations. Inhaled particulate matter can trigger formation of hydroxyl radicals, which have been implicated as one of the causes of particulate-induced lung disease. The extreme reactivity of hydroxyl radicals presents challenges to their detection and quantification. Here, three fluorescein derivatives [aminophenyl fluorescamine (APF, amplex ultrared, and dichlorofluorescein (DCFH] and two radical species, proxyl fluorescamine and tempo-9-ac have been compared for their usefulness to measure hydroxyl radicals generated in two different systems: a solution containing ferrous iron and a suspension of pyrite particles. Results APF, amplex ultrared, and DCFH react similarly to the presence of hydroxyl radicals. Proxyl fluorescamine and tempo-9-ac do not react with hydroxyl radicals directly, which reduces their sensitivity. Since both DCFH and amplex ultrared will react with reactive oxygen species other than hydroxyl radicals and another highly reactive species, peroxynitite, they lack specificity. Conclusion The most useful probe evaluated here for hydroxyl radicals formed from cell-free particle suspensions is APF due to its sensitivity and selectivity.

Regulated production of free radicals by the mitochondrial electron transport chain: Cardiac ischemic preconditioning.

Science.gov (United States)

Matsuzaki, Satoshi; Szweda, Pamela A; Szweda, Luke I; Humphries, Kenneth M

2009-11-30

Excessive production of free radicals by mitochondria is associated with, and likely contributes to, the progression of numerous pathological conditions. Nevertheless, the production of free radicals by the mitochondria may have important biological functions under normal or stressed conditions by activating or modulating redox-sensitive cellular signaling pathways. This raises the intriguing possibility that regulated mitochondrial free radical production occurs via mechanisms that are distinct from pathologies associated with oxidative damage. Indeed, the capacity of mitochondria to produce free radicals in a limited manner may play a role in ischemic preconditioning, the phenomenon whereby short bouts of ischemia protect from subsequent prolonged ischemia and reperfusion. Ischemic preconditioning can thus serve as an important model system for defining regulatory mechanisms that allow for transient, signal-inducing, production of free radicals by mitochondria. Defining how these mechanism(s) occur will provide insight into therapeutic approaches that minimize oxidative damage without altering normal cellular redox biology. The aim of this review is to present and discuss evidence for the regulated production of superoxide by the electron transport chain within the ischemic preconditioning paradigm of redox regulation.

The Radical Pair Mechanism and the Avian Chemical Compass: Quantum Coherence and Entanglement

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yiteng [Purdue Univ., West Lafayette, IN (United States); Kais, Sabre [Purdue Univ., West Lafayette, IN (United States); Berman, Gennady Petrovich [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2015-02-02

We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on 1) the hyperfine interaction involving electron spins and neighboring nuclear spins and 2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin dynamics of the radical pairs; and the magnetic field dependence of product yields caused by the radical pair mechanism. The main part of the review includes a description of the chemical compass in birds. We review: the general properties of the avian compass; the basic scheme of the radical pair mechanism; the reaction kinetics in cryptochrome; quantum coherence and entanglement in the avian compass; and the effects of noise. We believe that the quantum avian compass can play an important role in avian navigation and can also provide the foundation for a new generation of sensitive and selective magnetic-sensing nano-devices.

The Rise of Radicals in Bioinorganic Chemistry.

Science.gov (United States)

Gray, Harry B; Winkler, Jay R

2016-10-01

Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O 2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) and tryptophan (Trp) residues have been found in many O 2 -reactive enzymes, raising the possibility that they play an antioxidant protective role. In blue copper proteins with plastocyanin-like domains, Tyr/Trp clusters are uncommon in the low-potential single-domain electron-transfer proteins and in the two-domain copper nitrite reductases. The two-domain muticopper oxidases, however, exhibit clusters of Tyr and Trp residues near the trinuclear copper active site where O 2 is reduced. These clusters may play a protective role to ensure that reactive oxygen species are not liberated during O 2 reduction.

Adenine radicals generated in alternating AT duplexes by direct absorption of low-energy UV radiation.

Science.gov (United States)

Banyasz, Akos; Ketola, Tiia; Martínez-Fernández, Lara; Improta, Roberto; Markovitsi, Dimitra

2018-04-17

There is increasing evidence that the direct absorption of photons with energies that are lower than the ionization potential of nucleobases may result in oxidative damage to DNA. The present work, which combines nanosecond transient absorption spectroscopy and quantum mechanical calculations, studies this process in alternating adenine-thymine duplexes (AT)n. We show that the one-photon ionization quantum yield of (AT)10 at 266 nm (4.66 eV) is (1.5 ± 0.3) × 10-3. According to our PCM/TD-DFT calculations carried out on model duplexes composed of two base pairs, (AT)1 and (TA)1, simultaneous base pairing and stacking does not induce important changes in the absorption spectra of the adenine radical cation and deprotonated radical. The adenine radicals, thus identified in the time-resolved spectra, disappear with a lifetime of 2.5 ms, giving rise to a reaction product that absorbs at 350 nm. In parallel, the fingerprint of reaction intermediates other than radicals, formed directly from singlet excited states and assigned to AT/TA dimers, is detected at shorter wavelengths. PCM/TD-DFT calculations are carried out to map the pathways leading to such species and to characterize their absorption spectra; we find that, in addition to the path leading to the well-known TA* photoproduct, an AT photo-dimerization path may be operative in duplexes.

Cultured rat and purified human Pneumocystis carinii stimulate intra- but not extracellular free radical production in human neutrophils

DEFF Research Database (Denmark)

Jensen, T; Aliouat, E M; Lundgren, B

1998-01-01

The production of free radicals in human neutrophils was studied in both Pneumocystis carinii derived from cultures of L2 rat lung epithelial-like cells and Pneumocystis carinii purified from human lung. Using the cytochrome C technique, which selectively measured extracellular superoxide...... generation, hardly any free radical production was observed after stimulation with cultured rat-derived P. carinii. A chemiluminescence technique, which separately measured intra- and extracellular free radical production, was subsequently employed to differentiate the free radical generation....... It was established that 1) P. carinii stimulated intra- but not extracellular free radical production in human neutrophils, 2) opsonized cultured rat-derived P. carinii stimulated human neutrophils to a strong intracellular response of superoxide production, and 3) opsonized P. carinii, purified from human lung also...

Superoxide radical formation, superoxide dismutase and glutathione reductase activity in the brain of irradiated rats

International Nuclear Information System (INIS)

Stanimirovic, D.; Ivanovic, L.; Simovic, M.; Cernak, I.; Savic, J.

1989-01-01

In the forebrain cortex, basal ganglia and hippocampus of irradiated rats (whole body, X-ray, 9 Gy), nitroblue-tetrazolium (NBT) reduction was measured as a probe of superoxide radical formation 1 hr, 6 hrs, 24 hrs and 72 hrs after irradiation. Increased superoxide radical formation was found in parallel with increase of superoxide dismutase (SOD) activity and marked decrease of glutathione reductase (GR) activity which is the most pronounced in basal ganglia. The results indicate that in the postradiation period disproportion among free radical production and capacity of brain antioxidative system occurs. This disbalance is more expressed in the brain regions known as selective vulnerable (basal ganglia, hippocampus). (author). 10 refs.; 2 tabs

Reduction of Guanosyl Radical by Cysteine and Cysteine-Glycine Studied by Time-Resolved CIDNP

NARCIS (Netherlands)

Morozova, O.B.; Kaptein, R.; Yurkovskaya, A.V.

2012-01-01

As a model for chemical DNA repair, reduction of guanosyl radicals in the reaction with cysteine or the dipeptide cysteine-glycine has been studied by time-resolved chemically induced dynamic nuclear polarization (CIDNP). Radicals were generated photochemically by pulsed laser irradiation of a

Mechanism of pyrogallol red oxidation induced by free radicals and reactive oxidant species. A kinetic and spectroelectrochemistry study.

Science.gov (United States)

Atala, E; Velásquez, G; Vergara, C; Mardones, C; Reyes, J; Tapia, R A; Quina, F; Mendes, M A; Speisky, H; Lissi, E; Ureta-Zañartu, M S; Aspée, A; López-Alarcón, C

2013-05-02

Pyrogallol red (PGR) presents high reactivity toward reactive (radical and nonradical) species (RS). This property of PGR, together with its characteristic spectroscopic absorption in the visible region, has allowed developing methodologies aimed at evaluating the antioxidant capacity of foods, beverages, and human fluids. These methods are based on the evaluation of the consumption of PGR induced by RS and its inhibition by antioxidants. However, at present, there are no reports regarding the degradation mechanism of PGR, limiting the extrapolation to how antioxidants behave in different systems comprising different RS. In the present study, we evaluate the kinetics of PGR consumption promoted by different RS (peroxyl radicals, peroxynitrite, nitrogen dioxide, and hypochlorite) using spectroscopic techniques and detection of product by HPLC mass spectrometry. The same pattern of oxidation and spectroscopic properties of the products is observed, independently of the RS employed. Mass analysis indicates the formation of only one product identified as a quinone derivative, excluding the formation of peroxides or hydroperoxides and/or chlorinated compounds, in agreement with FOX's assays and oxygen consumption experiments. Cyclic voltammetry, carried out at different pH's, shows an irreversible oxidation of PGR, indicating the initial formation of a phenoxy radical and a second charge transfer reaction generating an ortho-quinone derivative. Spectroelectrochemical oxidation of PGR shows oxidation products with identical UV-visible absorption properties to those observed in RS-induced oxidation.

Free radicals and antioxidants in primary fibromyalgia: an oxidative stress disorder?

Science.gov (United States)

Bagis, Selda; Tamer, Lulufer; Sahin, Gunsah; Bilgin, Ramazan; Guler, Hayal; Ercan, Bahadir; Erdogan, Canan

2005-04-01

The role of free radicals in fibromyalgia is controversial. In this study, 85 female patients with primary fibromyalgia and 80 age-, height-, and weight-matched healthy women were evaluated for oxidant/antioxidant balance. Malondialdehyde is a toxic metabolite of lipid peroxidation used as a marker of free radical damage. Superoxide dismutase is an intracellular antioxidant enzyme and shows antioxidant capacity. Pain was assessed by visual analog scale. Tender points were assessed by palpation. Age, smoking, body mass index (BMI), and duration of disease were also recorded. Malondialdehyde levels were significantly higher and superoxide dismutase levels significantly lower in fibromyalgic patients than controls. Age, BMI, smoking, and duration of disease did not affect these parameters. We found no correlation between pain and number of tender points. In conclusion, oxidant/antioxidant balances were changed in fibromyalgia. Increased free radical levels may be responsible for the development of fibromyalgia. These findings may support the hypothesis of fibromyalgia as an oxidative disorder.

Laboratorio di Comunicazione Militante, Isola Art Centre, and MACAO: enhancing autonomous social organisation through artistic means and rethinking the radical imaginary and the radical imagination in curatorial practice.

Directory of Open Access Journals (Sweden)

Aria Spinelli

2017-10-01

Full Text Available This article analyses the relation between curatorial practice and political theory, through a recuperation and proposal of the philosophical work of Greek-French philosopher Cornelius Castoriadis. In it, I will isolated the terms the radical imaginary and the radical imagination, and argue that their relation to curatorial practice is exemplified in the politics of cultural spaces that use autonomous social organisation as their means for artistic production. In his writings, specifically in his manuscript The Imaginary Institution of Society (1998, Castoriadis uses the terms to describe the capacity of socialized human beings to rethink and criticize social structures, and sees the radical imaginary and the radical imagination as means of a radical social transformation towards autonomy, or rather towards autonomous social organisation. Within this framework, this article proposes a historical parallelism between three self-organised platforms for art and activism from Milan, such as Laboratorio di Comunicazione Militante, Isola Art Centre, and MACAO, arguing that they are three cases in which autonomous social organisation is a means for artistic and curatorial production. This historical parallelism, constructed around the concepts of the radical imaginary and the radical imagination, demonstrates how the work of Castoriadis is a valuable resource for contextualising and analysing processes politicization of artistic, curatorial and cultural practices. Based on his writings, this article wants to also highlight the importance of autonomous social organisation as a functional framework capable unpacking the complexity of the relation between artistic, curatorial and cultural practices and political and social activism.

Reaction of single-standard DNA with hydroxyl radical generated by iron(II)-ethylenediaminetetraacetic acid

International Nuclear Information System (INIS)

Prigodich, R.V.; Martin, C.T.

1990-01-01

This study demonstrates that the reaction of Fe(II)-EDTA and hydrogen peroxide with the single-stranded nucleic acids d(pT) 70 and a 29-base sequence containing a mixture of bases results in substantial damage which is not directly detected by gel electrophoresis. Cleavage of the DNA sugar backbone is enhanced significantly after the samples are incubated at 90 degree C in the presence of piperidine. The latter reaction is used in traditional Maxam-Gilbert DNA sequencing to detect base damage, and the current results are consistent with reaction of the hydroxyl radical with the bases in single-stranded DNA (although reaction with sugar may also produce adducts that are uncleaved but labile to cleavage by piperidine). We the authors propose that hydroxyl radicals may react preferentially with the nucleic acid bases in ssDNA and that reaction of the sugars in dsDNA is dominant because the bases are sequestered within the double helix. These results have implications both for the study of single-stranded DNA binding protein binding sites and for the interpretation of experiments using the hydroxyl radical to probe DNA structure or to footprint double-stranded DNA binding protein binding sites

Temperature Activated Diffusion of Radicals through Ion Implanted Polymers

DEFF Research Database (Denmark)

Wakelin, Edgar A.; Davies, Michael J.; Bilek, Marcela M. M.

2015-01-01

Plasma immersion ion implantation (PIII) is a promising technique for immobilizing biomolecules on the surface of polymers. Radicals generated in a subsurface layer by PIII treatment diffuse throughout the substrate, forming covalent bonds to molecules when they reach the surface. Understanding...... to the surface. The model makes useful predictions for the lifetime over which the surface is sufficiently active to covalently immobilize biomolecules and it can be used to determine radical fluence during biomolecule incubation for a range of storage and incubation temperatures so facilitating selection...

Regeneration of phenolic antioxidants from phenoxyl radicals: An ESR and electrochemical study of antioxidant hierarchy

DEFF Research Database (Denmark)

Jørgensen, Lars V.; Madsen, Helle L.; Thomsen, Marianne K.

1999-01-01

Radicals from the flavonoids quercetin, (+)-catechin, (+/-)-taxifolin and luteolin, and from all-rac-alpha-tocopherol have been generated electrochemically by one-electron oxidation in deaerated dimethylformamide (DMF), and characterised by electron spin resonance spectroscopy (ESR) after spin......-trapping by 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Simulations of the ESR spectrum based on estimated coupling constants of the spin-trapped quercetin radical, confirmed that this antioxidant radical is oxygen-centered. The complex mixture of radicals, quinoid intermediates and stable two-electron oxidation...

Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

International Nuclear Information System (INIS)

Fujimura, T.; Hayakawa, N.; Kuriyama, I.

1978-01-01

The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals

Directory of Open Access Journals (Sweden)

John C. Walton

2016-01-01

Full Text Available Oxime derivatives are easily made, are non-hazardous and have long shelf lives. They contain weak N–O bonds that undergo homolytic scission, on appropriate thermal or photochemical stimulus, to initially release a pair of N- and O-centred radicals. This article reviews the use of these precursors for studying the structures, reactions and kinetics of the released radicals. Two classes have been exploited for radical generation; one comprises carbonyl oximes, principally oxime esters and amides, and the second comprises oxime ethers. Both classes release an iminyl radical together with an equal amount of a second oxygen-centred radical. The O-centred radicals derived from carbonyl oximes decarboxylate giving access to a variety of carbon-centred and nitrogen-centred species. Methods developed for homolytically dissociating the oxime derivatives include UV irradiation, conventional thermal and microwave heating. Photoredox catalytic methods succeed well with specially functionalised oximes and this aspect is also reviewed. Attention is also drawn to the key contributions made by EPR spectroscopy, aided by DFT computations, in elucidating the structures and dynamics of the transient intermediates.

Improved Taguchi method based contract capacity optimization for industrial consumer with self-owned generating units

International Nuclear Information System (INIS)

Yang, Hong-Tzer; Peng, Pai-Chun

2012-01-01

Highlights: ► We propose an improved Taguchi method to determine the optimal contract capacities with SOGUs. ► We solve the highly discrete and nonlinear optimization problem for the contract capacities with SOGUs. ► The proposed improved Taguchi method integrates PSO in Taguchi method. ► The customer using the proposed optimization approach may save up to 12.18% of power expenses. ► The improved Taguchi method can also be well applied to the other similar problems. - Abstract: Contract capacity setting for industrial consumer with self-owned generating units (SOGUs) is a highly discrete and nonlinear optimization problem considering expenditure on the electricity from the utility and operation costs of the SOGUs. This paper proposes an improved Taguchi method that combines existing Taguchi method and particle swarm optimization (PSO) algorithm to solve this problem. Taguchi method provides fast converging characteristics in searching the optimal solution through quality analysis in orthogonal matrices. The integrated PSO algorithm generates new solutions in the orthogonal matrices based on the searching experiences during the evolution process to further improve the quality of solution. To verify feasibility of the proposed method, the paper uses the real data obtained from a large optoelectronics factory in Taiwan. In comparison with the existing optimization methods, the proposed improved Taguchi method has superior performance as revealed in the numerical results in terms of the convergence process and the quality of solution obtained.

Fermentation of Smilax china root by Aspergillus usami and Saccharomyces cerevisiae promoted concentration of resveratrol and oxyresveratrol and the free-radical scavenging activity.

Science.gov (United States)

Yoon, So-Ra; Yang, Seung-Hwan; Suh, Joo-Won; Shim, Soon-Mi

2014-07-01

Smilax china root, which is rich in resveratrol and oxyresveratrol, has been used as emergency foods as well as folk medicine. This study investigated changes in concentration of bioactive components and the free-radical scavenging capacity of Smilax china root during fermentation by Aspergillus usami and Saccharomyces cerevisiae. Resveratrol, oxyresveratrol and piceid were quantified as major constituents in Smilax china root by using UPLC-ESI-MS. The concentration of oxyresveratrol and resveratrol remarkably increased through fermentation and the transformation of piceid to resveratrol. Its concentration in 4% Smilax china root was 1.16-2.95 times higher than that of a 2% preparation throughout fermentation. The vitamin C equivalent antioxidant capacity of 2% Smilax china root was 1.51-1.91 times higher than that of 4% Smilax china root during fermentation. Meanwhile, ABTS free-radical scavenging capacity was enhanced up to 95.07 and 99.35% for 2% and 4% Smilax china root, respectively. Results from our study propose that bioactive components in Smilax China root were highly extracted by fermentation followed by saccharification and ethanol production, resulting in enhanced free-radical scavenging capacity. © 2013 Society of Chemical Industry. © 2013 Society of Chemical Industry.

Analytical profiling of selected antioxidants and total antioxidant capacity of goji (Lycium spp.) berries.

Science.gov (United States)

Protti, Michele; Gualandi, Isacco; Mandrioli, Roberto; Zappoli, Sergio; Tonelli, Domenica; Mercolini, Laura

2017-09-05

Goji berries and derived products represent a relevant source of micronutrients, most of which are natural antioxidants and contribute to the high nutritional quality of these fruits. Three brands of dried goji berries have been analysed by a multidisciplinary approach to get an insight into both their content of selected antioxidants and their antioxidant capacity (AC). The former goal has been achieved by developing a liquid chromatographic method coupled to mass spectrometry and combined to a fast solid phase extraction. Several significant representative antioxidant compounds belonging to the following classes: flavonoids, flavan-3-ols, phenolic acids, amino acids and derivatives, and carotenoids have been taken into account. Quercetin and rutin were found to be the predominant flavonoids, chlorogenic acid was the most abundant phenolic acid and zeaxanthin was the major carotenoid. The AC of the goji berries has been evaluated by four analytical methods in order to estimate the contributions of different reactions involved in radicals scavenging. In particular, AC has been determined using 3 standardised methods (DPPH, ABTS, ORAC) and a recently proposed electrochemical method, which measures the scavenging activity of antioxidants towards OH radicals generated both by hydrogen peroxide photolysis and the Fenton reaction. The results obtained from chemical composition and antioxidant capacity assays confirm the high nutritional and commercial value of goji berries and highlight that the three brands do not exhibit significant differences. Copyright © 2017 Elsevier B.V. All rights reserved.

Guest Editorial: Processes of Radicalization and De-Radicalization

Directory of Open Access Journals (Sweden)

Donatella Della Porta

2012-05-01

Full Text Available The study of radicalization and de-radicalization, understood as processes leading towards the increased or decreased use of political violence, is central to the question of how political violence emerges, how it can be prevented, and how it can be contained. The focus section of this issue of the International Journal of Conflict and Violence addresses radicalization and de-radicalization, seeking to develop a more comprehensive understanding of the processes, dynamics, and mechanisms involved and taking an interdisciplinary approach to overcome the fragmentation into separate disciplines and focus areas. Contributions by Pénélope Larzillière, Felix Heiduk, Bill Kissane, Hank Johnston, Christian Davenport and Cyanne Loyle, Veronique Dudouet, and Lasse Lindekilde address repressive settings, legitimacy, institutional aspects, organizational outcomes, and dynamics in Europe, Asia, Africa, and North and South America.

The peroxyl radical-induced oxidation of Escherichia coli FtsZ and its single tryptophan mutant (Y222W) modifies specific side-chains, generates protein cross-links and affects biological function

DEFF Research Database (Denmark)

Escobar-Álvarez, Elizabeth; Leinisch, Fabian; Araya, Gissela

2017-01-01

radicals (ROO•) generated from AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride) was studied. The non-oxidized proteins showed differences in their polymerization behavior, with this favored by the presence of Trp at position 222. AAPH-treatment of the proteins inhibited polymerization. Protein...... consumed by ROO•. Quantification of the number of moles of amino acid consumed per mole of ROO• shows that most of the initial oxidant can be accounted for at low radical fluxes, with Met being a major target. Western blotting provided evidence for di-tyrosine cross-links in the dimeric and trimeric...

Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

Energy Technology Data Exchange (ETDEWEB)

Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

2009-08-01

The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

Neem leaf extract as potential modifier of free radical interaction with RBC membrane

International Nuclear Information System (INIS)

Patil, Shilpa M.; Kulkarni, Satish G.; Rane, Charusheela

2004-01-01

Full text: Neem tree (Azadirachta indica) is well known as village pharmacy due to its multifaceted medicinal action in curing countless health problems. The leaf extract of Neem is known to purify blood by removing toxins and neutralizing free radicals. Using gamma irradiation as free radical generation process the efficacy of neem leaf extract in combating free radical attack on RBC membrane has been explored. The results narrating role of concentration and dose dependency in this radio modulation will be discussed

Free Radicals and Extrinsic Skin Aging

Directory of Open Access Journals (Sweden)

Borut Poljšak

2012-01-01

Full Text Available Human skin is constantly directly exposed to the air, solar radiation, environmental pollutants, or other mechanical and chemical insults, which are capable of inducing the generation of free radicals as well as reactive oxygen species (ROS of our own metabolism. Extrinsic skin damage develops due to several factors: ionizing radiation, severe physical and psychological stress, alcohol intake, poor nutrition, overeating, environmental pollution, and exposure to UV radiation (UVR. It is estimated that among all these environmental factors, UVR contributes up to 80%. UV-induced generation of ROS in the skin develops oxidative stress, when their formation exceeds the antioxidant defence ability of the target cell. The primary mechanism by which UVR initiates molecular responses in human skin is via photochemical generation of ROS mainly formation of superoxide anion (O2−•, hydrogen peroxide (H2O2, hydroxyl radical (OH•, and singlet oxygen (1O2. The only protection of our skin is in its endogenous protection (melanin and enzymatic antioxidants and antioxidants we consume from the food (vitamin A, C, E, etc.. The most important strategy to reduce the risk of sun UVR damage is to avoid the sun exposure and the use of sunscreens. The next step is the use of exogenous antioxidants orally or by topical application and interventions in preventing oxidative stress and in enhanced DNA repair.

Effect of curcumin against oxidation of biomolecules by hydroxyl radicals.

Science.gov (United States)

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.

Antioxidant Capacity of Selected Plant Extracts and Their Essential Oils

Directory of Open Access Journals (Sweden)

Charalampos Proestos

2013-01-01

Full Text Available The main objective of this study was the screening of some selected aromatic plants very popular in Greece, with respect to their total phenolic content, antioxidant capacity, reducing activity, and oxidative stability. All plants were extracted with the conventional method, reflux with methanol. The essential oils of the plants were also analyzed for their antioxidant properties. The total phenolic content was determined by the Folin-Ciocalteu method using gallic acid as the standard, while the phenolic substances were identified and quantified by High Performance Liquid Chromatography (HPLC coupled with a multi-wavelength ultraviolet-visible (UV-vis detector. The antioxidant capacity of the plant extracts was measured by their ability to scavenge free radicals such as (a DPPH (2,2-diphenyl-1-picrylhydrazyl and, (b ABTS (2,2′-azinobis-(3-ethylbenzothiaziline-6- sulfonate. The Folin-Ciocalteu method proved the existence of antioxidants in the aromatic plant extracts. Taking into account the results of the DPPH and ABTS methods, the free radical scavenging capacity was confirmed. Eventually, all plants exhibited low but noticeable protection levels against lipid oxidation, as determined by the Rancimat test.

Free Radical Imaging Using In Vivo Dynamic Nuclear Polarization-MRI.

Science.gov (United States)

Utsumi, Hideo; Hyodo, Fuminori

2015-01-01

Redox reactions that generate free radical intermediates are essential to metabolic processes, and their intermediates can produce reactive oxygen species, which may promote diseases related to oxidative stress. The development of an in vivo electron spin resonance (ESR) spectrometer and its imaging enables us noninvasive and direct measurement of in vivo free radical reactions in living organisms. The dynamic nuclear polarization magnetic resonance imaging (DNP-MRI), also called PEDRI or OMRI, is also a new imaging method for observing free radical species in vivo. The spatiotemporal resolution of free radical imaging with DNP-MRI is comparable with that in MRI, and each of the radical species can be distinguished in the spectroscopic images by changing the frequency or magnetic field of ESR irradiation. Several kinds of stable nitroxyl radicals were used as spin probes to detect in vivo redox reactions. The signal decay of nitroxyl probes, which is determined with in vivo DNP-MRI, reflects the redox status under oxidative stress, and the signal decay is suppressed by prior administration of antioxidants. In addition, DNP-MRI can also visualize various intermediate free radicals from the intrinsic redox molecules. This noninvasive method, in vivo DNP-MRI, could become a useful tool for investigating the mechanism of oxidative injuries in animal disease models and the in vivo effects of antioxidant drugs. © 2015 Elsevier Inc. All rights reserved.

Simple and Efficient Generation of Aryl Radicals from Aryl Triflates: Synthesis of Aryl Boronates and Aryl Iodides at Room Temperature.

Science.gov (United States)

Liu, Wenbo; Yang, Xiaobo; Gao, Yang; Li, Chao-Jun

2017-06-28

Despite the wide use of aryl radicals in organic synthesis, current methods to prepare them from aryl halides, carboxylic acids, boronic acids, and diazonium salts suffer from limitations. Aryl triflates, easily obtained from phenols, are promising aryl radical progenitors but remain elusive in this regard. Inspired by the single electron transfer process for aryl halides to access aryl radicals, we developed a simple and efficient protocol to convert aryl triflates to aryl radicals. Our success lies in exploiting sodium iodide as the soft electron donor assisted by light. This strategy enables the scalable synthesis of two types of important organic molecules, i.e., aryl boronates and aryl iodides, in good to high yields, with broad functional group compatibility in a transition-metal-free manner at room temperature. This protocol is anticipated to find potential applications in other aryl-radical-involved reactions by using aryl triflates as aryl radical precursors.

Results of third-generation epirubicin/cisplatin/xeloda adjuvant chemotherapy in patients with radically resected gastric cancer.

Science.gov (United States)

Cainap, Calin; Nagy, Viorica; Seicean, Andrada; Gherman, Alexandra; Laszlo, Istvan; Lisencu, Cosmin; Nadim, Al Hajar; Constantin, Anne-Marie; Cainap, Simona

2016-01-01

The purpose of this study was to evaluate the efficacy and toxicity of a third-generation chemotherapy regimen in the adjuvant setting to radically operated patients with gastric cancer. This proposed new adjuvant regimen was also compared with a consecutive retrospective cohort of patients treated with the classic McDonald regimen. Starting in 2006, a non-randomized prospective phase II study was conducted at the Institute of Oncology of Cluj-Napoca on 40 patients with stage IB-IV radically resected gastric adenocarcinoma. These patients were administered a chemotherapy regimen already considered to be standard treatment in the metastatic setting: ECX (epirubicin, cisplatin, xeloda) and were compared to a retrospective control group consisting of 54 patients, treated between 2001 and 2006 according to McDonald's trial. In a previous paper, we reported toxicities and the possible predictive factors for these toxicities; in the present article, we report on the results concerning predictive factors on overall survival (OS) and disease free survival (DFS). The proposed ECX treatment was not less effective than the standard suggested by McDonald's trial. Age was an independent prognostic factor in multivariate analysis. N3 stage was an independent prognostic factor for OS and DFS. N ratio >70% was an independent predictive factor for OS and locoregional disease control. The resection margins were independent prognostic factors for OS and DFS. The proposed treatment is not less effective compared with the McDonald's trial. Age was an independent prognostic factor in multivariate analysis. N3 stage represented an independent prognostic factor and N ratio >70% was a predictive factor for OS and DFS. The resection margins were proven to be independent prognostic factors for OS and DFS.

Comparisons of recent growth in actual demand, planned demand, and planned generating capacity at U. S. electric utilities

Energy Technology Data Exchange (ETDEWEB)

Bopp, A.E. (James Madison Univ., Harrisonburg, VA (United States))

1994-12-01

During the winter of 1993, a number of U.S. electric utilities and some regional power pools discovered that current load exceeded generating capacity. Load restrictions followed, as entire regions-not just isolated utilities or even states-cut back. Was 1993 a typical, or simply a preview of the future If a preview, how did this shortage occur For a number of years, utilities, regulatory agencies, and power pools have been planning to add capacity at a much lower rate than the rate at which load has been growing. The National Electricity Reliability Council (NERC) has projected that eight of it's nine regions will have demand growth exceed capacity growth. The only region where capacity is growing faster is in the Texas Region. There are four reasons behind this shortage: excess capacity in the 1980's, disbelief in current forecasts, passage of the Clean Air act bringing stricter regulation on power plants, and the herd mentality where utilities have all delayed new plant construction.

Tissue diversity in respiratory metabolism and free radical processes ...

African Journals Online (AJOL)

SAM

2014-04-23

Apr 23, 2014 ... marina seeds to desiccation contributes to an under- standing of the ... normal, thus increasing the generation of free radical ...... A review of recalcitrant seed physio- ... In: Kigel J, Galili G (eds) Seed development and germina-.

[Generation of Superoxide Radicals by Complex III in Heart Mitochondria and Antioxidant Effect of Dinitrosyl Iron Complexes at Different Partial Pressure of Oxygen].

Science.gov (United States)

Dudylina, A L; Ivanova, M V; Shumaev, K B; Ruuge, E K

2016-01-01

The EPR spin-trapping technique and EPR-oximetry were used to study generation of superoxide radicals in heart mitochondria isolated from Wistar rats under conditions of variable oxygen concentration. Lithium phthalocyanine and TEMPONE-15N-D16 were chosen to determine oxygen content in a gas-permeable capillary tube containing mitochondria. TIRON was used as a spin trap. We investigated the influence of different oxygen concentrations in incubation mixture and demonstrated that heart mitochondria can generate superoxide in complex III at different partial pressure of oxygen as well as under the conditions of deep hypoxia (partial pressure of oxygen, but the magnitude and kinetic characteristics of the effect depended on the concentration of the drug.

An electrical betweenness approach for vulnerability assessment of power grids considering the capacity of generators and load

Science.gov (United States)

Wang, Kai; Zhang, Bu-han; Zhang, Zhe; Yin, Xiang-gen; Wang, Bo

2011-11-01

Most existing research on the vulnerability of power grids based on complex networks ignores the electrical characteristics and the capacity of generators and load. In this paper, the electrical betweenness is defined by considering the maximal demand of load and the capacity of generators in power grids. The loss of load, which reflects the ability of power grids to provide sufficient power to customers, is introduced to measure the vulnerability together with the size of the largest cluster. The simulation results of the IEEE-118 bus system and the Central China Power Grid show that the cumulative distributions of node electrical betweenness follow a power-law and that the nodes with high electrical betweenness play critical roles in both topological structure and power transmission of power grids. The results prove that the model proposed in this paper is effective for analyzing the vulnerability of power grids.

Manipulation of radicals and ions in LFICP-aided fabrication of high efficiency solar cells

International Nuclear Information System (INIS)

Xu, S.

2013-01-01

In this talk, we report on the development and diagnostics of low frequency inductively coupled plasma (LFICP) reactor for fabrication of high efficiency silicon solar cells. Chemically active, thermally non-equilibrium plasma possess unique advantages for manipulation of plasma-generated radicals/ions and overall control of growth and self-organization processes that are crucial for fabrication of photovoltaic materials and solar cells. In low frequency inductively coupled plasmas, generation, selection and control of densities and fluxes of the radicals and ions can easily be controlled by the electron energy distributions and other plasma parameters. The electric field and thermal forces guide selective delivery of the radicals to the surface. Specific substrate activation and temperature determine the ion/heat fluxes from the gas phase to the charged surfaces. Detailed discussion includes the inter-connection between in-situ plasma diagnostics (Optical Emission Spectroscopy, Langmuir Probe diagnostics, and Quadruple Mass Spectrometry) and ex-situ material characterization (XRD, Raman, FTIR EDX, UV/Vis, SEM, Hall-effect and others). Special emphasis is paid to the identification and control strategies of the plasma-generated radicals/ions existed in both the ionized gas phase and on the deposition surfaces. We will show how radicals and ions can be manipulated to meet the structural, optical and electronic requirements for high efficiency photovoltaic cells. Solar cell fabricated by the LFICP plasma exhibits an extraordinarily photovoltaic performance with energy conversion efficiency exceeding 18%. (author)

Cell-mediated reduction of protein and peptide hydroperoxides to reactive free radicals

DEFF Research Database (Denmark)

Headlam, Henrietta A; Davies, Michael Jonathan

2003-01-01

Radical attack on proteins in the presence of O(2) gives protein hydroperoxides in high yields. These peroxides are decomposed by transition metal ions, reducing agents, UV light and heat, with the formation of a range of reactive radicals that are capable of initiating further damage. Evidence has...... been presented for the formation of alcohols as stable products of peroxide decomposition, and these have been employed as markers of oxidative damage in vivo. The mechanism of formation of these alcohols is unclear, with both radical and nonradical pathways capable of generating these products....... In this study we have investigated the reduction of peptide and protein hydroperoxides by THP-1 (human monocyte-like) cells and it is shown that this process is accompanied by radical formation as detected by EPR spin trapping. The radicals detected, which are similar to those detected from metal-ion catalyzed...

Titanium dioxide induced cell damage: A proposed role of the carboxyl radical

Energy Technology Data Exchange (ETDEWEB)

Dodd, Nicholas J.F. [Ecotoxicology and Stress Biology Research Centre, School of Biological Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Jha, Awadhesh N. [Ecotoxicology and Stress Biology Research Centre, School of Biological Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)], E-mail: a.jha@plymouth.ac.uk

2009-01-15

Titanium dioxide (TiO{sub 2}) nanoparticles have been shown to be genotoxic to cells exposed to ultraviolet A (UVA) radiation. Using the technique of electron spin resonance (ESR) spin trapping, we have confirmed that the primary damaging species produced on irradiation of TiO{sub 2} nanoparticles is the hydroxyl (OH) radical. We have applied this technique to TiO{sub 2}-treated fish and mammalian cells under in vitro conditions and observed the additional formation of carboxyl radical anions (CO{sub 2}{sup -}) and superoxide radical anions (O{sub 2}{sup -}). This novel finding suggests a hitherto unreported pathway for damage, involving primary generation of OH radicals in the cytoplasm, which react to give CO{sub 2}{sup -} radicals. The latter may then react with cellular oxygen to form O{sub 2}{sup -} and genotoxic hydrogen peroxide (H{sub 2}O{sub 2})

An evaluation of effects of large-scale introduction of renewable power on capacities and operation modes of power generation systems in Japan

International Nuclear Information System (INIS)

Yamamoto, Hiromi; Yabe, Kuniaki; Bando, Shigeru; Nagai, Yu

2014-01-01

This study aims to establish a methodology to adequately evaluate an optimal power generation mix in Japan taking into account load frequency control (LFC) capacity and operation modes of power plants in case of a large-scale introduction of photovoltaic and wind power. For this purpose, the authors gave such an improvement to the MM-OPG model, a power generation mix optimization model, which it can deal with different operation modes of pumped hydro power in addition to those of thermal power sources. Using the model, the authors calculated the optimal power generation mix and its corresponding operation modes of Japan's power systems in 2030 with additional insights to 2020, and obtained the following results. (1) Introduction of photovoltaic and wind can be substituted for a limited capacity of conventional power sources. The introduction of 150 GW that consists of 108GW of photovoltaic and 42GW of wind in 2030 can replace no greater than 0.5 GW of conventional power sources. (2) The introduction of the renewables will affect the operation patterns of thermal and pumped hydro power generation. The capacity factor of variable speed pumped hydro will be much greater than that of fixed speed pumped hydro since the former can supply LFC at pump modes as well as generation modes. The capacity factor of LNG combined cycle plants decreases from 43% to 29% in the case with the introduction of 150GW of renewables in 2030. On the same assumption, the average cost of power generation excluding the renewables increases by up to 0.55 JPY/kWh in 2030. (author)

First examples of intramolecular addition of primary amidyl radicals to olefins

Energy Technology Data Exchange (ETDEWEB)

Gaudreault, P.; Drouin, C.; Lessard, J. [Sherbrooke Univ., PQ (Canada). Dept. de Chimie

2005-07-01

This paper presents the first examples of radical cyclization involving a primary amidyl radical and a pendant olefin. Amidyl radicals have attracted interest in terms of their structure, reactivity, and ways to generate them. The intramolecular addition of an amidyl radical on a pendant olefin appears to be a powerful synthetic tool for creating nitrogen-containing heterocycles. Although several examples of cyclization involving secondary amidyl radicals are cited in the the literature, there are no examples of a successful cyclization involving a primary amidyl radical. This is because all attempts to prepare the usual radical precursors have failed when applied to olefinic primary amides. This study reveals that N-(phenylthio) derivatives of olefinic primary amides can be easily prepared and that nitrogen heterocycles resulting from their radical cyclization can be obtained in good to very good yields. Four olefinic primary amides were chosen as models for radical cyclization of primary amidyl radicals. They were prepared from the corresponding carboxylic acids via the acid chlorides. Conversion of primary amides into suitable amidyl radical precursors was also examined. The study showed that N-(phenylthio) amides could be easily prepared by following a slightly modified protocol developed by Esker and Newcomb, by reacting the anion of the amide with phenylsulfenyl chloride. In particular, olefinic N-(phenylthio) amides were prepared and used as primary amidyl radical precursors in a reaction with a solution of 2,2'-azobis(isobutyronitrile) in catalytic quantities and tributyltin hydride in benzene. The resulting yields of cyclic products ranged from 63 to 85 per cent. The intent of the study was to demonstrate that it is no longer necessary to prepare an N-protected precursor and then remove the protecting group after cyclization. Further studies are currently underway. 10 refs., 1 tab.

Comparison of antioxidant capacity of cow and ewe milk kefirs.

Science.gov (United States)

Yilmaz-Ersan, Lutfiye; Ozcan, Tulay; Akpinar-Bayizit, Arzu; Sahin, Saliha

2018-05-01

This research aimed to evaluate the effects of using either grain or commercial starter culture on the antioxidative capacity of cow and ewe milk kefirs. The antioxidant capacity of kefir samples during fermentation and 21 d of storage was assessed by using 3 assays: 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical cation decolorization; 2,2-diphenyl-1-picrylhydrazyl (DPPH • ) radical scavenging activity assay; and Fe +3 -reducing power (ferric reducing antioxidant power assay, FRAP). Vitamin E and β-carotene contents were also quantified. All kefir samples exhibited varying values for DPPH, ABTS, and FRAP assays depending on the starter culture and milk type. Vitamin E and β-carotene contents were similar in all kefir samples during storage. The results of this study suggest that milk type (cow or ewe) and culture type (kefir grains or commercial starter) were the significant parameters for the antioxidative activity of kefir. Copyright © 2018 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

[Effect of occupational stress on oxidation/antioxidant capacity in nurses].

Science.gov (United States)

Cao, Lili; Tian, Honger; Zhang, Qingdong; Zhu, Xinyun; Zhan, Yongguo; Su, Jingguo; Xu, Tian; Zhu, Huabin; Liu, Ling

2014-02-01

To investigate the effect of occupational stress on the oxidation/antioxidant capacity in nurses. A total of 131 nurses were included as study subjects. The occupational health information collection system (based on the Internet of things) was used for measurement of occupational stress. Levels of hydroxyl free radicals and antioxidant enzymes were determined. The serum level of superoxide dismutase (SOD) was the highest in nurses under the age of 30 and the lowest in those over 45 (P occupational stress factors for SOD. Job hazards were negative occupational stress factors for POD. Psychological satisfaction was negative occupational stress reaction for hydroxyl free radicals. Calmness was positive occupational stress reaction for SOD, and daily stress was a negative one. The positive occupational stress reactions for GSH-Px were psychological satisfaction and job satisfaction, and daily stress was negative reaction. Nurses with higher occupational stress have stronger oxidation and weaker antioxidant capacity, which intensifies oxidant-antioxidant imbalance and leads to oxidative stress damage.

Radical scavenging activities of Rio Red grapefruits and Sour orange fruit extracts in different in vitro model systems.

Science.gov (United States)

Jayaprakasha, G K; Girennavar, Basavaraj; Patil, Bhimanagouda S

2008-07-01

Antioxidant fractions from two different citrus species such as Rio Red (Citrus paradise Macf.) and Sour orange (Citrus aurantium L.) were extracted with five different polar solvents using Soxhlet type extractor. The total phenolic content of the extracts was determined by Folin-Ciocalteu method. Ethyl acetate extract of Rio Red and Sour orange was found to contain maximum phenolics. The dried fractions were screened for their antioxidant activity potential using in vitro model systems such as 1,1-diphenyl-2-picryl hydrazyl (DPPH), phosphomolybdenum method and nitroblue tetrazolium (NBT) reduction at different concentrations. The methanol:water (80:20) fraction of Rio Red showed the highest radical scavenging activity 42.5%, 77.8% and 92.1% at 250, 500 and 1000 ppm, respectively, while methanol:water (80:20) fraction of Sour orange showed the lowest radical scavenging activity at all the tested concentrations. All citrus fractions showed good antioxidant capacity by the formation of phosphomolybdenum complex at 200 ppm. In addition, superoxide radical scavenging activity was assayed using non-enzymatic (NADH/phenaxine methosulfate) superoxide generating system. All the extracts showed variable superoxide radical scavenging activity. Moreover, methanol:water (80:20) extract of Rio Red and methanol extract of Sour orange exhibited marked reducing power in potassium ferricyanide reduction method. The data obtained using above in vitro models clearly establish the antioxidant potential of citrus fruit extracts. However, comprehensive studies need to be conducted to ascertain the in vivo bioavailability, safety and efficacy of such extracts in experimental animals. To the best of our knowledge, this is the first report on antioxidant activity of different polar extracts from Rio Red and Sour oranges.

Sexual function following radical radiotherapy for bladder cancer

International Nuclear Information System (INIS)

Little, F.A.; Howard, G.C.W.

1998-01-01

Background and purpose: The effect of radical radiotherapy (RT) for bladder cancer on sexual function has not been previously investigated. The current study was designed as a pilot to assess sexual function in males pre- and post-radiotherapy. Materials and methods: An anonymous questionnaire was devised to examine the following sexual domains: libido, frequency of sexual function, erectile capacity, orgasm and ejaculation in the 6 months prior to radiotherapy and following treatment. Serum testosterone, FSH and LH were measured in 10 patients. Results: Eighteen patients completed the questionnaire from 10 to 56 months following irradiation, 13 of whom were able to achieve an erection prior to RT. Over half of these patients noted a decline in the quality of erections after RT, with a similar proportion noting decreased libido and frequency of sexual activity. Three patients lost the ability to have any erections whatsoever. Of the 10 patients retaining erectile capacity, three noted reduced frequency of early morning erections suggesting a physical aetiology, five had decreased frequency of ejaculation and four had reduced intensity of orgasms. Seventy-one percent (12/17) felt their sex life was worse following RT but only 56% (9/16) were concerned about the deterioration. Testosterone levels were normal in all but one patient. Conclusions: Radical RT to the bladder can cause a decrease in sexual function in males. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

Oxidation of caffeine by phosphate radical anion in aqueous ...

Indian Academy of Sciences (India)

Unknown

reactions in our body generate reactive oxygen species mainly comprising free radicals .... caffeine might be acting as a sensitizer to transfer energy to PDP to produce phosphate ... The lifetime of the excited singlet 21 state of caffeine is of the.

Radical Change by Entrepreneurial Design

National Research Council Canada - National Science Library

Roberts, Nancy C

1998-01-01

.... How radical change in public policy has occurred in the past is then documented. We find examples of radical change by chance, radical change by consensus, radical change by learning, and radical change by entrepreneurial design...

The late effect of radical radiotherapy for lung cancer on pulmonary function

International Nuclear Information System (INIS)

Ball, D.L.

1985-01-01

At the Peter MacCallum Hospital it is the policy to treat patients with non-small cell carcinoma of the lung with radical intent if there are no adverse prognostic factors. Spirometric testing was carried out before and at least three months after the completion of radiotherapy in 25 patients who were so treated. The results indicate that high dose radiotherapy (50-60 Gy) to the primary site and mediastinum is well tolerated; although 64% of patients experienced a decrease in vital capacity, this was usually of acceptable degree and in the remaining 36% the vital capacity actually increased

Density evaluation of remotely-supplied hydrogen radicals produced via tungsten filament method for SiCl4 reduction

Science.gov (United States)

Zohra Dahmani, Fatima; Okamoto, Yuji; Tsutsumi, Daiki; Ishigaki, Takamasa; Koinuma, Hideomi; Hamzaoui, Saad; Flazi, Samir; Sumiya, Masatomo

2018-05-01

Effect of the hydrogen radical on the reduction of a silicon tetrachloride (SiCl4) source was studied. The hydrogen radicals were generated using a tungsten (W) filament in a generation chamber, and were remotely supplied to another reaction chamber. The density of the hydrogen radical was estimated from the optical transmittance of 600-nm-wavelength light through phosphate glass doped with tungsten oxide (WO3). Lifetime of the hydrogen radical seemed sufficiently long, and its density as supplied to the reaction chamber was estimated to be on the order of 1012 cm‑3. Signal intensity of the peak corresponding to SiCl4 (m/z = 170) detected by quadrupole-mass measurement was confirmed to decrease owing to the reaction with the remotely-supplied hydrogen radical. This indicates the possibility that chemically-stable SiCl4, as one of the by-products of the Siemens process, can be reduced to produce silicon.

Quantification of Phenolic Compounds and In Vitro Radical Scavenging Abilities with Leaf Extracts from Two Varieties of Psidium guajava L.

Science.gov (United States)

Camarena-Tello, Julio César; Martínez-Flores, Héctor Eduardo; Garnica-Romo, Ma Guadalupe; Padilla-Ramírez, José Saúl; Saavedra-Molina, Alfredo; Alvarez-Cortes, Osvaldo; Bartolomé-Camacho, María Carmen; Rodiles-López, José Octavio

2018-02-27

Guava leaf ( Psidium guajava L.) extracts are used in both traditional medicine and the pharmaceutical industry. The antioxidant compounds in P. guajava leaves can have positive effects including anti-inflammatory, anti-hyperglycemic, hepatoprotective, analgesic, anti-cancer effects, as well as protecting against cardiovascular diseases. In the present study, phenolic compounds and in vitro antioxidant capacity were measured in extracts obtained with polar and non-polar solvents from leaves of two varieties of guava, Calvillo Siglo XXI and Hidrozac. The quantity of total phenolics and total flavonoids were expressed as equivalents of gallic acid and quercetin, respectively. Hydroxyl radical, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and Oxygen Radical Absorbance Capacity using fluorescein (ORAC-FL) in vitro tests were used to assess the radical scavenging abilities of the extracts. The total phenolics were higher in the aqueous fraction of the variety Calvillo Siglo XXI, while in the Hidrozac variety total phenolics were higher in the acetone and chloroform fractions. Total flavonoids were higher in all fractions in the variety Calvillo Siglo XXI. Total phenolics showed a highly positive correlation for ORAC-FL, and a moderately positive correlation with hydroxyl radicals. Finally, total flavonoids showed a slightly positive correlation for ORAC-FL and hydroxyl radicals. Both varieties of guava leaf extract showed excellent antioxidant properties.

Quantification of Phenolic Compounds and In Vitro Radical Scavenging Abilities with Leaf Extracts from Two Varieties of Psidium guajava L.

Directory of Open Access Journals (Sweden)

Julio César Camarena-Tello

2018-02-01

Full Text Available Guava leaf (Psidium guajava L. extracts are used in both traditional medicine and the pharmaceutical industry. The antioxidant compounds in P. guajava leaves can have positive effects including anti-inflammatory, anti-hyperglycemic, hepatoprotective, analgesic, anti-cancer effects, as well as protecting against cardiovascular diseases. In the present study, phenolic compounds and in vitro antioxidant capacity were measured in extracts obtained with polar and non-polar solvents from leaves of two varieties of guava, Calvillo Siglo XXI and Hidrozac. The quantity of total phenolics and total flavonoids were expressed as equivalents of gallic acid and quercetin, respectively. Hydroxyl radical, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS, 2,2-diphenyl-1-picrylhydrazyl (DPPH, and Oxygen Radical Absorbance Capacity using fluorescein (ORAC-FL in vitro tests were used to assess the radical scavenging abilities of the extracts. The total phenolics were higher in the aqueous fraction of the variety Calvillo Siglo XXI, while in the Hidrozac variety total phenolics were higher in the acetone and chloroform fractions. Total flavonoids were higher in all fractions in the variety Calvillo Siglo XXI. Total phenolics showed a highly positive correlation for ORAC-FL, and a moderately positive correlation with hydroxyl radicals. Finally, total flavonoids showed a slightly positive correlation for ORAC-FL and hydroxyl radicals. Both varieties of guava leaf extract showed excellent antioxidant properties.

Quantification of Phenolic Compounds and In Vitro Radical Scavenging Abilities with Leaf Extracts from Two Varieties of Psidium guajava L.

Science.gov (United States)

Martínez-Flores, Héctor Eduardo; Garnica-Romo, Ma. Guadalupe; Padilla-Ramírez, José Saúl; Saavedra-Molina, Alfredo; Alvarez-Cortes, Osvaldo; Bartolomé-Camacho, María Carmen; Rodiles-López, José Octavio

2018-01-01

Guava leaf (Psidium guajava L.) extracts are used in both traditional medicine and the pharmaceutical industry. The antioxidant compounds in P. guajava leaves can have positive effects including anti-inflammatory, anti-hyperglycemic, hepatoprotective, analgesic, anti-cancer effects, as well as protecting against cardiovascular diseases. In the present study, phenolic compounds and in vitro antioxidant capacity were measured in extracts obtained with polar and non-polar solvents from leaves of two varieties of guava, Calvillo Siglo XXI and Hidrozac. The quantity of total phenolics and total flavonoids were expressed as equivalents of gallic acid and quercetin, respectively. Hydroxyl radical, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and Oxygen Radical Absorbance Capacity using fluorescein (ORAC-FL) in vitro tests were used to assess the radical scavenging abilities of the extracts. The total phenolics were higher in the aqueous fraction of the variety Calvillo Siglo XXI, while in the Hidrozac variety total phenolics were higher in the acetone and chloroform fractions. Total flavonoids were higher in all fractions in the variety Calvillo Siglo XXI. Total phenolics showed a highly positive correlation for ORAC-FL, and a moderately positive correlation with hydroxyl radicals. Finally, total flavonoids showed a slightly positive correlation for ORAC-FL and hydroxyl radicals. Both varieties of guava leaf extract showed excellent antioxidant properties. PMID:29495514

Seasonal Difference in Antioxidant Capacity and Active Compounds Contents of Eucommia ulmoides Oliver Leaf

Directory of Open Access Journals (Sweden)

Jingfang Zhang

2013-02-01

Full Text Available Leaf of Eucommia ulmoides Oliver (EU is a Traditional Chinese Medicine and a functional food in China. Antioxidant contents of EU leaves, which were collected monthly during the period of May–October in three years, were determined. Samples’ antioxidant capacity was characterized by DPPH radical scavenging activity, hydroxyl radical scavenging activity, ferrous chelating ability, and antioxidant capacity in linoleic acid emulsion and in rapeseed oil assays. The results showed that contents of some active compounds and antioxidant activity were related to a certain time of the year. Samples collected in August showed high content of phenolics, and the samples collected in May contained higher amount of flavonoids than other samples. Leaves collected in May or June exhibited high contents of rutin, quercetin, geniposidic acid and aucubin. The August leaves showed stable and high DPPH radical scavenging activity, and ferrous chelating ability. May samples showed strong inhibitory effects on oxidation of rapeseed oil and linoleic acid. The DPPH radical scavenging activity was related to the total phenolics content. Flavonoids played an important role in the inhibitory effects on rapeseed oil and linoleic acid oxidation. Therefore, August and May were indicated as the best months to harvest EU leaves for industry.

IN VIVO EVIDENCE OF FREE RADICAL FORMATION AFTER ASBESTOS INSTILLATION: AN ESR SPIN TRAPPING INVESTIGATION

Science.gov (United States)

It has been postulated that the in vivo toxicity of asbestos results from its catalysis of free radical generation. We examined in vivo radical production using electron spin resonance (ESR) coupled with the spin trap alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (4-POBN); 180 d...

The games radicals play : special issue on free radicals and radical ions

OpenAIRE

Walton, J.C.; Williams, F.

2015-01-01

Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and a...

Time resolved resonance Raman spectra of anilino radical and aniline radical cation

International Nuclear Information System (INIS)

Tripathi, G.N.R.; Schuler, R.H.

1987-01-01

We report, in this paper, submicrosecond time resolved resonance Raman spectra of anilino radical and its radical cation as observed in pulse radiolytic studies of the oxidation of aniline in aqueous solution. By excitation in resonance with the broad and weak electronic transition of anilino radical at 400 nm (ε--1250 M -1 cm -1 ) we have observed, for the first time, the vibrational features of this radical. The Wilson ν 8 /sub a/ ring stretching mode at 1560 cm -1 is most strongly resonance enhanced. The ν 7 /sub a/ CN stretching band at 1505 cm -1 , which is shifted to higher frequency by 231 cm -1 with respect to aniline, is also prominent. The frequency of this latter mode indicates that the CN bond in the radical has considerable double bond character. The Raman spectrum of aniline radical cation, excited in resonance with the --425 nm electronic absorption (ε--4000 M -1 cm -1 ), shows features which are similar to phenoxyl radical. Most of the observed frequencies of this radical in solution are in good agreement with vibrational energies determined by recent laser photoelectron spectroscopic studies in the vapor phase. The bands most strongly enhanced in the resonance Raman spectrum are, however, weak in the photoelectron spectrum. While the vibrational frequencies observed for anilino radical and its isoelectronic cation are quite similar, the resonance enhancement patterns are very different. In particular the ν 14 b 2 mode of anilino radical observed at 1324 cm -1 is highly resonance enhanced because of strong vibronic coupling between the 400 nm 2 A 2 -- 2 B 1 and the higher 2 B 1 -- 2 B 1 electronic transitions

Standard Gibbs free energies of reactions of ozone with free radicals in aqueous solution: quantum-chemical calculations.

Science.gov (United States)

Naumov, Sergej; von Sonntag, Clemens

2011-11-01

Free radicals are common intermediates in the chemistry of ozone in aqueous solution. Their reactions with ozone have been probed by calculating the standard Gibbs free energies of such reactions using density functional theory (Jaguar 7.6 program). O(2) reacts fast and irreversibly only with simple carbon-centered radicals. In contrast, ozone also reacts irreversibly with conjugated carbon-centered radicals such as bisallylic (hydroxycylohexadienyl) radicals, with conjugated carbon/oxygen-centered radicals such as phenoxyl radicals, and even with nitrogen- oxygen-, sulfur-, and halogen-centered radicals. In these reactions, further ozone-reactive radicals are generated. Chain reactions may destroy ozone without giving rise to products other than O(2). This may be of importance when ozonation is used in pollution control, and reactions of free radicals with ozone have to be taken into account in modeling such processes.

Mass Proportion, Bioactive Compounds and Antioxidant Capacity of Carrot Peel as Affected by Various Solvents

Directory of Open Access Journals (Sweden)

Van Tang Nguyen

2016-11-01

Full Text Available The aim of this study was to determine the mass proportion of carrot root and the effects of four various solvents (methanol, water, ethanol and hexane on the contents of total phenolics and saponins as well as antioxidant capacity of carrot peel to identify an optimal solvent for effective extraction of bioactive compounds from carrot peel for further investigation. The results showed that carrot root consisted of body, heads and peel with their mass proportion of 83.19%, 5.01% and 14.19% by fresh weight, respectively. Among four solvents tested, methanol obtained the highest levels of extraction yield (54.02% by dry weight, total phenolic content (9.02 mg GAE/g dry weight and antioxidant capacity (DPPH radical scavenging capacity, cupric ion reducing antioxidant capacity, and ferric reducing antioxidant power from carrot peel, while water extracted the highest content of saponins (272.9 mg EE/g dry weight and possessed the maximum ABTS radical scavenging capacity. Therefore, methanol and water are considered for effective extraction of phenolics and saponins from carrot peel, respectively. The phenolic/saponin-enriched extracts are potential sources for further applications in the healthy food and/or pharmaceutical industries.

Radical behaviorist interpretation: Generating and evaluating an account of consumer behavior.

Science.gov (United States)

Foxall, G R

1998-01-01

This article considers an approach to the radical behaviorist interpretation of complex human social behavior. The chosen context is consumer psychology, a field currently dominated by cognitive models of purchase and consumption. The nature of operant interpretation is considered, and several levels of operant analysis of complex economic behavior in affluent marketing-oriented economies are developed. Empirical evidence for the interpretation is considered, and a case is made for the qualified use of the hypothetico-deductive method in the appraisal of operant interpretations of complex behaviors.

Photoisomerization and photodissociation dynamics of reactive free radicals

Energy Technology Data Exchange (ETDEWEB)

Bise, Ryan T. [Univ. of California, Berkeley, CA (United States)

2000-08-01

The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociative $\\tilde{A}$²A₁ and $\\tilde{B}$²A₂ states of CH₃S have been investigated. At all photon energies, CH₃ + S(³P_j), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH₃ umbrella mode and the S(³P_j) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N₂ photofragment. The relatively low fragment rotational excitation suggests dissociation via a symmetric C_2V transition state. Resolved vibrational structure of the N₂ photofragment is also observed in the photodissociation of the HNCN radical. The fragment vibrational and rotational distributions broaden with increased excitation energy. Simple dissociation models suggest that the HNCN radical isomerizes to a cyclic intermediate (c-HCNN) which then dissociates via a tight cyclic

Correlation of the radioprotective effect of the methyl gallate on the ruptures induction in DNA and it effect in the capture of free radicals

International Nuclear Information System (INIS)

Morales R, P.; Cabral P, A.; Cruz V, V.L.; Gonzalez B, F.; Zarco M, A.

2007-01-01

It is shown in alive, the capacity of the methyl gallate to reduce the induced ruptures in the DNA for γ radiation. As well as to capture free radicals in a system in vitro. This suggests that the methyl gallate can be a radioprotector that acts capturing free radicals. (Author)

Intramolecular transformation of thiyl radicals to α-aminoalkyl radicals: 'ab initio' calculations on homocystein

International Nuclear Information System (INIS)

Chhun, S.; Berges, J.; Bleton, V.; Abedinzadeh, Z.

2000-01-01

One-electron oxidation of thiols by oxidizing radicals leads to the formation of thiyl radical and carbon-centered radicals. It has been shown experimentally that in the absence of oxygen, the thiyl radicals derived from certain thiols of biological interest such as glutathion, cysteine and homocysteine decay rapidly by intramolecular rearrangement reactions into the carbon-centered radical. In the present work we have investigated theoretically the structure and the stability of thiyl and carbon-centered radicals of homocysteine in order to check the possibility of this rearrangement. (author)

Development and validation of a simple high performance thin layer chromatography method combined with direct 1,1-diphenyl-2-picrylhydrazyl assay to quantify free radical scavenging activity in wine.

Science.gov (United States)

Agatonovic-Kustrin, Snezana; Morton, David W; Yusof, Ahmad P

2016-04-15

The aim of this study was to: (a) develop a simple, high performance thin layer chromatographic (HPTLC) method combined with direct 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay to rapidly assess and compare free radical scavenging activity or anti-oxidant activity for major classes of polyphenolics present in wines; and (b) to investigate relationship between free radical scavenging activity to the total polyphenolic content (TPC) and total antioxidant capacity (TAC) in the wine samples. The most potent free radical scavengers that we tested for in the wine samples were found to be resveratrol (polyphenolic non-flavonoid) and rutin (flavonoid), while polyphenolic acids (caffeic acid and gallic acid) although present in all wine samples were found to be less potent free radical scavengers. Therefore, the total antioxidant capacity was mostly affected by the presence of resveratrol and rutin, while total polyphenolic content was mostly influenced by the presence of the less potent free radical scavengers gallic and caffeic acids. Copyright © 2015 Elsevier Ltd. All rights reserved.

Calcium mobilization by quinones and other free radical generating systems in rat hepatocytes

International Nuclear Information System (INIS)

Chen, E.C.; Chan, T.M.

1987-01-01

Using isolated rat hepatocytes, sublethal concentrations of quinones and other free radical generating systems were used to test the role of extracellular calcium (Ca) in activating glycogen phosphorylase and intracellular Ca mobilization. The α-agonist phenylephrine (Phe) was used for comparison. The EC50's were: Phe = 2.6 x 10 -7 M, menadione (K 3 ) = 4.5 x 10 -5 M, dicumarol = 2 x 10 -5 M. In normal Ca buffer, activation by K 3 was slower than Phe, being maximal at 2' but more sustained. Dicumarol and tert-butyl hydroperoxide (t-BH) activated phosphorylase similarly. The xanthine-xanthine oxidase (X-XO) system stimulated activation similar to K 3 . Dicumarol greatly augmented phosphorylase activation by K 3 but had no effect on Phe action. Depletion of extracellular Ca abolished Phe action, markedly diminished t-BH and dicumarol, but had no effect on K 3 or X-XO activation of phosphorylase. Ca efflux exchange measured in 45 Ca preloaded cells were stimulated equally by Phe, K 3 , dicumarol, or K 3 + dicumarol in the presence of extracellular Ca. Absence of extracellular Ca abolished Phe effect but minimally affected stimulation by K 3 or K 3 + dicumarol. These data suggest that activation of glycogen phosphorylase by sublethal doses of quinones may not reflect the degree and the mechanism of intracellular Ca mobilization

Regulatory Approaches for Adding Capacity to Existing Hydropower Facilities

Energy Technology Data Exchange (ETDEWEB)

Levine, Aaron L. [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Curtis, Taylor L. [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Kazerooni, Borna [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

2017-10-24

In 2015, hydroelectric generation accounted for more than 6 percent of total net electricity generation in the United States and 46 percent of electricity generation from all renewables. The United States has considerable hydroelectric potential beyond what is already being developed. Nearly 7 GW of this potential is found by adding capacity to existing hydropower facilities. To optimize the value of hydroelectric generation, the U.S. Department of Energy's Hydropower Vision Study highlights the importance of adding capacity to existing facilities. This report provides strategic approaches and considerations for Federal Energy Regulatory Commission licensed and exempt hydropower facilities seeking to increase generation capacity, which may include increases from efficiency upgrades. The regulatory approaches reviewed for this report include capacity and non-capacity amendments, adding capacity during relicensing, and adding capacity when converting a license to a 10-MW exemption.

Research progress on trifluoromethyl-based radical reaction process

Science.gov (United States)

Song, Hao

2017-12-01

Due to the unique properties imparted by the trifluoromethyl group, such as high electron density and strong lipotropy, which effectively improve acidity, lipophilicity and metabolic stability of the molecule itself, trifluoromethyl-substituted organic compounds are becoming increasingly important as structural motifs in pharmaceuticals, agrochemicals and organic materials. In this review, we present several methods developed for the direct introduction of a trifluoromethyl group, beginning with its rich and storied history. Then the present article addresses mechanism and process in carbon-carbon bond forming reaction based on radical process which is divided into three parts according to the way of CF3 radical generation. Finally, challenges and opportunities of researches on trifluoromethylation reactions facing are prospected.

On radicalizing behaviorism: A call for cultural analysis

Science.gov (United States)

Malagodi, E. F.

1986-01-01

Our culture at large continues many practices that work against the well-being of its members and its chances for survival. Our discipline has failed to realize its potential for contributing to the understanding of these practices and to the generation of solutions. This failure of realization is in part a consequence of the general failure of behavior analysts to view social and cultural analysis as a fundamental component of radical behaviorism. This omission is related to three prevailing practices of our discipline. First, radical behaviorism is characteristically defined as a “philosophy of science,” and its concerns are ordinarily restricted to certain epistemological issues. Second, theoretical extensions to social and cultural phenomena too often depend solely upon principles derived from the analysis of behavior. Third, little attention has been directed at examining the relationships that do, or that should, exist between our discipline and related sciences. These practices themselves are attributed to certain features of the history of our field. Two general remedies for this situation are suggested: first, that radical behaviorism be treated as a comprehensive world view in which epistemological, psychological, and cultural analyses constitute interdependent components; second, that principles derived from compatible social-science disciplines be incorporated into radical behaviorism. PMID:22478643

Benefit Evaluation of Wind Turbine Generators in Wind Farms Using Capacity-Factor Analysis and Economic-Cost Methods

DEFF Research Database (Denmark)

Chen, Zhe; Wang, L.; Yeh, T-H.

2009-01-01

Due to the recent price spike of the international oil and the concern of global warming, the development and deployment of renewable energy become one of the most important energy policies around the globe. Currently, there are different capacities and hub heights for commercial wind turbine gen...... height for WTGs that have been installed in Taiwan. Important outcomes affecting wind cost of energy in comparison with economic results using the proposed economic-analysis methods for different WFs are also presented.......Due to the recent price spike of the international oil and the concern of global warming, the development and deployment of renewable energy become one of the most important energy policies around the globe. Currently, there are different capacities and hub heights for commercial wind turbine...... generators (WTGs). To fully capture wind energy, different wind farms (WFs) should select adequate capacity of WTGs to effectively harvest wind energy and maximize their economic benefit. To establish selection criterion, this paper first derives the equations for capacity factor (CF) and pairing performance...

Screening of Six Medicinal Plant Extracts Obtained by Two Conventional Methods and Supercritical CO₂ Extraction Targeted on Coumarin Content, 2,2-Diphenyl-1-picrylhydrazyl Radical Scavenging Capacity and Total Phenols Content.

Science.gov (United States)

Molnar, Maja; Jerković, Igor; Suknović, Dragica; Bilić Rajs, Blanka; Aladić, Krunoslav; Šubarić, Drago; Jokić, Stela

2017-02-24

Six medicinal plants Helichrysum italicum (Roth) G. Don, Angelica archangelica L., Lavandula officinalis L., Salvia officinalis L., Melilotus officinalis L., and Ruta graveolens L. were used. The aim of the study was to compare their extracts obtained by Soxhlet (hexane) extraction, maceration with ethanol (EtOH), and supercritical CO₂ extraction (SC-CO₂) targeted on coumarin content (by high performance liquid chromatography with ultraviolet detection, HPLC-UV), 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) scavenging capacity, and total phenols (TPs) content (by Folin-Ciocalteu assay). The highest extraction yields were obtained by EtOH, followed by hexane and SC-CO₂. The highest coumarin content (316.37 mg/100 g) was found in M. officinalis EtOH extracts, but its SC-CO₂ extraction yield was very low for further investigation. Coumarin was also found in SC-CO₂ extracts of S. officinalis , R. graveolens , A. archangelica , and L. officinalis . EtOH extracts of all plants exhibited the highest DPPH scavenging capacity. SC-CO₂ extracts exhibited antiradical capacity similar to hexane extracts, while S. officinalis SC-CO₂ extracts were the most potent (95.7%). EtOH extracts contained the most TPs (up to 132.1 mg gallic acid equivalents (GAE)/g from H. italicum ) in comparison to hexane or SC-CO₂ extracts. TPs content was highly correlated to the DPPH scavenging capacity of the extracts. The results indicate that for comprehensive screening of different medicinal plants, various extraction techniques should be used in order to get a better insight into their components content or antiradical capacity.

Relation between track structure and LET effect on free radical formation for ion beam-irradiated alanine dosimeter

International Nuclear Information System (INIS)

Krushev, V.V.; Koizumi, Hitoshi; Ichikawa, Tsuneki; Yoshida, Hiroshi; Shibata, Hiromi; Tagawa, Seiichi; Yoshida, Yoichi

1994-01-01

The yield and local concentration of free radicals generated from alanine (α-aminopropionic acid) by irradiation with 3 MeV H + and He + ions were examined by means of electron spin resonance (ESR) and ESR power saturation methods at room temperature. The G-value of the radical formation showed a marked dependence on linear energy transfer (LET) of the ions. The G-value for the H + ion (average LET: 28 eV/nm) was almost the same as that for γ-irradiation and it was smaller by a factor of 1/4.7 for the He + ion (average LET: 225eV/nm). Combining the local concentration of the free radicals along the ion tracks with the G-values and the reported ion range, the radius of a track filled with free radicals was estimated to be 4 ∼ 5 nm by assuming a simple rod-shaped track with a constant radius and homogeneous distribution of the free radicals in it. The track radius scarcely depends on the LET within the range examined. The radiation energy deposited in the core region of the ion track was concluded to spread over the rod to generate free radicals. (author)

Application of the EPR technique to examine free radical qualities reducing infection of spring wheat grain with pathogenic fungi by He-Ne laser irradiation

International Nuclear Information System (INIS)

Gagoś, M.; Koper, R.; Sujak, A.; Misiak, L.E.; Kowalczuk, E.

2000-01-01

Samples of spring wheat grain, Jasna cv., infected with pathogenic fungi (Aspergillus niger, Penicillium sp., Fusarium, Mucor) were examined using an EPR technique. Considering the quantity of generated free radicals the fungi belonged to most toxine generating. Their toxicity was connected with the number of free radicals generated in examined grain. Grain was irradiated with He-Ne laser at known wavelength, power density and time of exposure what gave the mycostatic effect appearing in decrease of free radicals in grain samples. However, this process was not stable as the increase of free radicals was observed again with the regrowth of fungi after some days

Isolation and Characterization of the 2,2'-Azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) Radical Cation-Scavenging Reaction Products of Arbutin.

Science.gov (United States)

Tai, Akihiro; Ohno, Asako; Ito, Hideyuki

2016-09-28

Arbutin, a glucoside of hydroquinone, has shown strong 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation-scavenging activity, especially in reaction stoichiometry. This study investigated the reaction mechanism of arbutin against ABTS radical cation that caused high stoichiometry of arbutin in an ABTS radical cation-scavenging assay. HPLC analysis of the reaction mixture of arbutin and ABTS radical cation indicated the existence of two reaction products. The two reaction products were purified and identified to be a covalent adduct of arbutin with an ABTS degradation fragment and 3-ethyl-6-sulfonate benzothiazolone. A time-course study of the radical-scavenging reactions of arbutin and the two reaction products suggested that one molecule of arbutin scavenges three ABTS radical cation molecules to generate an arbutin-ABTS fragment adduct as a final reaction product. The results suggest that one molecule of arbutin reduced two ABTS radical cation molecules to ABTS and then cleaved the third ABTS radical cation molecule to generate two products, an arbutin-ABTS fragment adduct and 3-ethyl-6-sulfonate benzothiazolone.

Effects of treatment on free radicals in patients with pulmonary ...

African Journals Online (AJOL)

fense against Mycobacteria, enhanced ROS generation may promote tissue injury .... time of analysis for electrolytes and free radicals. The sputum of patients .... with high level INH resistance in MTB by using real time technology PCR with 3 ...

Some aspects of radiation-induced free-radical chemistry of biologically important molecules

International Nuclear Information System (INIS)

Sonntag, C. von

1992-01-01

Biologically relevant material is usually associated with considerable amounts of water. When ionizing radiation interacts with such material one must consider two modes of energy deposition: the direct effect (ionizing radiation is absorbed by the biomolecules) and the indirect effect (ionizing radiation is absorbed by the surrounding water). In the direct effect, radical cations plus electrons, and excited states of the biomolecules are formed. In the indirect effect the water is decomposed resulting in the formation of the water radicals OH,H and e aq - . These reactive intermediates then interact with the biomolecules. When such systems are irradiated oxygen is often present. As a result of this, the radicals formed in the biomolecules by the various routes are converted into the corresponding peroxyl radicals. In certain cases, e.g. with the nucleobases of DNA, radical cations can be produced in dilute aqueous solutions by radiation-generated SO 4 - radicals, and the fate of these nucleobase radical cations studied by pulse radiolysis and product analysis. Attention will be drawn to the fact that frequently some of the reaction products of the radical cations with water are identical to those formed by OH radical attack, but that there are also marked differences. Similarly, protonation of radical anions (formed by the reaction of solvated electrons with the biomolecules) and the reaction of H-atoms with these molecules can lead to radical intermediates with considerably differing characteristics. Our present knowledge of the variety of reactions of the peroxyl radicals occurring in aqueous solutions will be briefly discussed, emphasizing the large variety of HO 2 /O 2 - elimination reactions and pointing to the reversibility of the oxygen addition (RO 2 →R + O 2 ) in some systems recently studied. (author)

[In vitro anti-inflammatory and free radical scavenging activities of flavans from Ilex centrochinensis].

Science.gov (United States)

Li, Lu-jun; Yu, Li-juan; Li, Yan-ci; Liu, Meng-yuan; Wu, Zheng-zhi

2015-04-01

This study was carried out to evaluate the anti-inflammatory and free radical scavenging activities of flavans from flex centrochinensis S. Y. Hu in vitro and their structure-activity relationship. LPS-stimulated RAW 264.7 macrophage was used as inflammatory model. MTT assay for cell availability, Griess reaction for nitric oxide (NO) production, the content of TNF-alpha, IL-1beta, IL-6 and PGE, were detected with ELISA kits; DPPH, superoxide anion and hydroxyl free radicals scavenging activities were also investigated. According to the result, all flavans tested exhibited anti-inflammatory effect in different levels. Among them, compounds 1, 3, 4 and 6 showed potent anti-inflammatory effect through the inhibition of NO, TNF-alpha, IL-lp and IL-6, of which 1 was the most effective inhibitor, however, 2 and 5 were relatively weak or inactive. The order of free radical scavenging activities was similar to that of anti-inflammatory activities. Therefore, these results suggest that 3, 4 and 6, especially of 1, were,in part responsible for the anti-inflammatory and free radical scavenging activity of Ilex centrochinensis. Hydroxyl group at 4'-position of B-ring plays an important role in the anti-inflammatory and free radical scavenging capacities.