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Sample records for radical mechanisms functional

  1. Electronic states of aryl radical functionalized graphenes: Density functional theory study

    Science.gov (United States)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-06-01

    Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1-4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR-(Bz) n (n = 1-4) showed that the aryl radical binds to the carbon atom of GR, and a C-C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol-1. The electronic states of GR-(Bz) n were examined on the basis of theoretical results.

  2. Molecular Mechanisms behind Free Radical Scavengers Function against Oxidative Stress

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    Fereshteh Ahmadinejad

    2017-07-01

    Full Text Available Accumulating evidence shows that oxidative stress is involved in a wide variety of human diseases: rheumatoid arthritis, Alzheimer’s disease, Parkinson’s disease, cancers, etc. Here, we discuss the significance of oxidative conditions in different disease, with the focus on neurodegenerative disease including Parkinson’s disease, which is mainly caused by oxidative stress. Reactive oxygen and nitrogen species (ROS and RNS, respectively, collectively known as RONS, are produced by cellular enzymes such as myeloperoxidase, NADPH-oxidase (nicotinamide adenine dinucleotide phosphate-oxidase and nitric oxide synthase (NOS. Natural antioxidant systems are categorized into enzymatic and non-enzymatic antioxidant groups. The former includes a number of enzymes such as catalase and glutathione peroxidase, while the latter contains a number of antioxidants acquired from dietary sources including vitamin C, carotenoids, flavonoids and polyphenols. There are also scavengers used for therapeutic purposes, such as 3,4-dihydroxyphenylalanine (L-DOPA used routinely in the treatment of Parkinson’s disease (not as a free radical scavenger, and 3-methyl-1-phenyl-2-pyrazolin-5-one (Edaravone that acts as a free radical detoxifier frequently used in acute ischemic stroke. The cell surviving properties of L-DOPA and Edaravone against oxidative stress conditions rely on the alteration of a number of stress proteins such as Annexin A1, Peroxiredoxin-6 and PARK7/DJ-1 (Parkinson disease protein 7, also known as Protein deglycase DJ-1. Although they share the targets in reversing the cytotoxic effects of H2O2, they seem to have distinct mechanism of function. Exposure to L-DOPA may result in hypoxia condition and further induction of ORP150 (150-kDa oxygen-regulated protein with its concomitant cytoprotective effects but Edaravone seems to protect cells via direct induction of Peroxiredoxin-2 and inhibition of apoptosis.

  3. Role of the reacting free radicals on the antioxidant mechanism of curcumin

    Energy Technology Data Exchange (ETDEWEB)

    Galano, Annia, E-mail: agalano@prodigy.net.mx [Universidad Autonoma Metropolitana-Iztapalapa, Departamento de Quimica, Area de Quimica Analitica, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, C.P. 09340, Mexico D.F. (Mexico); Alvarez-Diduk, Ruslan; Ramirez-Silva, Maria Teresa; Alarcon-Angeles, Georgina; Rojas-Hernandez, Alberto [Universidad Autonoma Metropolitana-Iztapalapa, Departamento de Quimica, Area de Quimica Analitica, San Rafael Atlixco 186, Col. Vicentina, Iztapalapa, C.P. 09340, Mexico D.F. (Mexico)

    2009-09-18

    Density functional theory is used to study the antioxidant mechanism of curcumin. Five different mechanisms are considered: single electron transfer (SET), radical adduct formation (RAF), H atom transfer from neutral curcumin (HAT), H atom transfer from deprotonated curcumin (HAT-D), and sequential proton loss electron transfer (SPLET). The influence of the environment is investigated for polar and non-polar surroundings. The apparent contradictions among previous experimental results are explained by the role of the nature of the reacting free radical on the relative importance of the above mentioned mechanism. It is proposed that the curcumin + DPPH reaction actually takes place mainly through the SPLET mechanism, while the reaction with {sup {center_dot}}OCH{sub 3}, and likely with other alkoxyl radicals, is governed by the HAT mechanism. Branching ratios for the {sup {center_dot}}OCH{sub 3} + curcumin reaction are reported for the first time. The calculated overall rate constants for this reaction are 1.16 x 10{sup 10} (benzene) and 5.52 x 10{sup 9} (water) L mol{sup -1} s{sup -1}. The role of phenolic groups on the antioxidant activity of curcumin has been experimentally confirmed.

  4. Mechanisms of free radical-induced damage to DNA.

    Science.gov (United States)

    Dizdaroglu, Miral; Jaruga, Pawel

    2012-04-01

    Endogenous and exogenous sources cause free radical-induced DNA damage in living organisms by a variety of mechanisms. The highly reactive hydroxyl radical reacts with the heterocyclic DNA bases and the sugar moiety near or at diffusion-controlled rates. Hydrated electron and H atom also add to the heterocyclic bases. These reactions lead to adduct radicals, further reactions of which yield numerous products. These include DNA base and sugar products, single- and double-strand breaks, 8,5'-cyclopurine-2'-deoxynucleosides, tandem lesions, clustered sites and DNA-protein cross-links. Reaction conditions and the presence or absence of oxygen profoundly affect the types and yields of the products. There is mounting evidence for an important role of free radical-induced DNA damage in the etiology of numerous diseases including cancer. Further understanding of mechanisms of free radical-induced DNA damage, and cellular repair and biological consequences of DNA damage products will be of outmost importance for disease prevention and treatment.

  5. Erectile function after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Frey, Anders; Jakobsen, Henrik

    2016-01-01

    collected database and a cross-sectional, questionnaire-based study in patients following radical prostatectomy. Erectile function was assessed with the IIEF-5 and the question "Is your erectile function as good as before the surgery (yes/no)". Patients were included if they were sexually active before...

  6. FUNCTIONAL RESULTS OF ENDOSCOPIC EXTRAPERITONEAL RADICAL INTRAFASCIAL PROSTATECTOMY

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    D. V. Perlin

    2014-01-01

    Full Text Available Introduction. Endoscopic radical prostatectomy is a highly effective treatment for localized prostate cancer. Intrafascial prostate dissection ensures early recovery of urine continence function and erectile function. This article sums up our own experience of performing intrafascial endoscopic prostatectomy.Materials and methods. 25 patients have undergone this procedure. 12 months after surgery 88.2 % of the patients were fully continent, 11.7 % had symptoms of minimal stress urinary incontinence. We encountered no cases of positive surgical margins and one case of bio-chemical recurrence of the disease.Conclusion. Oncologically, intrafascial endoscopic radical prostatectomy is as effective as other modifications of radical prostatectomy and has the benefits of early recovery of urine continence function and erectile function

  7. Radical C-H functionalization to construct heterocyclic compounds.

    Science.gov (United States)

    Yu, Jin-Tao; Pan, Changduo

    2016-02-07

    Heterocyclic compounds are widely present in natural products, pharmaceuticals and bioactive molecules. Thus, organic and pharmaceutical chemists have been making extensive efforts to construct those heterocyclic frameworks through developing versatile and efficient synthetic strategies. The direct C-H functionalization via the radical pathway has emerged as a promising and dramatic approach towards heterocycles with high atom- and step-economy. Heterocyclic compounds such as coumarins, furans, benzofurans, xanthones, benzothiazoles, indoles, indolines, oxindoles, quinolines, isoquinolines, quinoxaline, and phenanthridines have been successfully synthesized by C-H functionalization through the radical pathway. In this review, recent advances on radical C-H functionalization to construct heterocyclic compounds are highlighted with discussions.

  8. Modeling of the Reaction Mechanism of Enzymatic Radical C–C Coupling by Benzylsuccinate Synthase

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    Maciej Szaleniec

    2016-04-01

    Full Text Available Molecular modeling techniques and density functional theory calculations were performed to study the mechanism of enzymatic radical C–C coupling catalyzed by benzylsuccinate synthase (BSS. BSS has been identified as a glycyl radical enzyme that catalyzes the enantiospecific fumarate addition to toluene initiating its anaerobic metabolism in the denitrifying bacterium Thauera aromatica, and this reaction represents the general mechanism of toluene degradation in all known anaerobic degraders. In this work docking calculations, classical molecular dynamics (MD simulations, and DFT+D2 cluster modeling was employed to address the following questions: (i What mechanistic details of the BSS reaction yield the most probable molecular model? (ii What is the molecular basis of enantiospecificity of BSS? (iii Is the proposed mechanism consistent with experimental observations, such as an inversion of the stereochemistry of the benzylic protons, syn addition of toluene to fumarate, exclusive production of (R-benzylsuccinate as a product and a kinetic isotope effect (KIE ranging between 2 and 4? The quantum mechanics (QM modeling confirms that the previously proposed hypothetical mechanism is the most probable among several variants considered, although C–H activation and not C–C coupling turns out to be the rate limiting step. The enantiospecificity of the enzyme seems to be enforced by a thermodynamic preference for binding of fumarate in the pro(R orientation and reverse preference of benzyl radical attack on fumarate in pro(S pathway which results with prohibitively high energy barrier of the radical quenching. Finally, the proposed mechanism agrees with most of the experimental observations, although the calculated intrinsic KIE from the model (6.5 is still higher than the experimentally observed values (4.0 which suggests that both C–H activation and radical quenching may jointly be involved in the kinetic control of the reaction.

  9. 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.

  10. Mechanisms of radical removal by SO2

    DEFF Research Database (Denmark)

    Rasmussen, Christian Lund; Glarborg, Peter; Marshall, Paul

    2007-01-01

    It is well established from experiments in premixed, laminar flames, jet-stirred reactors, flow reactors, and batch reactors that SO2 acts to catalyze hydrogen atom removal at stoichiometric and reducing conditions. However, the commonly accepted mechanism for radical removal, SO2 + H......(+M) reversible arrow HOSO(+M), HOSO + H/OH reversible arrow SO2 + H-2/H2O, has been challenged by recent theoretical and experimental results. Based on ab initio calculations for key reactions, we update the kinetic model for this chemistry and re-examine the mechanism of fuel/SO2 interactions. We find...... that the interaction of SO, with the radical pool is more complex than previously assumed, involving HOSO and SO, as well as, at high temperatures also HSO, SH, and S. The revised mechanism with a high rate constant for H + SO2 recombination and with SO + H2O, rather than SO2 + H-2, as major products of the HOSO + H...

  11. Studying mechanism of radical reactions: From radiation to nitroxides as research tools

    Science.gov (United States)

    Maimon, Eric; Samuni, Uri; Goldstein, Sara

    2018-02-01

    Radicals are part of the chemistry of life, and ionizing radiation chemistry serves as an indispensable research tool for elucidation of the mechanism(s) underlying their reactions. The ever-increasing understanding of their involvement in diverse physiological and pathological processes has expanded the search for compounds that can diminish radical-induced damage. This review surveys the areas of research focusing on radical reactions and particularly with stable cyclic nitroxide radicals, which demonstrate unique antioxidative activities. Unlike common antioxidants that are progressively depleted under oxidative stress and yield secondary radicals, nitroxides are efficient radical scavengers yielding in most cases their respective oxoammonium cations, which are readily reduced back in the tissue to the nitroxide thus continuously being recycled. Nitroxides, which not only protect enzymes, cells, and laboratory animals from diverse kinds of biological injury, but also modify the catalytic activity of heme enzymes, could be utilized in chemical and biological systems serving as a research tool for elucidating mechanisms underlying complex chemical and biochemical processes.

  12. Modification of Cys-418 of pyruvate formate-lyase by methacrylic acid, based on its radical mechanism.

    Science.gov (United States)

    Plaga, W; Vielhaber, G; Wallach, J; Knappe, J

    2000-01-21

    The recently determined crystal structure of pyruvate formate-lyase (PFL) suggested a new view of the mechanism of this glycyl radical enzyme, namely that intermediary thiyl radicals of Cys-418 and Cys-419 participate in different ways [Becker, A. et al. (1999) Nat. Struct. Biol. 6, 969-975]. We report here a suicide reaction of PFL that occurs with the substrate-analog methacrylate with retention of the protein radical (K(I)=0.42 mM, k(i)=0.14 min(-1)). Using [1-(14)C]methacrylate (synthesized via acetone cyanhydrin), the reaction end-product was identified by peptide mapping and cocrystallization experiments as S-(2-carboxy-(2S)-propyl) substituted Cys-418. The stereoselectivity of the observed Michael addition reaction is compatible with a radical mechanism that involves Cys-418 thiyl as nucleophile and Cys-419 as H-atom donor, thus supporting the functional assignments of these catalytic amino acid residues derived from the protein structure.

  13. Improved Mechanical Performance Fracture Properties and Reliability of Radical-Cured Thermosets

    Energy Technology Data Exchange (ETDEWEB)

    Redline, Erica Marie [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Bolintineanu, Dan S. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lane, J. Matthew [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Stevens, Mark J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Alam, Todd M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Celina, Mathias C. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2016-10-01

    The aim of this study was to alter polymerization chemistry to improve network homogeneity in free-radical crosslinked systems. It was hypothesized that a reduction in heterogeneity of the network would lead to improved mechanical performance. Experiments and simulations were carried out to investigate the connection between polymerization chemistry, network structure and mechanical properties. Experiments were conducted on two different monomer systems - the first is a single monomer system, urethane dimethacrylate (UDMA), and the second is a two-monomer system consisting of bisphenol A glycidyl dimethacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) in a ratio of 70/30 BisGMA/TEGDMA by weight. The methacrylate systems were crosslinked using traditional radical polymeriza- tion (TRP) with azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as an initiator; TRP systems were used as the control. The monomers were also cross-linked using activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) as a type of controlled radical polymerization (CRP). FTIR and DSC were used to monitor reac- tion kinetics of the systems. The networks were analyzed using NMR, DSC, X-ray diffraction (XRD), atomic force microscopy (AFM), and small angle X-ray scattering (SAXS). These techniques were employed in an attempt to quantify differences between the traditional and controlled radical polymerizations. While a quantitative methodology for characterizing net- work morphology was not established, SAXS and AFM have shown some promising initial results. Additionally, differences in mechanical behavior were observed between traditional and controlled radical polymerized thermosets in the BisGMA/TEGDMA system but not in the UDMA materials; this finding may be the result of network ductility variations between the two materials. Coarse-grained molecular dynamics simulations employing a novel model of the CRP reaction were carried out for

  14. Cytoprotective Mechanisms Mediated by Polyphenols from Chilean Native Berries against Free Radical-Induced Damage on AGS Cells.

    Science.gov (United States)

    Ávila, Felipe; Theoduloz, Cristina; López-Alarcón, Camilo; Dorta, Eva; Schmeda-Hirschmann, Guillermo

    2017-01-01

    The prevalence of cytoprotective mechanisms induced by polyphenols such as activation of intracellular antioxidant responses (ICM) and direct free radical scavenging was investigated in native Chilean species of strawberries, raspberries, and currants. Human gastric epithelial cells were co- and preincubated with polyphenolic-enriched extracts (PEEs) from Chilean raspberries ( Rubus geoides ), strawberries ( Fragaria chiloensis ssp. chiloensis f . chiloensis ), and currants ( Ribes magellanicum ) and challenged with peroxyl and hydroxyl radicals. Cellular protection was determined in terms of cell viability, glyoxalase I and glutathione s-transferases activities, and carboxymethyl lysine (CML) and malondialdehyde levels. Our results indicate that cytoprotection induced by ICM was the prevalent mechanism for Rubus geoides and F. chiloensis . This agreed with increased levels of glyoxalase I and glutathione S-transferase activities in cells preincubated with PEEs. ORAC index indicated that F. chiloensis was the most efficient peroxyl radical scavenger. Moreover, ICM mediated by F. chiloensis was effective in protecting cells from CML accumulation in contrast to the protective effects induced by free radical scavenging. Our results indicate that although both polyphenol-mediated mechanisms can exert protective effects, ICM was the most prevalent in AGS cells. These results suggest a potential use of these native berries as functional food.

  15. Reaction kinetics and mechanisms of organosilicon fungicide flusilazole with sulfate and hydroxyl radicals.

    Science.gov (United States)

    Mercado, D Fabio; Bracco, Larisa L B; Arques, Antonio; Gonzalez, Mónica C; Caregnato, Paula

    2018-01-01

    Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 × 10 9 s -1 M -1 for the reaction of the fungicide with HO and 4.6 × 10 8  s -1  M -1 for the same reaction with SO 4 - radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S 2 O 8 2- with flusilazole, were identified as α-aminoalkyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively. Copyright © 2017. Published by Elsevier Ltd.

  16. Quantum Chemical Study on the Antioxidation Mechanism of Piceatannol and Isorhapontigenin toward Hydroxyl and Hydroperoxyl Radicals.

    Directory of Open Access Journals (Sweden)

    Yang Lu

    Full Text Available A systematic study of the antioxidation mechanisms behind hydroxyl (•OH and hydroperoxyl (•OOH radical scavenging activity of piceatannol (PIC and isorhapontigenin (ISO was carried out using density functional theory (DFT method. Two reaction mechanisms, abstraction (ABS and radical adduct formation (RAF, were discussed. A total of 24 reaction pathways of scavenging •OH and •OOH with PIC and ISO were investigated in the gas phase and solution. The thermodynamic and kinetic properties of all pathways were calculated. Based on these results, we evaluated the antioxidant activity of every active site of PIC and ISO and compared the abilities of PIC and ISO to scavenge radicals. According to our results, PIC and ISO may act as effective •OH and •OOH scavengers in organism. A4-hydroxyl group is a very important active site for PIC and ISO to scavenge radicals. The introducing of -OH or -OCH3 group to the ortho-position of A4-hydroxyl group would increase its antioxidant activity. Meanwhile, the conformational effect was researched, the results suggest that the presence and pattern of intramolecular hydrogen bond (IHB are considerable in determining the antioxidant activity of PIC and ISO.

  17. 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.

  18. Cytoprotective Mechanisms Mediated by Polyphenols from Chilean Native Berries against Free Radical-Induced Damage on AGS Cells

    Directory of Open Access Journals (Sweden)

    Felipe Ávila

    2017-01-01

    Full Text Available The prevalence of cytoprotective mechanisms induced by polyphenols such as activation of intracellular antioxidant responses (ICM and direct free radical scavenging was investigated in native Chilean species of strawberries, raspberries, and currants. Human gastric epithelial cells were co- and preincubated with polyphenolic-enriched extracts (PEEs from Chilean raspberries (Rubus geoides, strawberries (Fragaria chiloensis ssp. chiloensis f. chiloensis, and currants (Ribes magellanicum and challenged with peroxyl and hydroxyl radicals. Cellular protection was determined in terms of cell viability, glyoxalase I and glutathione s-transferases activities, and carboxymethyl lysine (CML and malondialdehyde levels. Our results indicate that cytoprotection induced by ICM was the prevalent mechanism for Rubus geoides and F. chiloensis. This agreed with increased levels of glyoxalase I and glutathione S-transferase activities in cells preincubated with PEEs. ORAC index indicated that F. chiloensis was the most efficient peroxyl radical scavenger. Moreover, ICM mediated by F. chiloensis was effective in protecting cells from CML accumulation in contrast to the protective effects induced by free radical scavenging. Our results indicate that although both polyphenol-mediated mechanisms can exert protective effects, ICM was the most prevalent in AGS cells. These results suggest a potential use of these native berries as functional food.

  19. Radiation-induced polymerisation of 2,3-dihydrofuran: free-radical or cationic mechanism?

    International Nuclear Information System (INIS)

    Janovsky, Igor; Naumov, Sergej; Knolle, Wolfgang; Mehnert, Reiner

    2005-01-01

    Concentrated (10 mol%) solutions of 2,3-dihydrofuran in CFCl 2 CF 2 Cl matrix were irradiated at 77 K and several intermediates (dimer radical cation, dihydrofuryl radical, and polymer radicals) were observed by low-temperature EPR spectroscopy. The irradiated solutions yielded after melting a polymeric product, which was characterised by IR spectroscopy and gel permeation chromatography. The polydisperse polymer is assumed to be formed mainly by a cationic process initiated by a dimer carbocation. The free-radical mechanism via the dihydrofuryl radical leads to low molecular weight oligomers only. Quantum chemical calculations support the interpretation of the experimental results

  20. 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

  1. An efficient quantum mechanical method for radical pair recombination reactions.

    Science.gov (United States)

    Lewis, Alan M; Fay, Thomas P; Manolopoulos, David E

    2016-12-28

    The standard quantum mechanical expressions for the singlet and triplet survival probabilities and product yields of a radical pair recombination reaction involve a trace over the states in a combined electronic and nuclear spin Hilbert space. If this trace is evaluated deterministically, by performing a separate time-dependent wavepacket calculation for each initial state in the Hilbert space, the computational effort scales as O(Z 2 log⁡Z), where Z is the total number of nuclear spin states. Here we show that the trace can also be evaluated stochastically, by exploiting the properties of spin coherent states. This results in a computational effort of O(MZlog⁡Z), where M is the number of Monte Carlo samples needed for convergence. Example calculations on a strongly coupled radical pair with Z>10 6 show that the singlet yield can be converged to graphical accuracy using just M=200 samples, resulting in a speed up by a factor of >5000 over a standard deterministic calculation. We expect that this factor will greatly facilitate future quantum mechanical simulations of a wide variety of radical pairs of interest in chemistry and biology.

  2. Evaluation of potential reaction mechanisms leading to the formation of coniferyl alcohol α-linkages in lignin: a density functional theory study.

    Science.gov (United States)

    Watts, Heath D; Mohamed, Mohamed Naseer Ali; Kubicki, James D

    2011-12-21

    Five potential reaction mechanisms, each leading to the formation of an α-O-4-linked coniferyl alcohol dimer, and one scheme leading to the formation of a recently proposed free-radical coniferyl alcohol trimer were assessed using density functional theory (DFT) calculations. These potential reaction mechanisms were evaluated using both the calculated Gibbs free energies, to predict the spontaneity of the constituent reactions, and the electron-density mapped Fukui function, to determine the most reactive sites of each intermediate species. The results indicate that each reaction in one of the six mechanisms is thermodynamically favorable to those in the other mechanisms; what is more, the Fukui function for each free radical intermediate corroborates with the thermochemical results for this mechanism. This mechanism proceeds via the formation of two distinct free-radical intermediates, which then react to produce the four α-O-4 stereoisomers.

  3. Investigation of the role of bicyclic peroxy radicals in the oxidation mechanism of toluene.

    Science.gov (United States)

    Birdsall, Adam W; Andreoni, John F; Elrod, Matthew J

    2010-10-07

    The products of the primary OH-initiated oxidation of toluene were investigated using the turbulent flow chemical ionization mass spectrometry technique under different oxygen, NO, and initial OH radical concentrations as well as a range of total pressures. The bicyclic peroxy radical intermediate, a key proposed intermediate species in the Master Chemical Mechanism (MCM) for the atmospheric oxidation of toluene, was detected for the first time. The toluene oxidation mechanism was shown to have a strong oxygen concentration dependence, presumably due to the central role of the bicyclic peroxy radical in determining the stable product distribution at atmospheric oxygen concentrations. The results also suggest a potential role for bicyclic peroxy radical + HO(2) reactions at high HO(2)/NO ratios. These reactions are postulated to be a source of the inconsistencies between environmental chamber results and predictions from the MCM.

  4. Atmospheric Oxidation Mechanism of Furfural Initiated by Hydroxyl Radicals.

    Science.gov (United States)

    Zhao, Xiaocan; Wang, Liming

    2017-05-04

    Furfural is emitted into the atmosphere because of its potential applications as an intermediate to alkane fuels from biomass, industrial usages, and biomass burning. The kinetic and mechanistic information on the furfural chemistry is necessary to assess the fate of furfural in the atmosphere and its impact on the air quality. Here we studied the atmospheric oxidation mechanisms of furfural initiated by the OH radicals using quantum chemistry and kinetic calculations. The reaction of OH and furfural was initiated mainly by OH additions to C 2 and C 5 positions, forming R2 and R5 adducts, which could undergo rapid ring-breakage to form R2B and R5B, respectively. Our calculations showed that these intermediate radicals reacted rather slowly with O 2 under the atmospheric conditions because the additions of O 2 to these radicals are only slightly exothermic and highly reversible. Alternatively, these radicals would react directly with O 3 , NO 2 , HO 2 /RO 2 , etc. Namely, the atmospheric oxidation of furfural would unlikely result in ozone formation. Under typical atmospheric conditions, the main products in OH-initiated furfural oxidation include 2-oxo-3-pentene-1,5-dialdehyde, 5-hydroxy-2(5H)-furanone, 4-oxo-2- butenoic acid, and 2,5-furandione. These compounds will likely stay in the gas phase and are subject to further photo-oxidation.

  5. 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

  6. [Correlation Between Functional Groups and Radical Scavenging Activities of Acidic Polysaccharides from Dendrobium].

    Science.gov (United States)

    Liao, Ying; Yuan, Wen-yu; Zheng, Wen-ke; Luo, Ao-xue; Fan, Yi-jun

    2015-11-01

    To compare the radical scavenging activity of five different acidic polysaccharides, and to find the correlation with the functional groups. Alkali extraction method and Stepwise ethanol precipitation method were used to extract and concentrate the five Dendrobium polysaccharides, and to determine the contents of sulfuric acid and uronic acid of each kind of acidic polysaccharides, and the scavenging activity to ABTS+ radical and hydroxyl radical. Functional group structures were examined by FTIR Spectrometer. Five kinds of Dendrobium polysaccharides had different ability of scavenging ABTS+ free radical and hydroxyl free radical. Moreover, the study had shown that five kinds of antioxidant activity of acidic polysaccharides had obvious correlation withuronic acid and sulfuric acid. The antioxidant activity of each sample was positively correlated with the content of uronic acid, and negatively correlated with the content of sulfuric acid. Sulfuric acid can inhibit the antioxidant activity of acidic polysaccharide but uronic acid can enhance the free radical scavenging activity. By analyzing the structure characteristics of five acidic polysaccharides, all samples have similar structures, however, Dendrobium denneanum, Dendrobium devonianum and Dendrobium officinale which had β configuration have higher antioxidant activity than Dendrobium nobile and Dendrobium fimbriatum which had a configuration.

  7. Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

    DEFF Research Database (Denmark)

    Antonacci, Giuseppe; Ahlburg, Andreas; Fristrup, Peter

    2017-01-01

    The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group....... Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an SRN1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor...

  8. 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

  9. 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.

  10. 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.)

  11. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    International Nuclear Information System (INIS)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke

    2000-01-01

    The interaction of caffeic acid with e aq - , (CH 3 ) 2 (OH) CCH 2 · , CO 2 ·- , H · , ·OH and N 3 · radicals were studied by γ-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/·OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  12. Validation study of a web-based assessment of functional recovery after radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Vickers Andrew J

    2010-08-01

    Full Text Available Abstract Background Good clinical care of prostate cancer patients after radical prostatectomy depends on careful assessment of post-operative morbidities, yet physicians do not always judge patient symptoms accurately. Logistical problems associated with using paper questionnaire limit their use in the clinic. We have implemented a web-interface ("STAR" for patient-reported outcomes after radical prostatectomy. Methods We analyzed data on the first 9 months of clinical implementation to evaluate the validity of the STAR questionnaire to assess functional outcomes following radical prostatectomy. We assessed response rate, internal consistency within domains, and the association between survey responses and known predictors of sexual and urinary function, including age, time from surgery, nerve sparing status and co-morbidities. Results Of 1581 men sent an invitation to complete the instrument online, 1235 responded for a response rate of 78%. Cronbach's alpha was 0.84, 0.86 and 0.97 for bowel, urinary and sexual function respectively. All known predictors of sexual and urinary function were significantly associated with survey responses in the hypothesized direction. Conclusions We have found that web-based assessment of functional recovery after radical prostatectomy is practical and feasible. The instrument demonstrated excellent psychometric properties, suggested that validity is maintained when questions are transferred from paper to electronic format and when patients give responses that they know will be seen by their doctor and added to their clinic record. As such, our system allows ready implementation of patient-reported outcomes into routine clinical practice.

  13. Radical Initiated Hydrosilylation on Silicon Nanocrystal Surfaces: An Evaluation of Functional Group Tolerance and Mechanistic Study.

    Science.gov (United States)

    Yang, Zhenyu; Gonzalez, Christina M; Purkait, Tapas K; Iqbal, Muhammad; Meldrum, Al; Veinot, Jonathan G C

    2015-09-29

    Hydrosilylation is among the most common methods used for modifying silicon surface chemistry. It provides a wide range of surface functionalities and effective passivation of surface sites. Herein, we report a systematic study of radical initiated hydrosilylation of silicon nanocrystal (SiNC) surfaces using two common radical initiators (i.e., 2,2'-azobis(2-methylpropionitrile) and benzoyl peroxide). Compared to other widely applied hydrosilylation methods (e.g., thermal, photochemical, and catalytic), the radical initiator based approach is particle size independent, requires comparatively low reaction temperatures, and yields monolayer surface passivation after short reaction times. The effects of differing functional groups (i.e., alkene, alkyne, carboxylic acid, and ester) on the radical initiated hydrosilylation are also explored. The results indicate functionalization occurs and results in the formation of monolayer passivated surfaces.

  14. DFT study on the attacking mechanisms of H and OH radicals to G-C and A-T base pairs in water

    Energy Technology Data Exchange (ETDEWEB)

    Okutsu, N.; Shimamura, K.; Shimizu, E.; Kurita, N., E-mail: kurita@cs.tut.ac.jp [Department of Computer Science and Engineering, Toyohashi University of Technology, Toyohashi, Aichi, 441-8580 (Japan); Shulga, S. [Institute for Food Biotechnology and Genomics, National Academy of Sciences of Ukraine, Kyiv (Ukraine); Danilov, V. I. [Institute of Molecular Biology and Genetics, National Academy of Sciences of Ukraine, Kyiv (Ukraine)

    2016-02-01

    To elucidate the effect of radicals on DNA base pairs, we investigated the attacking mechanism of OH and H radicals to the G-C and A-T base pairs, using the density functional theory (DFT) calculations in water approximated by the continuum solvation model. The DFT calculations revealed that the OH radical abstracts the hydrogen atom of a NH{sub 2} group of G or A base and induces a tautomeric reaction for an A-T base pair more significantly than for a G-C base pair. On the other hand, the H radical prefers to bind to the Cytosine NH{sub 2} group of G-C base pair and induce a tautomeric reaction from G-C to G*-C*, whose activation free energy is considerably small (−0.1 kcal/mol) in comparison with that (42.9 kcal/mol) for the reaction of an A-T base pair. Accordingly, our DFT calculations elucidated that OH and H radicals have a significant effect on A-T and G-C base pairs, respectively. This finding will be useful for predicting the effect of radiation on the genetic information recorded in the base sequences of DNA duplexes.

  15. DFT study on the attacking mechanisms of H and OH radicals to G-C and A-T base pairs in water

    International Nuclear Information System (INIS)

    Okutsu, N.; Shimamura, K.; Shimizu, E.; Kurita, N.; Shulga, S.; Danilov, V. I.

    2016-01-01

    To elucidate the effect of radicals on DNA base pairs, we investigated the attacking mechanism of OH and H radicals to the G-C and A-T base pairs, using the density functional theory (DFT) calculations in water approximated by the continuum solvation model. The DFT calculations revealed that the OH radical abstracts the hydrogen atom of a NH 2 group of G or A base and induces a tautomeric reaction for an A-T base pair more significantly than for a G-C base pair. On the other hand, the H radical prefers to bind to the Cytosine NH 2 group of G-C base pair and induce a tautomeric reaction from G-C to G*-C*, whose activation free energy is considerably small (−0.1 kcal/mol) in comparison with that (42.9 kcal/mol) for the reaction of an A-T base pair. Accordingly, our DFT calculations elucidated that OH and H radicals have a significant effect on A-T and G-C base pairs, respectively. This finding will be useful for predicting the effect of radiation on the genetic information recorded in the base sequences of DNA duplexes

  16. Computational study of the structure-free radical scavenging relationship of procyanidins.

    Science.gov (United States)

    Mendoza-Wilson, Ana María; Castro-Arredondo, Sergio Ivan; Balandrán-Quintana, René Renato

    2014-10-15

    Procyanidins (PCs) are effective free radical scavengers, however, their antioxidant ability is variable because they have different degrees of polymerisation, are composed by distinct types of subunits and are very susceptible to changes in conformation. In this work the structure-free radical scavenging relationship of monomers, dimers and trimers of PCs was studied through the hydrogen atom transfer (HAT), sequential proton-loss electron-transfer (SPLET) and single electron transfer followed by proton transfer (SET-PT) mechanisms in aqueous phase, employing the Density Functional Theory (DFT) computational method. The structure-free radical scavenging relationship of PCs showed a very similar behaviour in HAT and SET-PT mechanisms, but very different in the SPLET mechanism. The structural factor that showed more effects on the ability of PCs to scavenge free radicals in aqueous phase was the conformation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the OH-addition pathway.

    Science.gov (United States)

    Shiroudi, Abolfazl; Deleuze, Michael S; Canneaux, Sébastien

    2014-07-03

    The oxidation mechanisms of naphthalene by OH radicals under inert (He) conditions have been studied using density functional theory along with various exchange-correlation functionals. Comparison has been made with benchmark CBS-QB3 theoretical results. Kinetic rate constants were correspondingly estimated by means of transition state theory and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Comparison with experiment confirms that, on the OH-addition reaction pathway leading to 1-naphthol, the first bimolecular reaction step has an effective negative activation energy around -1.5 kcal mol(-1), whereas this step is characterized by an activation energy around 1 kcal mol(-1) on the OH-addition reaction pathway leading to 2-naphthol. Effective rate constants have been calculated according to a steady state analysis upon a two-step model reaction mechanism. In line with experiment, the correspondingly obtained branching ratios indicate that, at temperatures lower than 410 K, the most abundant product resulting from the oxidation of naphthalene by OH radicals must be 1-naphthol. The regioselectivity of the OH(•)-addition onto naphthalene decreases with increasing temperatures and decreasing pressures. Because of slightly positive or even negative activation energies, the RRKM calculations demonstrate that the transition state approximation breaks down at ambient pressure (1 bar) for the first bimolecular reaction steps. Overwhelmingly high pressures, larger than 10(5) bar, would be required for restoring to some extent (within ∼5% accuracy) the validity of this approximation for all the reaction channels that are involved in the OH-addition pathway. Analysis of the computed structures, bond orders, and free energy profiles demonstrate that all reaction steps involved in the oxidation of naphthalene by OH radicals satisfy Leffler-Hammond's principle. Nucleus independent chemical shift indices and natural bond orbital analysis also show that the computed

  18. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab

    2000-03-01

    The interaction of caffeic acid with e{sub aq}{sup -}, (CH{sub 3}){sub 2}(OH) CCH{sub 2}{sup {center_dot}}, CO{sub 2}{sup {center_dot}}{sup -}, H{sup {center_dot}}, {center_dot}OH and N{sub 3}{sup {center_dot}} radicals were studied by {gamma}-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/{center_dot}OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  19. Preservation of Ejaculatory and Erectile Function after Radical Cystectomy for Urothelial Malignancy

    International Nuclear Information System (INIS)

    Salem, H.K.

    2005-01-01

    Treating cancer patients, sexual issues should not be forgotten. With increasing survival from urologic cancer, quality of life and quality of sexuality have became very important targets in treating those patients. Fertility to those patients who desire fatherhood is sometimes more important than cancer morbidity, especially young patients in the rural areas in our country, to the extent that they may refuse the operation. We describe a new technique to preserve the erectile function and antegrade ejaculation after radical cystectomy. Patients and Methods: Seven potent men with a median age of 40 years (range 35-50) presented with invasive transitional cell carcinoma (TCC) of the lateral or the anterior bladder wall. All patients wished to preserve the ejaculatory function and fertility potential. We described the surgical technique of nerve sparing radical cystectomy with preservation of the vas deferens, seminal vesicles, whole prostate and neurovascular bundles. The follow up period ranged from six months to three years (mean 20 months) to assess recurrence, erectile function and ejaculatory function. Erectile function is normal in all patients with satisfactory sexual intercourse. Antegrade ejaculation was documented in six cases. One of them fathered a child. No local or distant recurrence was detected in the seven patients at the last follow-up. The technique of radical cystectomy (with preservation of the vas deferens, whole prostate and seminal vesicle) is a good option in selected young men with bladder carcinoma in whom preservation of fertility is desirable

  20. 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

  1. 1,2-Fluorine Radical Rearrangements: Isomerization Events in Perfluorinated Radicals.

    Science.gov (United States)

    Van Hoomissen, Daniel J; Vyas, Shubham

    2017-11-16

    Devising effective degradation technologies for perfluoroalkyl substances (PFASs) is an active area of research, where the molecular mechanisms involving both oxidative and reductive pathways are still elusive. One commonly neglected pathway in PFAS degradation is fluorine atom migration in perfluoroalkyl radicals, which was largely assumed to be implausible because of the high C-F bond strength. Using density functional theory calculations, it was demonstrated that 1,2-F atom migrations are thermodynamically favored when the fluorine atom migrated from a less branched carbon center to a more branched carbon center. Activation barriers for these rearrangements were within 19-29 kcal/mol, which are possible to easily overcome at elevated temperatures or in photochemically activated species in the gas or aqueous phase. It was also found that the activation barriers for the 1,2-F atom migration are lowered as much as by 10 kcal/mol when common oxidative degradation products such as HF assisted the rearrangements or if the resulting radical center was stabilized by vicinal π-bonds. Natural bond orbital analyses showed that fluorine moves as a radical in a noncharge-separated state. These findings add an important reaction to the existing knowledge of mechanisms for PFAS degradation and highlights the fact that 1,2-F atom shifts may be a small channel for isomerization of these compounds, but upon availability of mineralization products, this isomerization process could become more prominent.

  2. Kinetics and mechanism of the reaction of recombination of vinyl and hydroxyl radicals

    Science.gov (United States)

    Knyazev, Vadim D.

    2017-10-01

    The recombination of the vinyl (C2H3) and the hydroxyl (OH) radicals was studied computationally using quantum chemistry and master equation/RRKM. The reaction mechanism includes the initial addition, several isomerization steps, and decomposition via seven different channels. The spectrum of products demonstrates temperature dependence in the 300-3000 K range. At low temperatures (below 1600 K), CH3 + HCO products are dominant but at elevated temperatures vinoxy radical (CH2CHO) and hydrogen atom become more important. The acetyl (CH3CO) + H products and formation of vinylidene (CH2C:) and water products are minor but non-negligible.

  3. Reaction between peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

    Science.gov (United States)

    Sikora, Adam; Zielonka, Jacek; Lopez, Marcos; Dybala-Defratyka, Agnieszka; Joseph, Joy; Marcinek, Andrzej; Kalyanaraman, Balaraman

    2013-01-01

    Recently we showed that peroxynitrite (ONOO−) reacts directly and rapidly with aromatic and aliphatic boronic acids (k ≈ 106 M−1s−1). Product analyses and substrate consumption data indicated that ONOO− reacts stoichiometrically with boronates, yielding the corresponding phenols as the major product (~85–90%), and the remaining products (10–15%) were proposed to originate from free radical intermediates (phenyl and phenoxyl radicals). Here we investigated in detail the minor, free radical pathway of boronate reaction with ONOO−. The electron paramagnetic resonance (EPR) spin-trapping technique was used to characterize the free radical intermediates formed from the reaction between boronates and ONOO−. Using 2-methyl-2-nitrosopropane (MNP) and 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) spin traps, phenyl radicals were trapped and detected. Although phenoxyl radicals were not detected, the positive effects of molecular oxygen, and inhibitory effects of hydrogen atom donors (acetonitrile, and 2-propanol) and general radical scavengers (GSH, NADH, ascorbic acid and tyrosine) on the formation of phenoxyl radical-derived nitrated product, suggest that phenoxyl radical was formed as the secondary species. We propose that the initial step of the reaction involves the addition of ONOO− to the boron atom in boronates. The anionic intermediate undergoes both heterolytic (major pathway) and homolytic (minor pathway) cleavage of the peroxy (O-O) bond to form phenol and nitrite as a major product (via a non-radical mechanism), or a radical pair PhB(OH)2O•−…•NO2 as a minor product. It is conceivable that phenyl radicals are formed by the fragmentation of PhB(OH)2O•− radical anion. According to the DFT quantum mechanical calculations, the energy barrier for the dissociation of PhB(OH)2O•− radical anion to form phenyl radicals is only a few kcal/mol, suggesting rapid and spontaneous fragmentation of PhB(OH)2O•− radical anion

  4. Repair Activity of trans-Resveratrol toward 2'-Deoxyguanosine Radicals.

    Science.gov (United States)

    Cheng, Xing; An, Ping; Li, Shujin; Zhou, Liping

    2018-04-26

    In the present study, the repair activity of trans-resveratrol toward 2'-deoxyguanosine (dGuo) radicals in polar and nonpolar solvents was studied using density functional theory. The hydrogen transfer/proton coupled electron transfer and single electron transfer (SET) mechanisms between trans-resveratrol and dGuo-radicals were considered. Taking into consideration the molar fraction of neutral trans-resveratrol (ROH) and anionic trans-resveratrol (RO - ), the overall rate constants for repairing dGuo-radicals by trans-resveratrol are 9.94 × 10 8 and 2.01 × 10 9 dm 3 mol -1 s -1 in polar and nonpolar solvents, respectively, and the overall rate constant of repairing cation radical (dGuo •+ ) by trans-resveratrol via an SET mechanism is 7.17 × 10 9 dm 3 mol -1 s -1 . The repair activity of RO - toward dGuo-radicals is better than that of ROH, but the repair activity of ROH toward dGuo •+ is better than that of RO - . Unfortunately, neither ROH nor RO - can repair the 2'-deoxyribose radicals of dGuo. It can therefore be concluded that trans-resveratrol is an effective antioxidant for repairing base radicals of dGuo and dGuo •+ . The study can help us understand the repair activity of trans-resveratrol toward dGuo radicals.

  5. Oxygen free radicals in rheumatoid arthritis

    NARCIS (Netherlands)

    P. Biemond (Pieter)

    1986-01-01

    textabstractCurrent knowledge strongly suggests that oxygen free radicals are involved in the pathogenesis of RA. Additional information about the mechanism of free radical attack is necessary in order to find out if interaction with the mechanism of free radical damage can be used in the treatment

  6. Separation of photo-induced radical pair in cryptochrome to a functionally critical distance

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Domratcheva, Tatiana; Schulten, Klaus

    2014-01-01

    Cryptochrome is a blue light receptor that acts as a sensor for the geomagnetic field and assists many animals in long-range navigation. The magnetoreceptor function arises from light-induced formation of a radical pair through electron transfer between a flavin cofactor (FAD) and a triad...... of tryptophan residues. Here, this electron transfer is investigated by quantum chemical and classical molecular dynamics calculations. The results reveal how sequential electron transfer, assisted by rearrangement of polar side groups in the cryptochrome interior, can yield a FAD-Trp radical pair state...... step can overcome in speed both recombination (electron back-transfer) and proton transfer involving the radical pair reached after primary electron transfer....

  7. Radiolysis study of the radical-like action mechanisms of an antioxidant: Sulfarlem

    International Nuclear Information System (INIS)

    Ruimy-Ifrah, Pascale

    1989-01-01

    Sulfarlem or p-anisyldithiolthione (ADT) is a sulfured heterocyclic compound which exhibits antioxidant properties. This work presents the quantitative study of the mono-electronic exchange mechanisms involved in this action. This study has been performed by gamma radiolysis and pulse radiolysis. The gamma radiolysis of ADT aerated ethanolic solutions has shown that O 2 . and RO 2 . radicals are not reactive towards ADT. In return, ADT is an efficient scavenger of R . radicals; the rate constant of this reaction being k (ADT + R . ) = 6.7 x 10 4 mol -1 .l.s -1 . The pulse radiolysis experiments allowed the characterization of ADT reduction by the solvated electron (k (e solv - + ADT) = 2.3 x 10 10 mol -1 .l.s -1 ), the determination of the absorption spectrum of the reduced species A . (maximum wavelength = 580 nm) and the rate constant of its evolution (k (A . + A . ) = 5.7 x 10 8 mol -1 .l.s -1 ). An analogous study has been performed with ADO, an ADT oxidized derivative, which appeared to be a less efficient free radicals scavenger. (author) [fr

  8. Functionalized polymer film surfaces via surface-initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Hu, Y.; Li, J.S.; Yang, W.T.; Xu, F.J.

    2013-01-01

    The ability to manipulate and control the surface properties of polymer films, without altering the substrate properties, is crucial to their wide-spread applications. In this work, a simple one-step method for the direct immobilization of benzyl chloride groups (as the effective atom transfer radical polymerization (ATRP) initiators) on the polymer films was developed via benzophenone-induced coupling of 4-vinylbenzyl chloride (VBC). Polyethylene (PE) and nylon films were selected as examples of polymer films to illustrate the functionalization of film surfaces via surface-initiated ATRP. Functional polymer brushes of (2-dimethylamino)ethyl methacrylate, sodium 4-styrenesulfonate, 2-hydroxyethyl methacrylate and glycidyl methacrylate, as well as their block copolymer brushes, have been prepared via surface-initiated ATRP from the VBC-coupled PE or nylon film surfaces. With the development of a simple approach to the covalent immobilization of ATRP initiators on polymer film surfaces and the inherent versatility of surface-initiated ATRP, the surface functionality of polymer films can be precisely tailored. - Highlights: ► Atom transfer radical polymerization initiators were simply immobilized. ► Different functional polymer brushes were readily prepared. ► Their block copolymer brushes were also readily prepared

  9. Reaction mechanisms and kinetics of the iminovinylidene radical with NO: Ab initio study

    Energy Technology Data Exchange (ETDEWEB)

    Hsiao, Ming-Kai; Chung, Yi-Hua; Hung, Yu-Ming; Chen, Hui-Lung, E-mail: chl3@faculty.pccu.edu.tw [Department of Chemistry and Institute of Applied Chemistry, Chinese Culture University, Taipei 111, Taiwan (China)

    2014-05-28

    The nitric oxide (NO) is a notorious compound for polluting environment. Recent year, removing nitric oxide from the atmosphere becomes a focus of the investigation. In our work, we study the iminovinylidene (HNCC) radical reacted with NO molecule. The mechanism and kinetic for reaction of the HNCC radical with the NO molecule is investigated via considering the possible channels of the N and O atoms of NO attacking the N and C atoms of the HNCC based on the high level ab initio molecular orbital calculations in conjunction with variational TST and RRKM calculations. The species involved have been optimized at the B3LYP/6-311++G(3df,2p) level and their single-point energies are refined by the CCSD(T)/aug-cc-PVQZ//B3LYP/6-311++G(3df,2p) method. The calculated potential energy surfaces indicated that energetically the most favorable channel for the HNCC + NO reaction was predicted to be the formation of HNC+CNO (P8) product via the addition reaction of the C atom of HNCC radical and the N atom of NO with the head to head orientation. To rationalize the scenario of the calculated results, we also employ the Fukui functions and HSAB theory to seek for a possible explanation. In addition, the reaction rate constants were calculated using VariFlex code, and the results show that the total rate coefficient, k{sub total}, at Ar pressure 760 Torr can be represented with an equation: k{sub total} = 6.433 × 10{sup −11} T {sup 0.100} exp(0.275 kcal mol{sup −1}/RT) at T = 298–3000 K, in units of cm{sup 3} molecule{sup −1} s{sup −1}.

  10. 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.

  11. Deciphering free-radical code of radiation effects

    International Nuclear Information System (INIS)

    Volovyk, S.; Bazyka, D.; Loganovsky, K.; Bebeshko, V.

    2007-01-01

    Complete text of publication follows. Objective: Ionizing radiation is fundamental environmental factor for life origin and evolution. Free radicals, primordial 'sea' for life conceiving and existence, induced by cosmic and terrestrial background radiation, are evolutionally archetypal, ubiquitous, and omnipotent in physiological- pathophysiological dichotomy. Classical free-radical paradigm in radiation biology and medicine, focused in essence on oxidative damage, needs new conceptualization and generalization. Methods: Suggested novel insights into free radicals dual immanent nature and functions in organism systems are based on original concepts of radicals dynamic charge transfer (CT) - redox ambivalence (interactional nucleo-, electro-, and ambiphilicity spectrum); pertinent chemical reactivity and selectivity delocalization model; physiological functional ambivalence and complementarity, and dynamic free-radical homeostasis. Results: Subtle perturbations in radicals CT spatiotemporal homeodynamics, in responsive signaling / controlling networks, concomitant alterations in genes expression, transcription, and apoptosis, redox control of mitochondrial ET chain, telomere/telomerase balance, DNA CT, circadian clock, hemispheric biochemical dominance/accentuation, including alteration of nitric oxide-superoxide complementarity, membranes permeability, neurotransmission pattern, synaptic circuitry, etc under radiation exposure have more fundamental impact on organism systems (especially CNS and CVS) deterioration than simple radicals inflicted oxidative (nitrosative) damage of cellular constituents. Conclusions: This novel conceptualization of free-radical paradigm constitutes new dimension in deciphering molecular mechanisms of radiation effects on subtle borderline norm-pathology and continuity-discontinuity dichotomy in organisms systems disorders - CT(redox)omics, which involves investigation of CT, redox, and spin states of free radicals, DNA bases

  12. 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.

  13. Sexual function with localized prostate cancer: active surveillance vs radical therapy

    NARCIS (Netherlands)

    van den Bergh, Roderick C. N.; Korfage, Ida J.; Roobol, Monique J.; Bangma, Chris H.; de Koning, Harry J.; Steyerberg, Ewout W.; Essink-Bot, Marie-Louise

    2012-01-01

    OBJECTIVE To compare sexual function of men with localized prostate cancer (PCa) on active surveillance (AS) with similar patients who received radical therapy. PATIENTS AND METHODS Two groups of men with screening-detected localized PCa were compared. The first were men on AS within the prospective

  14. 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.

  15. 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....

  16. 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.

  17. Laccase catalyzed grafting of-N-OH type mediators to lignin via radical-radical coupling

    DEFF Research Database (Denmark)

    Munk, Line; Punt, A. M.; Kabel, M. A.

    2017-01-01

    Lignin is an underexploited resource in biomass refining. Laccases (EC 1.10.3.2) catalyze oxidation of phenolic hydroxyls using O2 as electron acceptor and may facilitate lignin modification in the presence of mediators. This study assessed the reactivity of four different synthetic mediators...... better than HBT (1-hydroxybenzotriazole). Three different mechanisms are suggested to explain the grafting of HPI and HBT, all involving radical-radical coupling to produce covalent bonding to lignin. Lignin from exhaustive cellulase treatment of wheat straw was more susceptible to grafting than beech...... organosolv lignin with the relative abundance of grafting being 35% vs. 11% for HPI and 5% vs. 1% for HBT on these lignin substrates. The data imply that lignin can be functionalized via laccase catalysis with-N-OH type mediators....

  18. Mechanism of protection of adenosine from sulphate radical anion ...

    Indian Academy of Sciences (India)

    Unknown

    Keywords. Repair by caffeic acid; repair of adenosine radicals; oxidation by sulphate radical anions. ... known that hydroxycinnamic acids are natural anti- oxidants ... acid. 2. Experimental ..... ously and independently under kinetic conditions at.

  19. Magnetic exchange in {Gd(III)-radical} complexes: method assessment, mechanism of coupling and magneto-structural correlations.

    Science.gov (United States)

    Gupta, Tulika; Rajeshkumar, Thayalan; Rajaraman, Gopalan

    2014-07-28

    Density functional studies have been performed on ten different {Gd(III)-radical} complexes exhibiting both ferro and antiferromagnetic exchange interaction with an aim to assess a suitable exchange-correlation functional within DFT formalism. This study has also been extended to probe the mechanism of magnetic coupling and to develop suitable magneto-structural correlations for this pair. Our method assessments reveal the following order of increasing accuracy for the evaluation of J values compared to experimental coupling constants: B(40HF)LYP X3LYP < B3LYP < B2PLYP. Grimme's double-hybrid functional is found to be superior compared to other functionals tested and this is followed very closely by the conventional hybrid B3LYP functional. At the basis set front, our calculations reveal that the incorporation of relativistic effect is important in these calculations and the relativistically corrected effective core potential (ECP) basis set is found to yield better Js compared to other methods. The supposedly empty 5d/6s/6p orbitals of Gd(III) are found to play an important role in the mechanism of magnetic coupling and different contributions to the exchange terms are probed using Molecular Orbital (MO) and Natural Bond Orbital (NBO) analysis. Magneto-structural correlations for Gd-O distances, Gd-O-N angles and Gd-O-N-C dihedral angles are developed where the bond angles as well as dihedral angle parameters are found to dictate the sign and strength of the magnetic coupling in this series.

  20. Fluoropolymer materials and architectures prepared by controlled radical polymerizations

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie; Jankova Atanasova, Katja; Hvilsted, Søren

    2007-01-01

    This review initially summarizes the mechanisms, merits and limitations of the three controlled radical polymerizations: nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP) or metal catalyzed living radical polymerization, and reversible addition–fragmentation chain...... transfer (RAFT) polymerization. This is followed by two parts, one dealing with homo- and copolymerizations of fluorinated methacrylates and acrylates, and a second where fluorinated styrenes, alone or in combination with other monomers, are the main issues. In these parts, initiators (including...... properties and functionalities that can be obtained from these novel fluorinated materials and architectures are especially emphasized. Thus, various amphiphilic, biocompatible or low energy materials, fluorinated nanoparticles and nanoporous films/membranes as well as materials for submicron and nanolevel...

  1. The mechanisms of radical formation in L-α-alanine

    International Nuclear Information System (INIS)

    Bugay, A.A.; Onischuk, V.A.; Petrenko, T.L.; Teslenko, V.V.

    2000-01-01

    Modeling of radical transformations in L-α-alanine after irradiation was performed for isolated radicals and for clusters. Special attention was devoted to the explanation of the experimental results concerning selective proton transfer and behavior of cation-radicals because a unique interpretation of the corresponding experiments is very difficult. Both semi-empirical and ab initio methods were used depending on the size of system under investigation. The results obtained show the usefulness of the computer simulation for processes in rather complex materials used in dosimetry

  2. Radical scavenging activity of some natural tropolones by density functional theory

    Directory of Open Access Journals (Sweden)

    A. G. Al-Sehemi

    2017-07-01

    Full Text Available The ground state neutral geometries of some natural tropolones, i.e. stipitatonic acid (AF1, stipitalide (AF2, stipitaldehydic acid (AF3 and methyl stipitate (AF4 have been optimized by using Density Functional Theory (DFT at B3LYP/6-31G*, B3LYP/6-31G**, B3LYP/6-31+G* and B3LYP/6-31+G** levels of theory. The excited state geometries of AF1-AF4 were optimized by adopting the Time Dependent Density Functional Theory (TDDFT at the same levels of theory. The frequencies and cation species of AF1-AF4 were also computed at all the above mentioned levels of theory. We shed light on the electro-optical and molecular properties, e.g. energy gaps, highest occupied molecular orbitals, lowest unoccupied molecular orbitals, absorption wavelengths, electronegativity (χ, hardness (η, electrophilicity (ω, softness (S, electrophilicity index (ωi and the radical scavenging activity (RSA. Hydrogen atom transfer (HAT and one-electron transfer mechanisms have been discussed to shed light on the RSA. The smallest ionization potential and bond dissociation energy of AF4 are revealing that this compound would have more RSA than those of other counterparts.

  3. Recombination yield of geminate radical pairs in low magnetic fields - A Green's function method

    International Nuclear Information System (INIS)

    Doktorov, A.B.; Hansen, M.J.; Pedersen, J. Boiden

    2006-01-01

    An analytic expression for the recombination yield of a geminate radical pair with a single spin one half nuclei is derived. The expression is valid for any field strength of the static magnetic field. It is assumed that the spin mixing is caused solely by the hyperfine interaction of the nuclear spin and the difference in Zeeman energies of the two radical partners, that the recombination occurs at the distance of closest approach, and that there is a locally strong dephasing at contact. This is a special result of a new general approach where a Green's function technique is used to recast the stochastic Liouville equation into a low dimensional matrix equation that is particularly convenient for locally strong dephasing systems. The equation is expressed in terms of special values (determined by the magnetic parameters) of the Green's function for the relative motion of the radicals and it is therefore valid for any motional model, e.g. diffusion, one and two site models. The applicability of the strong dephasing approximation is illustrated by comparison with numerical exact results

  4. Synthesis and characterization of functional copolymer/organo-silicate nanoarchitectures through interlamellar complex-radical (coterpolymerization

    Directory of Open Access Journals (Sweden)

    2008-09-01

    Full Text Available The functional copolymers, having a combination of rigid/flexible linkages and an ability of complex-formation with interlayered surface of organo-silicate, and their nanocomposites have been synthesized by interlamellar complex-radical (coterpolymerization of intercalated monomer complexes of maleic anhydride (MA and itaconic acid (IA with dimethyl dodecylamine surface modified montmorillonite (organo-MMT (MA…DMDA-MMT and IA…DMDA-MMT n-butyl methacrylate (BMA and/or BMA/styrene monomer mixtures. The results of nanocomposite structure–composition– property relationship studies indicate that interlamellar complex-formation between anhydride/acid units and surface alkyl amine and rigid/flexible linkage balance in polymer chains are important factors providing the effective intercalation/ exfoliation of the polymer chains into the silicate galleries, the formation of nanostructural hybrids with higher thermal stability, dynamic mechanical behaviour and well dispersed morphology.

  5. Atmospheric Oxidation Mechanism and Kinetic Studies for OH and NO3 Radical-Initiated Reaction of Methyl Methacrylate

    Directory of Open Access Journals (Sweden)

    Rui Gao

    2014-03-01

    Full Text Available The mechanism for OH and NO3 radical-initiated oxidation reactions of methyl methacrylate (MMA was investigated by using density functional theory (DFT molecular orbital theory. Geometrical parameters of the reactants, intermediates, transition states, and products were fully optimized at the B3LYP/6-31G(d,p level. Detailed oxidation pathways were presented and discussed. The rate constants were deduced by the canonical variational transition-state (CVT theory with the small-curvature tunneling (SCT correction and the multichannel Rice-Ramspergere-Kassele-Marcus (RRKM theory, based on the potential energy surface profiles over the general atmospheric temperature range of 180–370 K. The calculated results were in reasonable agreement with experimental measurement.

  6. Robot-assisted radical cystoprostatectomy: Analysis of the complications and oncological and functional aspects.

    Science.gov (United States)

    Kanashiro, A; Gaya, J M; Palou, J; Gausa, L; Villavicencio, H

    2017-05-01

    To review our experience in robot-assisted radical cystectomy, assessing the complications and oncological and functional results. From 2007 to 2014, we performed 67 robot-assisted radical cystectomies combined with lymphadenectomy in 61 cases. The operations were performed on 37 patients due to muscle-invasive tumours and on 30 due to high-risk nonmuscle-invasive tumours. Urinary diversion was conducted extracorporeally, using a Studer neobladder in 47 cases. The mean blood loss was 300mL. No case required conversion to open surgery. The median number of lymph nodes extracted was 16 (range 3-33). Pathology revealed 16 pT0, 15 pTis,-pT1-pTa and 44 muscle-invasive tumours, 8 pN+ and 1 with positive margins. The mean hospital stay was 9 days. With a median follow-up of 16 months, 9 (13%) patients were readmitted after the discharge, most for infections associated with the vesical catheter and other catheters. Forty patients (59.7%) presented complications (most were Clavien grade 1-2). There was recurrence during the follow-up in 4 cases (6%), and 4 (5.9%) patients died from cancer. Nineteen (28.3%) patients had complications after 30 days, most of which were urinary tract infections. Of the 47 patients with a neobladder, 45 (96%) had proper daytime continence and 42 (89%) had proper nighttime continence. Ninety percent and 64% of the patients with previously normal sexual function and reduced sexual function, respectively, were able to preserve sexual function with or without drug treatment. Robot-assisted radical cystectomy plus lymphadenectomy, with extracorporeal reconstruction of the urinary diversion, offers good oncological and functional results without increasing the number of complications. Copyright © 2016 AEU. Publicado por Elsevier España, S.L.U. All rights reserved.

  7. ORGASMIC FUNCTION AFTER RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    D. Yu. Pushkar

    2014-07-01

    Full Text Available Objective: to study orgasmic function (OF in patients undergoing radical prostatectomy (RPE.Subjects and methods. Seventy-nine patients who had undergone RPE for locally advanced prostate cancer without hormone and radiation therapies were examined. The patients’ mean age was 59.3 years. The mean EF-IIEF domain score was 24.4. OF was estimated by IIEF question 10 and the authors’ questionnaire. The Spearman rank correction coefficient and Mann-Whitney U-Wilcoxon tests were used.Results. After RPE, there was a reduction in the mean IIEF question 10 score from 3.9 (confidence interval 3.7–4.1 to 3.3 (3–3.5 (p = 0.000. The following changes were found in orgasm intensity: no changes in 43 %, mild worsening in 42 %, severe worsening in 8 %, and enhancement in 4 %; orgasm could not be achieved in 4 % of the patients. Pain usually of low intensity was reported by 8.8 %. The poor factors for preserving OF were its low baseline level, elderly age, or severe post-RPE erectile dysfunction.Conclusion. There were significant OF changes after RPE, which should be kept in mind while treating this category of patients.

  8. Ring-Expansion/Contraction Radical Crossover Reactions of Cyclic Alkoxyamines: A Mechanism for Ring Expansion-Controlled Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Atsushi Narumi

    2018-06-01

    Full Text Available Macrocyclic polymers present an important class of macromolecules, displaying the reduced radius of gyration or impossibility to entangle. A rare approach for their synthesis is the ring expansion-controlled radical “vinyl” polymerization, starting from a cyclic alkoxyamine. We here describe ring-expansion radical crossover reactions of cyclic alkoxyamines which run in parallel to chain-propagation reactions in the polymerization system. The radical crossover reactions extensively occurred at 105–125 °C, eventually producing high molecular weight polymers with multiple inherent dynamic covalent bonds (NOC bonds. A subsequent ring-contraction radical crossover reaction and the second ring-expansion radical crossover reaction are also described. The major products for the respective three stages were shown to possess cyclic morphologies by the molecular weight profiles and the residual ratios for the NOC bonds (φ in %. In particular, the high φ values ranging from ca. 80% to 98% were achieved for this cyclic alkoxyamine system. This result verifies the high availability of this system as a tool demonstrating the ring-expansion “vinyl” polymerization that allows them to produce macrocyclic polymers via a one-step vinyl polymerization.

  9. On the mechanism of activation of copper-catalyzed atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Isse, Abdirisak Ahmed; Bortolamei, Nicola; De Paoli, Patrizia; Gennaro, Armando

    2013-01-01

    The mechanism of activation of atom transfer radical polymerization (ATRP) has been analyzed by investigating the kinetics of dissociative electron transfer (ET) to alkyl halides (RX) in acetonitrile. Using a series of alkyl halides, including both bromides and chlorides, the rate constants of ET (k ET ) to RX by electrogenerated aromatic radical anions (A· − ) acting as outer-sphere donors have been measured and analyzed according to the current theories of dissociative ET. This has shown that the kinetic data fit very well the “sticky” dissociative ET model with the formation of a weak adduct held together by electrostatic interactions. The rate constants of activation, k act , of some alkyl halides, namely chloroacetonitrile, methyl 2-bromopropionate and ethyl chloroacetate, by [Cu I L] + (L = tris(2-dimethylaminoethyl)amine, tris(2-pyridylmethyl)amine, 1,1,4,7,7-pentamethyldiethylenetriamine) have also been measured in the same experimental conditions. Comparisons of the measured k act values with those predicted assuming an outer-sphere ET for the complexes have shown that activation by Cu(I) is 7–10 orders of magnitude faster than required by outer-sphere ET. Therefore, the mechanism of RX activation by Cu(I) complexes used as catalysts in ATRP occurs by an inner-sphere ET or more appropriately by a halogen atom abstraction

  10. Fluorophore-based sensor for oxygen radicals in processing plasmas

    International Nuclear Information System (INIS)

    Choudhury, Faraz A.; Shohet, J. Leon; Sabat, Grzegorz; Sussman, Michael R.; Nishi, Yoshio

    2015-01-01

    A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye

  11. Fluorophore-based sensor for oxygen radicals in processing plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Choudhury, Faraz A.; Shohet, J. Leon, E-mail: shohet@engr.wisc.edu [Plasma Processing and Technology Laboratory and Department of Electrical and Computer Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Sabat, Grzegorz; Sussman, Michael R. [Department of Biochemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Nishi, Yoshio [Department of Electrical Engineering, Stanford University, Stanford, California 94305 (United States)

    2015-11-15

    A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye.

  12. Free radical scavenging and α-glucosidase inhibition, two potential mechanisms involved in the anti-diabetic activity of oleanolic acid

    International Nuclear Information System (INIS)

    Castellano, J.M.; Guinda, A.; Macias, L.; Santos-Lozano, J.M.; Lapetra, J.; Rada, M.

    2016-01-01

    This work investigates the role of oleanolic acid (OA), isolated from the olive (Olea europaea L.) leaf, as a radical scavenger and inhibitor of the hydrolyzing enzymes of dietary carbohydrates. New evidence is provided showing that OA may capture 2,2’-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) and peroxyl radicals, and also exert a strong and non-competitive inhibition of α-glucosidase (IC50 10.11 ± 0.30 µM). The kinetic and spectrometric analyses performed indicate that OA interacts with this enzyme inside a hydrophobic pocket, through an endothermic and non spontaneous process of a hydrophobic nature. These are two possible mechanisms by which OA may facilitate a better control of post-prandial hyperglycaemia and oxidative stress, so contributing to preserving insulin signalling. Obesity, insulin resistance and Type 2 Diabetes Mellitus are considered the first pandemics of the 21st century. In this sense, OA might be used in future preventive and therapeutic strategies, as an ingredient in new drugs and functional foods. [es

  13. Cellular and Molecular Mechanisms of the Production of Free Radicals during Exercise and Their Function on Skeletal Muscles

    Directory of Open Access Journals (Sweden)

    2017-06-01

    Full Text Available Physical activity is an integral part of human life. Among significant biological changes during physical activity are increase of metabolism and production of free radicals. Free radical can be defined as molecule or molecular fragments containing unpaired electron in the outer orbital, which react with nearby molecules to obtain stability. These highly reactive molecules have various deleterious effects, such as reduced force generation and increased muscle atrophy. There is evidence that ROS produced during exercise has positive adaptation effects. ROS production leads to increased expression of the anti-oxidants. These molecules, by neutralizing free radicals, neutralize the negative effects of ROS. In addition, exercise-induced ROS leads to the expression of PGC-1α  protein, having a significant impact on various aspects of cell metabolism, mitochondrial biogenesis and cellular respiration as well as metabolism of fat and glucose. This paper provides an overview of the evidence to date on the effects of ROS on exercising muscle. These aspects include the sources of ROS, their positive and negative cellular effects,  role of antioxidants, and ROS-dependent adaptations of muscle cells in response to physical exercise

  14. Imidazoline and imidazolidine nitroxides as controlling agents in nitroxide-mediated pseudoliving radical polymerization

    Science.gov (United States)

    Edeleva, M. V.; Marque, S. R. A.; Bagryanskaya, E. G.

    2018-04-01

    Controlled, or pseudoliving, radical polymerization provides unique opportunities for the synthesis of structurally diverse polymers with a narrow molecular-weight distribution. These reactions occur under relatively mild conditions with broad tolerance to functional groups in the monomers. The nitroxide-mediated pseudoliving radical polymerization is of particular interest for the synthesis of polymers for biomedical applications. This review briefly describes one of the mechanisms of controlled radical polymerization. The studies dealing with the use of imidazoline and imidazolidine nitroxides as controlling agents for nitroxide-mediated pseudoliving radical polymerization of various monomers are summarized and analyzed. The publications addressing the key steps of the controlled radical polymerization in the presence of imidazoline and imidazolidine nitroxides and new approaches to nitroxide-mediated polymerization based on protonation of both nitroxides and monomers are considered. The bibliography includes 154 references.

  15. Early enteral immune nutrition support after radical operation for gastric cancer on promoting the recovery of gastrointestinal function and immune function

    Directory of Open Access Journals (Sweden)

    Zhi-Gang Li

    2016-05-01

    Full Text Available Objective: To analyze the effect of early enteral immune nutrition support after radical operation for gastric cancer on the recovery of gastrointestinal function and immune function. Methods: A total of 106 cases of patients received radical operation for gastric cancer in our hospital were selected as research subjects, and according to different ways of postoperative nutrition intervention, all patients were divided into observation group (n=50 and control group (n=56. Control group received conventional enteral nutrition intervention, observation group received postoperative early enteral immune nutrition support, and then differences in postoperative intestinal mucosa barrier function, gastrointestinal hormone levels, immune function levels and nutrition-related indicator values were compared between two groups. Results: After observation group received enteral immune nutrition intervention, serum DAO, PS and D-lactate levels as well as urine L/M ratio were lower than those of control group; serum GAS, CCK, MTL and SP values of observation group after intervention were higher than those of control group, and GLU, VIP, GIP and SS values were lower than those of control group; CD4, IgG, NK cell, C3, C4, CH50 and S-IgA levels of observation group after intervention were higher than those of control group; serum ALB, PRE, TRF and RBP levels of observation group after intervention were higher than those of control group. Conclusion: Early enteral immune nutrition support after radical operation for gastric cancer is conducive to the recovery of gastrointestinal function and the promotion of immune state, eventually promotes patients’ postoperative overall recovery and has active clinical significance.

  16. Datasets used in the manuscript titled "Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms and organic aerosol"

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset documents that all of the data used in the manuscript "Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic...

  17. 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

  18. Insight into the Reaction Mechanism of Graphene Oxide with Oxidative Free Radical

    Institute of Scientific and Technical Information of China (English)

    ZHOU Xuejiao; XU Liangyou

    2017-01-01

    Graphene oxide(GO),as an important derivative of graphene,could be considered as a super aromatic molecule decorated with a range of reactive oxygen-containing groups on its surface,which endows graphene high reactivity with other molecules.In our previous work,we demonstrated that GO sheets were cut into small pieces(graphene quantum dots,GQDs) by oxidative free radicals(hydroxyl radical HO or oxygen radical [O]) under UV irradiation.It is notable that reactions involving free radicals are influenced by reaction conditions pronouncedly.However,researches on details about reactions of GO with free radicals have not been reported thus far.In this work,the effects of different factors on the photo-Fenton reaction of GO were studied.It is demonstrated that the reaction rate is closely related to the concentration of free radicals.It is speculated that through the optimization of reaction conditions,the reaction of graphene with free radicals could carry out efficiently for further applications.

  19. Sexual functioning and vaginal changes after radical vaginal trachelectomy in early stage cervical cancer patients: a longitudinal study

    DEFF Research Database (Denmark)

    Froeding, LP; Ottesen, C; Rung-Hansen, H

    2014-01-01

    Radical vaginal trachelectomy (RVT) offers low complication rate, good survival, and possibility for future childbearing for young women with early stage cervical cancer. However, the literature on quality of life (QOL) and sexual functioning in patients undergoing RVT is scarce.......Radical vaginal trachelectomy (RVT) offers low complication rate, good survival, and possibility for future childbearing for young women with early stage cervical cancer. However, the literature on quality of life (QOL) and sexual functioning in patients undergoing RVT is scarce....

  20. Salvage robotic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Samuel D Kaffenberger

    2014-01-01

    Full Text Available Failure of non-surgical primary treatment for localized prostate cancer is a common occurrence, with rates of disease recurrence ranging from 20% to 60%. In a large proportion of patients, disease recurrence is clinically localized and therefore potentially curable. Unfortunately, due to the complex and potentially morbid nature of salvage treatment, radical salvage surgery is uncommonly performed. In an attempt to decrease the morbidity of salvage therapy without sacrificing oncologic efficacy, a number of experienced centers have utilized robotic assistance to perform minimally invasive salvage radical prostatectomy. Herein, we critically evaluate the existing literature on salvage robotic radical prostatectomy with a focus on patient selection, perioperative complications and functional and early oncologic outcomes. These results are compared with contemporary and historical open salvage radical prostatectomy series and supplemented with insights we have gained from our experience with salvage robotic radical prostatectomy. The body of evidence by which conclusions regarding the efficacy and safety of robotic salvage radical prostatectomy can be drawn comprises fewer than 200 patients with limited follow-up. Preliminary results are promising and some outcomes have been favorable when compared with contemporary open salvage prostatectomy series. Advantages of the robotic platform in the performance of salvage radical prostatectomy include decreased blood loss, short length of stay and improved visualization. Greater experience is required to confirm the long-term oncologic efficacy and functional outcomes as well as the generalizability of results achieved at experienced centers.

  1. Improved mechanical and functional properties of elastomer/graphite nanocomposites prepared by latex compounding

    Energy Technology Data Exchange (ETDEWEB)

    Yang Jian [Key Laboratory for Nano-materials, Beijing University of Chemical Technology, Ministry of Education of China, Beijing 100029 (China); Key Laboratory on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029 (China); Tian Ming [Key Laboratory for Nano-materials, Beijing University of Chemical Technology, Ministry of Education of China, Beijing 100029 (China); Jia Qingxiu [Key Laboratory on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029 (China); Shi Junhong [Key Laboratory for Nano-materials, Beijing University of Chemical Technology, Ministry of Education of China, Beijing 100029 (China); Zhang Liqun [Key Laboratory for Nano-materials, Beijing University of Chemical Technology, Ministry of Education of China, Beijing 100029 (China); Key Laboratory on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029 (China)], E-mail: zhanglq@mail.buct.edu.cn; Lim Szuhui; Yu Zhongzhen [Centre for Advanced Materials Technology (CAMT), School of Aerospace, Mechanical and Mechatronic Engineering (J07), University of Sydney, Sydney, NSW 2006 (Australia); Mai Yiuwing [Centre for Advanced Materials Technology (CAMT), School of Aerospace, Mechanical and Mechatronic Engineering (J07), University of Sydney, Sydney, NSW 2006 (Australia)], E-mail: y.mai@usyd.edu.au

    2007-10-15

    The facile latex approach has been adopted to finely incorporate graphite nanosheets into elastomeric polymer matrix to obtain high-performance elastomeric nanocomposites with improved mechanical properties and functional properties. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction experiments show that the nanostructures of the final nanocomposites exhibit a high degree of exfoliation and intercalation of graphite in the nitrile-butadiene rubber (NBR) matrix. Mechanical and dynamic-mechanical tests demonstrate that the NBR/graphite nanocomposites possess greatly increased elastic modulus and tensile strength, and desirably strong interfaces. The unexpected self-crosslinking of elastomer/graphite nanocomposites was discovered and then verified by oscillating disc rheometry and equilibrium swelling experiments. After critically examining various polymer types by X-ray photoelectron spectroscopy, electron spin resonance and Fourier transform infrared spectroscopy, a radical initiation mechanism was proposed to explain the self-crosslinking reaction. These NBR/graphite nanocomposites possess significantly improved wear resistance and gas barrier properties, and superior electrical/thermal conductivity. Such versatile functional properties make NBR nanocomposites a promising new class of advanced materials.

  2. Improved mechanical and functional properties of elastomer/graphite nanocomposites prepared by latex compounding

    International Nuclear Information System (INIS)

    Yang Jian; Tian Ming; Jia Qingxiu; Shi Junhong; Zhang Liqun; Lim Szuhui; Yu Zhongzhen; Mai Yiuwing

    2007-01-01

    The facile latex approach has been adopted to finely incorporate graphite nanosheets into elastomeric polymer matrix to obtain high-performance elastomeric nanocomposites with improved mechanical properties and functional properties. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction experiments show that the nanostructures of the final nanocomposites exhibit a high degree of exfoliation and intercalation of graphite in the nitrile-butadiene rubber (NBR) matrix. Mechanical and dynamic-mechanical tests demonstrate that the NBR/graphite nanocomposites possess greatly increased elastic modulus and tensile strength, and desirably strong interfaces. The unexpected self-crosslinking of elastomer/graphite nanocomposites was discovered and then verified by oscillating disc rheometry and equilibrium swelling experiments. After critically examining various polymer types by X-ray photoelectron spectroscopy, electron spin resonance and Fourier transform infrared spectroscopy, a radical initiation mechanism was proposed to explain the self-crosslinking reaction. These NBR/graphite nanocomposites possess significantly improved wear resistance and gas barrier properties, and superior electrical/thermal conductivity. Such versatile functional properties make NBR nanocomposites a promising new class of advanced materials

  3. Free radicals and related reactive species as mediators of tissue injury and disease: implications for Health.

    Science.gov (United States)

    Kehrer, James P; Klotz, Lars-Oliver

    2015-01-01

    A radical is any molecule that contains one or more unpaired electrons. Radicals are normal products of many metabolic pathways. Some exist in a controlled (caged) form as they perform essential functions. Others exist in a free form and interact with various tissue components. Such interactions can cause both acute and chronic dysfunction, but can also provide essential control of redox regulated signaling pathways. The potential roles of endogenous or xenobiotic-derived free radicals in several human pathologies have stimulated extensive research linking the toxicity of numerous xenobiotics and disease processes to a free radical mechanism. In recent years, improvements in analytical methodologies, as well as the realization that subtle effects induced by free radicals and oxidants are important in modulating cellular signaling, have greatly improved our understanding of the roles of these reactive species in toxic mechanisms and disease processes. However, because free radical-mediated changes are pervasive, and a consequence as well as a cause of injury, whether such species are a major cause of tissue injury and human disease remains unclear. This concern is supported by the fact that the bulk of antioxidant defenses are enzymatic and the findings of numerous studies showing that exogenously administered small molecule antioxidants are unable to affect the course of most toxicities and diseases purported to have a free radical mechanism. This review discusses cellular sources of various radical species and their reactions with vital cellular constituents, and provides examples of selected disease processes that may have a free radical component.

  4. Semantic Radicals Contribute More Than Phonetic Radicals to the Recognition of Chinese Phonograms: Behavioral and ERP Evidence in a Factorial Study

    Directory of Open Access Journals (Sweden)

    Xieshun Wang

    2017-12-01

    Full Text Available The Chinese phonograms consist of a semantic radical and a phonetic radical. The two types of radicals have different functional contributions to their host phonogram. The semantic radical typically signifies the meaning of the phonogram, while the phonetic radical usually contains a phonological clue to the phonogram’s pronunciation. However, it is still unclear how they interplay with each other when we attempt to recognize a phonogram because previous studies rarely manipulated the functionality of the two types of radicals in a single design. Using a full factorial design, the present study aimed to probe this issue by directly manipulating the functional validity of the two types of radicals in a lexical decision task with both behavioral and event-related potential (ERP measurements. The results showed that recognition of phonograms which were related to their semantic radicals in meaning took a shorter reaction time, showed a lower error rate, and elicited a smaller P200 and a larger N400 than did recognition of those which had no semantic relation with their semantic radicals. However, the validity of phonetic radicals did not show any main effect or interaction with that of semantic radicals on either behavioral or ERP measurements. These results indicated that semantic radicals played a dominant role in the recognition of phonograms. Transparent semantic radicals, which provide valid semantic cues to phonograms, can facilitate the recognition of phonograms.

  5. Can Carbamates Undergo Radical Oxidation in the Soil Environment? A Case Study on Carbaryl and Carbofuran.

    Science.gov (United States)

    Ćwieląg-Piasecka, Irmina; Witwicki, Maciej; Jerzykiewicz, Maria; Jezierska, Julia

    2017-12-19

    Radical oxidation of carbamate insecticides, namely carbaryl and carbofuran, was investigated with spectroscopic (electron paramagnetic resonance [EPR] and UV-vis) and theoretical (density functional theory [DFT] and ab initio orbital-optimized spin-component scaled MP2 [OO-SCS-MP2]) methods. The two carbamates were subjected to reaction with • OH, persistent DPPH • and galvinoxyl radical, as well as indigenous radicals of humic acids. The influence of fulvic acids on carbamate oxidation was also tested. The results obtained with EPR and UV-vis spectroscopy indicate that carbamates can undergo direct reactions with various radical species, oxidizing themselves into radicals in the process. Hence, they are prone to participate in the prolongation step of the radical chain reactions occurring in the soil environment. Theoretical calculations revealed that from the thermodynamic point of view hydrogen atom transfer is the preferred mechanism in the reactions of the two carbamates with the radicals. The activity of carbofuran was determined experimentally (using pseudo-first-order kinetics) and theoretically to be noticeably higher in comparison with carbaryl and comparable with gallic acid. The findings of this study suggest that the radicals present in soil can play an important role in natural remediation mechanisms of carbamates.

  6. Free radicals in wood induced by γ-radiation

    International Nuclear Information System (INIS)

    Xu Honglin; Zhang Wenhui

    1994-01-01

    The free radicals in wood induced by γ-radiation were studied by electron spin resonance. The fine structure of the ESR signal from sawdust samples irradiated could be resolved into various radicals. These free radicals have a very long lifetime. The major spectrum for the free radicals will exponentially increased along with the radiation dose according to Y 1-Exp(-α a D). The intensity of radiation radicals is dependent on tree species. The stronger the intensity of mechanic free radicals is, the stronger the intensity of radiation free radicals

  7. 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.

  8. Orthographic Skills Important to Chinese Literacy Development: The Role of Radical Representation and Orthographic Memory of Radicals

    Science.gov (United States)

    Yeung, Pui-sze; Ho, Connie Suk-han; Chan, David Wai-ock; Chung, Kevin Kien-hoa

    2016-01-01

    A 3-year longitudinal study among 239 Chinese students in Grades 2-4 was conducted to investigate the relationships between orthographic skills (including positional and functional knowledge of semantic radicals and phonetic radicals, and orthographic memory of radicals) and Chinese literacy skills (word reading, word spelling, reading…

  9. Muonium and muonic radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Geeson, D.; Symons, M.C.R.

    1985-01-01

    An energetic positive muon which is injected in a liquid sample of substrate molecules (S) creates an ionization track consisting of substrate cations (S + ) and electrons. Near the end of this track the muon may combine with an electron to form muonium (Mu) which is observable in inert liquids, but which reacts by addition to form a radical. Alternatively, the electron can add to S to form S - , which then combines with the muon to form the radical. Furthermore, instead of ending up in Mu or in a radical the muon may stay in a diamagnetic environment as a solvated muon, or as a muon substituting a proton in a molecule. Of interest in these schemes are the mechanisms and rates of formation of muonated radicals and in particular the rate constants for their reactions to products. Investigations are based on the observation of Mu and the radical by means of the μSR technique in transverse magnetic fields. (Auth.)

  10. Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

    Science.gov (United States)

    Matasović, Brunislav; Bonifačić, Marija

    2011-06-01

    Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals CO2-rad , rad CH 2OH, rad CH(CH 3)OH, and rad CH(CH 3)O - have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production 60Co γ-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U rad radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U rad radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of α-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism ( Matasović and Bonifačić, 2007). Thus, while both rad CH 2OH and rad CH(CH 3)OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm -3 concentrations, pH 7, brought about chain debromination to occur in the case of rad CH(CH 3)OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of α-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U rad radicals have been estimated to amount to about ≥85 and 1200 dm 3 mol -1 s -1, respectively.

  11. Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

    Energy Technology Data Exchange (ETDEWEB)

    Tinga, D.J.; Bouma, J.; Aalders, J.G. (Dept. of Obstetrics and Gynaecology, State Univ. Hospital, Groningen (Netherlands)); Hollema, H. (Dept. of Pathology, State Univ. Hospital, Groningen (Netherlands))

    1990-01-01

    Forty-nine patients aged {le} 45 years, with cervical carcinoma stage IB ({le} 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors).

  12. Radical surgery compared with intracavitary cesium followed by radical surgery in cervical carcinoma stage IB

    International Nuclear Information System (INIS)

    Tinga, D.J.; Bouma, J.; Aalders, J.G.; Hollema, H.

    1990-01-01

    Forty-nine patients aged ≤ 45 years, with cervical carcinoma stage IB (≤ 3 cm) were treated with either primary radical surgery (n = 26), or intracavitary irradiation followed by radical surgery (n = 23). With primary surgery, ovarian function had been preserved in 15 of the 25 patients, who were alive and well. Seven of the primary surgery patients were irradiated postoperatively and 2 others with a central recurrence were cured by irradiation. One other patient, who was not irradiated postoperatively, had an intestinal metastasis and died of the disease. If any of the adverse prognostic factors (as reported in the literature) had been considered as an indication for postoperative irradiation, 17 patients instead of 7 would have been irradiated after primary radical surgery. In the comparable group of 23 patients treated by intracavitary irradiation and radical surgery (and in 4 cases postoperative irradiation as well) there was no recurrence. There was no significant statistical difference between the treatment results in the cesium + surgery group and those who underwent primary radical surgery. Young patients with early cervical carcinoma without prognostic indicators for postoperative irradiation can benefit from primary radical surgery, because their ovarian function can be preserved. (authors)

  13. Glutathione--hydroxyl radical interaction: a theoretical study on radical recognition process.

    Directory of Open Access Journals (Sweden)

    Béla Fiser

    Full Text Available Non-reactive, comparative (2 × 1.2 μs molecular dynamics simulations were carried out to characterize the interactions between glutathione (GSH, host molecule and hydroxyl radical (OH(•, guest molecule. From this analysis, two distinct steps were identified in the recognition process of hydroxyl radical by glutathione: catching and steering, based on the interactions between the host-guest molecules. Over 78% of all interactions are related to the catching mechanism via complex formation between anionic carboxyl groups and the OH radical, hence both terminal residues of GSH serve as recognition sites. The glycine residue has an additional role in the recognition of OH radical, namely the steering. The flexibility of the Gly residue enables the formation of further interactions of other parts of glutathione (e.g. thiol, α- and β-carbons with the lone electron pair of the hydroxyl radical. Moreover, quantum chemical calculations were carried out on selected GSH/OH(• complexes and on appropriate GSH conformers to describe the energy profile of the recognition process. The relative enthalpy and the free energy changes of the radical recognition of the strongest complexes varied from -42.4 to -27.8 kJ/mol and from -21.3 to 9.8 kJ/mol, respectively. These complexes, containing two or more intermolecular interactions, would be the starting configurations for the hydrogen atom migration to quench the hydroxyl radical via different reaction channels.

  14. Effect of shear stress and free radicals induced by ultrasound on erythrocytes

    International Nuclear Information System (INIS)

    Kondo, T.; Fukushima, Y.; Kon, H.; Riesz, P.

    1989-01-01

    The present study was undertaken to elucidate the mechanism of hemolysis induced by ultrasound. Ar or N2O gas was used to distinguish between cavitation with or without free radical formation (hydroxyl radicals and hydrogen atoms). Free radical formation was examined by the method of spin trapping combined with ESR. After sonication of erythrocyte suspensions, several structural and functional parameters of the erythrocyte membrane--hemolysis, membrane fluidity, membrane permeability, and membrane deformability--were examined. Although free radical formation was observed in the erythrocyte suspensions sonicated in the presence of Ar, no free radical formation was observed in the presence of N2O. However, the hemolysis behavior induced by ultrasound was similar in the presence of Ar or N2O. The membrane fluidity, permeability, and deformability of the remaining unlysed erythrocytes after sonication in the presence of Ar or N2O were unchanged and identical to those of the control cells. On the other hand, after gamma irradiation (700 Gy), the hemolysis behavior was quite different from that after sonication, and the membrane properties were significantly changed. These results suggest that hemolysis induced by sonication was due to mechanical shearing stress arising from cavitation, and that the membrane integrity of the remaining erythrocytes after sonication was the same as that of control cells without sonication. The triatomic gas, N2O, may be useful for ultrasonically disrupting cells without accompanying free radical formation

  15. Mechanisms for formation of organic acids in gas-phase reactions of ozone and hydroxyl radical with dialkenes and unsaturated carbonyls

    Science.gov (United States)

    Chien, Chao-Jung

    2001-07-01

    Carboxylic acids are ubiquitous throughout the troposphere and may contribute significant fractions of the free acidity in some remote areas. One of the important sources of these carboxylic acids is thought to be photochemical transformation of biogenic hydrocarbons such as isoprene. For the work reported here, atmospheric samples from University of North Carolina dual outdoor environmental chamber under simulated urban atmospheric conditions were analyzed for carboxylic acids. Both OH radicals and O3 initiated photooxidation reaction experiments were performed for isoprene, along with its structural analogs, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene, and their primary photooxidation products, methacrolein, acrolein, and methyl vinyl ketone. Among the detected carboxylic acids were formic, acetic, and several multifunctional carboxylic acids, including methacrylic, acrylic, glyoxylic, and glycolic acids. Quantification of most carboxylic acid products was also established. Formation yields of carboxylic acids from the reactions of O3 with studied compounds were determined, and time-concentration series of the reactants and carboxylic acid products were measured to facilitate mechanism formulation. While the reaction mechanisms of Criegee biradicals arising from decomposition of primary ozonides are proposed to account for the observed carboxylic acid products in the ozonolysis of unsaturated hydrocarbons, reactions of peroxy acyl radicals with HO2 and/or other peroxy radicals are thought to be responsible for the formation of carboxylic acids during the OH-initiated reactions in the presence of NOx. In this study, smog chamber simulations have also been performed for selected compounds using Morpho, a photochemical kinetic simulation software package. Explicit photochemical mechanisms with O 3 and OH radicals that lead to formation of carboxylic acids were elaborated and implemented, and the simulation results were compared with those from other chemical

  16. Comparison of Nerve-Sparing Radical Hysterectomy and Radical Hysterectomy: a Systematic Review and Meta-Analysis

    Directory of Open Access Journals (Sweden)

    Zhuowei Xue

    2016-05-01

    Full Text Available Background/Aims: Radical hysterectomy (RH for the treatment of cervical cancer frequently caused pelvic organ dysfunctions. This study aimed to compare the results of pelvic organ function and recurrence rate after Nerve sparing radical hysterectomy (NSRH and RH treatment through systematic review and meta-analysis. Methods: PubMed, Web of Science and China Knowledge Resource Integrated Database were searched from inception to 25 February 2015. Studies of cervical cancer which reported radical hysterectomy or nerve sparing radical hysterectomy were included. The quality of included studies was evaluated using the guidelines of Cochrane Handbook for Systematic Reviews of Interventions. Statistical analysis was performed using Review Manager 5.3 software (Cochrane Collaboration. Results: A total of 20 studies were finally included. Meta-analysis demonstrated that NSRH was associated with less bladder and anorectal dysfunction than RH. The time to bladder and anorectal function recovery after NSRH was shorter than RH. Patients undergoing NSRH also scored higher than patients undergoing RH at Female Sexual Function Index (FSFI. On the other hand, the local recurrence and overall recurrence rate were similar between NSRH and RH. Conclusion: NSRH may be an effective technique for lowering pelvic organ dysfunction and improving the function recovery without increasing the recurrence rate of cervical cancer.

  17. Hydroxyl radical reactivity with diethylhydroxylamine

    International Nuclear Information System (INIS)

    Gorse, R.A. Jr.; Lii, R.R.; Saunders, B.B.

    1977-01-01

    Diethylhydroxylamine (DEHA) reacts with gas-phase hydroxyl radicals on every third collision, whereas the corresponding reaction in aqueous solution is considerably slower. The high gas-phase reactivity explains the predicted inhibitory effect of DEHA in atmospheric smog processes. Results from the studies in the aqueous phase are helpful in predicting the mechanism of the reaction of DEHA with hydroxyl radicals

  18. Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Matasovic, Brunislav [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia); Bonifacic, Marija, E-mail: bonifacic@irb.h [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia)

    2011-06-15

    Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals {sup {center_dot}C}O{sub 2}{sup -}, {sup {center_dot}C}H{sub 2}OH, {sup {center_dot}C}H(CH{sub 3})OH, and {sup {center_dot}C}H(CH{sub 3})O{sup -} have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production {sup 60}Co {gamma}-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U{sup {center_dot}} radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U{sup {center_dot}} radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of {alpha}-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism (). Thus, while both {sup {center_dot}C}H{sub 2}OH and {sup {center_dot}C}H(CH{sub 3})OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm{sup -3} concentrations, pH 7, brought about chain debromination to occur in the case of {sup {center_dot}C}H(CH{sub 3})OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of {alpha}-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U{sup {center_dot}} radicals have been estimated to amount to about {>=}85 and 1200 dm{sup 3} mol{sup -1} s{sup -1

  19. Donor free radical explosive composition

    Science.gov (United States)

    Walker, Franklin E. [15 Way Points Rd., Danville, CA 94526; Wasley, Richard J. [4290 Colgate Way, Livermore, CA 94550

    1980-04-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising an organic compound or mixture of organic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and which is not an explosive, or an inorganic compound or mixture of inorganic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and selected from ammonium or alkali metal persulfates.

  20. n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions.

    Science.gov (United States)

    Zhang, Siyuan; Naab, Benjamin D; Jucov, Evgheni V; Parkin, Sean; Evans, Eric G B; Millhauser, Glenn L; Timofeeva, Tatiana V; Risko, Chad; Brédas, Jean-Luc; Bao, Zhenan; Barlow, Stephen; Marder, Seth R

    2015-07-20

    Dimers of 2-substituted N,N'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2 , yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2 ) dissociation and of D2 -to-A electron transfer, D2 reacts with A to form D(+) and A(-) by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D(+) /0.5 D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9 V vs. FeCp2 (+/0) ) (Cp=cyclopentadienyl) due to cancelation of trends in the D(+/0) potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions

    KAUST Repository

    Zhang, Siyuan

    2015-06-18

    Dimers of 2-substituted N,N\\'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2, yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2) dissociation and of D2-to-A electron transfer, D2 reacts with A to form D+ and A- by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D+/0.5D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9V vs. FeCp2+/0) (Cp=cyclopentadienyl) due to cancelation of trends in the D+/0 potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. n-Dopants Based on Dimers of Benzimidazoline Radicals: Structures and Mechanism of Redox Reactions

    KAUST Repository

    Zhang, Siyuan; Naab, Benjamin D.; Jucov, Evgheni V.; Parkin, Sean; Evans, Eric G B; Millhauser, Glenn L.; Timofeeva, Tatiana V.; Risko, Chad; Bredas, Jean-Luc; Bao, Zhenan; Barlow, Stephen; Marder, Seth R.

    2015-01-01

    Dimers of 2-substituted N,N'-dimethylbenzimidazoline radicals, (2-Y-DMBI)2 (Y=cyclohexyl (Cyc), ferrocenyl (Fc), ruthenocenyl (Rc)), have recently been reported as n-dopants for organic semiconductors. Here their structural and energetic characteristics are reported, along with the mechanisms by which they react with acceptors, A (PCBM, TIPS-pentacene), in solution. X-ray data and DFT calculations both indicate a longer C-C bond for (2-Cyc-DMBI)2 than (2-Fc-DMBI)2, yet DFT and ESR data show that the latter dissociates more readily due to stabilization of the radical by Fc. Depending on the energetics of dimer (D2) dissociation and of D2-to-A electron transfer, D2 reacts with A to form D+ and A- by either of two mechanisms, differing in whether the first step is endergonic dissociation or endergonic electron transfer. However, the D+/0.5D2 redox potentials-the effective reducing strengths of the dimers-vary little within the series (ca. -1.9V vs. FeCp2+/0) (Cp=cyclopentadienyl) due to cancelation of trends in the D+/0 potential and D2 dissociation energy. The implications of these findings for use of these dimers as n-dopants, and for future dopant design, are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. 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

  4. 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

  5. Spin relaxation of radicals in cryptochrome and its role in avian magnetoreception

    Energy Technology Data Exchange (ETDEWEB)

    Worster, Susannah; Kattnig, Daniel R.; Hore, P. J., E-mail: peter.hore@chem.ox.ac.uk [Department of Chemistry, Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ (United Kingdom)

    2016-07-21

    Long-lived spin coherence and rotationally ordered radical pairs have previously been identified as key requirements for the radical pair mechanism of the avian magnetic compass sense. Both criteria are hard to meet in a biological environment, where thermal motion of the radicals creates dynamic disorder and drives efficient spin relaxation. This has long been cited as a major stumbling block of the radical pair hypothesis. Here we combine Redfield relaxation theory with analytical solutions to a rotational diffusion equation to assess the impact of restricted rotational motion of the radicals on the operation of the compass. The effects of such motions are first investigated generally in small, model systems and are then critically examined in the magnetically sensitive flavin-tryptophan radical pair that is formed photochemically in the proposed magnetoreceptor protein, cryptochrome. We conclude that relaxation is slowest when rotational motion of the radicals within the protein is fast and highly constrained; that in a regime of slow relaxation, the motional averaging of hyperfine interactions has the potential to improve the sensitivity of the compass; and that consideration of motional effects can significantly alter the design criteria for an optimal compass. In addition, we demonstrate that motion of the flavin radical is likely to be compatible with its role as a component of a functioning radical-pair compass, whereas the motion of the tryptophan radical is less ideal, unless it is particularly fast.

  6. Redox properties of free radicals

    International Nuclear Information System (INIS)

    Neta, P.

    1981-01-01

    Results of electron transfer reactions observed and monitored by pulse radiolysis are reported. This technique allows determination of the first one-electron reduction or oxidation of a compound rather than the overall two-electron transfer usually reported. Pulse radiolysis allows the determination of absolute rate constants for reactions of free radicals and helps elucidate the mechanisms involved. Studies using this technique to study radicals derived from quinones, nitro compounds, pyridines, phenols, and anilines are reported. Radicals of biochemical interest arising from riboflavin, ascorbic acid, vitamin K 3 , vitamin E, MAD + , porphyrins, etc. have also been studied

  7. Radiochemistry - Applications in the study of radical mechanisms of biological interest

    International Nuclear Information System (INIS)

    Foos, Jacques

    1982-01-01

    In biology, oxygen reducing processes give rise to the formation of intermediate radicals. One of the major breakthroughs of radiation chemistry of aqueous solutions is the identification of these compounds. The author describes the techniques used to study the reaction of these radicals (of radiolytic origin) with biological molecules [fr

  8. Impact of OH Radical-Initiated H2CO3 Degradation in the Earth's Atmosphere via Proton-Coupled Electron Transfer Mechanism.

    Science.gov (United States)

    Ghoshal, Sourav; Hazra, Montu K

    2016-02-04

    The decomposition of isolated carbonic acid (H2CO3) molecule into CO2 and H2O (H2CO3 → CO2 + H2O) is prevented by a large activation barrier (>35 kcal/mol). Nevertheless, it is surprising that the detection of the H2CO3 molecule has not been possible yet, and the hunt for the free H2CO3 molecule has become challenging not only in the Earth's atmosphere but also on Mars. In view of this fact, we report here the high levels of quantum chemistry calculations investigating both the energetics and kinetics of the OH radical-initiated H2CO3 degradation reaction to interpret the loss of the H2CO3 molecule in the Earth's atmosphere. It is seen from our study that proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) are the two mechanisms by which the OH radical initiates the degradation of the H2CO3 molecule. Moreover, the PCET mechanism is potentially the important one, as the effective barrier, defined as the difference between the zero point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, for the PCET mechanism at the CCSD(T)/6-311++G(3df,3pd) level of theory is ∼3 to 4 kcal/mol lower than the effective barrier height associated with the HAT mechanism. The CCSD(T)/6-311++G(3df,3pd) level predicted effective barrier heights for the degradations of the two most stable conformers of H2CO3 molecule via the PCET mechanism are only ∼2.7 and 4.3 kcal/mol. A comparative reaction rate analysis at the CCSD(T)/6-311++G(3df,3pd) level of theory has also been carried out to explore the potential impact of the OH radical-initiated H2CO3 degradation relative to that from water (H2O), formic acid (FA), acetic acid (AA) and sulfuric acid (SA) assisted H2CO3 → CO2 + H2O decomposition reactions in both the Earth's troposphere and stratosphere. The comparison of the reaction rates reveals that, although the atmospheric concentration of the OH radical is

  9. Generation and propagation of radical reactions on proteins

    DEFF Research Database (Denmark)

    Hawkins, C L; Davies, Michael Jonathan

    2001-01-01

    The oxidation of proteins by free radicals is thought to play a major role in many oxidative processes within cells and is implicated in a number of human diseases as well as ageing. This review summarises information on the formation of radicals on peptides and proteins and how radical damage may...... be propagated and transferred within protein structures. The emphasis of this article is primarily on the deleterious actions of radicals generated on proteins, and their mechanisms of action, rather than on enzymatic systems where radicals are deliberately formed as transient intermediates. The final section...

  10. Orthotopic neobladder reconstruction after radical cystectomy in patients with a solitary functioning kidney: Clinical outcome and evaluation

    International Nuclear Information System (INIS)

    Aly, A.H.; Ezzat, A.; Hamed, A.

    2011-01-01

    To evaluate, in a prospective study, the clinical outcome of orthotopic neobladder reconstruction after radical cystectomy in patients with a solitary functioning kidney at the time of surgery. Patients and methods: This study included a total of 28 patients (25 males and three females) with muscle invasive bladder cancer and a solitary functioning kidney at the time of surgery who underwent radical cystectomy (anterior pelvic excentration for females) and urinary reconstruction using orthotopic neobladder at The National Cancer Institute, Cairo University between February 2004 and April 2009. The surgical procedures included ileocaecal neobladder in 19 patients, ileal neobladder (Studer) in five and sigmoid neobladder in four. All perioperative and long-term complications were recorded. The renal functions were evaluated using mainly serum creatinine level, abdominal ultrasonography and intravenous urography (IVU). Results: The mean age of patients was 51.4 years (range of 38-62 years) while the mean follow-up period was 41.4 months (range 18-62 months). Early complications included wound infections in five patients, urine leakage in six, abdominal dehiscence with deep venous thrombosis in two, intestinal obstruction and prolonged ileus in three. During the follow-up period, 21 renal units (75%) remained stable with normal serum creatinine level and normal radiological configuration of the kidney. The remaining seven patients (25%) developed varying degrees of renal deterioration either due to uretero-intestinal stricture in three patients (10.7%), who were all treated by open surgical revision of the anastomotic sites or due to stricture at the vesico-urethral anastomosis in four patients (14.3%) that had been successfully managed by endoscopic dilatation and internal ure-throtomy with stabilization of renal function. Severe metabolic acidosis occurred in one patient while mild forms occurred in three. These four patients required sodium bicarbonate therapy and

  11. 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

  12. 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

  13. 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...

  14. Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

    Directory of Open Access Journals (Sweden)

    Y. Tan

    2012-01-01

    Full Text Available Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA. Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

  15. Early stage cervical cancer, radical hysterectomy and sexual function: a longitudinal study

    DEFF Research Database (Denmark)

    Jensen, Pernille Tine

    Background: Limited knowledge exists regarding the impact of treatment on the sexual function of early stage cervical cancer patients. We investigated the longitudinal course of self-reported sexual function after radical hysterectomy (RH) alone. Methods: 173 patients with lymph node-negative early...... stage cervical cancer who had undergone RH and pelvic lymphadenectomy alone were assessed prospectively using a validated self-assessment questionnaire 5 weeks and 3, 6, 12, 18, and 24 months after RH. Results were compared with an age-matched control group from the general population. At 12 months post......-surgery, the patients completed an extended version of the questionnaire with additional items assessing the patient’s perception of changes in sexual function compared with before the cancer diagnosis. Results: Compared with control women, patients experienced severe orgasmic problems and uncomfortable sexual...

  16. The effect of adenosine A(2A) receptor antagonists on hydroxyl radical, dopamine, and glutamate in the striatum of rats with altered function of VMAT2.

    Science.gov (United States)

    Gołembiowska, Krystyna; Dziubina, Anna

    2012-08-01

    It has been shown that a decreased vesicular monoamine transporter (VMAT2) function and the disruption of dopamine (DA) storage is an early contributor to oxidative damage of dopamine neurons in Parkinson's disease (PD). In our previous study, we demonstrated that adenosine A(2A) receptor antagonists suppressed oxidative stress in 6-hydroxydopamine-treated rats suggesting that this effect may account for neuroprotective properties of drugs. In the present study, rats were injected with reserpine (10 mg/kg sc) and 18 h later the effect of the adenosine A(2A) receptor antagonists 8-(3-chlorostyryl)caffeine (CSC) and 4-(2-[7-amino-2-(2-furyl)[1,2,4]triazolo[2,3-a][1,3,5]triazin-5-ylamino]ethyl)phenol (ZM 241385) on extracellular DA, glutamate and hydroxyl radical formation was studied in the rat striatum using in vivo microdialysis. By disrupting VMAT2 function, reserpine depleted DA stores, and increased glutamate and hydroxyl radical levels in the rat striatum. CSC (1 mg/kg) but not ZM 241385 (3 mg/kg) increased extracellular DA level and production of hydroxyl radical in reserpinised rats. Both antagonists decreased the reserpine-induced increase in extracellular glutamate. L-3,4-Dihydroxyphenylalanine (L-DOPA) (25 mg/kg) significantly enhanced extracellular DA, had no effect on reserpine-induced hydroxyl radical production and decreased extracellular glutamate concentration. CSC but not ZM 241385 given jointly with L-DOPA increased the effect of L-DOPA on extracellular DA and augmented the reserpine-induced hydroxyl radical production. CSC and ZM 241385 did not influence extracellular glutamate level, which was decreased by L-DOPA. It seems that by decreasing the MAO-dependent DA metabolism rate, CSC raised cytosolic DA and by DA autoxidation, it induced hydroxyl radical overproduction. Thus, the methylxanthine A(2A) receptor antagonists bearing properties of MAO-B inhibitor, like CSC, may cause a risk of oxidative stress resulting from dysfunctional DA storage

  17. Correlation between location of transposed ovary and function in cervical cancer patients who underwent radical hysterectomy.

    Science.gov (United States)

    Yoon, Aera; Lee, Yoo-Young; Park, Won; Huh, Seung Jae; Choi, Chel Hun; Kim, Tae-Joong; Lee, Jeong-Won; Kim, Byoung-Gie; Bae, Duk-Soo

    2015-05-01

    The study investigated the association between the location of transposed ovaries and posttreatment ovarian function in patients with early cervical cancer (IB1-IIA) who underwent radical hysterectomy and ovarian transposition with or without adjuvant therapies. Retrospective medical records were reviewed to enroll the patients with early cervical cancer who underwent ovarian transposition during radical hysterectomy at Samsung Medical Center between July 1995 and July 2012. Serum follicle-stimulating hormone (FSH) level was used as a surrogate marker for ovarian function. Twenty-one patients were enrolled. The median age and body mass index (BMI) were 31 years (range, 24-39 years) and 21.3 kg/m² (range, 17.7-31.2 kg/m²), respectively. The median serum FSH level after treatment was 7.9 mIU/mL (range, 2.4-143.4 mIU/mL). The median distance from the iliac crest to transposed ovaries on erect plain abdominal x-ray was 0.5 cm (range, -2.7 to 5.2 cm). In multivariate analysis, posttreatment serum FSH levels were significantly associated with the location of transposed ovaries (β = -8.1, P = 0.032), concurrent chemoradiation (CCRT) as an adjuvant therapy (β = 71.08, P = 0.006), and BMI before treatment (underweight: β = -59.93, P = 0.05; overweight: β = -40.62, P = 0.041). Location of transposed ovaries, adjuvant CCRT, and BMI before treatment may be associated with ovarian function after treatment. We suggest that ovaries should be transposed as highly as possible during radical hysterectomy to preserve ovarian function in young patients with early cervical cancer who might be a candidate for adjuvant CCRT and who have low BMI before treatment.

  18. Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Nga Lee; Brown, Steven S.; Archibald, Alexander T.; Atlas, Elliot; Cohen, Ronald C.; Crowley, John N.; Day, Douglas A.; Donahue, Neil M.; Fry, Juliane L.; Fuchs, Hendrik; Griffin, Robert J.; Guzman, Marcelo I.; Herrmann, Hartmut; Hodzic, Alma; Iinuma, Yoshiteru; Jimenez, José L.; Kiendler-Scharr, Astrid; Lee, Ben H.; Luecken, Deborah J.; Mao, Jingqiu; McLaren, Robert; Mutzel, Anke; Osthoff, Hans D.; Ouyang, Bin; Picquet-Varrault, Benedicte; Platt, Ulrich; Pye, Havala O. T.; Rudich, Yinon; Schwantes, Rebecca H.; Shiraiwa, Manabu; Stutz, Jochen; Thornton, Joel A.; Tilgner, Andreas; Williams, Brent J.; Zaveri, Rahul A.

    2017-01-01

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models.

    This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

  19. Formation and spectroscopy of {alpha}-muoniated radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W

    2003-02-01

    Several novel {alpha}-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In {alpha}-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a {beta}-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison.

  20. Formation and spectroscopy of α-muoniated radicals

    International Nuclear Information System (INIS)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W.

    2003-01-01

    Several novel α-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In α-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a β-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison

  1. Introducing Stable Radicals into Molecular Machines.

    Science.gov (United States)

    Wang, Yuping; Frasconi, Marco; Stoddart, J Fraser

    2017-09-27

    Ever since their discovery, stable organic radicals have received considerable attention from chemists because of their unique optical, electronic, and magnetic properties. Currently, one of the most appealing challenges for the chemical community is to develop sophisticated artificial molecular machines that can do work by consuming external energy, after the manner of motor proteins. In this context, radical-pairing interactions are important in addressing the challenge: they not only provide supramolecular assistance in the synthesis of molecular machines but also open the door to developing multifunctional systems relying on the various properties of the radical species. In this Outlook, by taking the radical cationic state of 1,1'-dialkyl-4,4'-bipyridinium (BIPY •+ ) as an example, we highlight our research on the art and science of introducing radical-pairing interactions into functional systems, from prototypical molecular switches to complex molecular machines, followed by a discussion of the (i) limitations of the current systems and (ii) future research directions for designing BIPY •+ -based molecular machines with useful functions.

  2. Superoxide radical (O2-) reactivity with respect to glutathione

    International Nuclear Information System (INIS)

    Sekaki, A.; Gardes-Albert, M.; Ferradini, C.

    1984-01-01

    Influence of superoxide radicals formed during gamma irradiation of glutathione in aerated aqueous solutions is examined. Solutions are buffered at pH7 and contain sodium formate for capture of H and OH radicals which are transformed in COO - radicals and then O 2 - radicals. G value of glutathione disparition vs glutathione concentration are given with and without enzyme or catalase. Reaction mechanism are interpreted [fr

  3. Insertion of molecular oxygen into a palladium(II) methyl bond: a radical chain mechanism involving palladium(III) intermediates.

    Science.gov (United States)

    Boisvert, Luc; Denney, Melanie C; Hanson, Susan Kloek; Goldberg, Karen I

    2009-11-04

    The reaction of (bipy)PdMe(2) (1) (bipy = 2,2'-bipyridine) with molecular oxygen results in the formation of the palladium(II) methylperoxide complex (bipy)PdMe(OOMe) (2). The identity of the product 2 has been confirmed by independent synthesis. Results of kinetic studies of this unprecedented oxygen insertion reaction into a palladium alkyl bond support the involvement of a radical chain mechanism. Reproducible rates, attained in the presence of the radical initiator 2,2'-azobis(2-methylpropionitrile) (AIBN), reveal that the reaction is overall first-order (one-half-order in both [1] and [AIBN], and zero-order in [O(2)]). The unusual rate law (half-order in [1]) implies that the reaction proceeds by a mechanism that differs significantly from those for organic autoxidations and for the recently reported examples of insertion of O(2) into Pd(II) hydride bonds. The mechanism for the autoxidation of 1 is more closely related to that found for the autoxidation of main group and early transition metal alkyl complexes. Notably, the chain propagation is proposed to proceed via a stepwise associative homolytic substitution at the Pd center of 1 with formation of a pentacoordinate Pd(III) intermediate.

  4. Functionalization of lanthanum hydroxide nanowires by atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zhou Mi; Yuan Jinying; Yuan Weizhong; Yin Yingwu; Hong Xiaoyin

    2007-01-01

    Atom transfer radical polymerization (ATRP) has been used to prepare a core-shell hybrid nanostructure successfully: a hard core of single-crystalline lanthanum hydroxide nanowires and a soft shell of polystyrene (PS) brushes. Transmission electron microscopy (TEM) images indicated that the resulting products presented special structures and different thicknesses of polymer layers. The chemical components and grafted PS quantities of the samples were measured by Fourier transform infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). The polymers showed narrow polydispersity, which proved that the lanthanum hydroxide nanowires initiated the 'living'/controlled polymerization of styrene. With the modifiability of lanthanum hydroxide nanowires, the solubility increased, which affords a new way to functionalize nanowires

  5. 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

  6. Geminate free radical processes and magnetic field effects

    International Nuclear Information System (INIS)

    Eveson, Robert W.

    2000-01-01

    This thesis is concerned with the study of the dynamics of radical pair recombination reactions in solution by flash photolysis Electron Spin Resonance (ESR) and the influence of low static external magnetic fields upon them (MFE). An outline of the concepts of ESR is presented, followed by the theories of Chemically Induced Dynamic Electron Polarisation (CIDEP) of transient radical pairs. This is then followed by a brief review of the flash photolysis ESR apparatus and application of the Bloch equations to solve the equations of time-resolved ESR. Completing the theory section is an overview of the mechanisms by which magnetic fields alter the course of a geminate radical pair reaction in solution. Experimental CIDEP observations of the radical pair produced on photolysis of 1,3-dihydroxypropanone are simulated using polarisation theory and applied to a random-walk diffusion model to find, for the first time, the geminate reaction probability in solutions of varying viscosity. CIDEP spectra of the radical pair formed on photolysis of hydroxypropanone in contrast are not accounted for by current polarisation theory. The discrepancy is due to moderately fast relaxation of the acyl radical, CH 3 CO·, which alters the relative intensities in the ST 0 RPM pattern of the counter radical. Calculations taking into account this now provide an adequate basis for simulation of the spectrum. This method also, in principle, represents a new method for the measurement of phase relaxation times. Concluding the ESR work is a CIDEP study of 2,4,6-trimethylbenzoyl diphenylphosphine oxide. Unusual spin polarisation phenomena are found. The time-resolved optical absorption spectroscopy technique used for detecting low magnetic field effects on neutral radical pair reactions is described. Various improvements to the experiment are discussed which result in the observation of the low field effect for a neutral radical pair produced by Norrish type II chemistry. This is followed by an

  7. Free radical scavenging potency of quercetin catecholic colonic metabolites: Thermodynamics of 2H+/2e- processes.

    Science.gov (United States)

    Amić, Ana; Lučić, Bono; Stepanić, Višnja; Marković, Zoran; Marković, Svetlana; Dimitrić Marković, Jasmina M; Amić, Dragan

    2017-03-01

    Reaction energetics of the double (2H + /2e - ), i.e., the first 1H + /1e - (catechol→ phenoxyl radical) and the second 1H + /1e - (phenoxyl radical→ quinone) free radical scavenging mechanisms of quercetin and its six colonic catecholic metabolites (caffeic acid, hydrocaffeic acid, homoprotocatechuic acid, protocatechuic acid, 4-methylcatechol, and catechol) were computationally studied using density functional theory, with the aim to estimate the antiradical potency of these molecules. We found that second hydrogen atom transfer (HAT) and second sequential proton loss electron transfer (SPLET) mechanisms are less energy demanding than the first ones indicating 2H + /2e - processes as inherent to catechol moiety. The Gibbs free energy change for reactions of inactivation of selected free radicals indicate that catecholic colonic metabolites constitute an efficient group of more potent scavengers than quercetin itself, able to deactivate various free radicals, under different biological conditions. They could be responsible for the health benefits associated with regular intake of flavonoid-rich diet. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. 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

  9. Theoretical perspectives on the mechanism and kinetics of the OH radical-initiated gas-phase oxidation of PCB126 in the atmosphere

    International Nuclear Information System (INIS)

    Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

    2015-01-01

    Polychlorinated biphenyls (PCBs) primarily exist in the gas phase in air and may undergo atmospheric oxidation degradations, particularly the oxidation reaction initiated by OH radicals. In this work, the mechanism of the OH radical-initiated atmospheric oxidation of the most toxic PCB congener 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) was investigated by using quantum chemistry methods. The rate constants of the crucial elementary reactions were estimated by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The oxidation products of the reaction of PCB126 with OH radicals include 3,3′,4,4′,5-pentachlorobiphenyl-ols, chlorophenols, 2,3,4,7,8-pentachlorodibenzofuran, 2,3,4,6,7-pentachlorodibenzofuran, dialdehydes, 3,3′,4,4′,5-pentachloro-5′-nitro-biphenyl, and 4,5-dichloro-2-nitrophenol. Particularly, the formation of polychlorinated dibenzofurans (PCDFs) from the atmospheric oxidation of PCBs is revealed for the first time. The overall rate constant of the OH addition reaction is 2.52 × 10 −13 cm 3 molecule −1 s −1 at 298 K and 1 atm. The atmospheric lifetime of PCB126 determined by OH radicals is about 47.08 days which indicates that PCB126 can be transported long distances from local to global scales. - Highlights: • A comprehensive mechanism of OH-initiated oxidation of PCB126 was investigated. • The formation of PCDFs from the oxidation of PCBs is determined for the first time. • The rate constants for key elementary reactions were estimated by the RRKM theory. • The atmospheric lifetime of PCB126 determined by OH radicals is about 47.08 days

  10. Low dose radiation induced hormesis and its mechanism of free radicals

    International Nuclear Information System (INIS)

    Zhang Liyuan; Huo Hongmei; Zhang Yusong; Zhao Peifeng; Li Wei; Jiang Jiagui

    2008-01-01

    Objective: To investigate whether the supernatant (the stimulating fluid) centrifuged from myeloid cells suspension after low dose radiation in vitro can produce hormesis on the normal or radiation damage cells. The mechanism of free radical was probed. Methods: Mouse myeloid cell suspension was irradiated respectively by 0, 2 and 5 Gy, and cultured in vitro. MTT method was used to measure the reproductive activity of cells. Meanwhile, Cytochrome C reduction method was used to determine the concentration of O 2 - . Lastly, the concentration of O 2 - was decreased or increased by adding DPI or PMA, and the effect of such changes on 'the stimulating fluid' was observed. Results: Co-cultured with 'the stimulating fluid', the reproductive activity of the myeloid cells after large dose radiation or the normal myeloid cells were enhanced. Decreasing the concentration of O 2 - ; may degrade the proliferation of the cells after radiation damage; while increasing it may lead to the opposite result. Conclusions: The stimulating fluid can enhance the proliferation of the myeloid cells after radiation damage and also the normal ones. The mechanism of above-mentioned phenomena might be related with the changes of O 2 - concentration. (authors)

  11. Altered free radical metabolism in acute mountain sickness: implications for dynamic cerebral autoregulation and blood-brain barrier function

    DEFF Research Database (Denmark)

    Bailey, D M; Evans, K A; James, P E

    2008-01-01

    We tested the hypothesis that dynamic cerebral autoregulation (CA) and blood-brain barrier (BBB) function would be compromised in acute mountain sickness (AMS) subsequent to a hypoxia-mediated alteration in systemic free radical metabolism. Eighteen male lowlanders were examined in normoxia (21% O...... developed clinical AMS (AMS+) and were more hypoxaemic relative to subjects without AMS (AMS-). A more marked increase in the venous concentration of the ascorbate radical (A(*-)), lipid hydroperoxides (LOOH) and increased susceptibility of low-density lipoprotein (LDL) to oxidation was observed during...

  12. Heterogeneous kinetics, products, and mechanisms of ferulic acid particles in the reaction with NO3 radicals

    Science.gov (United States)

    Liu, Changgeng; Zhang, Peng; Wen, Xiaoying; Wu, Bin

    2017-03-01

    Methoxyphenols, as an important component of wood burning, are produced by lignin pyrolysis and considered to be the potential tracers for wood smoke emissions. In this work, the heterogeneous reaction between ferulic acid particles and NO3 radicals was investigated. Six products including oxalic acid, 4-vinylguaiacol, vanillin, 5-nitrovanillin, 5-nitroferulic acid, and caffeic acid were confirmed by gas chromatography-mass spectrometry (GC-MS). In addition, the reaction mechanisms were proposed and the main pathways were NO3 electrophilic addition to olefin and the meta-position to the hydroxyl group. The uptake coefficient of NO3 radicals on ferulic acid particles was 0.17 ± 0.02 and the effective rate constant under experimental conditions was (1.71 ± 0.08) × 10-12 cm3 molecule-1 s-1. The results indicate that ferulic acid degradation by NO3 can be an important sink at night.

  13. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  14. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali; Khashab, Niveen M.; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Coti, Karla K.; Bení tez, Diego S.; Tkatchouk, Ekaterina; Olsen, John Carl; Belowich, Matthew E.; Carmieli, Raanan; Khatib, Hussam A.; Goddard, William Andrew III; Wasielewski, Michael R.; Stoddart, Fraser Fraser Raser

    2009-01-01

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  15. The effect of near-infrared MLS laser radiation on cell membrane structure and radical generation.

    Science.gov (United States)

    Kujawa, Jolanta; Pasternak, Kamila; Zavodnik, Ilya; Irzmański, Robert; Wróbel, Dominika; Bryszewska, Maria

    2014-09-01

    The therapeutic effects of low-power laser radiation of different wavelengths and light doses are well known, but the biochemical mechanism of the interaction of laser light with living cells is not fully understood. We have investigated the effect of MLS (Multiwave Locked System) laser near-infrared irradiation on cell membrane structure, functional properties, and free radical generation using human red blood cells and breast cancer MCF-4 cells. The cells were irradiated with low-intensity MLS near-infrared (simultaneously 808 nm, continuous emission and 905 nm, pulse emission, pulse-wave frequency, 1,000 or 2,000 Hz) laser light at light doses from 0 to 15 J (average power density 212.5 mW/cm(2), spot size was 3.18 cm(2)) at 22 °C, the activity membrane bound acetylcholinesterase, cell stability, anti-oxidative activity, and free radical generation were the parameters used in characterizing the structural and functional changes of the cell. Near-infrared low-intensity laser radiation changed the acetylcholinesterase activity of the red blood cell membrane in a dose-dependent manner: There was a considerable increase of maximal enzymatic rate and Michaelis constant due to changes in the membrane structure. Integral parameters such as erythrocyte stability, membrane lipid peroxidation, or methemoglobin levels remained unchanged. Anti-oxidative capacity of the red blood cells increased after MLS laser irradiation. This irradiation induced a time-dependent increase in free radical generation in MCF-4 cells. Low-intensity near-infrared MLS laser radiation induces free radical generation and changes enzymatic and anti-oxidative activities of cellular components. Free radical generation may be the mechanism of the biomodulative effect of laser radiation.

  16. Critical appraisal of outcomes following open radical prostatectomy.

    Science.gov (United States)

    Galvin, David J; Eastham, James A

    2009-05-01

    Radical prostatectomy has evolved enormously over the last 25 years. Improvements include the use of smaller incisions, reduced blood loss, shorter hospital stays, and surgical refinement to improve the recovery of continence and potency. In addition, new technologies and minimally invasive techniques with the potential to further improve patient outcomes have been introduced. This article focuses on outcomes with open radical prostatectomy and is not meant to compare open radical prostatectomy and minimally invasive approaches. Despite a lack of randomized controlled trials, strong observational cohort studies demonstrate lower rates of positive surgical margins, high 10-year and 15-year biochemical recurrence-free rates, excellent prostate cancer-specific mortality rates, and improved recovery of urinary incontinence and erectile function after open radical prostatectomy. We review publications from the past 24 months regarding oncologic outcome, continence, and erectile function, as well as some earlier manuscripts that emphasize key aspects of open radical prostatectomy. Today open radical prostatectomy is a less-invasive procedure with low morbidity providing excellent control of clinically localized prostate cancer. Although open radical prostatectomy now accounts for a minority of radical prostatectomies in the United States, the concepts that have improved oncologic and quality-of-life outcomes are equally applicable to minimally invasive procedures.

  17. 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

  18. Structure and lyoluminescent reactions of free radicals of irradiated lactose

    International Nuclear Information System (INIS)

    Matyushkov, V.V.; Panasyuk, S.L.; Yudin, I.V.

    1983-01-01

    To determine mechanisms of processes, resulting in lyoluminescence the structure of fren radicals in γ-irradiated lactose was investigated by the method of electron paramagnetic resonance. Analysis of dependences of different radical content in irradiated crystals and lyoluminescent characteristics of these samples on the period of their storing enabled to confirm suggested earlier luminescence mechanism with lambdasub(max)=630 nm of irradiated carbon-hydrate in neutral and acid media. The possibility of controlling the content of different types of radicals in samples by lyoluminescent method was shown

  19. Long-lived gas-phase radicals from combustion

    Energy Technology Data Exchange (ETDEWEB)

    Kaneko, Takashi; Furusawa, Koji; Amano, Toshiji; Okubo, Yoichi; Tsuchiya, Jun' ichi; Yoshizawa, Fujiroku; Akutsu, Yoshiaki; Tamura, Masamitsu; Yoshida, Tadao (Univ. of Tokyo (Japan))

    1989-04-20

    On indoor air pollution or fire, it is feared that the gas-phase radicals from the combustion of inflammables or fuel seriously exert an influence on the organisms as harmful matter. The gas-phase radicals were studied using the electron spin resonance (ESR) spin-trapping technique. For the spin trap solution, 0.1 mol solution of {alpha}-phenyl-N-t-butylnitron in benzene was used. As a result, apparently long-lived and highly reactive oxygen-centered radicals were detected in the smoke from polyethylene, polypropylene, polystyrene, polymethylmethacrylate, cellulose, kerosene, benzene, acetone, methanol and butylalcohol. It is suggested that the production mechanism for the radicals should be different from olefin-NOx-air system reaction, which is considered for the radicals from cigarette smoke. 11 refs., 6 figs., 2 tabs.

  20. Thermodynamic and kinetic analysis of the reaction between biological catecholamines and chlorinated methylperoxy radicals

    Science.gov (United States)

    Dimić, Dušan S.; Milenković, Dejan A.; Marković, Jasmina M. Dimitrić; Marković, Zoran S.

    2018-05-01

    The antiradical potency of catecholamines (dopamine, epinephrine, norepinephrine, L-DOPA), metabolites of dopamine (homovanillic acid, 3-methoxytyramine and 3,4-dihydroxyphenylacetic acid) and catechol towards substituted methylperoxy radicals is investigated. The thermodynamic parameters, together with the kinetic approach, are used to determine the most probable mechanism of action. The natural bond orbital and quantum theory of atoms in molecules are utilised to explain the highest reactivity of trichloromethylperoxy radical. The preferred mechanism is dependent both on the thermodynamic and kinetic parameters . The number of chlorine atoms on radical, the presence of intra-molecular hydrogen bond and number of hydroxy groups attached to the aromatic ring significantly influence the mechanism. The results suggest that sequential proton loss electron transfer (SPLET) is the most probable for reaction with methylperoxy and hydrogen atom transfer (HAT) for reaction with trichloromethylperoxy radicals, with a gradual transition between SPLET and HAT for other two radicals. Due to the significant deprotonation of molecules containing the carboxyl group, the respective anions are also investigated. The HAT and SPLET mechanisms are highly competitive in reaction with MP radical, while the dominant mechanism towards chlorinated radicals is HAT. The reactions in methanol and benzene are also discussed.

  1. 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.

  2. Early-stage cervical carcinoma, radical hysterectomy, and sexual function. A longitudinal study

    DEFF Research Database (Denmark)

    Jensen, Pernille T; Groenvold, Mogens; Klee, Marianne C

    2004-01-01

    with an age-matched control group from the general population. RESULTS: Compared with control women, patients experienced severe orgasmic problems and uncomfortable sexual intercourse due to a reduced vaginal size during the first 6 months after RH, severe dyspareunia during the first 3 months, and sexual......BACKGROUND: Limited knowledge exists concerning the impact of radical hysterectomy (RH) alone on the sexual function of patients with early-stage cervical carcinoma. The authors investigated the longitudinal course of self-reported sexual function after RH. METHODS: The current study was comprised...... dissatisfaction during the 5 weeks after RH. A persistent lack of sexual interest and lubrication were reported throughout the first 2 years after RH. Long-term lack of sexual interest and insufficient vaginal lubrication were confirmed by the patient's self-reported changes 12 months after RH compared...

  3. Measuring Atmospheric Free Radicals Using Chemical Amplification

    Science.gov (United States)

    1988-05-01

    CH 3Br, H2S, and SO2 [Logan et al., 1981]. Recently, the OH radical has been determined as the dominant loss mechanism for isoprene and monoterpenes ...W. Heaps, D. Philen, and T. McGee, Bondary Layer Measurements of the OH Radical in the Vicinity of an Isolated Power Plant Plume: SO2 and NO2

  4. Early events following radiolytic and photogeneration of radical cations in hydrocarbons

    International Nuclear Information System (INIS)

    Werst, D.W.; Trifunac, A.D.

    1992-01-01

    Real-time studies in hydrocarbons have revealed a richness of chemistry involving the initial ionic species produced in radiolysis and photoionization. A modified radical cation mechanism patterned after the core mechanism for alkane radiolysis-formation of radical cations and their disappearance via ion-molecule reactions - is capable of explaining a wide range of observations in high-energy photochemistry, and thus unifies two high-energy regimes. Fundamental studies of radical cations suggest strategies for mitigating radiation effects in materials

  5. Radical reactions in vivo - an overview

    International Nuclear Information System (INIS)

    Saran, M.; Bors, W.

    1990-01-01

    Generation of radicals in vivo depends on metabolic activities. The reactions are usually influenced by (i) the presence and concentration of oxygen, (ii) the availability of transition metals (effects of binding and compartimentalization), (iii) the level of reductants and antioxidants (e.g. nutritional effects). The effects of radicals are thought to be due to (i) membrane damage (affecting passive or active transport through altered fluidity/function interrelationships, intercellular messenging through modifications in the synthesis of prostaglandins and leukotrienes); (ii) protein damage (e.g. affecting membrane transporters, channel proteins, receptor or regulatory proteins, immunomodulators); (iii) damage to DNA. Defense mechanisms consist of (i) prevention of the 'spreading' of primary damage by low molecular weight antioxidants (e.g. vitamin E, GSH, vitamin C, β-carotene, uric acid); (ii) prevention or limitation of 'secondary' damage by enzymes (e.g. GSH-peroxidase, catalase, superoxide dismutase, DT-diaphorase) and/or chelators; (iii) repair processes, e.g. lipid degradation/membrane repair enzymes (phospholipases, peroxidases, some transferases and reductases), protein disposal or repair enzymes (proteases, GSSG-reductase), DNA degradation or repair enzymes (exonucleases III, endonucleases III and IV, glycosylases, polymerases). Recent hypotheses on a messenging function of the superoxide anion O 2 - are discussed and possible implications of cross-reactions between O 2 - and nitric oxide (endothelium-derived relaxing factor EDRF) are shortly mentioned. (orig.)

  6. 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.

  7. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

    Science.gov (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

    2015-11-15

    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX TEMPO EEQQQTEDELQDK. The X TEMPO residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-C α backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b H ) and y + H (y H ) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  8. 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.

  9. [Research progress on free radicals in human body].

    Science.gov (United States)

    Wang, Q B; Xu, F P; Wei, C X; Peng, J; Dong, X D

    2016-08-10

    Free radicals are the intermediates of metabolism, widely exist in the human bodies. Under normal circumstances, the free radicals play an important role in the metabolic process on human body, cell signal pathway, gene regulation, induction of cell proliferation and apoptosis, so as to maintain the normal growth and development of human body and to inhibit the growth of bacteria, virus and cancer. However, when organic lesion occurs affected by external factors or when equilibrium of the free radicals is tipped in the human body, the free radicals will respond integratedly with lipids, protein or nucleic acid which may jeopardize the health of human bodies. This paper summarizes the research progress of the free radicals conducted in recent years, in relations to the perspective of the types, origins, test methods of the free radicals and their relationship with human's health. In addition, the possible mechanisms of environmental pollutants (such as polycyclic aromatic hydrocarbons) mediating oxidative stress and free radicals scavenging in the body were also summarized.

  10. Hydroxyl radical induced cross-linking of cytosine and tyrosine in nucleohistone

    International Nuclear Information System (INIS)

    Gajewski, E.; Dizdaroglu, M.

    1990-01-01

    Hydroxyl radical induced formation of a DNA-protein cross-link involving cytosine and tyrosine in nucleohistone in buffered aqueous solution is reported. The technique of gas chromatography-mass spectrometry was used for this investigation. A γ-irradiated aqueous mixture of cytosine and tyrosine was first investigated in order to obtain gas chromatographic-mass spectrometric properties of possible cytosine-tyrosine cross-links. One cross-link was observed, and its structure was identified as the product from the formation of a covalent bond between carbon 6 of cytosine and carbon 3 of tyrosine. With the use of gas chromatography-mass spectrometry with selected-ion monitoring, this cytosine-tyrosine cross-link was identified in acidic hydrolysates of calf thymus nucleohistone γ-irradiated in N 2 O-saturated aqueous solution. The yield of this DNA-protein cross-link in nucleohistone was found to be a linear function of the radiation dose in the range of 100-500 Gy (J·kg -1 ). This yield amounted to 0.05 nmol·J -1 . Mechanisms underlying the formation of the cytosine-tyrosine cross-link in nucleohistone were proposed to involve radical-radical and/or radical addition reactions of hydroxyl adduct radicals of cytosine and tyrosine moieties, forming a covalent bond between carbon 6 of cytosine and carbon 3 of tyrosine. When oxygen was present in irradiated solutions, no cytosine-tyrosine cross-links were observed

  11. Radical-pair based avian magnetoreception

    Science.gov (United States)

    Procopio, Maria; Ritz, Thorsten

    2014-03-01

    Behavioural experiments suggest that migratory birds possess a magnetic compass sensor able to detect the direction of the geomagnetic. One hypothesis for the basis of this remarkable sensory ability is that the coherent quantum spin dynamics of photoinduced radical pair reactions transduces directional magnetic information from the geomagnetic field into changes of reaction yields, possibly involving the photoreceptor cryptochrome in the birds retina. The suggested radical-pair based avian magnetoreception has attracted attention in the field of quantum biology as an example of a biological sensor which might exploit quantum coherences for its biological function. Investigations on such a spin-based sensor have focussed on uncovering the design features for the design of a biomimetic magnetic field sensor. We study the effects of slow fluctuations in the nuclear spin environment on the directional signal. We quantitatively evaluate the robustness of signals under fluctuations on a timescale longer than the lifetime of a radical pair, utilizing two models of radical pairs. Our results suggest design principles for building a radical-pair based compass sensor that is both robust and highly directional sensitive.

  12. Correction of Free Radical Lipid Oxidation in Internal Female Genital Inflammatory Diseases

    Directory of Open Access Journals (Sweden)

    A. D. Belyaevsky

    2008-01-01

    Full Text Available The paper descries a specific view on the mechanism responsible for development of the resistance of an inflammatory process in the female genital tract to drugs and on the role of a free radical process activation factor in the pathogenesis of the disease. Emphasis is laid on the importance of measures to diminish cell membrane permeability, by correcting their structural and functional states with antioxidants. Key words: inflammatory processes in the female genital organs, lipid peroxidation, antioxidative defense, cell membrane structural and functional state.

  13. Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

    Science.gov (United States)

    Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

    2016-12-01

    Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

  14. Mechanics of advanced functional materials

    CERN Document Server

    Wang, Biao

    2013-01-01

    Mechanics of Advanced Functional Materials emphasizes the coupling effect between the electric and mechanical field in the piezoelectric, ferroelectric and other functional materials. It also discusses the size effect on the ferroelectric domain instability and phase transition behaviors using the continuum micro-structural evolution models. Functional materials usually have a very wide application in engineering due to their unique thermal, electric, magnetic, optoelectronic, etc., functions. Almost all the applications demand that the material should have reasonable stiffness, strength, fracture toughness and the other mechanical properties. Furthermore, usually the stress and strain fields on the functional materials and devices have some important coupling effect on the functionality of the materials. Much progress has been made concerning the coupling electric and mechanical behaviors such as the coupled electric and stress field distribution in piezoelectric solids, ferroelectric domain patterns in ferr...

  15. Proton flux effects and prediction on the free radicals behavior of polyimide in vacuum using EPR measurements in ambient

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Chengyue [Physics Department, Harbin Institute of Technology, Harbin 150001 (China); National Key Lab of Materials Behaviors and Evaluation Technology in Space Environments, Harbin Institute of Technology, Harbin 150001 (China); Wu, Yiyong, E-mail: wuyiyong@hit.edu.cn [National Key Lab of Materials Behaviors and Evaluation Technology in Space Environments, Harbin Institute of Technology, Harbin 150001 (China); Xiao, Jingdong [National Key Lab of Materials Behaviors and Evaluation Technology in Space Environments, Harbin Institute of Technology, Harbin 150001 (China); Yu, Sui [Physics Department, Harbin Institute of Technology, Harbin 150001 (China); Yi, Zhong; Shen, Zicai [Chinese Academy of Sciences, Beijing 100029 (China); Wang, Li [Qian Xuesen Laboratory of Space Technology, Beijing 100029 (China); Wang, Yi [Lanzhou Institute of Physics, CAST, Lanzhou 730000 (China)

    2017-04-15

    Irradiation flux is an important parameter to the material irradiation damage investigation, for space material irradiation damage evaluation and the accelerated ground-based test, the irradiation flux effects cannot be ignored. In this paper, the polyimide was set as the research object, the irradiation flux effect and mechanism are investigated by the means of electron paramagnetic resonance test, and based on the free radical dynamic analysis, the dynamics mode of free radical population in vacumm can be established as a function of irradiation time (or proton irradiation flux). The results show that the free radical anneal process in vacuum follows the exponential mode, and the characteristic time constant τ{sub radical-vacuum} is about 1.9 h. Furthermore, a simplified method is proposed with the investigation of the free radical behavior of the irradiated surface modification polyimide (TiO{sub 2}/PI), and the characteristic time constant τ{sub bulk} is 1.9 h, which is almost the same to the value of τ{sub radical-vacuum}.

  16. Zwitterion radicals and anion radicals from electron transfer and solvent condensation with the fingerprint developing agent ninhydrin.

    Science.gov (United States)

    Schertz, T D; Reiter, R C; Stevenson, C D

    2001-11-16

    Ninhydrin (the fingerprint developing agent) spontaneously dehydrates in liquid ammonia and in hexamethylphosphoramide (HMPA) to form indantrione, which has a sufficiently large solution electron affinity to extract an electron from the solvent (HMPA) to produce the indantrione anion radical. In liquid NH(3), the presence of trace amounts of amide ion causes the spontaneous formation of an anion radical condensation product, wherein the no. 2 carbon (originally a carbonyl carbon) becomes substituted with -NH(2) and -OH groups. In HMPA, the indantrione anion radical spontaneously forms condensation products with the HMPA to produce a variety of zwitterionic radicals, wherein the no. 2 carbon becomes directly attached to a nitrogen of the HMPA. The mechanisms for the formation of the zwitterionic paramagnetic condensation products are analogous to that observed in the reaction of ninhydrin with amino acids to yield Ruhemann's Purple, the contrast product in fingerprint development. The formation of anion and zwitterionic radical condensation products from ninhydrin and nitrogen-containing solvents may represent an example of a host of analogous polyketone-solvent reactions.

  17. Collision dynamics of methyl radicals and highly vibrationally excited molecules using crossed molecular beams

    International Nuclear Information System (INIS)

    Chu, P.M.Y.

    1991-10-01

    The vibrational to translational (V→T) energy transfer in collisions between large highly vibrationally excited polyatomics and rare gases was investigated by time-of-flight techniques. Two different methods, UV excitation followed by intemal conversion and infrared multiphoton excitation (IRMPE), were used to form vibrationally excited molecular beams of hexafluorobenzene and sulfur hexafluoride, respectively. The product translational energy was found to be independent of the vibrational excitation. These results indicate that the probability distribution function for V→T energy transfer is peaked at zero. The collisional relaxation of large polyatomic molecules with rare gases most likely occurs through a rotationally mediated process. Photodissociation of nitrobenzene in a molecular beam was studied at 266 nm. Two primary dissociation channels were identified including simple bond rupture to produce nitrogen dioxide and phenyl radical and isomerization to form nitric oxide and phenoxy radical. The time-of-flight spectra indicate that simple bond rupture and isomerization occurs via two different mechanisms. Secondary dissociation of the phenoxy radicals to carbon monoxide and cyclopentadienyl radicals was observed as well as secondary photodissociation of phenyl radical to give H atom and benzyne. A supersonic methyl radical beam source is developed. The beam source configuration and conditions were optimized for CH 3 production from the thermal decomposition of azomethane. Elastic scattering of methyl radical and neon was used to differentiate between the methyl radicals and the residual azomethane in the molecular beam

  18. 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)

  19. Prospective, longitudinal, multi-modal functional imaging for radical chemo-IMRT treatment of locally advanced head and neck cancer: the INSIGHT study

    International Nuclear Information System (INIS)

    Welsh, Liam; Panek, Rafal; McQuaid, Dualta; Dunlop, Alex; Schmidt, Maria; Riddell, Angela; Koh, Dow-Mu; Doran, Simon; Murray, Iain; Du, Yong; Chua, Sue; Hansen, Vibeke; Wong, Kee H.; Dean, Jamie; Gulliford, Sarah; Bhide, Shreerang; Leach, Martin O.; Nutting, Christopher; Harrington, Kevin; Newbold, Kate

    2015-01-01

    Radical chemo-radiotherapy (CRT) is an effective organ-sparing treatment option for patients with locally advanced head and neck cancer (LAHNC). Despite advances in treatment for LAHNC, a significant minority of these patients continue to fail to achieve complete response with standard CRT. By constructing a multi-modality functional imaging (FI) predictive biomarker for CRT outcome for patients with LAHNC we hope to be able to reliably identify those patients at high risk of failing standard CRT. Such a biomarker would in future enable CRT to be tailored to the specific biological characteristics of each patients’ tumour, potentially leading to improved treatment outcomes. The INSIGHT study is a single-centre, prospective, longitudinal multi-modality imaging study using functional MRI and FDG-PET/CT for patients with LAHNC squamous cell carcinomas receiving radical CRT. Two cohorts of patients are being recruited: one treated with, and another treated without, induction chemotherapy. All patients receive radical intensity modulated radiotherapy with concurrent chemotherapy. Patients undergo functional imaging before, during and 3 months after completion of radiotherapy, as well as at the time of relapse, should that occur within the first two years after treatment. Serum samples are collected from patients at the same time points as the FI scans for analysis of a panel of serum markers of tumour hypoxia. The primary aim of the INSIGHT study is to acquire a prospective multi-parametric longitudinal data set comprising functional MRI, FDG PET/CT, and serum biomarker data from patients with LAHNC undergoing primary radical CRT. This data set will be used to construct a predictive imaging biomarker for outcome after CRT for LAHNC. This predictive imaging biomarker will be used in future studies of functional imaging based treatment stratification for patients with LAHNC. Additional objectives are: defining the reproducibility of FI parameters; determining robust

  20. Radical Decisions in Cancer: Redox Control of Cell Growth and Death

    International Nuclear Information System (INIS)

    Sainz, Rosa M.; Lombo, Felipe; Mayo, Juan C.

    2012-01-01

    Free radicals play a key role in many physiological decisions in cells. Since free radicals are toxic to cellular components, it is known that they cause DNA damage, contribute to DNA instability and mutation and thus favor carcinogenesis. However, nowadays it is assumed that free radicals play a further complex role in cancer. Low levels of free radicals and steady state levels of antioxidant enzymes are responsible for the fine tuning of redox status inside cells. A change in redox state is a way to modify the physiological status of the cell, in fact, a more reduced status is found in resting cells while a more oxidative status is associated with proliferative cells. The mechanisms by which redox status can change the proliferative activity of cancer cells are related to transcriptional and posttranscriptional modifications of proteins that play a critical role in cell cycle control. Since cancer cells show higher levels of free radicals compared with their normal counterparts, it is believed that the anti-oxidative stress mechanism is also increased in cancer cells. In fact, the levels of some of the most important antioxidant enzymes are elevated in advanced status of some types of tumors. Anti-cancer treatment is compromised by survival mechanisms in cancer cells and collateral damage in normal non-pathological tissues. Though some resistance mechanisms have been described, they do not yet explain why treatment of cancer fails in several tumors. Given that some antitumoral treatments are based on the generation of free radicals, we will discuss in this review the possible role of antioxidant enzymes in the survival mechanism in cancer cells and then, its participation in the failure of cancer treatments

  1. Kinetics and mechanisms of reactions of CF, CHF, and CF2 radicals

    International Nuclear Information System (INIS)

    Hsu, D.S.Y.; Umstead, M.E.; Lin, M.C.

    1978-01-01

    This chapter reviews briefly methods for the production of CF, CHF and CF 2 , and inmore detail, the reactions of these interesting and important radicals. Although a considerable, but not extensive, amount of work has been done on the reactions of CF 2 , little of the chemistry of CF and CHF is known. This chapter also includes the preliminary results of some experiments carried out in this Laboratory on the dynamics of some of the reactions involving these radicals. These results were largely arrived at through investigations of the degree of vibrational excitation of the HF and CO reaction products, determined by HF and CO laser emission and CO laser resonance absorption measurements. The coverage of this review is restricted to the gas phase chemistry of these radicals, and does not include their addition reactions to olefins

  2. Effects of Molecular Iodine and 4-tert-Butylcatechol Radical Inhibitor on the Radical Polymerization of Styrene

    Directory of Open Access Journals (Sweden)

    Mojtaba Bozorg

    2017-05-01

    Full Text Available The presence of molecular iodine was studied in relation the molecular weight and molecular weight distribution of polystyrene, produced by radical poly merization. Radical polymerization of styrene initiated by 2,2׳-azobisisobutyronitrile (AIBN was performed at 70°C in the presence of molecular iodine. The synthesized polymers were characterized by gel permeation chromatography (GPC and proton- nuclear magnetic resonance (1H NMR techniques. The results of these reactions including conversion data, number-average molecular weight and molecular weight distribution were compared with those obtained for styrene radical polymerization initiated by AIBN at the same temperature in the absence of molecular iodine. It was found that the presence of iodine had a profound effect on the molecular weight and its distribution in the produced polystyrene. This was attributed to the ability of iodine to control the polymerization of styrene initiated by AIBN via reverse iodine transfer polymerization (RITP mechanism. The polymer produced by this method had a molecular weight of 10600 g/mol with a molecular weight polydispersity index of 1.3. Due to the importance of induction period in reverse iodine transfer radical polymerization, increasing the temperature to 120°C during the induction period resulted in shorter induction periods and the produced species led to better control of the molecular weight. Also, due to the role of iodine molecules as a radical inhibitor, the presence of a secondary radical inhibitor, i.e. 4-tert-butylcatechol, along with the iodine was investigated in radical polymerization of polystyrene initiated by AIBN. It was observed that the secondary radical inhibitor prevented the consumption of the iodine molecules by the radicals produced from decomposition of the AIBN initiator; therefore, alkyl halides were not produced during the induction period.

  3. Nitroxide-mediated controlled radical polymerisation: towards control of molar mass Controlled Radical Polymerisation

    NARCIS (Netherlands)

    Bon, S.A.F.; Bergman, F.A.C.; Es, van J.J.G.S.; Klumperman, B.; German, A.L.; Matyjaszewski, K.

    1998-01-01

    The mechanism of the TEMPO-mediated controlled radical polymerization of styrene in bulk is discussed. It is shown that the isotropic correlation time (tc) of a nitroxide can be used as a measure of the diffusive rate coefficient of trapping (ketD). A general empirical relationship for the density

  4. TRANSITION METAL CATALYSIS IN CONTROLLED RADICAL POLYMERIZATION: ATOM TRANSFER RADICAL POLYMERIZATION. (R826735)

    Science.gov (United States)

    Novel and diversified macromolecular structures, which include polymers with designed topologies (top), compostions (middle), and functionalities (bottom), can be prepared by atom transfer radical polymerization processes. These polymers can be synthesized from a large variety of...

  5. 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

  6. Protonated o-semiquinone radical as a mimetic of the humic acids native radicals: A DFT approach to the molecular structure and EPR properties

    Science.gov (United States)

    Witwicki, Maciej; Jezierska, Julia

    2012-06-01

    Organic radicals are known to be an indispensable component of the humic acids (HA) structure. In HA two forms of radicals, stable (native) and short-lived (transient), are identified. Importantly, these radical forms can be easily differentiated by electron paramagnetic resonance (EPR) spectroscopy. This article provides a DFT-based insight into the electronic and molecular structure of the native radicals. The molecular models including an increase of the radical aromaticity and the hydrogen bonding between the radical and other functional groups of HA are taken under investigation. In consequence the interesting pieces of information on the structure of the native radical centers in HA are revealed and discussed, especially in terms of differences between the electronic structure of the native and transient forms.

  7. Factors predicting early return of continence after radical prostatectomy.

    Science.gov (United States)

    Sandhu, Jaspreet S; Eastham, James A

    2010-05-01

    Success of radical prostatectomy is measured by control of cancer and return of urinary and sexual function. Urinary incontinence is generally considered the greatest impairment in immediate postoperative urinary function. Multiple factors are associated with earlier return of urinary continence after radical prostatectomy. These factors can be divided into those known prior to surgery, and therefore possibly not modifiable, and factors that can be controlled during surgery or surgical planning. In addition, various postoperative maneuvers can help hasten urinary continence. This article examines the effect of known factors related to early return of urinary continence after radical prostatectomy.

  8. Formation and thermal transformations of radicals in γ-irradiated cellulose

    International Nuclear Information System (INIS)

    Ershov, B.G.; Isakova, O.V.

    1984-01-01

    The work is aimed at more detailed theoretical analysis of the structure of radicals in cellulose gamma-irradiated at 77 K, specification of the mechanism of their formation, as well as studying reactions of transformation of radicals in the case of temperature increase. It is established that in the case of cellulose gamma-irradiation radicals appear with the localization of an unpaired electron in 1 and 4 positions of the pyranose cycle the formation of which is accompanied by the disruption of the glycoside bound. Thermal transformations of these radicals are conditioned by their dehydration and occur with the formation of radicals of the allelow type

  9. Free radical reactions of daunorubicin

    International Nuclear Information System (INIS)

    Houee-Levin, C.

    1991-01-01

    Daunorubicin is an antitumor antibiotic activated in vivo by reduction. Its mechanism of action involves DNA and topoisomerase attack, but side effects are cytotoxicity related to free radical formation. Therefore the mechanism of the one-electron reduction of the drug and the reactions of the daunorubicin transients towards compounds of biological interest have been studied by the methods of radiolysis, in order to provide possible explanations of the drug mechanism of action. Their relative importance in cellular conditions is discussed [fr

  10. 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.

  11. 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

  12. Open radical prostatectomy after transurethral resection: perioperative, functional, oncologic outcomes.

    Science.gov (United States)

    Fragkoulis, Charalampos; Pappas, Athanasios; Theocharis, Georgios; Papadopoulos, Georgios; Stathouros, Georgios; Ntoumas, Konstantinos

    2018-04-01

    To demonstrate any differences in the perioperative, functional and oncologic outcomes after radical retropubic prostatectomy (RRP) among those patients having previously performed transurethral resection of prostate (TURP) and those not. A total of 35 patients were diagnosed with prostate cancer (T1a and T1b) after TURP, underwent RRP and completed a 1 year follow up (group A). They were matched with a cohort of another 35 men (group B) in terms of age, body mass index (BMI), prostatic specific antigen (PSA), Gleason score, prostate volume (before surgery), pathological stage and neurovascular bundle-sparing technique. That was a retrospective study completed between September 2011 and March 2014. Not a significant difference was demonstrated among the two groups of patients concerning the functional and oncologic results. On the other hand, previous prostate surgery made the operation procedure more demanding. Besides, operative time and blood loss (though not translated in transfusion rates) were higher among patients in group A. Besides, catheter removal in group A patients was performed later than their counterparts of group B. RRP after TURP is a relatively safe procedure and in the hands of experienced surgeons, a previously performed TURP, does not seem to compromise oncologic outcomes of the operation. Continence is preserved, though erectile function seems to be compromised compared with patients undergoing RRP without prior TURP. Moreover, defining the prostate and bladder neck margins can be challenging and the surgeon has to be aware of the difficulties that might confront.

  13. Specific Function of the Met-Tyr-Trp Adduct Radical and Residues Arg-418 and Asp-137 in the Atypical Catalase Reaction of Catalase-Peroxidase KatG*

    Science.gov (United States)

    Zhao, Xiangbo; Khajo, Abdelahad; Jarrett, Sanchez; Suarez, Javier; Levitsky, Yan; Burger, Richard M.; Jarzecki, Andrzej A.; Magliozzo, Richard S.

    2012-01-01

    Catalase activity of the dual-function heme enzyme catalase-peroxidase (KatG) depends on several structural elements, including a unique adduct formed from covalently linked side chains of three conserved amino acids (Met-255, Tyr-229, and Trp-107, Mycobacterium tuberculosis KatG numbering) (MYW). Mutagenesis, electron paramagnetic resonance, and optical stopped-flow experiments, along with calculations using density functional theory (DFT) methods revealed the basis of the requirement for a radical on the MYW-adduct, for oxyferrous heme, and for conserved residues Arg-418 and Asp-137 in the rapid catalase reaction. The participation of an oxyferrous heme intermediate (dioxyheme) throughout the pH range of catalase activity is suggested from our finding that carbon monoxide inhibits the activity at both acidic and alkaline pH. In the presence of H2O2, the MYW-adduct radical is formed normally in KatG[D137S] but this mutant is defective in forming dioxyheme and lacks catalase activity. KatG[R418L] is also catalase deficient but exhibits normal formation of the adduct radical and dioxyheme. Both mutants exhibit a coincidence between MYW-adduct radical persistence and H2O2 consumption as a function of time, and enhanced subunit oligomerization during turnover, suggesting that the two mutations disrupting catalase turnover allow increased migration of the MYW-adduct radical to protein surface residues. DFT calculations showed that an interaction between the side chain of residue Arg-418 and Tyr-229 in the MYW-adduct radical favors reaction of the radical with the adjacent dioxyheme intermediate present throughout turnover in WT KatG. Release of molecular oxygen and regeneration of resting enzyme are thereby catalyzed in the last step of a proposed catalase reaction. PMID:22918833

  14. Highly functionalized piperidines: Free radical scavenging, anticancer activity, DNA interaction and correlation with biological activity

    OpenAIRE

    Suvankar Das; Cristiane J. da Silva; Marina de M. Silva; Maria Dayanne de A. Dantas; Ângelo de Fátima; Ana Lúcia T. Góis Ruiz; Cleiton M. da Silva; João Ernesto de Carvalho; Josué C.C. Santos; Isis M. Figueiredo; Edeildo F. da Silva-Júnior; Thiago M. de Aquino; João X. de Araújo-Júnior; Goutam Brahmachari; Luzia Valentina Modolo

    2018-01-01

    Twenty-five piperidines were studied as potential radical scavengers and antitumor agents. Quantitative interaction of compounds with ctDNA using spectroscopic techniques was also evaluated. Our results demonstrate that the evaluated piperidines possesses different abilities to scavenge the radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) and the anion radical superoxide (·O2−). The piperidine 19 was the most potent radical DPPH scavenger, while the most effective to ·O2− scavenger was piperidine...

  15. 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.

  16. 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.

  17. 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)

  18. Free radicals in biology. Volume II

    International Nuclear Information System (INIS)

    Pryor, W.A.

    1976-01-01

    This volume continues the treatment of topics in free radical biology and free radical pathology from Volume I. In the first chapter, pyridinyl radicals, radicals which are models for those derived from NAD, are discussed. Pyridinyl radicals can be synthesized and isolated and directly studied in a number of chemical systems. The next chapter treats the role of glutathione in the cell. It is becoming even more apparent that this vital thiol controls a large number of important cellular functions. The GSH/GSSG balance has recently been implicated as a control for cellular development; this balance also may be important in relaying the effects of oxidants from one site to another in the body. The next chapter outlines the reactions of singlet oxygen; some of these involve free radicals and some do not. This reactive intermediate appears to be important both in photochemical smog and in cellular chemistry where singlet oxygen is produced by nonphotochemical processes. The production of free radicals from dry tissues, a controversial area with conflicting claims is reviewed. The next chapter outlines the current status of the studies of photochemical smog. The next two chapters treat specific reactive materials which are present in smog. The first discusses the chemistry of nitrogen oxides and ozone. The second chapter treats the chemistry of the peroxyacyl nitrites. These compounds, although present in only small concentration, are among the most toxic components of smog. The last two chapters treat radiation damage to proteins and radiation protection and radical reactions produced by radiation in nucleic acids

  19. 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.

  20. Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

    Science.gov (United States)

    Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

    2013-12-16

    We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction

  1. Thermal stability of carbonyl radicals. Part II. Reactions of methylglyoxyl and methylglyoxylperoxy radicals at 1 bar in the temperature range 275-311 K.

    Science.gov (United States)

    Jagiella, Stefan; Zabel, Friedhelm

    2008-04-07

    Reactions of methylglyoxyl and methylglyoxylperoxy radicals were investigated at a total pressure of 1 bar in oxygen. Methylglyoxyl radicals were generated by stationary photolysis of Br2-CH3C(O)C(O)H-NO2-O2-N2 mixtures at wavelengths > or =480 nm and of Cl2-CH3C(O)C(O)H-NO2-O2-N2 mixtures in the wavelength range 315-460 nm. In the bromine system, rate constant ratios for the reactions CH3C(O)CO --> CH3CO + CO (kdis) and CH3C(O)CO + O2 --> CH3C(O)C(O)O2 (kO2) were measured as a function of temperature in the range 275-311 K. Assuming the constant value kO2 = 5.1 x 10(-12) cm3 molecule(-1) s(-1) for our reaction conditions, kdis = 1.2 x 10(10.0+/-0.7) x exp(-11.7 +/- 3.8 kJ mol(-1)/RT) s(-1) (2sigma errors) was obtained for ptot = 1 bar (M = O2), in good agreement with the kinetic parameters calculated by Méreau et al. [R. Méreau, M.-T. Rayez, J.-C. Rayez, F. Caralp and R. Lesclaux, Phys. Chem. Chem. Phys., 2001, 3, 4712]. CH3C(O)C(O)O2 radicals oxidise NO2, forming NO3, CH3CO and CO2. This experimental result is supported by DFT and ab initio calculations. Possible mechanisms for the observed formation of several % of ketene and bromoacetyl peroxynitrate are discussed. Use of Cl rather than Br atoms to abstract the aldehydic H atom from methylglyoxal leads to chemically activated CH3C(O)CO radicals, thus substantially increasing the fraction of CH3C(O)CO radicals that decompose rather than add O2.

  2. GLYCOLALDEHYDE FORMATION VIA THE DIMERIZATION OF THE FORMYL RADICAL

    Energy Technology Data Exchange (ETDEWEB)

    Woods, Paul M.; Viti, Serena [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Slater, Ben; Raza, Zamaan; Brown, Wendy A.; Burke, Daren J., E-mail: p.woods@qub.ac.uk [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)

    2013-11-10

    Glycolaldehyde, the simplest monosaccharide sugar, has recently been detected in low- and high-mass star-forming cores. Following our previous investigation into glycolaldehyde formation, we now consider a further mechanism for the formation of glycolaldehyde that involves the dimerization of the formyl radical, HCO. Quantum mechanical investigation of the HCO dimerization process upon an ice surface is predicted to be barrierless and therefore fast. In an astrophysical context, we show that this mechanism can be very efficient in star-forming cores. It is limited by the availability of the formyl radical, but models suggest that only very small amounts of CO are required to be converted to HCO to meet the observational constraints.

  3. GLYCOLALDEHYDE FORMATION VIA THE DIMERIZATION OF THE FORMYL RADICAL

    International Nuclear Information System (INIS)

    Woods, Paul M.; Viti, Serena; Slater, Ben; Raza, Zamaan; Brown, Wendy A.; Burke, Daren J.

    2013-01-01

    Glycolaldehyde, the simplest monosaccharide sugar, has recently been detected in low- and high-mass star-forming cores. Following our previous investigation into glycolaldehyde formation, we now consider a further mechanism for the formation of glycolaldehyde that involves the dimerization of the formyl radical, HCO. Quantum mechanical investigation of the HCO dimerization process upon an ice surface is predicted to be barrierless and therefore fast. In an astrophysical context, we show that this mechanism can be very efficient in star-forming cores. It is limited by the availability of the formyl radical, but models suggest that only very small amounts of CO are required to be converted to HCO to meet the observational constraints

  4. Radical production in the radiolysis of benzene

    International Nuclear Information System (INIS)

    LaVerne, J.A.; Araos, M.S.

    1998-01-01

    Complete text of publication follows. Benzene is the prototypical aromatic compound and yet the radiation chemistry of the radicals formed in its radiolysis is not well understood. Temporal information on the yield of phenyl radical, the major radical produced in the radiolysis, is important for understanding the radiation chemistry of many other types of aromatic compounds including some polymers. The effects of track structure on the production of phenyl radicals have been examined using iodine-scavenging techniques. The variation of the yields of iodobenzene and the other major molecular products such as biphenyl as a function of iodine concentration gives a good indication of the competition kinetics occurring in particle tracks. Experimental results of the scavenger experiments will be shown and their implications in the radiolysis of condensed hydrocarbons will be discussed

  5. Aromatic-radical oxidation chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Glassman, I.; Brezinsky, K. [Princeton Univ., NJ (United States)

    1993-12-01

    The research effort has focussed on discovering an explanation for the anomalously high CO{sub 2} concentrations observed early in the reaction sequence of the oxidation of cyclopentadiene. To explain this observation, a number of plausible mechanisms have been developed which now await experimental verification. One experimental technique for verifying mechanisms is to probe the reacting system by perturbing the radical concentrations. Two forms of chemical perturbation of the oxidation of cyclopentadiene were begun during this past year--the addition of NO{sub 2} and CO to the reacting mixture.

  6. Theoretical study on the mechanism of the reaction of FOX-7 with OH and NO2 radicals: bimolecular reactions with low barrier during the decomposition of FOX-7

    Science.gov (United States)

    Zhang, Ji-Dong; Zhang, Li-Li

    2017-12-01

    The decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO2 radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO2 + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO2 + FOX-7 results in the formation of NO3 radical, which has never been detected experimentally during the decomposition of FOX-7.

  7. Electric fields control the orientation of peptides irreversibly immobilized on radical-functionalized surfaces.

    Science.gov (United States)

    Martin, Lewis J; Akhavan, Behnam; Bilek, Marcela M M

    2018-01-24

    Surface functionalization of an implantable device with bioactive molecules can overcome adverse biological responses by promoting specific local tissue integration. Bioactive peptides have advantages over larger protein molecules due to their robustness and sterilizability. Their relatively small size presents opportunities to control the peptide orientation on approach to a surface to achieve favourable presentation of bioactive motifs. Here we demonstrate control of the orientation of surface-bound peptides by tuning electric fields at the surface during immobilization. Guided by computational simulations, a peptide with a linear conformation in solution is designed. Electric fields are used to control the peptide approach towards a radical-functionalized surface. Spontaneous, irreversible immobilization is achieved when the peptide makes contact with the surface. Our findings show that control of both peptide orientation and surface concentration is achieved simply by varying the solution pH or by applying an electric field as delivered by a small battery.

  8. The Analytical Potential Energy Function of NH Radical Molecule in External Electric Field

    International Nuclear Information System (INIS)

    Wu Dong-Lan; Tan Bin; Wan Hui-Jun; Xie An-Dong; Ding Da-Jun

    2015-01-01

    The geometric structures of an NH radical in different external electric fields are optimized by using the density functional B3P86/cc-PV5Z method, and the bond lengths, dipole moments, vibration frequencies and IR spectrum are obtained. The potential energy curves are gained by the CCSD (T) method with the same basis set. These results indicate that the physical property parameters and potential energy curves may change with the external electric field, especially in the reverse direction electric field. The potential energy function of zero field is fitted by the Morse potential, and the fitting parameters are in good accordance with the experimental data. The potential energy functions of different external electric fields are fitted adopting the constructed potential model. The fitted critical dissociation electric parameters are shown to be consistent with the numerical calculation, and the relative errors are only 0.27% and 6.61%, hence the constructed model is reliable and accurate. The present results provide an important reference for further study of the molecular spectrum, dynamics and molecular cooling with Stark effect. (paper)

  9. Impact of radical nephrectomy on renal functional outcome in ...

    African Journals Online (AJOL)

    H.H. Qureshi

    2015-10-09

    Oct 9, 2015 ... Abstract. Introduction: Renal cell carcinoma (RCC) accounts for 3% of all adult tumors. The mainstay of treatment of. RCCs in the past has remained radical nephrectomy (RN). Studies have found a higher cumulative incidence of development of chronic renal insufficiency in patients undergoing RN for RCC ...

  10. Trends in radical prostatectomy.

    Science.gov (United States)

    Eastham, James; Tokuda, Yuji; Scardino, Peter

    2009-02-01

    The surgical treatment of prostate cancer ideally removes the entire cancer, avoids excessive blood loss or serious perioperative complications, and results in complete recovery of continence and potency. To achieve this, the surgeon must excise sufficient periprostatic tissue to cure the cancer while preserving the cavernosal nerves required for erectile function and the neuromusculature required for normal urinary and bowel function. Here we will examine recent trends in radical prostatectomy, focusing on surgical technique.

  11. Pulse radiolytic study of alpha-tocopherol radical mechanisms in ethanolic solution

    International Nuclear Information System (INIS)

    Jore, D.; Patterson, L.K.; Ferradini, C.

    1986-01-01

    Pulse radiolytic studies of alpha-tocopherol (alpha TH) oxidation-reduction processes were carried out with low doses (5 Gy) of high-energy electrons in O 2 -, N 2 -, and air-saturated ethanolic solutions. Depending on the concentration of oxygen in solution, two different radicals, A . and B ., were observed. The first, A ., was obtained under N 2 and results from alpha TH reaction with solvated electron (k alpha TH + e-solv = 3.4 X 10(8) mol-1 liter s-1) and with H 3 C-CH-OH, (R.) (k alpha TH + R. = 5 X 10(5) mol-1 liter s-1). B., observed under O 2 , is produced by alpha TH reaction with RO 2 . peroxyl radicals (k alpha TH + RO 2 . = 9.5 X 10(4) mol-1 liter s-1)

  12. 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)

  13. Towards an improved prediction of the free radical scavenging potency of flavonoids: the significance of double PCET mechanisms.

    Science.gov (United States)

    Amić, Ana; Marković, Zoran; Dimitrić Marković, Jasmina M; Stepanić, Višnja; Lučić, Bono; Amić, Dragan

    2014-01-01

    The 1H(+)/1e(-) and 2H(+)/2e(-) proton-coupled electron transfer (PCET) processes of free radical scavenging by flavonoids were theoretically studied for aqueous and lipid environments using the PM6 and PM7 methods. The results reported here indicate that the significant contribution of the second PCET mechanism, resulting in the formation of a quinone/quinone methide, effectively discriminates the active from inactive flavonoids. The predictive potency of descriptors related to the energetics of second PCET mechanisms (the second O-H bond dissociation enthalpy (BDE2) related to hydrogen atom transfer (HAT) mechanism, and the second electron transfer enthalpy (ETE2) related to sequential proton loss electron transfer (SPLET) mechanism) are superior to the currently used indices, which are related to the first 1H(+)/1e(-) processes, and could serve as primary descriptors in development of the QSAR (quantitative structure-activity relationships) of flavonoids. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Functions of Research in Radical Behaviorism for the Further Development of Behavior Analysis

    Science.gov (United States)

    Leigland, Sam

    2010-01-01

    The experimental analysis of behavior began as an inductively oriented, empirically based scientific field. As the field grew, its distinctive system of science--radical behaviorism--grew with it. The continuing growth of the empirical base of the field has been accompanied by the growth of the literature on radical behaviorism and its…

  15. 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.

  16. An EPR spin-probe and spin-trap study of the free radicals produced by plant plasma membranes

    Directory of Open Access Journals (Sweden)

    GORAN BACIC

    2005-02-01

    Full Text Available Plant plasma membranes are known to produce superoxide radicals, while the production of hydroxyl radical is thought to occur only in the cell wall. In this work it was demonstrated using combined spin-trap and spin-probe EPR spectroscopic techniques, that plant plasma membranes do produce superoxide and hydroxyl radicals but by kinetically different mechanisms. The results show that superoxide and hydroxyl radicals can be detected by DMPO spin-trap and that the mechanisms and location of their production can be differentiated using the reduction of spin-probes Tempone and 7-DS. It was shown that the mechanism of production of oxygen reactive species is NADH dependent and diphenylene iodonium inhibited. The kinetics of the reduction of Tempone, combined with scavengers or the absence of NADH indicates that hydroxyl radicals are produced by a mechanism independent of that of superoxide production. It was shown that a combination of the spin-probe and spin-trap technique can be used in free radical studies of biological systems, with a number of advantages inherent to them.

  17. Multi-level Quantum Mechanics and Molecular Mechanics Study of Ring Opening Process of Guanine Damage by Hydroxyl Radical in Aqueous Solution.

    Science.gov (United States)

    Liu, Peng; Wang, Qiong; Niu, Meixing; Wang, Dunyou

    2017-08-10

    Combining multi-level quantum mechanics theories and molecular mechanics with an explicit water model, we investigated the ring opening process of guanine damage by hydroxyl radical in aqueous solution. The detailed, atomic-level ring-opening mechanism along the reaction pathway was revealed in aqueous solution at the CCSD(T)/MM levels of theory. The potentials of mean force in aqueous solution were calculated at both the DFT/MM and CCSD(T)/MM levels of the theory. Our study found that the aqueous solution has a significant effect on this reaction in solution. In particular, by comparing the geometries of the stationary points between in gas phase and in aqueous solution, we found that the aqueous solution has a tremendous impact on the torsion angles much more than on the bond lengths and bending angles. Our calculated free-energy barrier height 31.6 kcal/mol at the CCSD(T)/MM level of theory agrees well with the one obtained based on gas-phase reaction profile and free energies of solvation. In addition, the reaction path in gas phase was also mapped using multi-level quantum mechanics theories, which shows a reaction barrier at 19.2 kcal/mol at the CCSD(T) level of theory, agreeing very well with a recent ab initio calculation result at 20.8 kcal/mol.

  18. Structural modification of the skin barrier by OH radicals: a reactive molecular dynamics study for plasma medicine

    International Nuclear Information System (INIS)

    Van der Paal, J; Verlackt, C C; Yusupov, M; Neyts, E C; Bogaerts, A

    2015-01-01

    While plasma treatment of skin diseases and wound healing has been proven highly effective, the underlying mechanisms, and more generally the effect of plasma radicals on skin tissue, are not yet completely understood. In this paper, we perform ReaxFF-based reactive molecular dynamics simulations to investigate the interaction of plasma generated OH radicals with a model system composed of free fatty acids, ceramides, and cholesterol molecules. This model system is an approximation of the upper layer of the skin (stratum corneum). All interaction mechanisms observed in our simulations are initiated by H-abstraction from one of the ceramides. This reaction, in turn, often starts a cascade of other reactions, which eventually lead to the formation of aldehydes, the dissociation of ceramides or the elimination of formaldehyde, and thus eventually to the degradation of the skin barrier function. (paper)

  19. Free radical scavenging activity and lipoxygenase inhibition of Mahonia aquifolium extract and isoquinoline alkaloids

    Directory of Open Access Journals (Sweden)

    Kettmann Viktor

    2007-07-01

    Full Text Available Abstract Roots and stem-bark of Mahonia aquifolium (Oregon grape (Berberidaceae are effectively used in the treatment of skin inflammatory conditions. In the present study, the effect of Mahonia aquifolium crude extract and its two representative alkaloid fractions containing protoberberine and bisbenzylisoquinoline (BBIQ alkaloids on activity of 12-lipoxygenase (12-LOX, was studied. The reactivity with 1,1-diphenyl-2-picryl-hydrazyl (DPPH, a free stable radical, was evaluated to elucidate the rate of possible lipid-derived radical scavenging in the mechanism of the enzyme inhibition. The results indicate that although the direct radical scavenging mechanism cannot be ruled out in the lipoxygenase inhibition by Mahonia aquifolium and its constituents, other mechanisms based on specific interaction between enzyme and alkaloids could play the critical role in the lipoxygenase inhibition rather than non-specific reactivity with free radicals.

  20. Transnational Islamic activism and radicalization : patterns, trends, and prognosticators.

    Energy Technology Data Exchange (ETDEWEB)

    Colbaugh, Richard; Engi, Dennis; LaViolette, Randall A.; Spomer, Judith E.

    2010-06-01

    The research described in this report developed the theoretical and conceptual framework for understanding, recognizing, and anticipating the origins, dynamic mechanisms, perceptions, and social structures of Islamic social reform movements in the Muslim homeland and in diaspora communities. This research has revealed valuable insights into the dynamic mechanisms associated with reform movements and, as such, offers the potential to provide indications and warnings of impending violence. This study produced the following significant findings: (1) A framework for understanding Islamic radicalization in the context of Social Movement Theory was developed and implemented. This framework provides a causal structure for the interrelationships among the myriad features of a social movement. (2) The degree to which movement-related activity shows early diffusion across multiple social contexts is a powerful distinguisher of successful and unsuccessful social movements. Indeed, this measurable appears to have significantly more predictive power than volume of such activity and also more power than various system intrinsics. (3) Significant social movements can occur only if both the intra-context 'infectivity' of the movement exceeds a certain threshold and the inter-context interactions associated with the movement occur with a frequency that is larger than another threshold. Note that this is reminiscent of, and significantly extends, well-known results for epidemic thresholds in disease propagation models. (4) More in-depth content analysis of blogs through the lens of Argumentation Theory has the potential to reveal new insights into radicalization in the context of Social Movement Theory. This connection has the potential to be of value from two important perspectives - first, this connection has the potential to provide more in depth insights into the forces underlying the emergence of radical behavior and second, this connection may provide insights into

  1. VEGF secretion during hypoxia depends on free radicals-induced Fyn kinase activity in mast cells

    International Nuclear Information System (INIS)

    Garcia-Roman, Jonathan; Ibarra-Sanchez, Alfredo; Lamas, Monica; Gonzalez Espinosa, Claudia

    2010-01-01

    Research highlights: → Bone marrow-derived mast cells (BMMCs) secrete functional VEGF but do not degranulate after Cobalt chloride-induced hypoxia. → CoCl 2 -induced VEGF secretion in mast cells occurs by a Ca 2+ -insensitive but brefeldin A and Tetanus toxin-sensitive mechanism. → Trolox and N-acetylcysteine inhibit hypoxia-induced VEGF secretion but only Trolox inhibits FcεRI-dependent anaphylactic degranulation in mast cells. → Src family kinase Fyn activation after free radical production is necessary for hypoxia-induced VEGF secretion in mast cells. -- Abstract: Mast cells (MC) have an important role in pathologic conditions such as asthma and chronic obstructive pulmonary disease (COPD), where hypoxia conduce to deleterious inflammatory response. MC contribute to hypoxia-induced angiogenesis producing factors such as vascular endothelial growth factor (VEGF), but the mechanisms behind the control of hypoxia-induced VEGF secretion in this cell type is poorly understood. We used the hypoxia-mimicking agent cobalt chloride (CoCl 2 ) to analyze VEGF secretion in murine bone marrow-derived mast cells (BMMCs). We found that CoCl 2 promotes a sustained production of functional VEGF, able to induce proliferation of endothelial cells in vitro. CoCl 2 -induced VEGF secretion was independent of calcium rise but dependent on tetanus toxin-sensitive vesicle-associated membrane proteins (VAMPs). VEGF exocytosis required free radicals formation and the activation of Src family kinases. Interestingly, an important deficiency on CoCl 2 -induced VEGF secretion was observed in Fyn kinase-deficient BMMCs. Moreover, Fyn kinase was activated by CoCl 2 in WT cells and this activation was prevented by treatment with antioxidants such as Trolox and N-acetylcysteine. Our results show that BMMCs are able to release VEGF under hypoxic conditions through a tetanus toxin-sensitive mechanism, promoted by free radicals-dependent Fyn kinase activation.

  2. VEGF secretion during hypoxia depends on free radicals-induced Fyn kinase activity in mast cells

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Roman, Jonathan; Ibarra-Sanchez, Alfredo; Lamas, Monica [Departamento de Farmacobiologia, Centro de Investigacion y de Estudios Avanzados del IPN (Cinvestav, IPN) (Mexico); Gonzalez Espinosa, Claudia, E-mail: cgonzal@cinvestav.mx [Departamento de Farmacobiologia, Centro de Investigacion y de Estudios Avanzados del IPN (Cinvestav, IPN) (Mexico)

    2010-10-15

    Research highlights: {yields} Bone marrow-derived mast cells (BMMCs) secrete functional VEGF but do not degranulate after Cobalt chloride-induced hypoxia. {yields} CoCl{sub 2}-induced VEGF secretion in mast cells occurs by a Ca{sup 2+}-insensitive but brefeldin A and Tetanus toxin-sensitive mechanism. {yields} Trolox and N-acetylcysteine inhibit hypoxia-induced VEGF secretion but only Trolox inhibits Fc{epsilon}RI-dependent anaphylactic degranulation in mast cells. {yields} Src family kinase Fyn activation after free radical production is necessary for hypoxia-induced VEGF secretion in mast cells. -- Abstract: Mast cells (MC) have an important role in pathologic conditions such as asthma and chronic obstructive pulmonary disease (COPD), where hypoxia conduce to deleterious inflammatory response. MC contribute to hypoxia-induced angiogenesis producing factors such as vascular endothelial growth factor (VEGF), but the mechanisms behind the control of hypoxia-induced VEGF secretion in this cell type is poorly understood. We used the hypoxia-mimicking agent cobalt chloride (CoCl{sub 2}) to analyze VEGF secretion in murine bone marrow-derived mast cells (BMMCs). We found that CoCl{sub 2} promotes a sustained production of functional VEGF, able to induce proliferation of endothelial cells in vitro. CoCl{sub 2}-induced VEGF secretion was independent of calcium rise but dependent on tetanus toxin-sensitive vesicle-associated membrane proteins (VAMPs). VEGF exocytosis required free radicals formation and the activation of Src family kinases. Interestingly, an important deficiency on CoCl{sub 2}-induced VEGF secretion was observed in Fyn kinase-deficient BMMCs. Moreover, Fyn kinase was activated by CoCl{sub 2} in WT cells and this activation was prevented by treatment with antioxidants such as Trolox and N-acetylcysteine. Our results show that BMMCs are able to release VEGF under hypoxic conditions through a tetanus toxin-sensitive mechanism, promoted by free radicals

  3. 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.; hide

    2013-01-01

    Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a Ponderosa pine forest during the summer 2010 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptv and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Since primary reaction partners for peroxy radicals are either measured (NO) or under-predicted (HO2 and RO2, i.e. self-reaction), missing sources are the most likely explanation for this result. A close comparison of model output with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (approximately 120 and 50 pptv min-1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within forests. We conclude that a similar mechanism may underlie many such observations.

  4. 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?

  5. 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 .

  6. Is brain copper deficiency in Alzheimer's, Lewy body, and Creutzfeldt Jakob diseases the common key for a free radical mechanism and oxidative stress-induced damage?

    Science.gov (United States)

    Deloncle, Roger; Guillard, Olivier

    2015-01-01

    In Alzheimer's (AD), Lewy body (LBD), and Creutzfeldt Jakob (CJD) diseases, similar pathological hallmarks have been described, one of which is brain deposition of abnormal protease-resistant proteins. For these pathologies, copper bound to proteins is able to protect against free radicals by reduction from cupric Cu++ to cupreous Cu+. We have previously demonstrated in bovine brain homogenate that free radicals produce proteinase K-resistant prion after manganese is substituted for copper. Since low brain copper levels have been described in transmissible spongiform encephalopathies, in substantia nigra in Parkinson's disease, and in various brain regions in AD, LBD, and CJD, a mechanism has been proposed that may underlie the neurodegenerative processes that occur when copper protection against free radicals is impaired. In peptide sequences, the alpha acid proton near the peptide bond is highly mobile and can be pulled out by free radicals. It will produce a trivalent α-carbon radical and induce a free radical chain process that will generate a D-amino acid configuration in the peptide sequence. Since only L-amino acids are physiologically present in mammalian (human) proteins, it may be supposed that only physiological L-peptides can be recycled by physiological enzymes such as proteases. If a D-amino acid is found in the peptide sequence subsequent to deficient copper protection against free radicals, it will not be recognized and might alter the proteasome L-amino acid recycling from brain peptides. In the brain, there will result an accumulation of abnormal protease-resistant proteins such as those observed in AD, LBD, and CJD.

  7. 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.

  8. Comparison of epoxide and free-radical mechanisms for activation of benzo[a]pyrene by Sprague-Dawley rat liver microsomes

    International Nuclear Information System (INIS)

    Selkirk, J.K.

    1980-01-01

    Coincubation of [6- 3 H]benzo[a]pyrene ([6- 3 H]BP) and [ 14 C]BP with SD rat liver microsomes produced metabolic profiles that showed that the C-6 of BP was not affected by formation of 4,5-dihydro-4,5-dihydroxy-BP, 7,8-dihydro-7,8-dihydroxy-BP, and 9,10-dihydro-9,10-dihydroxy-BP nor the 3- and 9-phenols of BP. Complete retention of tritium at C-6, except in the three quinones, confirmed the radical-cation model for formation of the 6-oxo-radical followed by oxidation to quinone. Epoxide formation at the carcinogenically active regions of BP appeared to biochemically isolate from 6-position activation and suggested that the microsomal epoxide pathway is unrelated to the radicalcation scheme. These molar ratios derived from double-label experiments reinforced the current literature that indicates the epoxide mechanism as the major pathway toward carcinogenic forms of BP

  9. Measurements of hydroxyl and hydroperoxy radicals during CalNex-LA: Model comparisons and radical budgets

    Science.gov (United States)

    Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Michoud, V.; Gilman, J. B.; Kuster, W. C.; Veres, P. R.; Graus, M.; de Gouw, J. A.; Roberts, J.; Young, C.; Washenfelder, R.; Brown, S. S.; Thalman, R.; Waxman, E.; Volkamer, R.; Tsai, C.; Stutz, J.; Flynn, J. H.; Grossberg, N.; Lefer, B.; Alvarez, S. L.; Rappenglueck, B.; Mielke, L. H.; Osthoff, H. D.; Stevens, P. S.

    2016-04-01

    Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex-LA 2010 campaign using the laser-induced fluorescence-fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero-dimensional model using the Regional Atmospheric Chemical Mechanism-2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.

  10. Protein Tyrosine Nitration: Biochemical Mechanisms and Structural Basis of its Functional Effects

    Science.gov (United States)

    Radi, Rafael

    2012-01-01

    CONSPECTUS The nitration of protein tyrosine residues to 3-nitrotyrosine represents an oxidative postranslational modification that unveils the disruption of nitric oxide (•NO) signaling and metabolism towards pro-oxidant processes. Indeed, excess levels of reactive oxygen species in the presence of •NO or •NO-derived metabolites lead to the formation of nitrating species such as peroxynitrite. Thus, protein 3-nitrotyrosine has been established as a biomarker of cell, tissue and systemic “nitroxidative stress”. Moreover, tyrosine nitration modifies key properties of the amino acid (i.e. phenol group pKa, redox potential, hydrophobicity and volume). Thus, the incorporation of a nitro group (−NO2) to protein tyrosines can lead to profound structural and functional changes, some of which contribute to altered cell and tissue homeostasis. In this Account, I describe our current efforts to define 1) biologically-relevant mechanisms of protein tyrosine nitration and 2) how this modification can cause changes in protein structure and function at the molecular level. First, the relevance of protein tyrosine nitration via free radical-mediated reactions (in both peroxynitrite-dependent or independent pathways) involving the intermediacy of tyrosyl radical (Tyr•) will be underscored. This feature of the nitration process becomes critical as Tyr• can take variable fates, including the formation of 3-nitrotyrosine. Fast kinetic techniques, electron paramagnetic resonance (EPR) studies, bioanalytical methods and kinetic simulations have altogether assisted to characterize and fingerprint the reactions of tyrosine with peroxynitrite and one-electron oxidants and its further evolution to 3-nitrotyrosine. Recent findings show that nitration of tyrosines in proteins associated to biomembranes is linked to the lipid peroxidation process via a connecting reaction that involves the one-electron oxidation of tyrosine by lipid peroxyl radicals (LOO•). Second

  11. The entry of free radicals into polystyrene latex particles

    International Nuclear Information System (INIS)

    Adams, M.E.; Trau, M.; Gilbert, R.C.; Napper, D.R.

    1988-01-01

    Mechanistic understanding of the processes governing the kinetics of emulsion polymerization has both scientific and technical interest. One component of this process that is poorly understood at present is that of free radical entry into latex particles. Measurements were made of the entry rate coefficient as a function of temperature for free radicals entering polystyrene latex particles in seeded emulsion polymerizations initiated by γ-rays. The activation energy for entry was found to be less than 24 ± 3 kJ mol -1 , consistent with entry being controlled by a physical (e.g. diffusional) rather than a chemical process. Measurement of the entry rate coefficient as a function of the γ-ray dose rate suggested that the factors that determine the entry rate when the primary free radicals are uncharged are similar to those that determine the entry rate for charged free radicals derived from chemical initiation by peroxydisulfate. This result was consistent with measurements of the entry rate coefficient of charged free radicals derived from peroxydisulfate; these data were found to be virtually independent of both the extent of the latex surface coverage by the anionic surfactant sodium dodecyl sulfate and the ionic strength of the continuous phase. The data refute several proposals given in the literature for the rate-determining step for entry, being inconsistent with control by collision of free radicals with the latex particles, surfactant desorption, and an electrostatic barrier arising from the colloidal nature of the entering free radical. The origin of the activation energy for entry remains obscure

  12. Supplementary data for the mechanism for cleavage of three typical glucosidic bonds induced by hydroxyl free radical

    Directory of Open Access Journals (Sweden)

    Yujie Dai

    2017-12-01

    Full Text Available The data presented in this article are related to the research article entitled “The mechanism for cleavage of three typical glucosidic bonds induced by hydroxyl free radical” (Dai et al., 2017 [1]. This article includes the structures of three kinds of disaccharides such as maltose, fructose and cellobiose, the diagrammatic sketch of the hydrogen abstraction reaction of the disaccharides by hydroxyl radical, the structure of the transition states for pyran ring opening of moiety A and cleavage of α(1→2 glycosidic bond starting from the hydrogen abstraction of C6–H in moiety A of sucrose, the transition state structure for cleavage of α(1→2 glycosidic bond starting from the hydrogen abstraction of C1′-H in moiety B of sucrose, the transition state structure, sketch for the reaction process and relative energy change of the reaction pathway for direct cleavage of α(1→4 glycosidic bond starting from hydrogen abstraction of C6′–H of moiety B of maltose.

  13. Metal-Free α-C(sp3–H Functionalized Oxidative Cyclization of Tertiary N,N-Diaryl Amino Alcohols: Theoretical Approach for Mechanistic Pathway

    Directory of Open Access Journals (Sweden)

    Zakir Ullah

    2017-03-01

    Full Text Available The mechanistic pathway of TEMPO/I2-mediated oxidative cyclization of N,N-diaryl amino alcohols 1 was investigated. Based on direct empirical experiments, three key intermediates (aminium radical cation 3, α-aminoalkyl radical 4, and iminium 5, four types of reactive species (radical TEMPO, cationic TEMPO, TEMPO-I, and iodo radical, and three types of pathways ((1 SET/PCET mechanism; (2 HAT/1,6-H transfer mechanism; (3 ionic mechanism were assumed. Under the assumption, nine free energy diagrams were acquired through density functional theory calculations. From the comparison of solution-phase free energy, some possible mechanisms were excluded, and then the chosen plausible mechanisms were concretized using the more stable intermediate 7.

  14. Mechanistic investigations of novel photoinitiators for radical polymerization

    International Nuclear Information System (INIS)

    Griesser, M.

    2012-01-01

    Nowadays, there is a wide variety of photoinitiators (PIs) available for radical polymerizations. A common example are two-component (Type II) systems such as benzophenone and tertiary amines. However these systems also suffer from problems due to bimolecularity. These include the possible back electron transfer (BET) leading to deactivation, as well as the solvent cage effect, occurring in highly viscous media. The aim of this thesis was to investigate the reaction mechanism of several photoinitiating systems, which show superior performance. Moreover, they exhibit additional benefits such as circumvention of oxygen inhibition by decarboxylation. Thereby this work helps to understand the molecular basis of the performance of different PI systems. In vestigated PIs included benzaldoxime esters, covalently linked benzophenone and N-phenylglycine as well as derivatives of both systems. Furthermore a PI based on benzophenone extended by ethynyl moeities is discussed. The main tool in this investigation was photo-CIDNP (chemically induced dynamic nuclear polarization), an NMR based technique for studying radical reactions. A complementary view was obtained with TR-EPR (time-resolved electron paramagnetic resonance), which provides direct information about the active radical species. The results were further compared with quantum mechanical calculations (DFT) of the magnetic properties of the radicals. The theoretical approach was further applied to other paramagnetic species such as donor-acceptor systems. (author) [de

  15. Oxidation and Free Radical Decay in Vitamin E-stabilized, Radiation Cross-linked UHMWPE

    International Nuclear Information System (INIS)

    Oral, E.

    2006-01-01

    A novel a-tocopherol (vitamin E, α-T)-stabilized, cross-linked ultra-high molecular weight polyethylene (UHMWPE) (αTPE) was developed for total joint arthroplasty as a bearing surface with low wear and improved mechanical properties. Accelerated aging showed α-T protects irradiated UHMWPE against oxidation. However, accelerated aging may not truly reflect in vivo and shelf oxidation. We used real-time aging to monitor the evolution of oxidation and free radical signals of α-T to determine the mechanism of oxidative stability. UHMWPE blocks (30x30x10 mm) were machined and γ-irradiated (85 kGy) in argon. The blocks were doped in α-T for 5 hours at 120 degree and homogenized for 64 hours at 120 degree in argon, packaged in vacuum and γ-sterilized (25 kGy). Samples were aged in air at room temperature, in air at 40 degree and in water at 40 degree. Measurements were at 1, 2, 3, 4 and 7 months. Sections cut from the aged blocks (150μm) were boiled in hexane overnight to extract free species and evaluated by FTIR. Oxidation indices were calculated by taking the area under the carbonyl peak and normalizing it to a skeletal peak. ESR was used to determine the content and type of free radicals. Control was 100-kGy irradiated, unstabilized UHMWPE. αTPE showed a small amount of oxidation, which stabilized after 2 months. This indicated that the decay of the hydroperoxides formed by the reaction of the residual free radicals with oxygen was exhausted by α-T due to its ability to scavenge free radicals. In contrast, control UHMWPE continued to oxidize because the residual free radicals likely continued to form hydroperoxides and additional free radicals, furthering the oxidation reactions. There was a shift in the free radical signature of both αTPE and control from the sextet alkyl/allyl radicals to a sharp singlet during aging. Most likely, trapped free radicals move along the crystal stems until they react with another free radical or until they reach the crystal

  16. Free radical explosive composition

    Science.gov (United States)

    Walker, Franklin E.; Wasley, Richard J.

    1979-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a getter additive comprising a compound or mixture of compounds capable of capturing or deactivating free radicals or ions under mechanical or electrical shock conditions and which is not an explosive. Exemplary getter additives are isocyanates, olefins and iodine.

  17. Experimental and theoretical understanding of the gas phase oxidation of atmospheric amides with OH radicals: kinetics, products, and mechanisms.

    Science.gov (United States)

    Borduas, Nadine; da Silva, Gabriel; Murphy, Jennifer G; Abbatt, Jonathan P D

    2015-05-14

    Atmospheric amides have primary and secondary sources and are present in ambient air at low pptv levels. To better assess the fate of amides in the atmosphere, the room temperature (298 ± 3 K) rate coefficients of five different amides with OH radicals were determined in a 1 m(3) smog chamber using online proton-transfer-reaction mass spectrometry (PTR-MS). Formamide, the simplest amide, has a rate coefficient of (4.44 ± 0.46) × 10(-12) cm(3) molec(-1) s(-1) against OH, translating to an atmospheric lifetime of ∼1 day. N-methylformamide, N-methylacetamide and propanamide, alkyl versions of formamide, have rate coefficients of (10.1 ± 0.6) × 10(-12), (5.42 ± 0.19) × 10(-12), and (1.78 ± 0.43) × 10(-12) cm(3) molec(-1) s(-1), respectively. Acetamide was also investigated, but due to its slow oxidation kinetics, we report a range of (0.4-1.1) × 10(-12) cm(3) molec(-1) s(-1) for its rate coefficient with OH radicals. Oxidation products were monitored and quantified and their time traces were fitted using a simple kinetic box model. To further probe the mechanism, ab initio calculations are used to identify the initial radical products of the amide reactions with OH. Our results indicate that N-H abstractions are negligible in all cases, in contrast to what is predicted by structure-activity relationships. Instead, the reactions proceed via C-H abstraction from alkyl groups and from formyl C(O)-H bonds when available. The latter process leads to radicals that can readily react with O2 to form isocyanates, explaining the detection of toxic compounds such as isocyanic acid (HNCO) and methyl isocyanate (CH3NCO). These contaminants of significant interest are primary oxidation products in the photochemical oxidation of formamide and N-methylformamide, respectively.

  18. IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

    Science.gov (United States)

    Schafer, Freya Q.; Yue Qian, Steven; Buettner, Garry R.

    2013-01-01

    Brain tissue being rich in polyunsaturated fatty acids, is very susceptible to lipid peroxidation. Iron is well known to be an important initiator of free radical oxidations. We propose that the principal route to iron-mediated lipid peroxidations is via iron-oxygen complexes rather than the reaction of iron with hydrogen peroxide, the Fenton reaction. To test this hypothesis, we enriched leukemia cells (K-562 and L1210 cells) with docosahexaenoic acid (DHA) as a model for brain tissue, increasing the amount of DHA from approximately 3 mole % to 32 mole %. These cells were then subjected to ferrous iron and dioxygen to initiate lipid peroxidation in the presence or absence of hydrogen peroxide. Lipid-derived radicals were detected using EPR spin trapping with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN). As expected, lipid-derived radical formation increases with increasing cellular lipid unsaturation. Experiments with Desferal demonstrate that iron is required for the formation of lipid radicals from these cells. Addition of iron to DHA-enriched L1210 cells resulted in significant amounts of radical formation; radical formation increased with increasing amount of iron. However, the exposure of cells to hydrogen peroxide before the addition of ferrous iron did not increase cellular radical formation, but actually decreased spin adduct formation. These data suggest that iron-oxygen complexes are the primary route to the initiation of biological free radical oxidations. This model proposes a mechanism to explain how catalytic iron in brain tissue can be so destructive. PMID:10872752

  19. Differential mechanism of Escherichia coli Inactivation by (+)-limonene as a function of cell physiological state and drug's concentration.

    Science.gov (United States)

    Chueca, Beatriz; Pagán, Rafael; García-Gonzalo, Diego

    2014-01-01

    (+)-limonene is a lipophilic antimicrobial compound, extracted from citrus fruits' essential oils, that is used as a flavouring agent and organic solvent by the food industry. A recent study has proposed a common and controversial mechanism of cell death for bactericidal antibiotics, in which hydroxyl radicals ultimately inactivated cells. Our objective was to determine whether the mechanism of Escherichia coli MG1655 inactivation by (+)-limonene follows that of bactericidal antibiotics. A treatment with 2,000 μL/L (+)-limonene inactivated 4 log10 cycles of exponentially growing E. coli cells in 3 hours. On one hand, an increase of cell survival in the ΔacnB mutant (deficient in a TCA cycle enzyme), or in the presence of 2,2'-dipyridyl (inhibitor of Fenton reaction by iron chelation), thiourea, or cysteamine (hydroxyl radical scavengers) was observed. Moreover, the ΔrecA mutant (deficient in an enzyme involved in SOS response to DNA damage) was more sensitive to (+)-limonene. Thus, this indirect evidence indicates that the mechanism of exponentially growing E. coli cells inactivation by 2,000 μL/L (+)-limonene is due to the TCA cycle and Fenton-mediated hydroxyl radical formation that caused oxidative DNA damage, as observed for bactericidal drugs. However, several differences have been observed between the proposed mechanism for bactericidal drugs and for (+)-limonene. In this regard, our results demonstrated that E. coli inactivation was influenced by its physiological state and the drug's concentration: experiments with stationary-phase cells or 4,000 μL/L (+)-limonene uncovered a different mechanism of cell death, likely unrelated to hydroxyl radicals. Our research has also shown that drug's concentration is an important factor influencing the mechanism of bacterial inactivation by antibiotics, such as kanamycin. These results might help in improving and spreading the use of (+)-limonene as an antimicrobial compound, and in clarifying the controversy about

  20. Peroxyl radical- and photo-oxidation of glucose 6- phosphate dehydrogenase generates cross-links and functional changes via oxidation of tyrosine and tryptophan residues

    DEFF Research Database (Denmark)

    Leinisch, Fabian; Mariotti, Michele; Rykær, Martin

    2017-01-01

    indicate that pathophysiological processes and multiple human diseases are associated with the accumulation of damaged proteins. In this study we investigated the mechanisms and consequences of exposure of the key metabolic enzyme glucose-6-phosphate dehydrogenase (G6PDH) to peroxyl radicals (ROO...

  1. ESR study of the anion radicals of 5-nitropyrimidines: conversion to iminoxy radicals

    International Nuclear Information System (INIS)

    Sevilla, M.D.; Clark, C.; Failor, R.

    1976-01-01

    The anion radicals of a number of 5-nitropyrimidines have been investigated by ESR spectroscopy. The anions are formed by electrolysis in dimethylformamide and by electron attachment in aqueous glasses, 12 M LiCl--D 2 O and 8 M NaOD. The electrolysis of 5-nitrouracil and 5-nitro-6-methyluracil results in relatively stable anion radicals. The results for 5-nitrouracil give evidence for two or perhaps three anions which differ only by the degree of ring nitrogen protonation. The results for 5-nitro-6-methyluracil suggest that the nitro group of the anion is twisted so that it is coupled only weakly to the ring π-electron system. The anions of 5-nitrouracil, 5-nitroorotic acid, 5-nitrobarbituric acid, and 5-nitro-6-methyluracil have been produced in the alkaline and neutral aqueous glasses. The anisotropic spectra found have been analyzed with the aid of computer simulations which assume axial symmetry. For example, the analysis of the spectrum of 5-nitrouracil anion in 12 M LiCl yields A/sub parallel//sup N/ = 33; A/sub perpendicular to//sup N/ = 5, a 6 /sup H/ = 5.5 G, g/sub parallel/ = 2.0016, and g/sub perpendicular to/ = 2.0059. A concentration dependence in the splittings is noted and discussed. Ultraviolet photolysis of the anions of 5-nitro-6-methyluracil and 5-nitrobarbituric acid results in the formation of iminoxy radicals. Mechanisms of formation of the iminoxy radicals are discussed and results found in this work are compared to results found in single crystals and aqueous solution

  2. μSR spectroscopy on free radicals: a complement to ESR spectroscopy

    International Nuclear Information System (INIS)

    Cox, S.F.J.; Symons, M.C.R.

    1986-12-01

    The paper on ''μSR spectroscopy on free radicals'' was presented to the conference on ''Muon spin, rotation, relaxation and resonance'' Uppsala, 1986. The spectroscopic techniques for both ESR and μSR are described, along with the interpretation of the spectra, hyperfine coupling constants and radical structure. A comparison of ESR and μSR data is carried out with respect: to 1) isotope effects in organic radicals, 2) isotope effects in solids, -the isotropic muonium defect centres, and 3) the muonium defect centres in semiconductors. Radical categories examined using ESR and μSR are discussed, including new species, formation mechanisms, and ionic species. (U.K.)

  3. Spin trapping of radicals formed in gamma-irradiated methanol: effect of the irradiation temperature from 77K to 300K

    International Nuclear Information System (INIS)

    Schlick, S.; Kevan, L.

    1976-01-01

    The neutral radicals formed in gamma-irradiated methanol were studied by spin trapping with phenyl-t-butylnitrone (PBN) in an attempt to probe the primary neutral radicals formed. In the temperature range from approximately 157 K to 300 K both CH 2 OH and CH 3 O spin adducts are observed and their limiting ratio at high PBN concentrations is CH 2 OH/CH 3 O=1.5 over this temperature range. Below approximately 157 K this ratio increases exponentially with decreasing temperature with an apparent activation energy of 5.8 kJ/mole (1.4 kcal/mole); this is consistent with the finding that only CH 2 OH radicals are formed by gamma radiolysis at 77 K. Several possible models for the primary neutral radicals formed in gamma-irradiated methanol and their subsequent reactions as a function of irradiation temperature are discussed. It is suggested that the primary radical formation mechanisms are similar in the gas and liquid phases and become temperature dependent when molecular motion is arrested in the solid. (Auth.)

  4. 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.

  5. Rapid Hydrogen Shift Reactions in Acyl Peroxy Radicals

    DEFF Research Database (Denmark)

    Knap, Hasse Christian; Jørgensen, Solvejg

    2017-01-01

    -shift with X = 6, 7, 8, or 9) in the hydroperoxy acyl peroxy radicals, this H-shift is a reversible reaction and it scrambles between two peroxides, hydroperoxy acyl peroxy and peroxy peroxoic acid radicals. The forward reaction rate constants of the 1,X-OOH H-shift reactions are estimated to be above 103 s–1...... with transition state theory corrected with Eckart quantum tunnelling correction. The ratio between the forward and reverse reaction rate constant of the 1,X-OOH H-shift reactions is around ∼105. Therefore, the equilibrium is pushed toward the production of peroxy peroxoic acid radicals. These very fast 1,X-OOH H......We have used quantum mechanical chemical calculations (CCSD(T)-F12a/cc-pVDZ-F12//M06-2X/aug-cc-pVTZ) to investigate the hydrogen shift (H-shift) reactions in acyl peroxy and hydroperoxy acyl peroxy radicals. We have focused on the H-shift reactions from a hydroperoxy group (OOH) (1,X-OOH H...

  6. 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.

  7. 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...

  8. Postoperative digestive function after radical versus conservative surgical philosophy for deep endometriosis infiltrating the rectum.

    Science.gov (United States)

    Roman, Horace; Vassilieff, Maud; Tuech, Jean Jacques; Huet, Emmanuel; Savoye, Guillaume; Marpeau, Loïc; Puscasiu, Lucian

    2013-05-01

    To compare delayed digestive outcomes in women managed by two different surgical philosophies: a radical approach mainly related to colorectal resection, and a conservative approach involving rectal shaving and rectal nodule excision. "Before and after" comparative retrospective study. University tertiary referral center. Seventy-five patients managed by surgery for deep endometriosis infiltrating the rectum. Twenty-four women were managed during a period when surgeons pursued a radical philosophy toward treatment, and 51 women were managed during a period when a conservative philosophy was adopted. Standardized gastrointestinal questionnaires: the Gastrointestinal Quality of Life Index, the Knowles-Eccersley-Scott Symptom Questionnaire, the Bristol Stool Score, and the Fecal Incontinence Quality of Life Score. Preoperative patient characteristics, rectal nodule features, and associated localizations of the disease were comparable between the two groups. During the radical period, colorectal resection was carried out in 67% of patients, whereas during the second period only 20% of women underwent colorectal resection. Women managed according to the conservative philosophy had significantly improved results on the Knowles-Eccersley-Scott Symptom Questionnaire, Gastrointestinal Quality of Life Index, and depression/self-perception Fecal Incontinence Quality of Life Score, and significantly improved values for various items related to postoperative constipation: unsuccessful evacuatory attempts, feeling incomplete evacuation, abdominal pain, time taken to evacuate, difficulty evacuating causing a painful effort, and stool consistency. It seems that reducing the rate of colorectal resection leads to better functional outcomes in women presenting with rectal endometriosis, lending support to the conservative surgical philosophy over mandatory colorectal resection. Copyright © 2013 American Society for Reproductive Medicine. Published by Elsevier Inc. All rights

  9. 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)

  10. Considerations on the mechanism of action of artemisinin antimalarials: part 1--the 'carbon radical' and 'heme' hypotheses.

    Science.gov (United States)

    Haynes, Richard K; Cheu, Kwan-Wing; N'Da, David; Coghi, Paolo; Monti, Diego

    2013-08-01

    The isolation of artemisinin from the traditional medicinal herb qīng hāo (Artemisia annua), its characterization as a peroxide and preparation of the derivatives dihydroartemisinin, artemether and artesunate in the 1970s and 1980s by Chinese scientists under the umbrella of Project 523 collectively represents one of the great events in medicine in the latter third of the 20(th) Century. Artemisinins have become the most important component of chemotherapy of malaria: although used initially in monotherapy, they are now used in combination therapies or ACTs with longer half-life quinolines or arylmethanols. Nevertheless, the recent emergence of artemisinin-tolerant strains of the malaria parasite as reflected in increased clearance times of parasitaemia in patients treated with ACTs represents the greatest threat to control of malaria since resistance to chloroquine was first reported over 55 years ago. Importantly, the event brings into sharp focus the realization that relatively little is precisely understood, as opposed to widely assumed, for the mechanism of drug action of artemisinins and their synthetic peroxide analogues. Thus, we review here their antimalarial activities, the use of artemisinins in combination therapies, drug-drug interactions with the quinolines and arylmethanols, and metabolism of the artemisinins and synthetic peroxides. The mechanism of action of quinolines and arylmethanols, in particular their ability to induce redistribution of heme into the parasite cytosol, is also highlighted. This collective information is then used as a counterpoint to screen the validity of two of the prevailing hypotheses of drug action of artemisinins and synthetic peroxides, namely i. 'the C-radical hypothesis' wherein the peroxide undergoes 'bioactivation' by ferrous iron to generate C-radicals that are held to be the cytotoxic agents and ii. the 'heme hypothesis' wherein ferrous heme may generate either the same type of 'cytotoxic' C-radical, or the

  11. Comprehensive analysis of sexual function outcome in prostate cancer patients after robot-assisted radical prostatectomy.

    Science.gov (United States)

    Woo, Seung Hyo; Kang, Dong Il; Ha, Yun-Sok; Salmasi, Amirali Hassanzadeh; Kim, Jeong Hyun; Lee, Dong-Hyeon; Kim, Wun-Jae; Kim, Isaac Yi

    2014-02-01

    The recovery of potency following radical prostatectomy is complex and has a very wide range. In this study, we analyzed in detail the precise pattern of recovery of potency following robot-assisted radical prostatectomy (RARP). Prospectively collected database of patients with a minimum follow-up of 1 year after RARP were evaluated retrospectively. Of 503 patients identified, 483 patients completed the sexual health inventory for men (SHIM) preoperatively and postoperatively every 3 months for the first 12 months. Overall potency, usage of phosphodiesterase type-5 (PDE-5) inhibitors, and return to baseline erectile function were evaluated. Potency was defined as having erection that is sufficient for sexual intercourse more than 50% of attempts, while quality potency was defined as being potent without the use of PDE-5 inhibitors. Preoperatively, the overall potency and quality potency rate were 67.1% and 48.1%, respectively. Postoperatively, the overall potency rate was 61.4%, while the quality potency rate was 37.2%. In multivariate regression analysis, independent predictors of potency recovery were young age (21, the overall potency and quality potency rate were 79.7% and 41.2%, respectively. More importantly, only 21.4% of the men with normal erection preoperatively (SHIM>21) returned to baseline erectile function (SHIM>21) 12 months after surgery. This study indicates that young age (<60), preoperative potency, and bilateral preservation of NVBs were positive predictors of potency recovery following RARP. However, an overwhelming majority of men experience a deterioration in the overall quality of erection after RARP.

  12. 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.

  13. 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

  14. Radiation-induced radical ions in calcium sulfite

    Science.gov (United States)

    Bogushevich, S. E.

    2006-07-01

    We have used EPR to study the effect of γ radiation on calcium sulfite. We have observed and identified the radiation-induced radical ions SO 2 - (iso) with g = 2.0055 and SO 2 - (orth-1) with g1 = 2.0093, g2 = 2.0051, g3 = 2.0020, identical to the initial and thermally induced SO 2 - respectively, SO 3 - (iso) with g = 2.0031 and SO 3 - (axial) with g⊥ = 2.0040, g∥ = 2.0023, identical to mechanically induced SO 3 - . We have established the participation of radiation-induced radical ions SO 3 - in formation of post-radiation SO 2 - .

  15. 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.

  16. Hydroxyl Radical-Mediated Novel Modification of Peptides: N-Terminal Cyclization through the Formation of α-Ketoamide.

    Science.gov (United States)

    Lee, Seon Hwa; Kyung, Hyunsook; Yokota, Ryo; Goto, Takaaki; Oe, Tomoyuki

    2015-01-20

    The hydroxyl radical-mediated oxidation of peptides and proteins constitutes a large group of post-translational modifications that can result in structural and functional changes. These oxidations can lead to hydroxylation, sulfoxidation, or carbonylation of certain amino acid residues and cleavage of peptide bonds. In addition, hydroxyl radicals can convert the N-terminus of peptides to an α-ketoamide via abstraction of the N-terminal α-hydrogen and hydrolysis of the ketimine intermediate. In the present study, we identified N-terminal cyclization as a novel modification mediated by a hydroxyl radical. The reaction of angiotensin (Ang) II (DRVYIHPF) and the hydroxyl radical generated by the Cu(II)/ascorbic acid (AA) system or UV/hydrogen peroxide system produced N-terminal cyclized-Ang II (Ang C) and pyruvamide-Ang II (Ang P, CH3COCONH-RVYIHPF). The structure of Ang C was confirmed by mass spectrometry and comparison to an authentic standard. The subsequent incubation of isolated Ang P in the presence of Cu(II)/AA revealed that Ang P was the direct precursor of Ang C. The proposed mechanism involves the formation of a nitrogen-centered (aminyl) radical, which cyclizes to form a five-membered ring containing the alkoxy radical. The subsequent β-scission reaction of the alkoxyl radical results in the cleavage of the terminal CH3CO group. The initial aminyl radical can be stabilized by chelation to the Cu(II) ions. The affinity of Ang C toward the Ang II type 1 receptor was significantly lower than that of Ang II or Ang P. Ang C was not further metabolized by aminopeptidase A, which converts Ang II to Ang III. Hydroxyl radical-mediated N-terminal cyclization was also observed in other Ang peptides containing N-terminal alanine, arginine, valine, and amyloid β 1-11 (DAEFRHDSGYE).

  17. Transients observed in the low temperature photolysis of alkyl radicals and divalent sulfur substrates

    International Nuclear Information System (INIS)

    Adam, F.C.

    1976-01-01

    The 253.7 nm photolysis of the isometric butyl radicals is described. These radicals are produced by electron capture during the γ-radiolysis of the corresponding butyl chlorides diluted in a rigid glass of 3-methylpentane-d14 at 77K. Thus t-butyl gives an equilibrium mixture of i-butyl and methyl radicals. Solvent radicals, M, are also produced and these obscure the former species in 3-MP-h14. Likewise sec-butyl radicals give rise to the ethyl, n-butyl, methyl and small amounts of the i-butyl radicals. Solvent radicals also rearrange and degrade in the photolytic beam, and the mechanism by which these processes occur is discussed. The procedure has also been used to study the formation and photolability of the alkyl thinyl and perthyl radicals occuring in the photolysis of RSH, RSR and RSSR. The thinyl radical is found to be unstable and gives the alkyl radical and atomic sulfur while the perthiyl radical is stable to radiation > 240 nm. (author)

  18. Radiation-initiated free-radical fragmentation of biologically active glycerides

    International Nuclear Information System (INIS)

    Akhrem, A.A.; Kisel', M.A.; Shadyro, O.I.; Yurkova, I.L.

    1993-01-01

    Oxidation reactions of the free-radical type play a decisive role in the initial processes of radiation damage. The most suitable substrates for such reactions are lipids. Lipids are a basic structural element of biomembranes and are involved in the barrier function and biocatalytic activity of such membranes. Free-radical degradation of membrane lipids can lead to serious damage and ultimately to destruction of the living cell. A well-studied type of free-radical conversion of lipids is oxidation of polyunsaturated fatty acid residues, so-called peroxide oxidation of lipids. In this paper, using as examples dimyristoylphosphatidyl glycerol (DMPG), monoglycerides, and glycerophosphate, the authors investigated the possibility of free-radical degradation in compounds of a lipid nature containing the α,β-bifunctional group

  19. Learning curve of robot-assisted laparoscopic radical prostatectomy for a single experienced surgeon: comparison with simultaneous laparoscopic radical prostatectomy.

    Science.gov (United States)

    Ku, Ja Yoon; Ha, Hong Koo

    2015-04-01

    Despite the large number of analytical reports regarding the learning curve in the transition from open to robot-assisted radical prostatectomy (RARP), few comparative results with laparoscopic radical prostatectomy (LRP) have been reported. Thus, we evaluated operative and postoperative outcomes in RARP versus 100 simultaneously performed LRPs. A single surgeon had performed more than 1,000 laparoscopic operations, including 415 cases of radical nephrectomy, 85 radical cystectomies, 369 radical prostatectomies, and treatment of 212 other urological tumors, since 2009. We evaluated operative (operation time, intraoperative transfusion, complications, hospital stay, margin status, pathological stage, Gleason score) and postoperative (continence and erectile function) parameters in initial cases of RARP without tutoring compared with 100 recently performed LRPs. Mean operation time and length of hospital stay for RARP and LRP were 145.5±43.6 minutes and 118.1±39.1 minutes, and 6.4±0.9 days and 6.6±1.1 days, respectively (p=0.003 and p=0.721). After 17 cases, the mean operation time for RARP was similar to LRP (less than 2 hours). Positive surgical margins in localized cancer were seen in 11.1% and 8.9% of cases in RARP and LRP, respectively (p=0.733). At postoperative 3 months, sexual intercourse was reported in 14.0% and 12.0%, and pad-free continence in 96.0% and 81.0% in patients with RARP and LRP, respectively (p=0.796 and p=0.012). Previous large-volume experience of LRPs may shorten the learning curve for RARP in terms of oncological outcome. Additionally, previous experience with laparoscopy may improve the functional outcomes of RARP.

  20. Free radical reactions of hematoporphyrin: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Ahmed, Mohammed; Guleria, Apurav; Singh, Ajay K.; Sarkar, S.K.

    2011-01-01

    Radiation chemistry of porphyrin derivatives has been given much attention in recent years. Although till date photo dynamic therapy (PDT) with Hematoporphyrin (HP) has already proved its effectiveness in the treatment of cancer, the molecular mechanisms by which this therapy-destroys tumour cells as well as its optimal physical parameters are still not fully understood. Thus it becomes necessary to understand the interaction of different free radicals with HP. Pulse radiolysis studies have been performed to understand the interaction of different free radicals with HP. The product formation along with bleaching and presence of a number of transients makes it difficult to pin point the mode and site of free radical attack. The radiation-induced formation of various transients (HP-OH, HO - , HP + ) in aqueous solution was investigated at various pHs by pulse radiolysis technique by means of N 3 , O - and CCl 3 O 2 radicals with and without triethyl-amine, under different dose conditions. The observed intermediates are characterized by their kinetic and spectroscopic data. The absorption spectrum of each transient could be differentiated from each other by their absorption maxima, extinction coefficients and kinetics. A clear indication of product formation has also been observed by employing continuous electron pulse and the solution shows a green coloration. It is conceivable that under certain conditions, similar transients may be produced when HP is used as a sensitizer in radiation chemotherapy of cancer patients. Our study may throw some light into the breakdown mechanism of haemoglobin to BV in addition to the understanding of free radical interaction of HP. (author)

  1. Innovation Processes and Entrepreneurial Culture for Radical Innovations

    Directory of Open Access Journals (Sweden)

    Ľubica Knošková

    2015-02-01

    Full Text Available To survive and prosper, the organizations need to embed the processes and mechanisms to discover major technology and consumer trends and respond to them through new growth areas. Based on profound literature review providing insight into organizational factors that affect firms’ ability to manage innovation this paper asks which innovation processes and entrepreneurial culture support radical innovations. The aim of the paper is to specify the company behaviour that leads to innovative outputs with high level of novelty in country specific context of Slovakia. We conducted two-stage empirical research in 2009 and 2014 mapping companies’ approach to innovation management during the last 10 years. After surveying 102 firms in the first stage and 287 firms in the second stage we derive success factors for radical innovations. The findings demonstrate growing importance of corporate strategic orientation, highly developed innovation processes and parallel mechanisms for radical innovation, ability to manage internally and externally open innovation and support entrepreneurial culture. This study makes unique contribution to the understanding of innovation processes, organizational factors, and their significance and dynamics. It should attract managerial attention to recognize the importance of innovation management factors for building firm’s innovation competency.

  2. Kinetics and mechanism of carbon-8 methylation of purine bases and nucleosides by methyl radical

    International Nuclear Information System (INIS)

    Zady, M.F.; Wong, J.L.

    1977-01-01

    The kinetics of homolytic methylation of the model purine compound caffeine at carbon-8 were determined as a function of several reaction variables. The methyl radical was generated from tert-butyl peracetate (BPA) either thermally (65 to 95 0 C) or photochemically (greater than 300 nm, 25 0 C). The thermal reaction k (25 0 C) was found to be 3.09 x 10 -8 s -1 from the linear log k (pseudo-first-order) vs. l/T plot. The light reactions using the 450- and 1200-W mercury lamps proceeded with k (25 0 C) 450- and 2160-fold greater, respectively. The derived activation energies are consistent with an S/sub E/Ar reaction. Increasing the concentration of caffeine from 0.25 M to 1.67 M in the presence of 3 molar equiv of BPA did not cause any side reaction. The pH-rate profile can be predicted by rate equations, which are derived on the basis of an electrophilic substitution occurring on the free base and conjugate acid of a heteroaromatic system. A competition study using tetrahydrofuran reveals the presence of a radical sigma complex IIIa and a charge transfer complex IIIb as intermediates for methylation under neutral and acidic conditions, respectively. Their rate-determining nature was indicated by the small positive kinetic isotope effect and the inverse solvent isotope effects: k/sub H 3 O + //k/sub D 3 O + / = 0.87 and k/sub H 2 O//k/sub D 2 O/ = 0.32. Thus, in acidic medium, a preequilibrium proton transfer to form the caffeine conjugate acid precedes the rate-controlling formation of IIIb. In neutral solution, the rate-determining step appears to be the protonation of the radical nitrogen in IIIa converting it to III. The acid-catalyzed caffeine-BPA reaction was shown to be general for other purines such as adenine, adenosine, guanine, guanosine, hypoxanthine, and inosine

  3. Aminoxyl (nitroxyl) radicals in the early decomposition of the nitramine RDX.

    Science.gov (United States)

    Irikura, Karl K

    2013-03-14

    The explosive nitramine RDX (1,3,5-trinitrohexahydro-s-triazine) is thought to decompose largely by homolytic N-N bond cleavage, among other possible initiation reactions. Density-functional theory (DFT) calculations indicate that the resulting secondary aminyl (R2N·) radical can abstract an oxygen atom from NO2 or from a neighboring nitramine molecule, producing an aminoxyl (R2NO·) radical. Persistent aminoxyl radicals have been detected in electron-spin resonance (ESR) experiments and are consistent with autocatalytic "red oils" reported in the experimental literature. When the O-atom donor is a nitramine, a nitrosamine is formed along with the aminoxyl radical. Reactions of aminoxyl radicals can lead readily to the "oxy-s-triazine" product (as the s-triazine N-oxide) observed mass-spectrometrically by Behrens and co-workers. In addition to forming aminoxyl radicals, the initial aminyl radical can catalyze loss of HONO from RDX.

  4. 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)

  5. Production of free radical by magnetized sheet plasma with vertical gas-flow

    International Nuclear Information System (INIS)

    Tonegawa, Akira; Takatori, Masahiko; Kawamura, Kazutaka

    1995-01-01

    Free radicals play an important role in plasma processing, environment problem, and space plasma and so on because of their outstanding physical properties. Although much work has been done on the free radicals in the reactive plasma, very little is known about the production mechanism of the free radicals against various plasma parameters. To overcome this problem, we have proposed to do a new system of a magnetized sheet plasma with vertical gas-flow. The sheet plasma is a special type of strongly magnetized highly ionized slab plasma. This system is controlled to the parameters of radicals and plasma independently. Therefore, it is possible to make a quantitative analysis of free radicals as the simple one. In this paper, we describe the magnetized sheet plasma with vertical gas-flow system and report the preliminary results of production of the free radical. In particular, we show to produce and control the OH free radical which has been the most commonly studied combustion species

  6. 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)

  7. Radical fragmentation of six-membered oxygen-containing heterocycles

    International Nuclear Information System (INIS)

    Petryaev, E.P.; Kosobutskij, V.S.; Shadyro, O.I.

    1982-01-01

    Using chromatography, the composition and radiation-chemical yields of final products of desctruction of six-member saturated oxygen-containing heterocycles (the effect of #betta#-radiation on aqueous solutions of tetrahydropyran, 1,3-dioxane, 2,2 dimethyl-1,3 dioxane, 1,4-dioxane, paraldehyde) have been determined. It is established that the identified products are formed at the expense of decomposition of primary radicals of the initial compounds and point to the realization of the following fragmentation ways: 1) #betta#-scattering, 2) #betta#-scattering with a subsequent 1,5 migration of an H atom, 3) simultaneous rupture of two vicinal, relative to the radical center, bonds. A formation mechanism of the substances desctruction products is suggested. Material balance of the product yields of 1,3-dioxane radical synchronous decomposition is presented

  8. Sulfate radical degradation of acetaminophen by novel iron-copper bimetallic oxidation catalyzed by persulfate: Mechanism and degradation pathways

    Science.gov (United States)

    Zhang, Yuanchun; Zhang, Qian; Hong, Junming

    2017-11-01

    A novel iron coupled copper oxidate (Fe2O3@Cu2O) catalyst was synthesized to activate persulfate (PS) for acetaminophen (APAP) degradation. The catalysts were characterized via field-emission scanning electron microscopy and energy-dispersive X-ray spectrometry. The effects of the catalyst, PS concentration, catalyst dosage, initial pH, dissolved oxygen were analyzed for treatment optimization. Results indicated that Fe2O3@Cu2O achieved higher efficiency in APAP degradation than Fe2O3/PS and Cu2O/PS systems. The optimal removal efficiency of APAP (90%) was achieved within 40 min with 0.6 g/L PS and 0.3 g/L catalyst. To clarify the mechanism for APAP degradation, intermediates were analyzed with gas chromatography-mass spectrometry. Three possible degradation pathways were identified. During reaction, Cu(I) was found to react with Fe(III) to generate Fe(II), which is the most active phase for PS activation. Through the use of methanol and tert-butyl alcohol (TBA) as radical trappers, SO4rad - was identified as the main radical species that is generated during oxidation.

  9. Oxygen free radical altered immunoglobin G in the etiopathogenesis of rheumatoid arthritis

    NARCIS (Netherlands)

    H.A. Kleinveld (Henk)

    1990-01-01

    textabstractThe particular association of RA with anti-lgG antibodies suggests an important role of lgG in the etiology and pathology of RA. One of the suggested mechanisms by which lgG could be altered is exposure to oxygen free radicals. During inflammation large amounts of oxygen free radicals

  10. Simple preparation of thiol-ene particles in glycerol and surface functionalization by thiol-ene chemistry (TEC) and surface chain transfer free radical polymerization (SCT-FRP)

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Chiaula, Valeria; Yu, Liyun

    2018-01-01

    functionalization of excess thiol groups via photochemical thiol-ene chemistry (TEC) resulting in a functional monolayer. In addition, surface chain transfer free radical polymerization (SCT-FRP) was used for the first time to introduce a thicker polymer layer on the particle surface. The application potential...

  11. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy.

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P; Nguyen, Huong T H; Dang, Andy; Tureček, František

    2018-01-16

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z 4 + H] +● fragment ion-radicals of the R-C ● H-CONH- type, initially formed by N-C α bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [ ● DAAR + H] + isomers and used to assign structures to the action spectra. The potential energy surface of [ ● DAAR + H] + isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [ ● XAAR + H] + ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone C α positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H] ● -ETD fragments containing Asp, Asn, Glu, and Gln residues. Graphical Abstract ᅟ.

  12. Spontaneous Isomerization of Peptide Cation Radicals Following Electron Transfer Dissociation Revealed by UV-Vis Photodissociation Action Spectroscopy

    Science.gov (United States)

    Imaoka, Naruaki; Houferak, Camille; Murphy, Megan P.; Nguyen, Huong T. H.; Dang, Andy; Tureček, František

    2018-01-01

    Peptide cation radicals of the z-type were produced by electron transfer dissociation (ETD) of peptide dications and studied by UV-Vis photodissociation (UVPD) action spectroscopy. Cation radicals containing the Asp (D), Asn (N), Glu (E), and Gln (Q) residues were found to spontaneously isomerize by hydrogen atom migrations upon ETD. Canonical N-terminal [z4 + H]+● fragment ion-radicals of the R-C●H-CONH- type, initially formed by N-Cα bond cleavage, were found to be minor components of the stable ion fraction. Vibronically broadened UV-Vis absorption spectra were calculated by time-dependent density functional theory for several [●DAAR + H]+ isomers and used to assign structures to the action spectra. The potential energy surface of [●DAAR + H]+ isomers was mapped by ab initio and density functional theory calculations that revealed multiple isomerization pathways by hydrogen atom migrations. The transition-state energies for the isomerizations were found to be lower than the dissociation thresholds, accounting for the isomerization in non-dissociating ions. The facile isomerization in [●XAAR + H]+ ions (X = D, N, E, and Q) was attributed to low-energy intermediates having the radical defect in the side chain that can promote hydrogen migration along backbone Cα positions. A similar side-chain mediated mechanism is suggested for the facile intermolecular hydrogen migration between the c- and [z + H]●-ETD fragments containing Asp, Asn, Glu, and Gln residues. [Figure not available: see fulltext.

  13. Phenylpropanoid Glycoside Analogues: Enzymatic Synthesis, Antioxidant Activity and Theoretical Study of Their Free Radical Scavenger Mechanism

    Science.gov (United States)

    López-Munguía, Agustín; Hernández-Romero, Yanet; Pedraza-Chaverri, José; Miranda-Molina, Alfonso; Regla, Ignacio; Martínez, Ana; Castillo, Edmundo

    2011-01-01

    Phenylpropanoid glycosides (PPGs) are natural compounds present in several medicinal plants that have high antioxidant power and diverse biological activities. Because of their low content in plants (less than 5% w/w), several chemical synthetic routes to produce PPGs have been developed, but their synthesis is a time consuming process and the achieved yields are often low. In this study, an alternative and efficient two-step biosynthetic route to obtain natural PPG analogues is reported for the first time. Two galactosides were initially synthesized from vanillyl alcohol and homovanillyl alcohol by a transgalactosylation reaction catalyzed by Kluyveromyces lactis β-galactosidase in saturated lactose solutions with a 30%–35% yield. To synthesize PPGs, the galactoconjugates were esterified with saturated and unsaturated hydroxycinnamic acid derivatives using Candida antarctica Lipase B (CaL-B) as a biocatalyst with 40%–60% yields. The scavenging ability of the phenolic raw materials, intermediates and PPGs was evaluated by the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH•) method. It was found that the biosynthesized PPGs had higher scavenging abilities when compared to ascorbic acid, the reference compound, while their antioxidant activities were found similar to that of natural PPGs. Moreover, density functional theory (DFT) calculations were used to determine that the PPGs antioxidant mechanism proceeds through a sequential proton loss single electron transfer (SPLET). The enzymatic process reported in this study is an efficient and versatile route to obtain PPGs from different phenylpropanoid acids, sugars and phenolic alcohols. PMID:21674039

  14. Electron transfer oxidation of DNA radicals by paranitroacetophenone

    Energy Technology Data Exchange (ETDEWEB)

    Whillans, D W; Adams, G E [Mount Vernon Hospital, Northwood (UK)

    1975-12-01

    The reaction of a typical electron-affinic sensitizer, paranitroacetophenone (PNAP) with the model compounds thymine, thymidine, thymidylic acid, deoxyribose and single and double-stranded DNA has been investigated by pulse radiolysis. Radicals formed by one-electron reduction of the bases and of DNA reacted rapidly and efficiently with PNAP by electron transfer. A small yield of transfer (< 10 per cent) was also observed arising from oxidation of the radicals formed by the small proportion of OH which reacted at the sugar moieties in DNA. In contrast, electron transfer oxidation by PNAP of radicals formed by the addition of OH to the base moieties, e.g. thymine, was not an efficient process. Further, addition of the sensitizer to the thymine OH-adduct proceeded at a rate that was too low to measure the pulse radiolysis. We conclude that, since the major sites of OH reaction by DNA are the heterocyclic bases (> 80 per cent), oxidation of the resultant radicals is unlikely to be a major step in the mechanism of sensitization by this typical hypoxic-cell sensitizer.

  15. Exploring how lead users develop radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher; Gemuenden, Hans Georg; Hienerth, C.

    2008-01-01

    in order to transform their radically new solutions into functional prototypes and then to convince established manufacturers of the technological and market potential of their innovations. Using a comparative case study design in the high-tech field of medical equipment technology, we find that individual...... the supply of diversified knowledge, the development and coordination of a network for further development of the innovation, and initial tests of technical or market feasibility. Our findings have implications for manufacturing firms that wish to design radical innovation projects with (individual) lead...

  16. Analysis of combustion in an ATAC engine with measurement of radical luminescence; Radical hakko keisoku ni yoru ATAC engine no nensho kaiseki

    Energy Technology Data Exchange (ETDEWEB)

    Park, Y; Oguma, H; Ueda, H; Iida, N [Keio University, Tokyo (Japan)

    1997-10-01

    In order to make clear of the combustion mechanism and the frame structure in two stake, so called, active thermo-atmosphere combustion (ATAC) engine fueled by gasoline and methanol, we measured the 2-demensional images of OH, CH and C2 radical band spectra in both ATAC and SI combustion mode. From the results of pressure data in the cylinder, the heat release rate was calculated. We evaluated the correlation of radical luminescence intensity and the rate of heat release. 3 refs., 4 figs., 2 tabs.

  17. Tobacco Smoke: Involvement of Reactive Oxygen Species and Stable Free Radicals in Mechanisms of Oxidative Damage, Carcinogenesis and Synergistic Effects with Other Respirable Particles

    Science.gov (United States)

    Valavanidis, Athanasios; Vlachogianni, Thomais; Fiotakis, Konstantinos

    2009-01-01

    Tobacco smoke contains many toxic, carcinogenic and mutagenic chemicals, as well as stable and unstable free radicals and reactive oxygen species (ROS) in the particulate and the gas phase with the potential for biological oxidative damage. Epidemiological evidence established that smoking is one of the most important extrinsic factor of premature morbidity and mortality. The objective of this study was to investigate oxidative and carcinogenic mechanisms of tobacco and synergistic action with other respirable particles in the respiratory system of smokers. Electron Paramagnetic Resonance (EPR) and spin-trapping techniques were used to study stable free radicals in the cigarette tar, and unstable superoxide anion (O2•−) and hydroxyl (HO•) radicals in the smoke Results showed that the semiquinone radical system has the potential for redox recycling and oxidative action. Further, results proved that aqueous cigarette tar (ACT) solutions can generate adducts with DNA nucleobases, particularly the mutagenic 8-hydroxy-2’-deoxyguanosine (a biomarker for carcinogenesis). Also, we observed synergistic effects in the generation of HO•, through the Fenton reaction, with environmental respirable particles (asbestos fibres, coal dust, etc.) and ambient particulate matter (PM), such as PM10, PM2.5 and diesel exhaust particles (DEP). The highest synergistic effects was observed with the asbestos fibres (freshly grounded), PM2.5 and DEP. Finally, we discuss results from our previous study of conventional cellulose acetate filters and “bio-filters” with hemoglobin impregnated activated carbon, which showed that these filters do not substantially alter the free radical content of smoke in the particulate and in the gaseous phase. PMID:19440393

  18. Tobacco Smoke: Involvement of Reactive Oxygen Species and Stable Free Radicals in Mechanisms of Oxidative Damage, Carcinogenesis and Synergistic Effects with Other Respirable Particles

    Directory of Open Access Journals (Sweden)

    Konstantinos Fiotakis

    2009-02-01

    Full Text Available Tobacco smoke contains many toxic, carcinogenic and mutagenic chemicals, as well as stable and unstable free radicals and reactive oxygen species (ROS in the particulate and the gas phase with the potential for biological oxidative damage. Epidemiological evidence established that smoking is one of the most important extrinsic factor of premature morbidity and mortality. The objective of this study was to investigate oxidative and carcinogenic mechanisms of tobacco and synergistic action with other respirable particles in the respiratory system of smokers. Electron Paramagnetic Resonance (EPR and spin- trapping techniques were used to study stable free radicals in the cigarette tar, and unstable superoxide anion (O2·- and hydroxyl (HO· radicals in the smoke Results showed that the semiquinone radical system has the potential for redox recycling and oxidative action. Further, results proved that aqueous cigarette tar (ACT solutions can generate adducts with DNA nucleobases, particularly the mutagenic 8-hydroxy-2’-deoxyguanosine (a biomarker for carcinogenesis.Also, we observed synergistic effects in the generation of HO·, through the Fenton reaction, with environmental respirable particles (asbestos fibres, coal dust, etc. and ambient particulate matter (PM, such as PM10, PM2.5 and diesel exhaust particles (DEP. The highest synergistic effects was observed with the asbestos fibres (freshly grounded, PM2.5 and DEP. Finally, we discuss results from our previous study of conventional cellulose acetate filters and “bio-filters” with hemoglobin impregnated activated carbon, which showed that these filters do not substantially alter the free radical content of smoke in the particulate and in the gaseous phase.

  19. Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

    Science.gov (United States)

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 d...

  20. 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.

  1. 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.

  2. 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.

  3. Kinetics and mechanism of the gas-phase reaction of Cl atoms and OH radicals with fluorobenzene at 296 K

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, MD

    2002-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms and OH radicals with fluorobenzene, C6H5F, in 700 Torr of N-2 or air diluent at 296 K. Reaction of Cl atoms with C6H5F proceeds via two pathways: H-atom abstraction to give HCl and the C6H4F...... with Cl atoms via a mechanism which, at least in part, leads neither to production of C6H5Cl nor to reformation of C6H5F. As the steady-state Cl atom concentration is increased, the fraction of the C6H5F-Cl adduct undergoing reaction with Cl atoms increases causing an increase in the effective rate...

  4. Spectroscopic detection, characterization and dynamics of free radicals relevant to combustion processes

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Terry [The Ohio State Univ., Columbus, OH (United States)

    2015-06-04

    Combustion chemistry is enormously complex. The chemical mechanisms involve a multitude of elementary reaction steps and a comparable number of reactive intermediates, many of which are free radicals. Computer simulations based upon these mechanisms are limited by the validity of the mechanisms and the parameters characterizing the properties of the intermediates and their reactivity. Spectroscopy can provide data for sensitive and selective diagnostics to follow their reactions. Spectroscopic analysis also provides detailed parameters characterizing the properties of these intermediates. These parameters serve as experimental gold standards to benchmark predictions of these properties from large-scale, electronic structure calculations. This work has demonstrated the unique capabilities of near-infrared cavity ringdown spectroscopy (NIR CRDS) to identify, characterize and monitor intermediates of key importance in complex chemical reactions. Our studies have focussed on the large family of organic peroxy radicals which are arguably themost important intermediates in combustion chemistry and many other reactions involving the oxidation of organic compounds. Our spectroscopic studies have shown that the NIR Ã - ˜X electronic spectra of the peroxy radicals allows one to differentiate among chemical species in the organic peroxy family and also determine their isomeric and conformic structure in many cases. We have clearly demonstrated this capability on saturated and unsaturated peroxy radicals and β-hydroxy peroxy radicals. In addition we have developed a unique dual wavelength CRDS apparatus specifically for the purpose of measuring absolute absorption cross section and following the reaction of chemical intermediates. The utility of the apparatus has been demonstrated by measuring the cross-section and self-reaction rate constant for ethyl peroxy.

  5. Oxidation of free, peptide and protein tryptophan residues mediated by AAPH-derived free radicals: role of alkoxyl and peroxyl radicals

    DEFF Research Database (Denmark)

    Fuentes-Lemus, E.; Dorta, E.; Escobar, E.

    2016-01-01

    The oxidation of tryptophan (Trp) residues, mediated by peroxyl radicals (ROOc), follows a complex mechanism involving free radical intermediates, and short chain reactions. The reactivity of Trp towards ROOc should be strongly affected by its inclusion in peptides and proteins. To examine...... the latter, we investigated (by fluorescence) the kinetic of the consumption of free, peptide- and protein-Trp residues towards AAPH (2,20 -azobis(2-amidinopropane)dihydrochloride)-derived free radicals. Interestingly, the initial consumption rates (Ri ) were only slightly influenced by the inclusion of Trp...... concentrations (10–50 mM), the values of Ri were nearly constant; and at high Trp concentrations (50 mM to 1 mM), a slower increase of Ri than expected for chain reactions. Similar behavior was detected for all three systems (free Trp, and Trp in peptides and proteins). For the first time we are showing...

  6. Sugar Radical Formation by a Proton Coupled Hole Transfer in 2′-Deoxyguanosine Radical Cation (2′-dG•+): A Theoretical Treatment

    Science.gov (United States)

    Kumar, Anil; Sevilla, Michael D.

    2009-01-01

    Previous experimental and theoretical work has established that electronic excitation of a guanine cation radical in nucleosides or in DNA itself leads to sugar radical formation by deprotonation from the dexoxyribose sugar. In this work we investigate a ground electronic state pathway for such sugar radical formation in a hydrated one electron oxidized 2′-deoxyguanosine (dG•+ + 7H2O), using density functional theory (DFT) with the B3LYP functional and the 6-31G* basis set. We follow the stretching of the C5′-H bond in dG•+ to gain an understanding of the energy requirements to transfer the hole from the base to sugar ring and then to deprotonate to proton acceptor sites in solution and on the guanine ring. The geometries of reactant (dG•+ + 7H2O), transition state (TS) for deprotonation of C5′ site and product (dG(•C5′, N7-H+) + 7 H2O) were fully optimized. The zero point energy (ZPE) corrected activation energy (TS) for the proton transfer (PT) from C5′ is calculated to be 9.0 kcal/mol and is achieved by stretching the C5′-H bond by 0.13 Å from its equilibrium bond distance (1.099 Å). Remarkably, this small bond stretch is sufficient to transfer the “hole” (positive charge and spin) from guanine to the C5′ site on the deoxyribose group. Beyond the TS, the proton (H+) spontaneously adds to water to form a hydronium ion (H3O+) as an intermediate. The proton subsequently transfers to the N7 site of the guanine (product). The 9 kcal/mol barrier suggests slow thermal conversion of the cation radical to the sugar radical but also suggests that localized vibrational excitations would be sufficient to induce rapid sugar radical formation in DNA base cation radicals. PMID:19754084

  7. Efficiency of radical yield in alkylthymine and alkyluracil by high-LET irradiation

    International Nuclear Information System (INIS)

    Nakagawa, Seiko; Ohta, Nobuaki; Murakami, Takeshi

    2010-01-01

    Penthylthymines and hexyl-, nonyl-, and decyl- uracils were irradiated by C-ion (3.5 GeV) and γ-ray at 77 K. ESR spectra were measured to study radiation induced radicals in the temperature range from 108 to 273 K. A dihydro-5-yl (5-yl) radical formed by H addition to C6 carbon and a secondary alkyl radical by C-H bond fission at the second carbon from the end of the alkyl group were produced at 108 K. A dihydrouracil-6-yl (6-yl) radical formed by H addition to C5 carbon increased with increasing temperature for alkyluracils. The spectral feature obtained by C-ion irradiation was coincident with that by γ-irradiation. Total radical yields increased by alkylation and with increasing the length of alkyl chain. Yields of both 5-yl and secondary alkyl radicals irradiated by C-ion were less than those by γ-ray for penthylthymines and hexyluracil. On the contrary, radical yields were almost the same between ion and γ-ray irradiation for nonyl- and decyl-uracil. Mechanism of radical formation and effect of high-LET irradiation were discussed.

  8. 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...

  9. Radical polymerization in holographic grating formation in PQ-PMMA photopolymer part II: Consecutive exposure and dark decay

    Science.gov (United States)

    Yu, Dan; Liu, Hongpeng; Geng, Yaohui; Wang, Weibo; Zhao, Yuanyuan

    2014-11-01

    Photochemical radical polymerization in phenathrenequinone doped poly(methyl methacrylate) photopolymer are investigated theoretically and experimentally under consecutive exposure. The detailed photochemical mechanisms are analyzed. Based on the rate equations of photochemical reactions, the diffusion models with nonlocal response are proposed to describe the kinetic process of radical polymerization and the significance of photochemical processes for the grating formation. In experiments, the temporal evolution of diffraction efficiency in grating formation is measured under consecutive exposure and after exposure. The percentages of these radical polymerizations, namely the polymerization of PQ with matrix, the bimolecular combination of MMA molecules, and the disproportionation of MMA molecules, are extracted quantitatively by comparing theory with experiments. It is indicated that the polymerization of PQ with matrix is primary photochemical process which dominated the grating formation under consecutive exposure. In this period, the contribution of chain polymerization of MMA radicals is weak for the grating formation. After reaching the peak values of grating strength, the influence of the free MMA molecules and photoproduct macromolecules on the grating decay is discussed in a long-term period. The diffusion coefficients of MMA and photoproduct are extracted by fitting the curves using double exponential function. MMA’s diffusion contributed to the fast decay process of grating after exposure and photoproduct’s diffusion contributed to the slow and long decay of grating. The results break previous understanding about the diffusion of single photoproduct macromolecules lead to the dark decay of grating. This investigation can provide a significant foundation for improving modulation depth and long-term stability by photochemical mechanism.

  10. Free Radical Damage in Ischemia-Reperfusion Injury: An Obstacle in Acute Ischemic Stroke after Revascularization Therapy

    Directory of Open Access Journals (Sweden)

    Ming-Shuo Sun

    2018-01-01

    Full Text Available Acute ischemic stroke is a common cause of morbidity and mortality worldwide. Thrombolysis with recombinant tissue plasminogen activator and endovascular thrombectomy are the main revascularization therapies for acute ischemic stroke. However, ischemia-reperfusion injury after revascularization therapy can result in worsening outcomes. Among all possible pathological mechanisms of ischemia-reperfusion injury, free radical damage (mainly oxidative/nitrosative stress injury has been found to play a key role in the process. Free radicals lead to protein dysfunction, DNA damage, and lipid peroxidation, resulting in cell death. Additionally, free radical damage has a strong connection with inducing hemorrhagic transformation and cerebral edema, which are the major complications of revascularization therapy, and mainly influencing neurological outcomes due to the disruption of the blood-brain barrier. In order to get a better clinical prognosis, more and more studies focus on the pharmaceutical and nonpharmaceutical neuroprotective therapies against free radical damage. This review discusses the pathological mechanisms of free radicals in ischemia-reperfusion injury and adjunctive neuroprotective therapies combined with revascularization therapy against free radical damage.

  11. Comparative sensitivities of functional MRI sequences in detection of local recurrence of prostate carcinoma after radical prostatectomy or external-beam radiotherapy.

    Science.gov (United States)

    Roy, Catherine; Foudi, Fatah; Charton, Jeanne; Jung, Michel; Lang, Hervé; Saussine, Christian; Jacqmin, Didier

    2013-04-01

    The aim of this retrospective study was to determine the respective accuracies of three types of functional MRI sequences-diffusion-weighted imaging (DWI), dynamic contrast-enhanced (DCE) MRI, and 3D (1)H-MR spectroscopy (MRS)-in the depiction of local prostate cancer recurrence after two different initial therapy options. From a cohort of 83 patients with suspicion of local recurrence based on prostate-specific antigen (PSA) kinetics who were imaged on a 3-T MRI unit using an identical protocol including the three functional sequences with an endorectal coil, we selected 60 patients (group A, 28 patients who underwent radical prostatectomy; group B, 32 patients who underwent external-beam radiation) who had local recurrence ascertained on the basis of a transrectal ultrasound-guided biopsy results and a reduction in PSA level after salvage therapy. All patients presented with a local relapse. Sensitivity with T2-weighted MRI and 3D (1)H-MRS sequences was 57% and 53%, respectively, for group A and 71% and 78%, respectively, for group B. DCE-MRI alone showed a sensitivity of 100% and 96%, respectively, for groups A and B. DWI alone had a higher sensitivity for group B (96%) than for group A (71%). The combination of T2-weighted imaging plus DWI plus DCE-MRI provided a sensitivity as high as 100% in group B. The performance of functional imaging sequences for detecting recurrence is different after radical prostatectomy and external-beam radiotherapy. DCE-MRI is a valid and efficient tool to detect prostate cancer recurrence in radical prostatectomy as well as in external-beam radiotherapy. The combination of DCE-MRI and DWI is highly efficient after radiation therapy. Three-dimensional (1)H-MRS needs to be improved. Even though it is not accurate enough, T2-weighted imaging remains essential for the morphologic analysis of the area.

  12. 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.

  13. Radiolytic reduction of nifurtimose by CO2-· free radicals

    International Nuclear Information System (INIS)

    Filali-Mouhim, A.; Champion, B.; Jore, D.; Ferradini, C.; Hickel, B.

    1991-01-01

    Nifurtimox is an antiparasitic drug often used in the treatment of the Chagas disease. Its therapeutic action seems to involve its monoelectronic reduction leading to a reduced radical capable of providing superoxide anion by reaction with oxygen. The oxidation reduction mechanisms involved in this action have been studied by steady state and pulse radiolysis methods. This study is devoted to the monoelectronic exchanges observed in the absence of air, the reducing radicals being the CO 2 - · anions [fr

  14. Hearing Status after Radical Mastoidectomy without Tympanoplasty.

    Science.gov (United States)

    Khan, Shamaila Nawaz; Udaipurwala, Iqbal Hussain; Mehmood, Talat; Rahat, Zahid Mehmood

    2017-12-01

    To find out the impairment of hearing associated with radical mastoidectomy by measuring the quantitative difference in the functional hearing level before and after radical mastoidectomy operation without tympanoplasty. Cross-sectional comparative study. Department of Otorhinolaryngology and Head Neck Surgery, Bahawal Victoria Hospital, Bahawalpur and PNS Shifa Hospital, Karachi, from November 2009 to January 2013. Eighty-five patients, diagnosed clinically as chronic suppurative otitis media with extensive cholesteatoma having history of ear discharge and hearing impairment for more than 6 weeks duration and requiring radical mastoidectomy for treatment, were included in this study. Pure tone audiogram was done before and after radical mastoidectomy. Hearing impairment was compared in each patient before and after the operation. Among the 85 patients, 54 (63.5%) were males and 31 (36.5%) were females, with the age ranged between 18 to 63 years, mean age being 42.31 4.8 years. The mean increase in hearing loss after radical mastoidectomy in air conduction was 7.19 dB, bone conduction was 4.16 dB, and air-bone gap was 3.75 dB (0.001). The ear became dry and safe in 82 patients (96.5%) out of a total of 85, and only 3 patients required revision surgery at a second stage. Radical mastoidectomy has a least negligible effect on hearing status and one should not limit this technique due to the concern of aggravated hearing in patients with extensive cholesteatoma at the cost of dry and safe ears, which should be of prime importance.

  15. J/{psi} production in {radical}(s)=7 TeV pp collisions

    Energy Technology Data Exchange (ETDEWEB)

    Kramer, Frederick

    2012-07-01

    In the first part of this work the inclusive cross section for J/{psi} production in inelastic {radical}(s) = 7 TeV pp collisions has been determined within vertical stroke y vertical stroke < 0.9 and in the decay channel J/{psi} {yields} e{sup +}e{sup -}. The result for the integrated value is: {sigma}{sub J/{psi}}(vertical stroke y vertical stroke < 0.9) = 10.7 {+-} 0.8 (stat.) {+-} 1.4 (syst.) {+-} 0.4 (lumi.) {mu}b. Together with the ALICE measurement in the {mu}{sup +}{mu}{sup -} decay channel at forward rapidities and data from other experiments this result fills the gap at mid-rapidity for a comprehensive measurement of the J/{psi} rapidity distribution. Furthermore, results of the differential analysis as a function of the J/{psi} transverse momentum were presented. Finally the data are shown together with various theoretical predictions representing the current status of the three most common theoretical approaches for the description of quarkonia production: the Color-Singlet Model, the Color-Evaporation Model and NRQCD.

  16. 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...

  17. 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

  18. Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

    Science.gov (United States)

    Wennberg, P. O.; Hanisco, T. F.; Jaegle, L.; Jacob, D. J.; Hintsa, E. J.; Lanzendorf, E. J.; Anderson, J. G.; Gao, R.-S.; Keim, E. R.; Donnelly, S. G.; hide

    1998-01-01

    The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3, in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of 03 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day.This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.

  19. Highly functionalized piperidines: Free radical scavenging, anticancer activity, DNA interaction and correlation with biological activity

    Directory of Open Access Journals (Sweden)

    Suvankar Das

    2018-01-01

    Full Text Available Twenty-five piperidines were studied as potential radical scavengers and antitumor agents. Quantitative interaction of compounds with ctDNA using spectroscopic techniques was also evaluated. Our results demonstrate that the evaluated piperidines possesses different abilities to scavenge the radical 2,2-diphenyl-1-picrylhydrazyl (DPPH and the anion radical superoxide (·O2−. The piperidine 19 was the most potent radical DPPH scavenger, while the most effective to ·O2− scavenger was piperidine 10. In general, U251, MCF7, NCI/ADR-RES, NCI-H460 and HT29 cells were least sensitive to the tested compounds and all compounds were considerably more toxic to the studied cancer cell lines than to the normal cell line HaCaT. The binding mode of the compounds and ctDNA was preferably via intercalation. In addition, these results were confirmed based on theoretical studies. Finally, a linear and exponential correlation between interaction constant (Kb and GI50 for several human cancer cell was observed.

  20. On the distribution functions in the quantum mechanics and Wigner functions

    International Nuclear Information System (INIS)

    Kuz'menkov, L.S.; Maksimov, S.G.

    2002-01-01

    The problem on the distribution functions, leading to the similar local values of the particles number, pulse and energy, as in the quantum mechanics, is formulated and solved. The method is based on the quantum-mechanical determination of the probability density. The derived distribution function coincides with the Wigner function only for the spatial-homogeneous systems. The Bogolyubov equations chain, the Liouville equation for the distribution quantum functions by any number of particles in the system, the general expression for the tensor of the dielectric permittivity of the plasma electron component are obtained [ru

  1. Surface reactivity of Ge[111] for organic functionalization by means of a radical-initiated reaction: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Rubio-Pereda, Pamela, E-mail: rubio.pereda@gmail.com [Centro de Investigación Científica y de Educación Superior de Ensenada 3918, Código Postal 22860, Ensenada, Baja California (Mexico); Takeuchi, Noboru, E-mail: takeuchi@cnyn.unam.mx [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Apartado Postal 14, Código Postal 22800, Ensenada, Baja California (Mexico)

    2016-08-30

    Highlights: • The surface reactivity of the Ge [111] surface is studied with DFT for the attachment of organic molecules by means of a radical-initiated reaction. • A hydrogen vacancy in the hydrogen terminated Ge [111] surface exhibits an accumulation of charge and electron pairing. • These characteristics make the hydrogen vacancy less reactive for the attachment of unsaturated organic molecules. • The adsorption of acetylene is probable to occur while the adsorption of ethylene and styrene is substantially less probable to occur. • The hydrogen terminated Ge [111] surface is found to be less reactive than its two-dimensional analogue, the hydrogen-terminated germanene. - Abstract: The study of interfacial chemistry at semiconductor surfaces has become an important area of research. Functionalities such as molecular recognition, biocompatibility of surfaces, and molecular computing, could be achieved by the combinations of organic chemistry with the semiconductor technology. One way to accomplish this goal is by means of organic functionalization of semiconductor surfaces such as the bulk-terminated germanium surfaces, more specifically the Ge[111]. In this work, we theoretically study, by applying density functional theory, the surface reactivity of the bulk-terminated Ge[111] surface for organic functionalization by means of a radical-initiated reaction of unsaturated molecules such as acetylene, ethylene and styrene with a hydrogen vacancy on a previously hydrogen-terminated Ge[111] surface. Results derived from this work are compared with those obtained in our previous calculations on the germanene surface, following the same chemical route. Our calculations show an accumulation of electronic charge at the H-vacancy having as a result electron pairing due to strong lattice-electron coupling and therefore a diminished surface reactivity. Calculation of the transition states for acetylene and ethylene indicates that the surface reactivity of the

  2. Fifteen years of experience radical cystectomy and intestinal urinary diversion

    Directory of Open Access Journals (Sweden)

    M. I. Vasil’chenko

    2017-01-01

    Full Text Available Objective. Examination of the results of surgical treatment and analysis of the surgical technique and perioperative parameters in a series of radical cystectomy on the basis of its own 15 years of experience in the formation of orthotopic and heterotopic urinary reservoir of the ileum segment by developed and patented techniques in different versions: open radical cystectomy, laparoscopic radical cystectomy and robotassisted radical cystectomy.Materials and methods. A retrospective analysis of 310 radical cystectomy performed from 2000 to 2015, on the occasion of various pathologies of the bladder and prostate, as well as cancers of other organs (uterus, colon with involvement in the process of bladder tumor. Plastics of the bladder was performed from the segment of the terminal ileum. Formation of orthotopic bladder was performed by the method of M.I. Vasilchenko (RF patent for invention № 2337630 “Method of orthotopic bladder plastics” by M.I. Vasilchenko. The ureters are implanted by antireflux procedure. If unable to perform orthotopic bladder plastics recovery and self-urination, patients underwent the formation of heterotopic enteral reservoir with a holding valve.Results. It assesses the functionality and viability of organic shaped orthotopic and heterotopic urinary neocystis in the early and late postoperative periods in different versions. The proposed techniques have a beneficial effect on the improvement of the functional state and stabilization of the upper urinary tract. Analysis of morbidity and mortality was determined according to the classification of surgical complications on the Clavien–Dindo. This approach allowed to identify most of the complications and prevent an underestimation of the main negative results. Estimated oncologic efficacy of minimally invasive interventions laparoscopic radical cystectomy and robot-assisted radical cystectomy not inferior open radical cystectomy.Conclusions. Formation of

  3. 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)

  4. Effects and mechanism of diclofenac degradation in aqueous solution by US/Zn0.

    Science.gov (United States)

    Huang, Ting; Zhang, Guangming; Chong, Shan; Liu, Yucan; Zhang, Nan; Fang, Shunyan; Zhu, Jia

    2017-07-01

    A system of ultrasound radiation coupled with Zn 0 was applied to degrade diclofenac. The effects of initial pH, dosage of Zn 0 and ultrasound density were investigated. To further explore the mechanism of the microcosmic reaction, the fresh and used Zn 0 powders were characterized by SEM, XRD and XPS. Radical scavengers were used to determine the oxidation performance of strong oxidizing free radicals on diclofenac, including hydroxyl radicals and superoxide radicals. The results showed that the optimum removal of diclofenac reached to over 85% at pH of 2.0 in 15min, with Zn 0 dosage of 0.1g/L and ultrasound density of 0.6W/cm 3 . TOC removal of 72.6% in 15min and dechlorination efficiency of diclofenac reached 70% in 30min. Characterization results showed that a ZnO membrane was generated on the surface of Zn particles after use. According to the mass spectrometry results, several possible pathways of diclofenac degradation were proposed, and most diclofenac was turned into micro-molecules or CO 2 finally. The synergistic effect of US/Zn 0 in the reactions led to a proposed degradation mechanism in which zinc could directly attack the target contaminant diclofenac because of its good reducibility with the auxiliary functions of ultrasonic irradiation, mechanical shearing and free radical oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

    Science.gov (United States)

    Liu, Matthew J; Wiegel, Aaron A; Wilson, Kevin R; Houle, Frances A

    2017-08-10

    A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular

  6. 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.

  7. Theoretical study on the mechanism and kinetics of the reaction of 2,2‧,4,4‧-tetrabrominated diphenyl ether (BDE-47) with OH radicals

    Science.gov (United States)

    Cao, Haijie; He, Maoxia; Han, Dandan; Sun, Yanhui; Xie, Ju

    2011-03-01

    The mechanism and kinetic properties of OH-initiated gas-phase reaction of 2,2',4,4'-tetrabrominated diphenyl ether (BDE-47) have been studied at the MPWB1K/6-311 + G(3df,2p)//MPWB1K/6-31G(d) level of theory. Two types of reactions including hydroxyl addition and hydrogen abstraction have been considered. The calculation results indicate that addition reactions except for the bromo-substituted addition reaction have lower energy barriers than hydrogen abstraction reactions. Hydroxyl radical is most likely to be added to non-substituted C atoms (C(3), C(5), and C(6) atoms). Moreover, for all the reactions with OH radical, the bromo-substituted C atoms encountered the highest barrier compared to that of the rest C atoms. The rate constants and product branching ratios of each pathway have been deduced over a wide range of 200-1000 K using canonical variational transition state (CVT) theory with small curvature tunneling (SCT) contribution. This study can be regarded as an attempt to investigate the OH-initiated photochemical reaction mechanism of polybrominated diphenyl ethers (PBDEs).

  8. 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...

  9. Management of erectile dysfunction post-radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Saleh A

    2015-02-01

    Full Text Available Alan Saleh, Hamid Abboudi, MB Ghazal-Aswad, Erik K Mayer, Justin A Vale Division of Surgery and Cancer, Imperial College Healthcare NHS Trust, St Mary's Hospital, London, UK Abstract: Radical prostatectomy is a commonly performed procedure for the treatment of localized prostate cancer. One of the long-term complications is erectile dysfunction. There is little consensus on the optimal management; however, it is agreed that treatment must be prompt to prevent fibrosis and increase oxygenation of penile tissue. It is vital that patient expectations are discussed, a realistic time frame of treatment provided, and treatment started as close to the prostatectomy as possible. Current treatment regimens rely on phosphodiesterase 5 inhibitors as a first-line therapy, with vacuum erection devices and intraurethral suppositories of alprostadil as possible treatment combination options. With nonresponders to these therapies, intracavernosal injections are resorted to. As a final measure, patients undergo the highly invasive penile prosthesis implantation. There is no uniform, objective treatment program for erectile dysfunction post-radical prostatectomy. Management plans are based on poorly conducted and often underpowered studies in combination with physician and patient preferences. They involve the aforementioned drugs and treatment methods in different sequences and doses. Prospective treatments include dietary supplements and gene therapy, which have shown promise with there proposed mechanisms of improving erectile function but are yet to be applied successfully in human patients. Keywords: erectile dysfunction, phosphodiesterase 5 inhibitors, vacuum erection devices, intraurethral suppositories, intracavernosal injections

  10. Free radical mediated formation of 3-monochloropropanediol (3-MCPD) fatty acid diesters.

    Science.gov (United States)

    Zhang, Xiaowei; Gao, Boyan; Qin, Fang; Shi, Haiming; Jiang, Yuangrong; Xu, Xuebing; Yu, Liangli Lucy

    2013-03-13

    The present study was conducted to test the hypothesis that a free radical was formed and mediated the formation of 3-monochloropropanediol (3-MCPD) fatty acid diesters, a group of food contaminants, from diacylglycerols at high temperature under a low-moisture condition for the first time. The presence of free radicals in a vegetable oil kept at 120 °C for 20 min was demonstrated using an electron spin resonance (ESR) spectroscopy examination with 5,5-dimethylpyrroline-N-oxide (DMPO) as the spin trap agent. ESR investigation also showed an association between thermal treatment degree and the concentration of free radicals. A Fourier transform infrared spectroscopy (FT-IR) analysis of sn-1,2-stearoylglycerol (DSG) at 25 and 120 °C suggested the possible involvement of an ester carbonyl group in forming 3-MCPD diesters. On the basis of these results, a novel free radical mediated chemical mechanism was proposed for 3-MCPD diester formation. Furthermore, a quadrupole-time of flight (Q-TOF) MS/MS investigation was performed and detected the DMPO adducts with the cyclic acyloxonium free radical (CAFR) and its product MS ions, proving the presence of CAFR. Furthermore, the free radical mechanism was validated by the formation of 3-MCPD diesters through reacting DSG with a number of organic and inorganic chlorine sources including chlorine gas at 120 and 240 °C. The findings of this study might lead to the improvement of oil and food processing conditions to reduce the level of 3-MCPD diesters in foods and enhance food safety.

  11. Free radical scavenging and COX-2 inhibition by simple colon metabolites of polyphenols: A theoretical approach.

    Science.gov (United States)

    Amić, Ana; Marković, Zoran; Marković, Jasmina M Dimitrić; Jeremić, Svetlana; Lučić, Bono; Amić, Dragan

    2016-12-01

    Free radical scavenging and inhibitory potency against cyclooxygenase-2 (COX-2) by two abundant colon metabolites of polyphenols, i.e., 3-hydroxyphenylacetic acid (3-HPAA) and 4-hydroxyphenylpropionic acid (4-HPPA) were theoretically studied. Different free radical scavenging mechanisms are investigated in water and pentyl ethanoate as a solvent. By considering electronic properties of scavenged free radicals, hydrogen atom transfer (HAT) and sequential proton loss electron transfer (SPLET) mechanisms are found to be thermodynamically probable and competitive processes in both media. The Gibbs free energy change for reaction of inactivation of free radicals indicates 3-HPAA and 4-HPPA as potent scavengers. Their reactivity toward free radicals was predicted to decrease as follows: hydroxyl>alkoxyls>phenoxyl≈peroxyls>superoxide. Shown free radical scavenging potency of 3-HPAA and 4-HPPA along with their high μM concentration produced by microbial colon degradation of polyphenols could enable at least in situ inactivation of free radicals. Docking analysis with structural forms of 3-HPAA and 4-HPPA indicates dianionic ligands as potent inhibitors of COX-2, an inducible enzyme involved in colon carcinogenesis. Obtained results suggest that suppressing levels of free radicals and COX-2 could be achieved by 3-HPAA and 4-HPPA indicating that these compounds may contribute to reduced risk of colon cancer development. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. The kinetics of free radical metathetical and addition reactions in silane solutions

    International Nuclear Information System (INIS)

    Aloni, R.

    1976-12-01

    In this work radiolytic technique was employed for the initiation of free radical chainreactions in silane solution. The kinetic analysis of the chain mechanism in various solutions enabled the determination of the Arrhenius parameters for metathesis, addition and unimolecular decomposition reactions which make up the chainpropagation sequence in the systems studied. The following radical reactions were investigated: chlorine atom abstraction from chloromethanes by SiCl 3 and Et 3 Si radicals, and chlorine atom abstraction from chloroethanes by Et 3 Si radicals; unimolecular decomposition reactions and hydrogen atom abstraction, *from the solvent, of chloroethyl radicals in triethylsilane solutions; addition and abstraction reactions of Et 3 Si radicals with chloroolefins. Arrhenius parameters were determined for abstraction of chlorine atom from CH 3 Cl, CH 2 Cl 2 , CHCl 3 and CCl 4 , by SiCl 3 radicals and from CCl 4 , CHCl 3 , CH 2 Cl 2 , CCl 3 CN, C 2 Cl 5 H, sym-C 2 Cl 4 H 2 , asym-C 2 Cl 4 H 2 , 1.1.1-C 2 Cl 3 H 3 , 1.1.1-C 2 Dl 3 F 3 and 1.1-C 2 Cl 2 H 4 by Et 3 Si radicals. (author)

  13. Distribution of free radical products among the bases of x-irradiated DNA model systems: an ESR study

    International Nuclear Information System (INIS)

    Spalletta, R.A.

    1984-01-01

    Exposure of solid state DNA to ionizing radiation results in an ESR spectrum that has been attributed to a nonstoichiometric distribution of free radicals among the bases. At low temperatures radical cations appear to be stabilized on the purines while radical anions are stabilized on the pyrimidines. This distribution could arise from at least two different mechanisms. The first, charge transfer, involves the transfer of electrons and/or holes between stacked bases. In the second, saturation asymmetry, the free radical distribution arises from differences in the dose saturation characteristics of individual bases. The present study addresses the relative importance of charge transfer versus saturation asymmetry in the production of these population differences. Radicals formed by dissolving irradiated polycrystalline pyrimidines in aqueous solutions containing NtB or PBN spin traps were analyzed using ESR. The relative importance of the two free radical production and distribution mechanisms was assessed using DNA model systems. Saturation asymmetry plays a significant role in determining the free radical population while charge transfer was unambiguously observed in only one, the complex of dAMP and TMP. The results demonstrate that any quantitative analysis of charge transfer must take saturation asymmetry into account

  14. 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.

  15. Free Radicals and Antioxidants in Cardiovascular Health and Disease

    African Journals Online (AJOL)

    Free radicals can be overproduced or the natural antioxidant system defenses weakened, first resulting in oxidative stress, and then leading to oxidative injury ... Keywords: Oxidative stress, cardiovascular disease, atherosclerosis, inflammation, cell signaling and transduction mechanisms, antioxidants, dietary phenolics.

  16. Free radical scavenging activity and phenolic contents of ...

    African Journals Online (AJOL)

    Anthocleista djalonensis extract is widely used in Nigerian folk medicine to treat conditions whose pathogenesis implicate oxidative stress, such as diabetes and hepatitis. However, little is known of the mechanism underlying these activities. In this study, the free radical scavenging potential of a methanol extract of A.

  17. Outcomes After Radical Prostatectomy in Men Receiving Prior Pelvic Radiation for Non-Prostate Malignancies

    Science.gov (United States)

    Masterson, Timothy A.; Wedmid, Alexei; Sandhu, Jaspreet S.; Eastham, James A.

    2010-01-01

    Purpose Morbidity associated with salvage radical prostatectomy for locally recurrent prostate cancer after primary radiotherapy is well documented, but little is known about the impact on surgical difficulty and outcomes for radical prostatectomy in men who have had prior pelvic radiotherapy for non-prostate malignancies. We report functional outcomes of 9 patients treated at our institution. Materials and Methods From 1993 to 2007, 9 patients underwent radical prostatectomy following external beam radiotherapy for testicular seminoma (6), anorectal cancer (2), and colon cancer (1). Clinical information was obtained from a prospective prostate cancer database. Results Radical prostatectomy was completed without identifiable injury to adjacent structures in all 9 patients. Four patients had significant pelvic fibrosis, 3 required bilateral neurovascular bundle resection. Neurovascular bundle preservation was performed in the remaining 6 patients, 4 with good preoperative erectile function. However, no patient recovered erectile function postoperatively at a median follow-up time of 75 months (range 12 to 172). Of preoperatively continent men, 57% required ≤1 pad daily and 43% were completely dry, achieving complete urinary control at a median follow-up time of 7.5 months (range 2 to 20). Two patients developed anastomotic stricture, one being associated with concomitant ureteral stricture. Conclusions Radical prostatectomy after pelvic radiotherapy for non-prostate malignancies was not associated with increased intraoperative morbidity. However, rates of anastomotic stricture, erectile dysfunction, and urinary incontinence appear to be higher than those observed after radical prostatectomy in men with no prior radiotherapy and comparable to those seen in the salvage radical prostatectomy setting. PMID:19239447

  18. A Model of Rapid Radicalization Behavior Using Agent-Based Modeling and Quorum Sensing

    Science.gov (United States)

    Schwartz, Noah; Drucker, Nick; Campbell, Kenyth

    2012-01-01

    Understanding the dynamics of radicalization, especially rapid radicalization, has become increasingly important to US policy in the past several years. Traditionally, radicalization is considered a slow process, but recent social and political events demonstrate that the process can occur quickly. Examining this rapid process, in real time, is impossible. However, recreating an event using modeling and simulation (M&S) allows researchers to study some of the complex dynamics associated with rapid radicalization. We propose to adapt the biological mechanism of quorum sensing as a tool to explore, or possibly explain, rapid radicalization. Due to the complex nature of quorum sensing, M&S allows us to examine events that we could not otherwise examine in real time. For this study, we employ Agent Based Modeling (ABM), an M&S paradigm suited to modeling group behavior. The result of this study was the successful creation of rapid radicalization using quorum sensing. The Battle of Mogadishu was the inspiration for this model and provided the testing conditions used to explore quorum sensing and the ideas behind rapid radicalization. The final product has wider applicability however, using quorum sensing as a possible tool for examining other catalytic rapid radicalization events.

  19. Anatomical landmarks of radical prostatecomy.

    Science.gov (United States)

    Stolzenburg, Jens-Uwe; Schwalenberg, Thilo; Horn, Lars-Christian; Neuhaus, Jochen; Constantinides, Costantinos; Liatsikos, Evangelos N

    2007-03-01

    In the present study, we review current literature and based on our experience, we present the anatomical landmarks of open and laparoscopic/endoscopic radical prostatectomy. A thorough literature search was performed with the Medline database on the anatomy and the nomenclature of the structures surrounding the prostate gland. The correct handling of puboprostatic ligaments, external urethral sphincter, prostatic fascias and neurovascular bundle is necessary for avoiding malfunction of the urogenital system after radical prostatectomy. When evaluating new prostatectomy techniques, we should always take into account both clinical and final oncological outcomes. The present review adds further knowledge to the existing "postprostatectomy anatomical hazard" debate. It emphasizes upon the role of the puboprostatic ligaments and the course of the external urethral sphincter for urinary continence. When performing an intrafascial nerve sparing prostatectomy most urologists tend to approach as close to the prostatic capsula as possible, even though there is no concurrence regarding the nomenclature of the surrounding fascias and the course of the actual neurovascular bundles. After completion of an intrafascial technique the specimen does not contain any periprostatic tissue and thus the detection of pT3a disease is not feasible. This especially becomes problematic if the tumour reaches the resection margin. Nerve sparing open and laparoscopic radical prostatectomy should aim in maintaining sexual function, recuperating early continence after surgery, without hindering the final oncological outcome to the procedure. Despite the different approaches for radical prostatectomy the key for better results is the understanding of the anatomy of the bladder neck and the urethra.

  20. miCLIP-MaPseq, a Substrate Identification Approach for Radical SAM RNA Methylating Enzymes.

    Science.gov (United States)

    Stojković, Vanja; Chu, Tongyue; Therizols, Gabriel; Weinberg, David E; Fujimori, Danica Galonić

    2018-06-13

    Although present across bacteria, the large family of radical SAM RNA methylating enzymes is largely uncharacterized. Escherichia coli RlmN, the founding member of the family, methylates an adenosine in 23S rRNA and several tRNAs to yield 2-methyladenosine (m 2 A). However, varied RNA substrate specificity among RlmN enzymes, combined with the ability of certain family members to generate 8-methyladenosine (m 8 A), makes functional predictions across this family challenging. Here, we present a method for unbiased substrate identification that exploits highly efficient, mechanism-based cross-linking between the enzyme and its RNA substrates. Additionally, by determining that the thermostable group II intron reverse transcriptase introduces mismatches at the site of the cross-link, we have identified the precise positions of RNA modification using mismatch profiling. These results illustrate the capability of our method to define enzyme-substrate pairs and determine modification sites of the largely uncharacterized radical SAM RNA methylating enzyme family.

  1. 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(3Pj), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH3 umbrella mode and the S(3Pj) 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 C2V 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

  2. COMPUTATIONAL STUDY OF INTERSTELLAR GLYCINE FORMATION OCCURRING AT RADICAL SURFACES OF WATER-ICE DUST PARTICLES

    International Nuclear Information System (INIS)

    Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

    2012-01-01

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH . radical and H 3 O + surface defects. The coupling of incoming CO molecules with the surface OH . radicals on the ice clusters yields the formation of the COOH . radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol –1 and –22 kcal mol –1 , respectively. The COOH . radicals couple with incoming NH=CH 2 molecules (experimentally detected in the ISM) to form the NHCH 2 COOH . radical glycine through energy barriers of 12 kcal mol –1 , exceedingly high at ISM cryogenic temperatures. Nonetheless, when H 3 O + is present, one proton may be barrierless transferred to NH=CH 2 to give NH 2 =CH 2 + . This latter may react with the COOH . radical to give the NH 2 CH 2 COOH +. glycine radical cation which can then be transformed into the NH 2 CHC(OH) 2 +. species (the most stable form of glycine in its radical cation state) or into the NH 2 CHCOOH . neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh-physical conditions of the ISM may trigger reactions of cosmochemical interest. The relevance of surface H 3 O

  3. Computational Study of Interstellar Glycine Formation Occurring at Radical Surfaces of Water-ice Dust Particles

    Science.gov (United States)

    Rimola, Albert; Sodupe, Mariona; Ugliengo, Piero

    2012-07-01

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH• radical and H3O+ surface defects. The coupling of incoming CO molecules with the surface OH• radicals on the ice clusters yields the formation of the COOH• radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol-1 and -22 kcal mol-1, respectively. The COOH• radicals couple with incoming NH=CH2 molecules (experimentally detected in the ISM) to form the NHCH2COOH• radical glycine through energy barriers of 12 kcal mol-1, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H3O+ is present, one proton may be barrierless transferred to NH=CH2 to give NH2=CH2 +. This latter may react with the COOH• radical to give the NH2CH2COOH+• glycine radical cation which can then be transformed into the NH2CHC(OH)2 +• species (the most stable form of glycine in its radical cation state) or into the NH2CHCOOH• neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh-physical conditions of the ISM may trigger reactions of cosmochemical interest. The relevance of surface H3O+ ions to facilitate chemical

  4. Free Radicals Formation of Irradiated Lyophilized Can-Cellous Human and Bovine Bone

    International Nuclear Information System (INIS)

    Abbas, Basril; Sudiro, Sutjipto; Hilmy, Nazly

    2000-01-01

    Radiation sterilization of lyophilized human and bovine bone as allograft and xenograft have been produced and used in orthopaedic practice in Indonesia routinely. It is well known from radio biologic studies that one of the most pronounce effects of ionizing radiation on biologic species produced the free radicals that influence the physico-chemical as well as the mechanical properties of irradiated bone. The aim of our study is to investigate the free radicals formation of irradiated lyophilized cancellous triple A bone (Autolyzed Antigen-Extracted Allograft) produced by Batan Research Tissue Bank in Jakarta. The cancellous triple A were prepared according to AATB (American Association of Tissue Bank) method. Gamma Irradiations was done at doses of 10, 20 and 30 kGy with a dose rate of 7,5 kGy/h at room temperature (30 o C± 2 o C). Measurements of free radicals was done at 24 o C ±1 o C within 30 minutes after irradiational and measurement were continued up to 9 months of storage using a JES-REIX ESR Spectrophotometer (JEOL) with Mn exp. ++ standard. Parameters measured, were the effects of mechanical grinding, water immersion and irradiation dose on free radicals formation in the bone. Results show that the signal area of ESR spectra from irradiated bovine bone of 30 kGy was higher than those of human bone I.e. 1,4 x 10 exp. 7 dan 6,4 x 10 exp. 6 Au (arbitrary unit)/g samples respectively. The signal of ESR spectra increased linearly with increasing dose in the range of 10-30 kGy and it will reduce about 30% caused by water immersion. The ESR signal reduced sharply after 2 days and gradually decreased up to 14 days and then became constant up to 9 months of storage at room temperature. A certain method of crushing can produce free radicals. Key Words: free radical, irradiation, allograft, xenograft, mechanical-grinding

  5. Induction of radiation resistance and radio-protective mechanism. On the reactive oxygen and free radical

    International Nuclear Information System (INIS)

    Yukawa, Osami

    2003-01-01

    Radical scavenging system for reactive oxygen species (ROS) leading to radio-protection is reviewed on findings in animals, tissues and cells. Protection against oxygen toxicity in evolution can be seen in anaerobes' superoxide dismutase (SOD) over 3500 million years ago. ROS is generated endogenously and also by radiation. However, the intracellular sites of the generated ROS are different depending on its cause. The protection is done through enzymes like SOD, peroxidase, catalase, glutathione-related enzymes and through substances like GSH, α-tocopherol, ascorbic acid etc. Induction of ROS scavenging substances related with radio-resistance includes the responses to the low dose radiation (5-50 cGy) in those enzymes described above; to middle to high dose radiation (1-30 Gy) in a similar and in other unknown mechanisms; to exposure of ROS like H 2 O 2 at low concentration; and to antioxidant treatment. The cross-resistance between radiation and drugs suggests necessity of this induction. (N.I.)

  6. Conceptual foundations of quantum mechanics

    International Nuclear Information System (INIS)

    Shimony, A.

    1989-01-01

    Radical innovation in the quantum mechanical framework such as objective indefiniteness, objective chance, objective probability, potentiality, entanglement and quantum nonlocality are discussed and related to the standard formalism. Examples are given which though problematic in classical mechanics are simply explained with these new concepts. Evidence is presented that the conceptual innovations of quantum mechanics cannot be separated from its predictive power. Proposals for solving ''the reduction of the wave packet'' anomaly are presented. Further radical innovations in quantum mechanics are anticipated. (U.K.)

  7. 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...

  8. Effect of primary and secondary radicals on chain breaks in ribosomal RNA in E. coli ribosomes

    International Nuclear Information System (INIS)

    Singh, H.; Bishop, J.

    1984-01-01

    It has been shown previously that, in dilute aerated solutions, ribosomes are inactivated by OH radicals and by secondary radicals produced from added alcohols (Singh and Vadasz 1983 a). In de-aerated solutions, both radicalH and e - sub(aq) also inactivate ribosomes (Singh and Vadasz 1983 b). The results of these studies and other on different systems (Adams et al. 1973, Aldrich and Cundall 1969, Dewey and Stein 1970, Masuda et al. 1971, Nabben et al. 1982, 1983, Samuni et al. 1980, Singh and Singh 1982) have shown that damage to biological systems occurs by diverse mechanisms. One of these mechanisms involves chain breaks in RNA (Pollard and Weller 1967). The purpose of this study was to determine which of the primary and secondary radicals cause chain breaks in ribosomal RNA (rRNA) within the ribosomes. (author)

  9. Development of a new free radical absorption capacity assay method for antioxidants: aroxyl radical absorption capacity (ARAC).

    Science.gov (United States)

    Nagaoka, Shin-ichi; Nagai, Kanae; Fujii, Yuko; Ouchi, Aya; Mukai, Kazuo

    2013-10-23

    A new free radical absorption capacity assay method is proposed with use of an aroxyl radical (2,6-di-tert-butyl-4-(4'-methoxyphenyl)phenoxyl radical) and stopped-flow spectroscopy and is named the aroxyl radical absorption capacity (ARAC) assay method. The free radical absorption capacity (ARAC value) of each tocopherol was determined through measurement of the radical-scavenging rate constant in ethanol. The ARAC value could also be evaluated through measurement of the half-life of the aroxyl radical during the scavenging reaction. For the estimation of the free radical absorption capacity, the aroxyl radical was more suitable than the DPPH radical, galvinoxyl, and p-nitrophenyl nitronyl nitroxide. The ARAC value in tocopherols showed the same tendency as the free radical absorption capacities reported previously, and the tendency was independent of an oxygen radical participating in the scavenging reaction and of a medium surrounding the tocopherol and oxygen radical. The ARAC value can be directly connected to the free radical-scavenging rate constant, and the ARAC method has the advantage of treating a stable and isolable radical (aroxyl radical) in a user-friendly organic solvent (ethanol). The ARAC method was also successfully applied to a palm oil extract. Accordingly, the ARAC method would be useful in free radical absorption capacity assay of antioxidative reagents and foods.

  10. 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).

  11. 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)

  12. Structure and Intramolecular Proton Transfer of Alanine Radical Cations

    International Nuclear Information System (INIS)

    Lee, Gab Yong

    2012-01-01

    The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the NH 2 group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [NH 3 + -CHCH 3 -COO·], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol

  13. The impact of the self-interaction error on the density functional theory description of dissociating radical cations: ionic and covalent dissociation limits.

    Science.gov (United States)

    Gräfenstein, Jürgen; Kraka, Elfi; Cremer, Dieter

    2004-01-08

    Self-interaction corrected density functional theory was used to determine the self-interaction error for dissociating one-electron bonds. The self-interaction error of the unpaired electron mimics nondynamic correlation effects that have no physical basis where these effects increase for increasing separation distance. For short distances the magnitude of the self-interaction error takes a minimum and increases then again for decreasing R. The position of the minimum of the magnitude of the self-interaction error influences the equilibrium properties of the one-electron bond in the radical cations H2+ (1), B2H4+ (2), and C2H6+ (3), which differ significantly. These differences are explained by hyperconjugative interactions in 2 and 3 that are directly reflected by the self-interaction error and its orbital contributions. The density functional theory description of the dissociating radical cations suffers not only from the self-interaction error but also from the simplified description of interelectronic exchange. The calculated differences between ionic and covalent dissociation for 1, 2, and 3 provide an excellent criterion for determining the basic failures of density functional theory, self-interaction corrected density functional theory, and other methods. Pure electronic, orbital relaxation, and geometric relaxation contributions to the self-interaction error are discussed. The relevance of these effects for the description of transition states and charge transfer complexes is shown. Suggestions for the construction of new exchange-correlation functionals are given. In this connection, the disadvantages of recently suggested self-interaction error-free density functional theory methods are emphasized. (c) 2004 American Institute of Physics

  14. Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Mingyi [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com [School of Science, Tianjin University, Tianjin 30072 (China); Wu, Tao [School of Science, Tianjin University, Tianjin 30072 (China); Zhang, Sai; Li, Xianxian [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Li, Yi, E-mail: liyi@tju.edu.cn [School of Science, Tianjin University, Tianjin 30072 (China)

    2014-12-15

    Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.

  15. Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

    International Nuclear Information System (INIS)

    Tang, Mingyi; Xu, Xiaoyang; Wu, Tao; Zhang, Sai; Li, Xianxian; Li, Yi

    2014-01-01

    Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide

  16. Research concerning ionic and free radical reactions in radiation chemistry. Progress report, September 15, 1976--September 15, 1977

    International Nuclear Information System (INIS)

    Williams, T.F.

    1977-01-01

    Progress is reported on ESR studies of fluorocarbon radicals and intermediate radicals. A detailed study was made of the dimethyl, diethyl, and di-n-propyl carbonates. Studies were continued on hydrogen-atom abstraction reactions at low temperatures with view to evaluating the contribution from quantum-mechanical tunneling. Detection of the transient dimer radical anion of acetonitrile in the upper crystalline phase at -50 0 C is reported. Abstracts of current reports are included on electron attachment to fluorocarbons hydrogen atom abstraction by methyl radicals. EPR spectra of the tetrafluoroethylene radical anion, and addition of tetrafluoroethylene to the tetrafluoroethylene radical anion

  17. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  18. 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.

  19. Copolymers containing phosphorescent iridium(III) complexes obtained by free and controlled radical polymerization techniques

    NARCIS (Netherlands)

    Ulbricht, C.; Becer, C.R.; Winter, A.; Veldman, D.; Schubert, U.S.

    2008-01-01

    A methacrylate-functionalized phosphorescent Ir(III)-complex has been synthesized, characterized, and applied as a monomer in radical copolymerizations. Together with methyl methacrylate, the complex has been copolymerized under free radical polymerization conditions. Aiming for host-guest-systems,

  20. Structure-function relations in physiology education: Where's the mechanism?

    Science.gov (United States)

    Lira, Matthew E; Gardner, Stephanie M

    2017-06-01

    Physiology demands systems thinking: reasoning within and between levels of biological organization and across different organ systems. Many physiological mechanisms explain how structures and their properties interact at one level of organization to produce emergent functions at a higher level of organization. Current physiology principles, such as structure-function relations, selectively neglect mechanisms by not mentioning this term explicitly. We explored how students characterized mechanisms and functions to shed light on how students make sense of these terms. Students characterized mechanisms as 1 ) processes that occur at levels of organization lower than that of functions; and 2 ) as detailed events with many steps involved. We also found that students produced more variability in how they characterized functions compared with mechanisms: students characterized functions in relation to multiple levels of organization and multiple definitions. We interpret these results as evidence that students see mechanisms as holding a more narrow definition than used in the biological sciences, and that students struggle to coordinate and distinguish mechanisms from functions due to cognitive processes germane to learning in many domains. We offer the instructional suggestion that we scaffold student learning by affording students opportunities to relate and also distinguish between these terms so central to understanding physiology. Copyright © 2017 the American Physiological Society.

  1. Robotic Radical Cystectomy: Where are We Today, Where will We be Tomorrow?

    Directory of Open Access Journals (Sweden)

    Kyle A. Richards

    2010-01-01

    Full Text Available While open radical cystectomy remains the gold-standard treatment for muscle-invasive bladder cancer and high-risk non–muscle invasive disease, robotic assisted radical cystectomy (RARC has been gaining popularity over the past decade. The robotic approach has the potential advantages of less intraoperative blood loss, shorter hospital stay, less post-operative narcotic requirement, quicker return of bowel function, and earlier convalescence with an acceptable surgical learning curve for surgeons adept at robotic radical prostatectomy. While short to intermediate term oncologic results from several small RARC series are promising, bladder cancer remains a potentially lethal malignancy necessitating long-term follow-up. This article aims to review the currently published literature, important technical aspects of the operation, oncologic and functional outcomes, and the future direction of RARC.

  2. Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

    Science.gov (United States)

    De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

    2005-01-21

    Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

  3. Study by electron spin resonance of the free radicals created under irradiation in glycine

    International Nuclear Information System (INIS)

    Thomet, P.; Rassat, A.; Servoz-Gavin, P.; Choudens, H. de

    1967-01-01

    The free radicals created by different radiations in glycine are measured by electron spin resonance and their number is evaluated in function of the absorbed dose. This number decreases when the LET of the radiations increases ; in other words,high LET radiations gives less radiochemical effects; in contrary with the fact that high LET radiations creates more damage in biological materials. The decreasing with time of the number of free radicals and the speed of this decrease is a function of temperature; by the study of the kinetics of this decrease, an attempt has been made to prove the presence of three radicals. (authors) [fr

  4. Atmospheric implications of simultaneous nighttime measurements of NO3 radicals and hono

    International Nuclear Information System (INIS)

    Pitts, J.N. Jr.; Biermann, H.W.; Atkinson, R.; Winer, A.M.

    1984-01-01

    Atmospheric concentrations of gaseous HONO and the NO 3 radical were measured simultaneously for the first time using long path differential optical absorption spectroscopy. Diurnal profiles are reported for two successive nights following days of moderate pollution at Riverside, California, together with concurrent measurements of NO 2 , O 3 and NO concentrations and an upper limit for HCHO levels. These measurements permit an examination of selected aspects of the nighttime atmospheric chemistry of HONO and the NO 3 radical and related species. Our data do not support a recently proposed homogeneous gas phase mechanism for HONO formation initiated by the reaction of the NO 3 radical with HCHO

  5. 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.

  6. Preparing polymer brushes on polytetrafluoroethylene films by free radical polymerization

    International Nuclear Information System (INIS)

    Sun Wei; Chen Yiwang; Deng Qilan; Chen Lie; Zhou Lang

    2006-01-01

    Films of polytetrafluoroethylene (PTFE) were exposed to sodium naphthalenide (Na/naphtha) etchant so as to defluorinate the surface for obtaining hydroxyl functionality. Surface-initiators were immobilized on the PTFE films by esterification of 4,4'-azobis(4-cyanopentanoic acid) (ACP) and the hydroxyl groups covalently linked to the surface. Grafting of polymer brushes on the PTFE films was carried out by the surface-initiated free radical polymerization. Homopolymers brushes of methyl methacrylate (MMA) were prepared by free radical polymerization from the azo-functionalized PTFE surface. The chemical composition and topography of the graft-functionalized PTFE surfaces were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance (ATR) FT-IR spectroscopy and atomic force microscopy (AFM). Water contact angles on PTFE films were reduced by surface grafting of MMA

  7. Exploring the Role of Persulfate in the Activation Process: Radical Precursor Versus Electron Acceptor.

    Science.gov (United States)

    Yun, Eun-Tae; Yoo, Ha-Young; Bae, Hyokwan; Kim, Hyoung-Il; Lee, Jaesang

    2017-09-05

    This study elucidates the mechanism behind persulfate activation by exploring the role of various oxyanions (e.g., peroxymonosulfate, periodate, and peracetate) in two activation systems utilizing iron nanoparticle (nFe 0 ) as the reducing agent and single-wall carbon nanotubes (CNTs) as electron transfer mediators. Since the tested oxyanions serve as both electron acceptors and radical precursors in most cases, oxidative degradation of organics was achievable through one-electron reduction of oxyanions on nFe 0 (leading to radical-induced oxidation) and electron transfer mediation from organics to oxyanions on CNTs (leading to oxidative decomposition involving no radical formation). A distinction between degradative reaction mechanisms of the nFe 0 /oxyanion and CNT/oxyanion systems was made in terms of the oxyanion consumption efficacy, radical scavenging effect, and EPR spectral analysis. Statistical study of substrate-specificity and product distribution implied that the reaction route induced on nFe 0 varies depending on the oxyanion (i.e., oxyanion-derived radical), whereas the similar reaction pathway initiates organic oxidation in the CNT/oxyanion system irrespective of the oxyanion type. Chronoamperometric measurements further confirmed electron transfer from organics to oxyanions in the presence of CNTs, which was not observed when applying nFe 0 instead.

  8. Serum Hydroxyl Radical Scavenging Capacity as Quantified with Iron-Free Hydroxyl Radical Source

    Science.gov (United States)

    Endo, Nobuyuki; Oowada, Shigeru; Sueishi, Yoshimi; Shimmei, Masashi; Makino, Keisuke; Fujii, Hirotada; Kotake, Yashige

    2009-01-01

    We have developed a simple ESR spin trapping based method for hydroxyl (OH) radical scavenging-capacity determination, using iron-free OH radical source. Instead of the widely used Fenton reaction, a short (typically 5 seconds) in situ UV-photolysis of a dilute hydrogen peroxide aqueous solution was employed to generate reproducible amounts of OH radicals. ESR spin trapping was applied to quantify OH radicals; the decrease in the OH radical level due to the specimen’s scavenging activity was converted into the OH radical scavenging capacity (rate). The validity of the method was confirmed in pure antioxidants, and the agreement with the previous data was satisfactory. In the second half of this work, the new method was applied to the sera of chronic renal failure (CRF) patients. We show for the first time that after hemodialysis, OH radical scavenging capacity of the CRF serum was restored to the level of healthy control. This method is simple and rapid, and the low concentration hydrogen peroxide is the only chemical added to the system, that could eliminate the complexity of iron-involved Fenton reactions or the use of the pulse-radiolysis system. PMID:19794928

  9. Radical prostatectomy: evolution of surgical technique from the laparoscopic point of view

    Directory of Open Access Journals (Sweden)

    Xavier Cathelineau

    2010-04-01

    Full Text Available PURPOSE: To review the literature and present a current picture of the evolution in radical prostatectomy from the laparoscopic point of view. MATERIALS AND METHODS: We conducted an extensive Medline literature search. Articles obtained regarding laparoscopic radical prostatectomy (LRP and our experience at Institut Montsouris were used for reassessing anatomical and technical issues in radical prostatectomy. RESULTS: LRP nuances were reassessed by surgical teams in order to verify possible weaknesses in their performance. Our basic approach was to carefully study the anatomy and pioneer open surgery descriptions in order to standardized and master a technique. The learning curve is presented in terms of an objective evaluation of outcomes for cancer control and functional results. In terms of technique-outcomes, there are several key elements in radical prostatectomy, such as dorsal vein control-apex exposure and nerve sparing with particular implications in oncological and functional results. Major variations among the surgical teams' performance and follow-up prevented objective comparisons in radical prostatectomy. The remarkable evolution of LRP needs to be supported by comprehensive results. CONCLUSIONS: Radical prostatectomy is a complex surgical operation with difficult objectives. Surgical technique should be standardized in order to allow an adequate and reliable performance in all settings, keeping in mind that cancer control remains the primary objective. Reassessing anatomy and a return to basics in surgical technique is the means to improve outcomes and overcome the difficult task of the learning curve, especially in minimally access urological surgery.

  10. Coupling functions: Universal insights into dynamical interaction mechanisms

    Science.gov (United States)

    Stankovski, Tomislav; Pereira, Tiago; McClintock, Peter V. E.; Stefanovska, Aneta

    2017-10-01

    The dynamical systems found in nature are rarely isolated. Instead they interact and influence each other. The coupling functions that connect them contain detailed information about the functional mechanisms underlying the interactions and prescribe the physical rule specifying how an interaction occurs. A coherent and comprehensive review is presented encompassing the rapid progress made recently in the analysis, understanding, and applications of coupling functions. The basic concepts and characteristics of coupling functions are presented through demonstrative examples of different domains, revealing the mechanisms and emphasizing their multivariate nature. The theory of coupling functions is discussed through gradually increasing complexity from strong and weak interactions to globally coupled systems and networks. A variety of methods that have been developed for the detection and reconstruction of coupling functions from measured data is described. These methods are based on different statistical techniques for dynamical inference. Stemming from physics, such methods are being applied in diverse areas of science and technology, including chemistry, biology, physiology, neuroscience, social sciences, mechanics, and secure communications. This breadth of application illustrates the universality of coupling functions for studying the interaction mechanisms of coupled dynamical systems.

  11. Radical Transparency in Journalism: Digital Evolutions from Historical Precedents

    Directory of Open Access Journals (Sweden)

    Luke Justin Heemsbergen

    2013-06-01

    Full Text Available This paper argues that transparency projects retain a political hue from the social-technological context from which they are created. Thus, radical transparency is considered as an opportunity to evolve both journalistic and democratic practices. Transparency in practice reveals diverse expectations of how journalists reporting should be used, and these expectations in turn, seem dependent on specific worldviews. This paper presents a comparative analysis of the effects of the current exemplar of radical journalism, WikiLeaks. It compares Wikileaks to its historical equivalents, including Hansard in the 18th century, and the reporting of open diplomacy in the early 20th century. This analysis shows how journalism evolves along with radical transparency projects, and how the current context of networked radical transparency can, and will, be made into news with specific political effects. In conclusion, this paper argues that practitioners should be aware of the political hues that new transparency mechanisms afford. Being cognizant of context and design choices can increase the degree to which new initiatives can have a deep systemic impact—as well as acknowledge the qualities and repercussions of that impact.

  12. Some biochemical consequences of the spatial distribution of ionizing radiation-produced free radicals

    International Nuclear Information System (INIS)

    Ward, J.F.

    1981-01-01

    Ionizing radiation deposits energy nonhomogeneously in the medium through which it passes. Mozumder and Magee (Radiat. Res. 28, 203-214(1966)) have classified the events as spurs, blobs, and short tracks. These are defined by size and amount of energy deposited. Thus the initial chemically reactive species are distributed in an inhomogeneous manner. In these volumes of high radical concentration, radical-radical reactions can occur which can only be scavenged by solutes at high concentration. Making the reasonable assumption that similar events occur intracellularly, the consequences of such events must be considered. In the case of DNA, several authors have shown that OH radicals diffuse only tens of angstroms prior to reaction. In the volume from which these radicals originate, DNA is necessarily at high concentration and consequently will interact with the radicals formed in the spur, etc. Such events are probably the source of radiation-production double-strand breaks in cellular DNA. However, the radicals cause other types of damage than strand breaks-potential strand breaks and base damage. An attempt is made to present the interrelation of multiply damaged sites - their constitution, the problems they present to cell repair mechanisms, and their possible relationship to cell survival

  13. Radical transfer between proteins: role of tyrosine, tryptophan and protein peroxyl radicals

    International Nuclear Information System (INIS)

    Irwin, J.A.; Ostdal, H.; Davies, M.J.

    1998-01-01

    Reaction of the Fe(III) forms of the heme proteins myoglobin (Mb) and horseradish peroxidase (HRP) with H 2 O 2 gives rise to high-oxidation-state heme-derived species which can be described as a Fe(IV)-oxo porphyrin radical-cation ('Compound 1'). In the case of Mb, the Fe(IV)-oxo porphyrin radical-cation undergoes rapid electron transfer with the surrounding protein to give protein (globin)-derived radicals and an Fe(lV)-oxo species ('Compound 2'). The globin-derived radicals have been shown to be located at two (or more) sites: Tyr-103 or Trp-14, with the latter radical known to react with oxygen to give a Trp-derived peroxyl radical (Mb-Trp-OO*). With HRP, the Fe(lV)-oxo porphyrin radical-cation carries out two successive one-electron oxidation reactions at the exposed heme edge to give firstly 'Compound 2' [the Fe(lV)oxo species] and then the resting Fe(III) state of the enzyme. n this study we have investigated whether the Trp-14 peroxyl radical from Mb and the Compound 1 and 2 species from HRP (in the absence and presence of free Tyr) can oxidise amino acids, peptides and proteins. Such reactions constitute intermolecular protein-to-protein radical transfer reactions and hence protein chain-oxidation. We have also examined whether these oxidants react with antioxidants. Reaction of these heme-protein derived oxidants with amino acids, proteins and antioxidants has been carried out at room temperature for defined periods of time before freeze-quenching to 77K to halt reaction. The radical species present in the reaction system at the time of freezing were subsequently examined by EPR spectroscopy at 77K. Three free amino acids, Tyr, Trp and Cys (with Cys the least efficient) have been shown to react rapidly with Mb-Trp-OO*, as evidenced by the loss of the characteristic EPR features of Mb-Trp-OO* on inclusion of increasing concentrations of the amino acids. All other amino acids are much less reactive. Evidence has also been obtained for (inefficient) hydrogen

  14. Nitroxyl free radicals formed from hindered amine light stabilizers under 60Co γ-ray irradiation

    International Nuclear Information System (INIS)

    Wang Huiliang; Chen Wenxiu

    2006-01-01

    Nitroxyl free radicals formed from several low molecular weight (LMW) hindered amine light stabilizers (HALS) under 60 Co γ-ray irradiation was studied with electron spin resonance (ESR) spectroscopy. All the HALSs irradiated in air formed nitroxyl free radicals under irradiation in air. For most of the HALSs, concentration of the nitroxyl free radicals increased linearly and quickly with absorbed dose in 0-10 kGy range, but increased slowly, or even kept constant, with doses of greater than 10 kGy. Concentration of nitroxyl free radicals formed from LMW HALS was usually higher than high molecular weight HALS. Tetramethyl HALS was easier to form nitroxyl free radicals than pentamethyl HLAS. Concentration of nitroxyl free radicals formed from the samples irradiated in oxygen was about two times higher than that the samples irradiated in air. Mechanisms of the nitroxyl free radical formation from the γ-ray irradiated HALSs were was discussed. (authors)

  15. Quantum mechanics of history: The decoherence functional in quantum mechanics

    International Nuclear Information System (INIS)

    Dowker, H.F.; Halliwell, J.J.

    1992-01-01

    We study a formulation of quantum mechanics in which the central notion is that of a quantum-mechanical history---a sequence of events at a succession of times. The primary aim is to identify sets of ''decoherent'' (or ''consistent'') histories for the system. These are quantum-mechanical histories suffering negligible interference with each other, and, therefore, to which probabilities may be assigned. These histories may be found for a given system using the so-called decoherence functional. When the decoherence functional is exactly diagonal, probabilities may be assigned to the histories, and all probability sum rules are satisfied exactly. We propose a condition for approximate decoherence, and argue that it implies that most probability sum rules will be satisfied to approximately the same degree. We also derive an inequality bounding the size of the off-diagonal terms of the decoherence functional. We calculate the decoherence functional for some simple one-dimensional systems, with a variety of initial states. For these systems, we explore the extent to which decoherence is produced using two different types of coarse graining. The first type of coarse graining involves imprecise specification of the particle's position. The second involves coupling the particle to a thermal bath of harmonic oscillators and ignoring the details of the bath (the Caldeira-Leggett model). We argue that both types of coarse graining are necessary in general. We explicitly exhibit the degree of decoherence as a function of the temperature of the bath, and of the width to within which the particle's position is specified. We study the diagonal elements of the decoherence functional, representing the probabilities for the possible histories of the system

  16. Pertinent issues related to laparoscopic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Sidney C. Abreu

    2003-12-01

    Full Text Available PURPOSE: We describe the critical steps of the laparoscopic radical prostatectomy (LRP technique and discuss how they impact upon the pertinent issues regarding prostate cancer surgery: blood loss, potency and continence. RESULTS: A major advantage of LRP is the reduced operative blood loss. The precise placement of the dorsal vein complex stitch associated with the tamponading effect of the CO2 pneumoperitoneum significantly decrease venous bleeding, which is the main source of blood loss during radical prostatectomy. At the Cleveland Clinic, the average blood loss of our first 100 patients was 322.5 ml, resulting in low transfusion rates. The continuous venous bleeding narrowed pelvic surgical field and poor visibility can adversely impact on nerve preservation during open radical prostatectomy. Laparoscopy, with its enhanced and magnified vision in a relatively bloodless field allows for excellent identification and handling of the neurovascular bundles. During open retropubic radical prostatectomy, the pubic bone may impair visibility and access to the urethral stump, and the surgeon must tie the knots relying on tactile sensation alone. Consequently, open prostatectomy is associated with a prolonged catheterization period of 2 - 3 weeks. Comparatively, during laparoscopic radical prostatectomy all sutures are meticulously placed and each is tied under complete visual control, resulting in a precise mucosa-to-mucosa approximation. CONCLUSION: The laparoscopic approach may represent a reliable less invasive alternative to the conventional open approach. Despite the encouraging preliminary anatomical and functional outcomes, prospective randomized comparative trials are required to critically evaluate the role of laparoscopy for this sophisticated and delicate operation.

  17. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    It has been reported that a growing number of youngsters from Western Europe are engaging in conflicts motivated by religious and political conflicts in the Middle East. This paper explores the reasons behind this seemingly religious radicalization from the point of view of the youngsters...... youngsters and parents of youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging and recognition have to be taken into account in our understanding of homegrown religious radicalization...

  18. Photodissociation dynamics and spectroscopy of free radical combustion intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Osborn, David Lewis [Univ. of California, Berkeley, CA (United States)

    1996-12-01

    The photodissociation spectroscopy and dynamics of free radicals is studied by the technique of fast beam photofragment translational spectroscopy. Photodetachment of internally cold, mass-selected negative ions produces a clean source of radicals, which are subsequently dissociated and detected. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states of the radical. In addition, the photodissociation dynamics, product branching ratios, and bond energies are probed at fixed photon energies by measuring the translational energy, P(ET), and angular distribution of the recoiling fragments using a time- and position-sensitive detector. Ab initio calculations are combined with dynamical and statistical models to interpret the observed data. The photodissociation of three prototypical hydrocarbon combustion intermediates forms the core of this work.

  19. Electron paramagnetic resonance study of radicals formed by radiolysis at 77 K of nitroalkanes and of their solutions in organic glasses. Chromatography analysis of radiolysis products of nitromethane in ethanol solution in a vitreous medium

    International Nuclear Information System (INIS)

    Rosilio, C.

    1969-01-01

    With a view to explaining the formation of the final products resulting from the photolysis and the radiolysis of nitro-alkanes, we have attempted to identify the paramagnetic species formed as intermediates during the radiolysis. Our work has covered the structure and the reactivity of the radicals formed by 7 irradiation of the nitrogen containing derivatives at 77 K, and on the mechanism of formation and of disappearance of these radicals in the various matrices used. The radicals resulting from the removal of a hydrogen atom in the α position of the NO 2 group, and the radicals resulting from addition reactions on the nitrogen group characterized by an unpaired electron on the nitrogen have been identified, either during the radiolysis of pure nitroalkanes, or during the radiolysis of nitro-alkanes in solution in organic glasses at 77 K. A study has been made of the conformation and the movements of radicals in the matrices, and the mechanism of formation of the observed radicals produced generally by the capture by the nitro-alkanes of primary radiolysis species. The nitro-alkanes in ethanol solution can behave as traps both for electrons and for free radicals. The study of the radiolysis of nitro-alkanes in solution in a polar ethanol glass has been completed with chemical analyses on the final radiolysis products; it has been possible to deduce the capture efficiency of trapped electrons and of free radicals by nitro-alkanes in ethanol. For this we have determined the radio-chemical yields of hydrogen, acetaldehyde and glycol as a function of the capture agent concentration, for the nitro-methane-ethanol system. A mechanism for the disappearance of the observed radicals is proposed. (author) [fr

  20. Atmospheric chemistry of isoflurane, desflurane, and sevoflurane: kinetics and mechanisms of reactions with chlorine atoms and OH radicals and global warming potentials.

    Science.gov (United States)

    Sulbaek Andersen, Mads P; Nielsen, Ole J; Karpichev, Boris; Wallington, Timothy J; Sander, Stanley P

    2012-06-21

    The smog chamber/Fourier-transform infrared spectroscopy (FTIR) technique was used to measure the rate coefficients k(Cl + CF(3)CHClOCHF(2), isoflurane) = (4.5 ± 0.8) × 10(-15), k(Cl + CF(3)CHFOCHF(2), desflurane) = (1.0 ± 0.3) × 10(-15), k(Cl + (CF(3))(2)CHOCH(2)F, sevoflurane) = (1.1 ± 0.1) × 10(-13), and k(OH + (CF(3))(2)CHOCH(2)F) = (3.5 ± 0.7) × 10(-14) cm(3) molecule(-1) in 700 Torr of N(2)/air diluent at 295 ± 2 K. An upper limit of 6 × 10(-17) cm(3) molecule(-1) was established for k(Cl + (CF(3))(2)CHOC(O)F). The laser photolysis/laser-induced fluorescence (LP/LIF) technique was employed to determine hydroxyl radical rate coefficients as a function of temperature (241-298 K): k(OH + CF(3)CHFOCHF(2)) = (7.05 ± 1.80) × 10(-13) exp[-(1551 ± 72)/T] cm(3) molecule(-1); k(296 ± 1 K) = (3.73 ± 0.08) × 10(-15) cm(3) molecule(-1), and k(OH + (CF(3))(2)CHOCH(2)F) = (9.98 ± 3.24) × 10(-13) exp[-(969 ± 82)/T] cm(3) molecule(-1); k(298 ± 1 K) = (3.94 ± 0.30) × 10(-14) cm(3) molecule(-1). The rate coefficient of k(OH + CF(3)CHClOCHF(2), 296 ± 1 K) = (1.45 ± 0.16) × 10(-14) cm(3) molecule(-1) was also determined. Chlorine atoms react with CF(3)CHFOCHF(2) via H-abstraction to give CF(3)CFOCHF(2) and CF(3)CHFOCF(2) radicals in yields of approximately 83% and 17%. The major atmospheric fate of the CF(3)C(O)FOCHF(2) alkoxy radical is decomposition via elimination of CF(3) to give FC(O)OCHF(2) and is unaffected by the method used to generate the CF(3)C(O)FOCHF(2) radicals. CF(3)CHFOCF(2) radicals add O(2) and are converted by subsequent reactions into CF(3)CHFOCF(2)O alkoxy radicals, which decompose to give COF(2) and CF(3)CHFO radicals. In 700 Torr of air 82% of CF(3)CHFO radicals undergo C-C scission to yield HC(O)F and CF(3) radicals with the remaining 18% reacting with O(2) to give CF(3)C(O)F. Atmospheric oxidation of (CF(3))(2)CHOCH(2)F gives (CF(3))(2)CHOC(O)F in a molar yield of 93 ± 6% with CF(3)C(O)CF(3) and HCOF as minor products. The IR

  1. 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.

  2. Laparoscopic radical trachelectomy.

    Science.gov (United States)

    Rendón, Gabriel J; Ramirez, Pedro T; Frumovitz, Michael; Schmeler, Kathleen M; Pareja, Rene

    2012-01-01

    The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old female with stage IB1 adenocarcinoma of the cervix who desired future fertility. She underwent a laparoscopic radical trachelectomy and bilateral pelvic lymph node dissection. The operative time was 340 min, and the estimated blood loss was 100mL. There were no intraoperative or postoperative complications. The final pathology showed no evidence of residual disease, and all pelvic lymph nodes were negative. At 20 mo of follow-up, the patient is having regular menses but has not yet attempted to become pregnant. There is no evidence of recurrence. Laparoscopic radical trachelectomy with pelvic lymphadenectomy in a young woman who desires future fertility may also be an alternative technique in the treatment of early cervical cancer in developing countries.

  3. Evolution of material properties during free radical photopolymerization

    Science.gov (United States)

    Wu, Jiangtao; Zhao, Zeang; Hamel, Craig M.; Mu, Xiaoming; Kuang, Xiao; Guo, Zaoyang; Qi, H. Jerry

    2018-03-01

    Photopolymerization is a widely used polymerization method in many engineering applications such as coating, dental restoration, and 3D printing. It is a complex chemical and physical process, through which a liquid monomer solution is rapidly converted to a solid polymer. In the most common free-radical photopolymerization process, the photoinitiator in the solution is exposed to light and decomposes into active radicals, which attach to monomers to start the polymerization reaction. The activated monomers then attack Cdbnd C double bonds of unsaturated monomers, which leads to the growth of polymer chains. With increases in the polymer chain length and the average molecular weight, polymer chains start to connect and form a network structure, and the liquid polymer solution becomes a dense solid. During this process, the material properties of the cured polymer change dramatically. In this paper, experiments and theoretical modeling are used to investigate the free-radical photopolymerization reaction kinetics, material property evolution and mechanics during the photopolymerization process. The model employs the first order chemical reaction rate equations to calculate the variation of the species concentrations. The degree of monomer conversion is used as an internal variable that dictates the mechanical properties of the cured polymer at different curing states, including volume shrinkage, glass transition temperature, and nonlinear viscoelastic properties. To capture the nonlinear behavior of the cured polymer under low temperature and finite deformation, a multibranch nonlinear viscoelastic model is developed. A phase evolution model is used to describe the mechanics of the coupling between the crosslink network evolution and mechanical loading during the curing process. The comparison of the model and the experimental results indicates that the model can capture property changes during curing. The model is further applied to investigate the internal stress

  4. Radical Evil

    Directory of Open Access Journals (Sweden)

    Carlos Manrique

    2007-12-01

    Full Text Available There is an aporia in Kant’s analysis of evil: he defines radical evilas an invisible disposition of the will, but he also demands an inferential connection between visible evil actions and this invisible disposition. This inference,however, undermines the radical invisibility of radical evil according to Kant’s own definition of the latter. Noting how this invisibility of moral worth is a distinctive feature of Kant’s approach to the moral problem, the paper then asks why, in the Groundwork, he nonetheless forecloses a question about evil that seems to be consistent with this approach. It is argued that to account for this aporia and this foreclosure, one has to interrogate the way in which the category of religion orients Kant’s incipient philosophy of history in Die Religion.

  5. Tandem Michael addition/radical cyclizations for the construction of highly functionalized cyclopentanes

    Czech Academy of Sciences Publication Activity Database

    Holan, Martin; Pohl, Radek; Císarová, I.; Jahn, Ullrich

    2012-01-01

    Roč. 106, - (2012), s1298-s1298 ISSN 0009-2770. [EuCheMS Chemistry Congress /4./. 26.08.2012-30.08.2012, Prague] Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclization * diastereoselectivity * Michael addiction * radical reactions * domino reactions Subject RIV: CC - Organic Chemistry

  6. Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions

    Czech Academy of Sciences Publication Activity Database

    Holan, Martin; Pohl, Radek; Císařová, I.; Klepetářová, Blanka; Jones, P. G.; Jahn, Ullrich

    2015-01-01

    Roč. 21, č. 27 (2015), s. 9877-9888 ISSN 0947-6539 R&D Projects: GA ČR GA13-40188S Institutional support: RVO:61388963 Keywords : cyclization * domino reactions * electron transfer * Michael addition * radical reactions Subject RIV: CC - Organic Chemistry Impact factor: 5.771, year: 2015

  7. Hyperfine interactions of a muoniated ethyl radical in supercritical CO2

    International Nuclear Information System (INIS)

    Cormier, Philip; Taylor, Becky; Ghandi, Khashayar

    2009-01-01

    A muoniated ethyl radical was studied in supercritical carbon dioxide. The muon and the proton hyperfine coupling constants were measured over temperatures ranging from 305 to 475 K, and a density range from 0.2 to 0.7 (g cm -3 ). A decrease was found in the muon hyperfine coupling constants as a function of the density, which can be attributed to the interaction between the CO 2 molecule and the p-orbital of the ethyl radical. The changes to the α-proton and β-proton hyperfine coupling constants with density are attributed to changes in the overall geometry in the formed radical. This system was modeled using quantum calculations.

  8. Distribution of stable free radicals among amino acids of isolated soy proteins.

    Science.gov (United States)

    Lei, Qingxin; Liebold, Christopher M; Boatright, William L; Shah Jahan, M

    2010-09-01

    Application of deuterium sulfide to powdered isolated soy proteins (ISP) was used to quench stable free radicals and produce a single deuterium label on amino acids where free radicals reside. The deuterium labels rendered increases of isotope ratio for the specific ions of radical-bearing amino acids. Isotope ratio measurements were achieved by gas chromatography/mass spectrometry (GC/MS) analyses after the amino acids were released by acidic hydrolysis and converted to volatile derivatives with propyl chloroformate. The isotope enrichment data showed the stable free radicals were located on Ala, Gly, Leu, Ile, Asx (Asp+Asn), Glx (Glu+Gln), and Trp but not on Val, Pro, Met, Phe, Lys, and His. Due to the low abundance of Ser, Thr, and Cys derivatives and the impossibility to accurately measure their isotope ratios, the radical bearing status for these amino acids remained undetermined even though their derivatives were positively identified from ISP hydrolysates. The relative isotope enrichment for radical-bearing amino acids Ala, Gly, Leu, Ile, Asx (Asp+Asn), Glx (Glu+Gln), and Trp were 8.67%, 2.96%, 2.90%, 3.94%, 6.03%, 3.91%, and 21.48%, respectively. Isotope ratio increase for Tyr was also observed but further investigation revealed such increase was mainly from nonspecific deuterium-hydrogen exchange not free radical quenching. The results obtained from the present study provide important information for a better understanding of the mechanisms of free radical formation and stabilization in "dry" ISP.

  9. Mechanisms of free radical chemistry and biochemistry of benzene

    International Nuclear Information System (INIS)

    Karam, L.R.; Simic, M.G.

    1989-01-01

    o-Tyrosine (o-Tyr) was used as a specific biomarker for OH radicals generated in biosystems. Specificity of o-Tyr as an OH biomarker was based on previous studied in systems exposed to ionizing radiations. Fresh muscle tissue incubated with benzene for 1 hr at 38 degree C exhibits formation of o-Tyr as seen in the cases of ethanol- and carbon tetrachloride-exposed systems. Gas chromatography/mass spectrometry selective ion monitoring measurements of o-Tyr yields in chicken breast muscle incubated with water or benzene indicate levels of less than 0.1 ppm and 3.0 ± 0.5 ppm of o-Tyr, respectively. Formation of OH is presumed to originate via a Haber-Weiss reaction of H 2 O 2 with Fe (II) preceded by the formation of O 2 and H 2 O 2 from distorted mitochondria

  10. Free radicals in chemical carcinogenesis.

    Science.gov (United States)

    Clemens, M R

    1991-12-15

    During the past decade, remarkable progress has been made in our understanding of cancer-causing agents, mechanisms of cancer formation and the behavior of cancer cells. Cancer is characterized primarily by an increase in the number of abnormal cells derived from a given normal tissue, invasion of adjacent tissues by these abnormal cells, and lymphatic or blood-borne spread of malignant cells to regional lymph nodes and to distant sites (metastasis). It has been estimated that about 75-80% of all human cancers are environmentally induced, 30-40% of them by diet. Only a small minority, possibly no more than 2% of all cases, result purely from inherent genetic changes. Several lines of evidence confirm that the fundamental molecular event or events that cause a cell to become malignant occur at the level of the DNA and a variety of studies indicate that the critical molecular event in chemical carcinogenesis is the interaction of the chemical agent with DNA. The demonstration that DNA isolated from tumor cells can transfect normal cells and render them neoplastic provides direct proof that an alteration of the DNA is responsible for cancer. The transforming genes, or oncogenes, have been identified by restriction endonuclease mapping. One of the characteristics of tumor cells generated by transformation with viruses, chemicals, or radiation is their reduced requirement for serum growth factors. A critical significance of electrophilic metabolites of carcinogenes in chemical carcinogenesis has been demonstrated. A number of "proximate" and "ultimate" metabolites, especially those of aromatic amines, were described. The "ultimate" forms of carcinogens actually interact with cellular constituents to cause neoplastic transformation and are the final metabolic products in most pathways. Recent evidence indicates that free radical derivatives of chemical carcinogens may be produced both metabolically and nonenzymatically during their metabolism. Free radicals carry no

  11. Development of sensors for monitoring oxygen and free radicals in plant physiology

    Science.gov (United States)

    Chaturvedi, Prachee

    Oxygen plays a critical role in the physiology of photosynthetic organisms, including bioenergetics, metabolism, development, and stress response. Oxygen levels affect photosynthesis, respiration, and alternative oxidase pathways. Likewise, the metabolic rate of spatially distinct plant cells (and therefore oxygen flux) is known to be affected by biotic stress (e.g., herbivory) and environmental stress (e.g., salt/nutrient stress). During aerobic metabolism, cells produce reactive oxygen species (ROS) as a by product. Plants also produce ROS during adaptation to stress (e.g., abscisic acid (ABA) mediated stress responses). If stress conditions are prolonged, ROS levels surpass the capacity of detoxifying mechanisms within the cell, resulting in oxidative damage. While stress response pathways such as ABA-mediated mechanisms have been well characterized (e.g., water stress, inhibited shoot growth, synthesis of storage proteins in seeds), the connection between ROS production, oxygen metabolism and stress response remains unknown. In part, this is because details of oxygen transport at the interface of cell(s) and the surrounding microenvironment remains nebulous. The overall goal of this research was to develop oxygen and Free radical sensors for studying stress signaling in plants. Recent developments in nanomaterials and data acquisition systems were integrated to develop real-time, non-invasive oxygen and Free radical sensors. The availability of these sensors for plant physiologists is an exciting opportunity to probe the functional realm of cells and tissues in ways that were not previously possible.

  12. Renal function and urological complications after radical hysterectomy with postoperative radiotherapy and platinum-based chemotherapy for cervical cancer.

    Science.gov (United States)

    Okadome, Masao; Saito, Toshiaki; Kitade, Shoko; Ariyoshi, Kazuya; Shimamoto, Kumi; Kawano, Hiroyuki; Minami, Kazuhito; Nakamura, Motonobu; Shimokawa, Mototsugu; Okushima, Kazuhiro; Kubo, Yuichiro; Kunitake, Naonobu

    2018-02-01

    We aimed to clarify renal functional changes long term and serious urological complications in women with cervical cancer who undergo radical hysterectomy followed by pelvic radiotherapy and/or platinum-based chemotherapy to treat the initial disease. Data on 380 women who underwent radical hysterectomy at the National Kyushu Cancer Center from January 1997 to December 2013 were reviewed. Main outcome measures were the estimated glomerular filtration rate (eGFR) and monitored abnormal urological findings. Postoperative eGFR was significantly lower than preoperative eGFR in 179 women with surgery alone and in 201 women with additional pelvic radiotherapy and/or chemotherapy (both P types of univariate analyses for eGFR reduction in women after treatment showed that older age, advanced stage, pelvic radiotherapy, and platinum-based chemotherapy were significant variables on both analyses. Two types of multivariate analyses showed that platinum-based chemotherapy or pelvic radiotherapy were associated with impaired renal function (odds ratio 1.96, 95% confidence interval 1.08-3.54 and odds ratio 2.85, 95% confidence interval 1.12-7.24, for the respective analyses). There was a higher rate of bladder wall thickening in women with pelvic radiotherapy had than those without it (17.4% vs. 2.7%, P chemotherapy and/or postoperative pelvic radiotherapy. Serious and life-threatening urological complications are rare, but surgeons should be aware of the possibility during the long follow-up. © The Author 2017. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  13. A statistical mechanical approach to restricted integer partition functions

    Science.gov (United States)

    Zhou, Chi-Chun; Dai, Wu-Sheng

    2018-05-01

    The main aim of this paper is twofold: (1) suggesting a statistical mechanical approach to the calculation of the generating function of restricted integer partition functions which count the number of partitions—a way of writing an integer as a sum of other integers under certain restrictions. In this approach, the generating function of restricted integer partition functions is constructed from the canonical partition functions of various quantum gases. (2) Introducing a new type of restricted integer partition functions corresponding to general statistics which is a generalization of Gentile statistics in statistical mechanics; many kinds of restricted integer partition functions are special cases of this restricted integer partition function. Moreover, with statistical mechanics as a bridge, we reveal a mathematical fact: the generating function of restricted integer partition function is just the symmetric function which is a class of functions being invariant under the action of permutation groups. Using this approach, we provide some expressions of restricted integer partition functions as examples.

  14. Radical constructivism: Between realism and solipsism

    Science.gov (United States)

    Martínez-Delgado, Alberto

    2002-11-01

    This paper criticizes radical constructivism of the Glasersfeld type, pointing out some contradictions between the declared radical principles and their theoretical and practical development. These contradictions manifest themselves in a frequent oscillation between solipsism and realism, despite constructivist claims to be an anti-realist theory. The paper also points out the contradiction between the relativism of the radical constructivist principles and the constructivist exclusion of other epistemological or educational paradigms. It also disputes the originality and importance of the radical constructivist paradigm, suggesting the idea of an isomorphism between radical constructivist theory and contemplative realism. In addition, some pedagogical and scientific methodological aspects of the radical constructivist model are examined. Although radical constructivism claims to be a rational theory and advocates deductive thinking, it is argued that there is no logical deductive connection between the radical principles of constructivism and the radical constructivist ideas about scientific research and learning. The paper suggests the possibility of an ideological substratum in the construction and hegemonic success of subjective constructivism and, finally, briefly advances an alternative realist model to epistemological and educational radical constructivism.

  15. COMPUTATIONAL STUDY OF INTERSTELLAR GLYCINE FORMATION OCCURRING AT RADICAL SURFACES OF WATER-ICE DUST PARTICLES

    Energy Technology Data Exchange (ETDEWEB)

    Rimola, Albert; Sodupe, Mariona [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra (Spain); Ugliengo, Piero, E-mail: albert.rimola@uab.cat [Dipartimento di Chimica, NIS Centre of Excellence and INSTM (Materials and Technology National Consortium), UdR Torino, Universita di Torino, Via P. Giuria 7, 10125 Torino (Italy)

    2012-07-20

    Glycine is the simplest amino acid, and due to the significant astrobiological implications that suppose its detection, the search for it in the interstellar medium (ISM), meteorites, and comets is intensively investigated. In the present work, quantum mechanical calculations based on density functional theory have been used to model the glycine formation on water-ice clusters present in the ISM. The removal of either one H atom or one electron from the water-ice cluster has been considered to simulate the effect of photolytic radiation and of ionizing particles, respectively, which lead to the formation of OH{sup .} radical and H{sub 3}O{sup +} surface defects. The coupling of incoming CO molecules with the surface OH{sup .} radicals on the ice clusters yields the formation of the COOH{sup .} radicals via ZPE-corrected energy barriers and reaction energies of about 4-5 kcal mol{sup -1} and -22 kcal mol{sup -1}, respectively. The COOH{sup .} radicals couple with incoming NH=CH{sub 2} molecules (experimentally detected in the ISM) to form the NHCH{sub 2}COOH{sup .} radical glycine through energy barriers of 12 kcal mol{sup -1}, exceedingly high at ISM cryogenic temperatures. Nonetheless, when H{sub 3}O{sup +} is present, one proton may be barrierless transferred to NH=CH{sub 2} to give NH{sub 2}=CH{sub 2}{sup +}. This latter may react with the COOH{sup .} radical to give the NH{sub 2}CH{sub 2}COOH{sup +.} glycine radical cation which can then be transformed into the NH{sub 2}CHC(OH){sub 2}{sup +.} species (the most stable form of glycine in its radical cation state) or into the NH{sub 2}CHCOOH{sup .} neutral radical glycine. Estimated rate constants of these events suggest that they are kinetically feasible at temperatures of 100-200 K, which indicate that their occurrence may take place in hot molecular cores or in comets exposed to warmer regions of solar systems. Present results provide quantum chemical evidence that defects formed on water ices due to the harsh

  16. Bioconjugate functionalization of thermally carbonized porous silicon using a radical coupling reaction†

    Science.gov (United States)

    Sciacca, Beniamino; Alvarez, Sara D.; Geobaldo, Francesco; Sailor, Michael J.

    2011-01-01

    The high stability of Salonen’s thermally carbonized porous silicon (TCPSi) has attracted attention for environmental and biochemical sensing applications, where corrosion-induced zero point drift of porous silicon-based sensor elements has historically been a significant problem. Prepared by the high temperature reaction of porous silicon with acetylene gas, the stability of this silicon carbide-like material also poses a challenge—many sensor applications require a functionalized surface, and the low reactivity of TCPSi has limited the ability to chemically modify its surface. This work presents a simple reaction to modify the surface of TCPSi with an alkyl carboxylate. The method involves radical coupling of a dicarboxylic acid (sebacic acid) to the TCPSi surface using a benzoyl peroxide initiator. The grafted carboxylic acid species provides a route for bioconjugate chemical modification, demonstrated in this work by coupling propylamine to the surface carboxylic acid group through the intermediacy of pentafluorophenol and 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide hydrochloride (EDC). The stability of the carbonized porous Si surface, both before and after chemical modification, is tested in phosphate buffered saline solution and found to be superior to either hydrosilylated (with undecylenic acid) or thermally oxidized porous Si surfaces. PMID:20967329

  17. Endoscopic extraperitoneal radical prostatectomy after radical resection of pT1-pT2 rectal cancer: a report of thirty cases.

    Science.gov (United States)

    Liu, Zhuo; Li, Dechuan; Chen, Yinbo

    2017-01-01

    Endoscopic extraperitoneal radical prostatectomy (EERPE) has gained popularity for the treatment of localized prostate cancer. However, prior complex lower abdominal or pelvic surgery can complicate subsequent EERPE. To date, there have been few reports on patients who underwent EERPE after radical resection of pT1-pT2 rectal cancer. To present our experience with EERPE in patients after radical resection of pT1-pT2 rectal carcinoma and introduce a simple and effective way to create an extraperitoneal working space. Thirty patients after radical resection of pT1-pT2 rectal carcinoma were treated with EERPE for biopsy-proven localized prostate cancer. Operation time, estimated blood loss, conversion to open surgery rate, transfusion rate and transurethral catheter time were recorded. Meanwhile, functional outcome (continence and potency) and oncological outcome were reviewed. The average operative time was 168 min. Mean blood loss was 195 ml. There was no need for conversion to open surgery or transfusion. The catheter was removed on postoperative day (POD) 7.8. After a mean follow-up time of 53.1 months, 3 patients had a prostate-specific antigen level relapse over 0.1 ng/ml. At the follow-up time, 26 patients were completely continent, and 4 needed 1-2 pads/day. Of the 6 patients who underwent neurovascular bundle preservation, none have experienced return of erections at the last follow-up time. Endoscopic extraperitoneal radical prostatectomy after radical resection of rectal carcinoma appears promising, with feasibility in experienced hands. The operative data, postoperative urinary incontinence and oncological outcomes appear encouraging, but the rate of erectile dysfunction seems to be disappointing.

  18. Free radical reactions of isoxazole and pyrazole derivatives of hispolon: kinetics correlated with molecular descriptors.

    Science.gov (United States)

    Shaikh, Shaukat Ali M; Barik, Atanu; Singh, Beena G; Modukuri, Ramani V; Balaji, Neduri V; Subbaraju, Gottumukkala V; Naik, Devidas B; Priyadarsini, K Indira

    2016-12-01

    Hispolon (HS), a natural polyphenol found in medicinal mushrooms, and its isoxazole (HI) and pyrazole (HP) derivatives have been examined for free radical reactions and in vitro antioxidant activity. Reaction of these compounds with one-electron oxidant, azide radicals ([Formula: see text]) and trichloromethyl peroxyl radicals ([Formula: see text]), model peroxyl radicals, studied by nanosecond pulse radiolysis technique, indicated formation of phenoxyl radicals absorbing at 420 nm with half life of few hundred microseconds (μs). The formation of phenoxyl radicals confirmed that the phenolic OH is the active centre for free radical reactions. Rate constant for the reaction of these radicals with these compounds were in the order k HI ≅ k HP  >   k HS . Further the compounds were examined for their ability to inhibit lipid peroxidation in model membranes and also for the scavenging of 2,2'-diphenyl-1-picrylhydrazyl (DPPH) radical and superoxide ([Formula: see text]) radicals. The results suggested that HP and HI are less efficient than HS towards these radical reactions. Quantum chemical calculations were performed on these compounds to understand the mechanism of reaction with different radicals. Lower values of adiabatic ionization potential (AIP) and elevated highest occupied molecular orbital (HOMO) for HI and HP compared with HS controlled their activity towards [Formula: see text] and [Formula: see text] radicals, whereas the contribution of overall anion concentration was responsible for higher activity of HS for DPPH, [Formula: see text], and lipid peroxyl radical. The results confirm the role of different structural moieties on the antioxidant activity of hispolon derivatives.

  19. Methane coupling reaction in an oxy-steam stream through an OH radical pathway by using supported alkali metal catalysts

    KAUST Repository

    Liang, Yin

    2014-03-24

    A universal reaction mechanism involved in the oxidative coupling of methane (OCM) is demonstrated under oxy-steam conditions using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from a H 2O-O2 reaction followed by C-H activation in CH 4 with an OH radical. Thus, the presence of water enhances both the CH4 conversion rate and the C2 selectivity. This OH radical pathway that is selective for the OCM was observed for the catalyst without Mn, which suggests clearly that Mn is not the essential component in a selective OCM catalyst. The experiments with different catalyst compositions revealed that the OH.-mediated pathway proceeded in the presence of catalysts with different alkali metals (Na, K) and different oxo anions (W, Mo). This difference in catalytic activity for OH radical generation accounts for the different OCM selectivities. As a result, a high C2 yield is achievable by using Na2WO4/SiO2, which catalyzes the OH.-mediated pathway selectively. Make it methane: A universal reaction mechanism involved in the oxidative coupling of methane is demonstrated under oxy-stream conditions by using alkali-metal-based catalysts. Rigorous kinetic measurements indicated a reaction mechanism that is consistent with OH radical formation from an H2O-O2 reaction, followed by C-H activation in CH4 with an OH radical. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Relative stability of radicals derived from artemisinin: A semiempirical and DFT study

    Science.gov (United States)

    Arantes, C.; de Araujo, M. T.; Taranto, A. G.; de M. Carneiro, J. W.

    The semiempirical AM1 and PM3 methods, as well as the density functional (DFT/B3LYP) approach using the 6-31g(d) basis set, were employed to calculate the relative stability of intermediate radicals derived from artemisinin, a sesquiterpene lactone having an endoperoxide bridge that is essential for its antimalarial activity. The compounds studied have their nonperoxidic oxygen atom of the trioxane ring and/or the carbonyl group replaced by a CH2 unit. Relative stabilities were calculated by means of isodesmic equations using artemisinin as reference. It was found that replacement of oxygen atoms decreases the relative stability of the anionic radical intermediates. In contrast, for compounds with inverted stereochemistry the intermediate radicals were found to be more stable than those with the artemisinin-like stereochemistry. These relative stabilities may modulate the antimalarial potency. Radicals centered on carbon are always more stable than the corresponding radicals centered on oxygen.

  1. Radical-mediated annulation reactions. A versatile strategy for the preparation of a series of carbocycles.

    Science.gov (United States)

    Sibi, M P; Chen, J; Rheault, T R

    2001-11-15

    [reaction--see text] A series of novel 6-endo [4 + 2] and 7-endo [5 + 2] radical-mediated annulation reactions are described. These annulation sequences involve an intermolecular radical addition followed by intramolecular trapping with an allyltin moiety incorporated into the radical precursor fragment. This methodology allows for access to functionalized 6- and 7-membered carbocycles as well as bicyclic compounds with good to excellent levels of stereocontrol.

  2. Compensatory Structural and Functional Adaptation after Radical Nephrectomy for Renal Cell Carcinoma According to Preoperative Stage of Chronic Kidney Disease.

    Science.gov (United States)

    Choi, Don Kyoung; Jung, Se Bin; Park, Bong Hee; Jeong, Byong Chang; Seo, Seong Il; Jeon, Seong Soo; Lee, Hyun Moo; Choi, Han-Yong; Jeon, Hwang Gyun

    2015-10-01

    We investigated structural hypertrophy and functional hyperfiltration as compensatory adaptations after radical nephrectomy in patients with renal cell carcinoma according to the preoperative chronic kidney disease stage. We retrospectively identified 543 patients who underwent radical nephrectomy for renal cell carcinoma between 1997 and 2012. Patients were classified according to preoperative glomerular filtration rate as no chronic kidney disease--glomerular filtration rate 90 ml/minute/1.73 m(2) or greater (230, 42.4%), chronic kidney disease stage II--glomerular filtration rate 60 to less than 90 ml/minute/1.73 m(2) (227, 41.8%) and chronic kidney disease stage III--glomerular filtration rate 30 to less than 60 ml/minute/1.73 m(2) (86, 15.8%). Computerized tomography performed within 2 months before surgery and 1 year after surgery was used to assess functional renal volume for measuring the degree of hypertrophy of the remnant kidney, and the preoperative and postoperative glomerular filtration rate per unit volume of functional renal volume was used to calculate the degree of hyperfiltration. Among all patients (mean age 56.0 years) mean preoperative glomerular filtration rate, functional renal volume and glomerular filtration rate/functional renal volume were 83.2 ml/minute/1.73 m(2), 340.6 cm(3) and 0.25 ml/minute/1.73 m(2)/cm(3), respectively. The percent reduction in glomerular filtration rate was statistically significant according to chronic kidney disease stage (no chronic kidney disease 31.2% vs stage II 26.5% vs stage III 12.8%, p kidney was not statistically significant (no chronic kidney disease 18.5% vs stage II 17.3% vs stage III 16.5%, p=0.250). The change in glomerular filtration rate/functional renal volume was statistically significant (no chronic kidney disease 18.5% vs stage II 20.1% vs stage III 45.9%, p chronic kidney disease stage (p <0.001). Patients with a lower preoperative glomerular filtration rate had a smaller reduction in

  3. Molybdenum disulfide for ultra-low detection of free radicals: electrochemical response and molecular modeling

    Science.gov (United States)

    Gupta, Ankur; Rawal, Takat B.; Neal, Craig J.; Das, Soumen; Rahman, Talat S.; Seal, Sudipta

    2017-06-01

    Two-dimensional (2D) molybdenum disulfide (MoS2) offers attractive properties due to its band gap modulation and has led to significant research-oriented applications (i.e. DNA and protein detection, cell imaging (fluorescent label) etc.). In biology, detection of free radicals (i.e. reactive oxygen species and reactive nitrogen (NO*) species are very important for early discovery and treatment of diseases. Herein, for the first time, we demonstrate the ultra-low (pico-molar) detection of pharmaceutically relevant free radicals using MoS2 for electrochemical sensing. We present pico- to nano- molar level sensitivity in smaller MoS2 with S-deficiency as revealed by x-ray photoelectron spectroscopy. Furthermore, the detection mechanism and size-dependent sensitivity have been investigated by density functional theory (DFT) showing the change in electronic density of states of Mo atoms at edges which lead to the preferred adsorption of H2O2 on Mo edges. The DFT analysis signifies the role of size and S-deficiency in the higher catalytic activity of smaller MoS2 particles and, thus, ultra-low detection.

  4. Muoniated acyl and thioacyl radicals

    International Nuclear Information System (INIS)

    McKenzie, Iain; Brodovitch, Jean-Claude; Ghandi, Khashayar; Percival, Paul W.

    2006-01-01

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and 14 N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and 14 N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy

  5. Muoniated acyl and thioacyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, Iain [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Brodovitch, Jean-Claude [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Ghandi, Khashayar [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Percival, Paul W. [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada)]. E-mail: percival@sfu.ca

    2006-03-31

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and {sup 14}N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and {sup 14}N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy.

  6. Identification of mitochondrial electron transport chain-mediated NADH radical formation by EPR spin-trapping techniques.

    Science.gov (United States)

    Matsuzaki, Satoshi; Kotake, Yashige; Humphries, Kenneth M

    2011-12-20

    The mitochondrial electron transport chain (ETC) is a major source of free radical production. However, due to the highly reactive nature of radical species and their short lifetimes, accurate detection and identification of these molecules in biological systems is challenging. The aim of this investigation was to determine the free radical species produced from the mitochondrial ETC by utilizing EPR spin-trapping techniques and the recently commercialized spin-trap, 5-(2,2-dimethyl-1,3-propoxycyclophosphoryl)-5-methyl-1-pyrroline N-oxide (CYPMPO). We demonstrate that this spin-trap has the preferential quality of having minimal mitochondrial toxicity at concentrations required for radical detection. In rat heart mitochondria and submitochondrial particles supplied with NADH, the major species detected under physiological pH was a carbon-centered radical adduct, indicated by markedly large hyperfine coupling constant with hydrogen (a(H) > 2.0 mT). In the presence of the ETC inhibitors, the carbon-centered radical formation was increased and exhibited NADH concentration dependency. The same carbon-centered radical could also be produced with the NAD biosynthesis precursor, nicotinamide mononucleotide, in the presence of a catalytic amount of NADH. The results support the conclusion that the observed species is a complex I derived NADH radical. The formation of the NADH radical could be blocked by hydroxyl radical scavengers but not SOD. In vitro experiments confirmed that an NADH-radical is readily formed by hydroxyl radical but not superoxide anion, further implicating hydroxyl radical as an upstream mediator of NADH radical production. These findings demonstrate the identification of a novel mitochondrial radical species with potential physiological significance and highlight the diverse mechanisms and sites of production within the ETC.

  7. 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.

  8. Investigation on the recombination kinetics of the pyrolytic free-radicals in the irradiated polyimide

    International Nuclear Information System (INIS)

    Sun Chengyue; Wu Yiyong; Yue Long; Shi Yaping; Xiao Jingdong

    2012-01-01

    Highlights: ► Free radicals behavior was exposure during the irradiation and anneal during the post storage. ► Both of the recombination and oxygen reaction affect the post-annealing evolution of free radicals. ► The activation energy and the surface reaction rate were calculated by the analysis of the free radical anneal process. - Abstract: The free radical behavior of 60 and 110 keV proton-irradiated polyimide were investigated using electron paramagnetic resonance measurements. The results indicate that during proton irradiation, a type of pyrolytic carbon free radical was formed with a g value of 2.0025. The radical population was found, after proton irradiation to decrease in a combination of an exponential and linear modes with an annealing time in the range of 50–120 °C. The exponential part indicated a radical recombination process while the linear part is due to the reaction of the radical with the ambient. Using the annealing results, the recombination activation energy of the radicals was determined as 12.4 ± 0.2 and 17.6 ± 0.2 kJ/mol for 60 and 110 keV irradiated polyimide, respectively, with a surface reaction rate of about 0.02/h. It is possible that the kinetic study presented here is used as one of the criteria for predicting the optical properties of polyimide material in spacecraft. The mechanism of the free radical evolution will be discussed in this paper.

  9. OH, HO2, and HO2* Radical Chemistry During PROPHET-AMOS 2016: Measurements and Model Comparison

    Science.gov (United States)

    Bottorff, B.; Lew, M.; Rickly, P.; Stevens, P. S.

    2017-12-01

    The hydroxyl (OH) and peroxy radicals, both the hydroperoxy radical (HO2) and organic peroxy radicals (RO2), play an important role in atmospheric chemistry. In addition to controlling lifetimes of many trace gases important to issues of global climate change, reactions of these radicals can also lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in remote forest environments have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOX conditions. In the summer of 2016, OH, HO2 and HO2* (HO2 + αRO2) radicals were measured using the Indiana University Laser-Induced Fluorescence Fluorescence Assay by Gas Expansion (LIF-FAGE) technique as part of the Program for Research on Oxidants: PHtochemistry, Emissions, and Transport- Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS). This campaign took place in a forested area in northern Michigan characterized by high mixing ratios of isoprene and low mixing ratios of NOX. Ambient measurements from this campaign will be compared to previous measurements at this site and to modeled predictions using both the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism. Potential interferences associated with the OH measurements will also be examined.

  10. Enzymatic and free radical formation of cis- and trans- epoxyeicosatrienoic acids in vitro and in vivo.

    Science.gov (United States)

    Aliwarga, Theresa; Raccor, Brianne S; Lemaitre, Rozenn N; Sotoodehnia, Nona; Gharib, Sina A; Xu, Libin; Totah, Rheem A

    2017-11-01

    Epoxyeicosatrienoic acids (EETs) are metabolites of arachidonic acid (AA) oxidation that have important cardioprotective and signaling properties. AA is an ω-6 polyunsaturated fatty acid (PUFA) that is prone to autoxidation. Although hydroperoxides and isoprostanes are major autoxidation products of AA, EETs are also formed from the largely overlooked peroxyl radical addition mechanism. While autoxidation yields both cis- and trans-EETs, cytochrome P450 (CYP) epoxygenases have been shown to exclusively catalyze the formation of all regioisomer cis-EETs, on each of the double bonds. In plasma and red blood cell (RBC) membranes, cis- and trans-EETs have been observed, and both have multiple physiological functions. We developed a sensitive ultra-performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) assay that separates cis- and trans- isomers of EETs and applied it to determine the relative distribution of cis- vs. trans-EETs in reaction mixtures of AA subjected to free radical oxidation in benzene and liposomes in vitro. We also determined the in vivo distribution of EETs in several tissues, including human and mouse heart, and RBC membranes. We then measured EET levels in heart and RBC of young mice compared to old. Formation of EETs in free radical reactions of AA in benzene and in liposomes exhibited time- and AA concentration-dependent increase and trans-EET levels were higher than cis-EETs under both conditions. In contrast, cis-EET levels were overall higher in biological samples. In general, trans-EETs increased with mouse age more than cis-EETs. We propose a mechanism for the non-enzymatic formation of cis- and trans-EETs involving addition of the peroxyl radical to one of AA's double bonds followed by bond rotation and intramolecular homolytic substitution (S H i). Enzymatic formation of cis-EETs by cytochrome P450 most likely occurs via a one-step concerted mechanism that does not allow bond rotation. The ability to accurately measure

  11. Selectivity of alkyl radical formation from branched alkanes studied by electron spin resonance and electron spin echo spectroscopy

    International Nuclear Information System (INIS)

    Tsuneki, Ichikawa; Hiroshi, Yoshida

    1992-01-01

    Alkyl radicals generated from branched alkanes by γ radiation are being measuring by electron spin resonance and electron spin echo spectroscopy. This research is being conducted to determine the mechanism of selective alkyl radical formation in low-temperature solids

  12. Reactivity Of Radiolytically-Produced Nitrogen Oxide Radicals Toward Aromatic Compounds

    International Nuclear Information System (INIS)

    Elias, Gracy

    2010-01-01

    radiolysis of the modifier (Cs-7SB), which solvates both metal complexes, is responsible for this change. These reactions presumably occur due to reactions with radiolytically-produced nitrogen-centered radicals like (sm b ullet)NO, (sm b ullet)NO 2 and (sm b ullet)NO 3 . Anisole (C 6 H 5 -OCH 3 ) was used in this study as a surrogate for Cs-7SB, since both are aryl ethers. Toluene was used as a surrogate for Cs-7SB because of the alkyl group on the benzene ring in both molecules. Anisole, highly reactive in acids, is a small molecule compared to Cs-7SB and the nitration products are easier to identify compared to those for the larger Cs-7SB molecule. Toluene is less reactive than anisole. Therefore, the highly reactive anisole and the less reactive toluene were considered in this study as model compounds to compare the reaction mechanisms and the nitrated products in acidic media under irradiation. Experiments were designed to elucidate the mechanism of the nitration of aromatic rings in γ-irradiated aqueous nitric acid. Since a suite of radical and ionic reactive species are produced in this condensed-phase system, solutions of nitric acid, neutral nitrate and neutral nitrite were irradiated in separate experiments to isolate selected reactive species. Product nitration species were assessed by high performance liquid chromatography (HPLC) with a reversed phase C-18 column and photodiode array detector. The nitrated anisole product distributions were the same with and without radiation in acidic solution, although more products were formed with radiation. In the irradiated acidic condensed phase, radiation-enhanced nitrous acid-catalyzed nitrosonium ion electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions. In contrast, the distribution of nitrated derivatives for toluene showed nitronium ion electrophilic substitution in the unirradiated acidic medium as a result of thermal nitration only at elevated temperatures

  13. Effect of Free Radicals & Antioxidants on Oxidative Stress: A Review

    Directory of Open Access Journals (Sweden)

    Ashok Shinde

    2012-01-01

    Full Text Available Recently free radicals have attracted tremendous importance in the field of medicine including dentistry and molecular biology. Free radicals can be either harmful or helpful to the body. When there is an imbalance between formation and removal of free radicals then a condition called as oxidative stress is developed in body. To counteract these free radicals body has protective antioxidant mechanisms which have abilities to lower incidence of various human morbidities and mortalities. Many research groups in the past have tried to study and confirm oxidative stress. Many authors also have studied role of antioxidants in reducing oxidative stress. They have come across with controversial results and furthermore it is not yet fully confirmed whether oxidative stress increases the need for dietary antioxidants. Recently, an association between periodontitis and cardiovascular disease has received considerable attention. Various forms of antioxidants have been introduced as an approach to fight dental diseases and improve general gingival health. The implication of oxidative stress in the etiology of many chronic and degenerative diseases suggests that antioxidant therapy represents a promising avenue for treatment. This study was conducted with the objective of reviewing articles relating to this subject. A Pub Med search of all articles containing key words free radicals, oxidative stress, and antioxidants was done. A review of these articles was undertaken.

  14. 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...

  15. 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

  16. 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.

  17. 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.

  18. EPR Spectroscopy of Radical Ions of a 2,3-Diamino-1,4-naphthoquinone Derivative.

    Science.gov (United States)

    Tarábek, Ján; Wen, Jin; Dron, Paul I; Pospíšil, Lubomír; Michl, Josef

    2018-05-18

    We report the electron paramagnetic resonance spectra of the radical cation and radical anion of 1,2,2,3-tetramethyl-2,3-dihydro-1 H-naphtho[2,3- d]imidazole-4,9-dione (1) and its doubly 13 C labeled analogue 2, of interest for singlet fission. The hyperfine coupling constants are in excellent agreement with density functional theory calculations and establish the structures beyond doubt. Unlike the radical cation 1 •+ , the radical anion 1 •- and its parent 1 have pyramidalized nitrogen atoms and inequivalent methyl groups 15 and 16, in agreement with the calculations. The distinction is particularly clear with the labeled analogue 2 •- .

  19. Benchmarking DFT and TD-DFT Functionals for the Ground and Excited States of Hydrogen-Rich Peptide Radicals.

    Science.gov (United States)

    Riffet, Vanessa; Jacquemin, Denis; Cauët, Emilie; Frison, Gilles

    2014-08-12

    We assess the pros and cons of a large panel of DFT exchange-correlation functionals for the prediction of the electronic structure of hydrogen-rich peptide radicals formed after electron attachment on a protonated peptide. Indeed, despite its importance in the understanding of the chemical changes associated with the reduction step, the question of the attachment site of an electron and, more generally, of the reduced species formed in the gas phase through electron-induced dissociation (ExD) processes in mass spectrometry is still a matter of debate. For hydrogen-rich peptide radicals in which several positive groups and low-lying π* orbitals can capture the incoming electron in ExD, inclusion of full Hartree-Fock exchange at long-range interelectronic distance is a prerequisite for an accurate description of the electronic states, thereby excluding several popular exchange-correlation functionals, e.g., B3LYP, M06-2X, or CAM-B3LYP. However, we show that this condition is not sufficient by comparing the results obtained with asymptotically correct range-separated hybrids (M11, LC-BLYP, LC-BPW91, ωB97, ωB97X, and ωB97X-D) and with reference CASSCF-MRCI and EOM-CCSD calculations. The attenuation parameter ω significantly tunes the spin density distribution and the excited states vertical energies. The investigated model structures, ranging from methylammonium to hexapeptide, allow us to obtain a description of the nature and energy of the electronic states, depending on (i) the presence of hydrogen bond(s) around the cationic site(s), (ii) the presence of π* molecular orbitals (MOs), and (iii) the selected DFT approach. It turns out that, in the present framework, LC-BLYP and ωB97 yields the most accurate results.

  20. Muonium-containing vinyl radicals

    International Nuclear Information System (INIS)

    Rhodes, C.J.; Symons, M.C.R.; Roduner, E.; Heming, M.

    1987-01-01

    Exposure of trimethylsilylacetylene and bis(trimethylsilyl)acetylene to positive muons gave radicals whose muon-electron hyperfine coupling constants establish that the corresponding vinyl radicals were formed. (author)

  1. Properties of the radicals formed by one-electron oxidation of acetaminophen - a pulse radiolysis study

    International Nuclear Information System (INIS)

    Bisby, R.H.; Tabassum, N.

    1988-01-01

    The semi-iminoquinone radical of acetaminophen, which has previously been proposed as a possible hepatotoxic intermediate in the cytochrome P-450 catalysed oxidation of acetaminophen, has been generated and studied by pulse radiolysis. In the absence of other reactive solutes, the radical decays rapidly by second order kinetics with a rate constant (2k 2 ) of (2.2 ± 0.4) x 10 9 M -1 sec -1 . In alkaline solutions the radical deprotonates with a pK of 11.1 ± 0.1 to form a radical-anion. The acetaminophen radical-anion reacts with resorcinol at high pH values, leading to the formation of a transient equilibrium from which the one-electron reduction potential of the semi-iminoquinone radical of acetaminophen is estimated to be + 0.707 ± 0.01 V at pH 7. This value predicts that acetaminophen should be oxidised by thiyl radicals. This was confirmed by pulse radiolysis experiments for reaction of the cysteinyl radical, for which rate constants of 7 x 10 6 M -1 sec -1 at pH7 and 2.7 x 10 8 M -1 sec -1 at pH 11.3 were obtained. The reaction of O 2 with the acetaminophen semi-iminoquinone radical could not be detected by pulse radiolysis, and alternative mechanisms for superoxide radical formation are discussed. (author)

  2. Properties of the radicals formed by one-electron oxidation of acetaminophen - a pulse radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Bisby, R H; Tabassum, N

    1988-07-15

    The semi-iminoquinone radical of acetaminophen, which has previously been proposed as a possible hepatotoxic intermediate in the cytochrome P-450 catalysed oxidation of acetaminophen, has been generated and studied by pulse radiolysis. In the absence of other reactive solutes, the radical decays rapidly by second order kinetics with a rate constant (2k/sub 2/) of (2.2 +- 0.4) x 10/sup 9/ M/sup -1/ sec/sup -1/. In alkaline solutions the radical deprotonates with a pK of 11.1 +- 0.1 to form a radical-anion. The acetaminophen radical-anion reacts with resorcinol at high pH values, leading to the formation of a transient equilibrium from which the one-electron reduction potential of the semi-iminoquinone radical of acetaminophen is estimated to be + 0.707 +- 0.01 V at pH 7. This value predicts that acetaminophen should be oxidised by thiyl radicals. This was confirmed by pulse radiolysis experiments for reaction of the cysteinyl radical, for which rate constants of 7 x 10/sup 6/ M/sup -1/ sec/sup -1/ at pH7 and 2.7 x 10/sup 8/ M/sup -1/ sec/sup -1/ at pH 11.3 were obtained. The reaction of O/sub 2/ with the acetaminophen semi-iminoquinone radical could not be detected by pulse radiolysis, and alternative mechanisms for superoxide radical formation are discussed.

  3. Radicals in arithmetic

    NARCIS (Netherlands)

    W.J. Palenstijn (Willem Jan)

    2014-01-01

    htmlabstractLet K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement

  4. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    Energy Technology Data Exchange (ETDEWEB)

    Kispert, Lowell D [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Focsan, A Ligia [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Konovalova, Tatyana A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence, Jesse [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Bowman, Michael K [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Molnar, Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Deli, Jozsef [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2007-06-11

    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car•+) but also neutral radicals (#Car•) by proton loss from the methyl groups at positions 5 or 5', and possibly 9 or 9' and 13 or 13'. Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car•+ which agree with the ENDOR for carotenoid α-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity [Lycopene (III) versus 8'-apo-β-caroten-8'-al (IV)]; hydrogen bonding [Lutein (V) versus III]; host [silica-alumina versus MCM-41 molecular sieve]; and substituted metal in MCM-41. Loss of H+ from the 5(5'), 9(9') or 13(13') methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I •+…Chl•-), lower in energy than 1Chl*. Formation of I •+ results in bond

  5. Exploratory Decision-Tree Modeling of Data from the Randomized REACTT Trial of Tadalafil Versus Placebo to Predict Recovery of Erectile Function After Bilateral Nerve-Sparing Radical Prostatectomy.

    Science.gov (United States)

    Montorsi, Francesco; Oelke, Matthias; Henneges, Carsten; Brock, Gerald; Salonia, Andrea; d'Anzeo, Gianluca; Rossi, Andrea; Mulhall, John P; Büttner, Hartwig

    2016-09-01

    Understanding predictors for the recovery of erectile function (EF) after nerve-sparing radical prostatectomy (nsRP) might help clinicians and patients in preoperative counseling and expectation management of EF rehabilitation strategies. To describe the effect of potential predictors on EF recovery after nsRP by post hoc decision-tree modeling of data from A Study of Tadalafil After Radical Prostatectomy (REACTT). Randomized double-blind double-dummy placebo-controlled trial in 423 men aged decision-tree models, using the International Index of Erectile Function-Erectile Function (IIEF-EF) domain score at the end of double-blind treatment, washout, and open-label treatment as response variable. Each model evaluated the association between potential predictors: presurgery IIEF domain and IIEF single-item scores, surgical approach, nerve-sparing score (NSS), and postsurgery randomized treatment group. The first decision-tree model (n=422, intention-to-treat population) identified high presurgery sexual desire (IIEF item 12: ≥3.5 and decision-tree analyses identified high presurgery sexual desire, confidence, and intercourse satisfaction as key predictors for EF recovery. Patients meeting these criteria might benefit the most from conserving surgery and early postsurgery EF rehabilitation. Strategies for improving EF after surgery should be discussed preoperatively with all patients; this information may support expectation management for functional recovery on an individual patient level. Understanding how patient characteristics and different treatment options affect the recovery of erectile function (EF) after radical surgery for prostate cancer might help physicians select the optimal treatment for their patients. This analysis of data from a clinical trial suggested that high presurgery sexual desire, sexual confidence, and intercourse satisfaction are key factors predicting EF recovery. Patients meeting these criteria might benefit the most from conserving

  6. Effects of radical scavengers on aqueous solutions exposed to heavy-ion irradiation using the liquid microjet technique

    Science.gov (United States)

    Nomura, Shinji; Tsuchida, Hidetsugu; Furuya, Ryousuke; Miyahara, Kento; Majima, Takuya; Itoh, Akio

    2015-12-01

    The effects of the radical scavenger ascorbic acid on water radiolysis are studied by fast heavy-ion irradiation of aqueous solutions of ascorbic acid, using the liquid microjet technique under vacuum. To understand the reaction mechanisms of hydroxyl radicals in aqueous solutions, we directly measure secondary ions emitted from solutions with different ascorbic acid concentrations. The yield of hydronium secondary ions is strongly influenced by the reaction between ascorbic acid and hydroxyl radicals. From analysis using a simple model considering chemical equilibria, we determine that the upper concentration limit of ascorbic acid with a radical scavenger effect is approximately 70 μM.

  7. Effects of radical scavengers on aqueous solutions exposed to heavy-ion irradiation using the liquid microjet technique

    Energy Technology Data Exchange (ETDEWEB)

    Nomura, Shinji [Department of Nuclear Engineering, Kyoto University, Kyoto 615-8530 (Japan); Tsuchida, Hidetsugu, E-mail: tsuchida@nucleng.kyoto-u.ac.jp [Department of Nuclear Engineering, Kyoto University, Kyoto 615-8530 (Japan); Quantum Science and Engineering Center, Kyoto University, Uji 611-0011 (Japan); Furuya, Ryousuke; Miyahara, Kento [Department of Nuclear Engineering, Kyoto University, Kyoto 615-8530 (Japan); Majima, Takuya; Itoh, Akio [Department of Nuclear Engineering, Kyoto University, Kyoto 615-8530 (Japan); Quantum Science and Engineering Center, Kyoto University, Uji 611-0011 (Japan)

    2015-12-15

    The effects of the radical scavenger ascorbic acid on water radiolysis are studied by fast heavy-ion irradiation of aqueous solutions of ascorbic acid, using the liquid microjet technique under vacuum. To understand the reaction mechanisms of hydroxyl radicals in aqueous solutions, we directly measure secondary ions emitted from solutions with different ascorbic acid concentrations. The yield of hydronium secondary ions is strongly influenced by the reaction between ascorbic acid and hydroxyl radicals. From analysis using a simple model considering chemical equilibria, we determine that the upper concentration limit of ascorbic acid with a radical scavenger effect is approximately 70 μM.

  8. Effects of radical scavengers on aqueous solutions exposed to heavy-ion irradiation using the liquid microjet technique

    International Nuclear Information System (INIS)

    Nomura, Shinji; Tsuchida, Hidetsugu; Furuya, Ryousuke; Miyahara, Kento; Majima, Takuya; Itoh, Akio

    2015-01-01

    The effects of the radical scavenger ascorbic acid on water radiolysis are studied by fast heavy-ion irradiation of aqueous solutions of ascorbic acid, using the liquid microjet technique under vacuum. To understand the reaction mechanisms of hydroxyl radicals in aqueous solutions, we directly measure secondary ions emitted from solutions with different ascorbic acid concentrations. The yield of hydronium secondary ions is strongly influenced by the reaction between ascorbic acid and hydroxyl radicals. From analysis using a simple model considering chemical equilibria, we determine that the upper concentration limit of ascorbic acid with a radical scavenger effect is approximately 70 μM.

  9. Multiple free-radical scavenging capacity in serum

    Science.gov (United States)

    Oowada, Shigeru; Endo, Nobuyuki; Kameya, Hiromi; Shimmei, Masashi; Kotake, Yashige

    2012-01-01

    We have developed a method to determine serum scavenging-capacity profile against multiple free radical species, namely hydroxyl radical, superoxide radical, alkoxyl radical, alkylperoxyl radical, alkyl radical, and singlet oxygen. This method was applied to a cohort of chronic kidney disease patients. Each free radical species was produced with a common experimental procedure; i.e., uv/visible-light photolysis of free-radical precursor/sensitizer. The decrease in free-radical concentration by the presence of serum was quantified with electron spin resonance spin trapping method, from which the scavenging capacity was calculated. There was a significant capacity change in the disease group (n = 45) as compared with the healthy control group (n = 30). The percent values of disease’s scavenging capacity with respect to control group indicated statistically significant differences in all free-radical species except alkylperoxyl radical, i.e., hydroxyl radical, 73 ± 12% (p = 0.001); superoxide radical, 158 ± 50% (p = 0.001); alkoxyl radical, 121 ± 30% (p = 0.005); alkylperoxyl radical, 123 ± 32% (p>0.1); alkyl radical, 26 ± 14% (p = 0.001); and singlet oxygen, 57 ± 18% (p = 0.001). The scavenging capacity profile was illustrated using a radar chart, clearly demonstrating the characteristic change in the disease group. Although the cause of the scavenging capacity change by the disease state is not completely understood, the profile of multiple radical scavenging capacities may become a useful diagnostic tool. PMID:22962529

  10. Does penile rehabilitation have a role in the treatment of erectile dysfunction following radical prostatectomy?

    Science.gov (United States)

    Blecher, Gideon; Almekaty, Khaled; Kalejaiye, Odunayo; Minhas, Suks

    2017-01-01

    In men undergoing radical treatment for prostate cancer, erectile function is one of the most important health-related quality-of-life outcomes influencing patient choice in treatment. Penile rehabilitation has emerged as a therapeutic measure to prevent erectile dysfunction and expedite return of erectile function after radical prostatectomy. Penile rehabilitation involves a program designed to increase the likelihood of return to baseline-level erectile function, as opposed to treatment, which implies the therapeutic treatment of symptoms, a key component of post-radical prostatectomy management. Several pathological theories form the basis for rehabilitation, and a plethora of treatments are currently in widespread use. However, whilst there is some evidence supporting the concept of penile rehabilitation from animal studies, randomised controlled trials are contradictory in outcomes. Similarly, urological guidelines are conflicted in terms of recommendations. Furthermore, it is clear that in spite of the lack of evidence for the role of penile rehabilitation, many urologists continue to employ some form of rehabilitation in their patients after radical prostatectomy. This is a significant burden to health resources in public-funded health economies, and no effective cost-benefit analysis has been undertaken to support this practice. Thus, further research is warranted to provide both scientific and clinical evidence for this contemporary practice and the development of preventative strategies in treating erectile dysfunction after radical prostatectomy.

  11. Preoperative radiochemotherapy and radical surgery in comparison with radical surgery alone

    International Nuclear Information System (INIS)

    Mohr, C.; Schettler, D.; Bohndorf, W.

    1994-01-01

    A multicentric, randomized study of squamous cell carcinoma (SCC) of the oral cavity and the oropharynx has been undertaken by DOeSAK. The results after radical surgery alone have been compared with the results of combined preoperative radiochemotherapy followed by radical surgery. Patients with primary (biopsy proven) SCC of the oral cavity or the oropharynx with tumor nodes metastasis (TNM) stages T2-4, N0-3, M0 were included in the study. A total of 141 patients were treated by radical surgery alone, whereas 127 patients were treated by radical surgery preceded by preoperative radiochemotherapy. The pre-operative treatment consisted of conventionally fractioned irradiation on the primary and the regional lymph nodes with a total dose of 36 Gy (5 x 2 Gy per week) and low-dose cisplatin chemotherapy with 5 x 12.5 mg cisplatin per m 2 of body surface during the first week of treatment. Radical surgery according to be DOeSAK definitions (DOeSAK, 1982) was performed after a delay of 10-14 days. During the follow-up period, 28.2% of all patients suffered from locoregional recurrence, and 27.2% of the patients died. The percentages were higher after radical surgery alone for locoregional recurrence (31% and 15.6%) and for death (28% and 18.6%). The life-table analysis showed improved survival rates of 4.5% after 1 year and 8.3% after 2 years in the group of patients treated with combined therapy. The demonstrated improvement appeared to be significant with the Gehan-Wilcoxon test as well as with the log rank test below a P value of 5%. (au) (29 refs.)

  12. Pentachlorophenol radical cations generated on Fe(III)-montmorillonite initiate octachlorodibenzo-p-dioxin formation in clays: DFT and FTIR studies

    Science.gov (United States)

    Gu, Cheng; Liu, Cun; Johnston, Cliff T.; Teppen, Brian J.; Li, Hui; Boyd, Stephen A.

    2011-01-01

    Octachlorodibenzodioxin (OCDD) forms spontaneously from pentachlorophenol (PCP) on the surfaces of Fe(III)-saturated smectite clay (1). Here, we used in situ FTIR methods and quantum mechanical calculations to determine the mechanism by which this reaction is initiated. As the clay was dehydrated, vibrational spectra showed new peaks that grew and then reversibly disappeared as the clay rehydrated. First principle DFT calculations of hydrated Fe-PCP clusters reproduced these transient FTIR peaks when inner-sphere complexation and concomitant electron transfer produced Fe(II) and PCP radical cations. Thus, our experimental (FTIR) and theoretical (quantum mechanical) results mutually support the hypothesis that OCDD formation on Fe-smectite surfaces is initiated by the reversible formation of metastable PCP radical cations via single electron transfer from PCP to Fe(III). The negatively charged clay surface apparently selects for this reaction mechanism by stabilizing PCP radical cations. PMID:21254769

  13. Radicals in arithmetic

    NARCIS (Netherlands)

    Palenstijn, Willem Jan

    2014-01-01

    Let K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement group. We give

  14. Radicalization as a Vector: Exploring Non-Violent and Benevolent Processes of Radicalization.

    Directory of Open Access Journals (Sweden)

    Ken Reidy

    2018-03-01

    Full Text Available Successful radicalization posits three outcomes: extremism, terrorism or both. As these are undesirable, radicalization is understood as wholly malevolent and governments work to prevent and/or stop it. Nonetheless, a handful of scholars have recognized that the same radicalization process which results in either outcome may, theoretically at least, also have beneficial outcomes such as environmental awareness or human rights. This article explores one such outcome. Based on interviews with British Muslim aid workers (n=6 operating in Jihadist conflict zones post Arab spring and using constructivist grounded theory, it illustrates how the research participants radicalized to humanitarianism which resulted in them assisting the most plighted of Muslims by deploying to the most wanton of areas: ones commonly referred to as Jihadist conflict zones. Evidently, these destinations are shared with Jihadists and given the array of other observable similarities (socio-demographics and [pre-]mobilization behaviours, these morally opposed groups become conflated by the security services. This is further compounded by the fact that Jihadists manipulate and/or impersonate aid workers so as to funnel people and funds. To distinguish both, this article documents the benevolent pathway of the research participants and juxtaposes it to scholarly knowledge on Jihadist pathways. Socialization was revealed to be the key distinguishing feature rather than descriptive risk factors (such as ideology or moral outrage because the process of radicalization was not found to be the start of the radicalized pathway. It concludes that benevolently radicalized Islamic groups constitute an effective means of pathway divergence for particular typologies by offering an attractive and prosocial alternative to Jihadism. This strengths-based preventative approach (“what’s right” takes the form of a community-centric market competitor to Jihadism rather than a problem

  15. Free radical scavenging activity of coenzyme Q measured by a chemiluminescent assay

    International Nuclear Information System (INIS)

    Battino, Maurizio; Ferri, Elida; Girotti, Stefano; Lenaz, Giorgio

    1991-01-01

    Involvement of coenzyme Q (CoQ) in anti-oxydant activities, in addition to its major redox role, has frequently been suggested in recent years. In order to elucidate if CoQ could really be engaged in scavenging free radicals produced endogenously in a biological system, an experimental system was developed in which beef heart mitochondria in the presence of a saturating NADH concentration and of rotenone produce free radicals. The presence of oxygen-reactive forms was easily detected by a luminol-dependent chemiluminescence process. The chemi-luminescence assay showed that short-chain CoQ homologues can act as pro-oxidants, enhancing free radical effects, while exogenous coenzyme Q 10 could scavenge free radicals, especially at very low concentration. In this system, exogenous CoQ 10 was more effective than α-tocopherol at the same concentration in scavenging free radicals. The molecular mechanism that leads to this activity is still unclear, but these results are of biochemical importance because they indicate that CoQ may act as an anti=oxidant in situations mimicking physiopathological conditions. This direct chemiluminescent method is promising for studies of biochemical processes which involve active oxygen species. (author). 24 refs.; 4 figs

  16. Synthesis and Photochemistry of 1-Iodocyclohexene:Influence of Ultrasound on Ionic vs. Radical Behaviour

    Directory of Open Access Journals (Sweden)

    Jaroslav Blasko

    2007-02-01

    Full Text Available Simultaneous application of UV light and ultrasonic irradiation to a reaction mixture containing 1-iodocyclohexene is reported. The irradiation of 1-iodocyclohexene in methanol was carried out with or without addition of zinc. The effect of ultrasound or mechanical stirring on this solid-liquid system was also compared. The irradiation of 1-iodocyclohexene in methanol in the presence of zinc increases the yield of the nucleophilic trapping product, compared with the yield after irradiation in the absence of zinc. The photodegradation of 1-iodocyclohexene was slightly accelerated after addition of zinc. A rapid formation of radical product was accompanied by substantial decrease of 1-iodocyclohexene after application of ultrasound and irradiation without the zinc. The ultrasound significantly affects the photobehaviour of this reaction, predominantly its radical route. The joint application of ultrasound and zinc contributes positively to the production of radical and ionic products. The sonochemical stirring is more effective than mechanical stirring.

  17. Radical cations of quadricyclane and norbornadiene in polar ZSM-5 matrices: Radical cation photochemical transformations without photons

    International Nuclear Information System (INIS)

    Barnabas, M.V.; Trifunac, A.D.

    1994-01-01

    Radical cations of quadricyclane (Q) and norbornadiene (NBD) are produced by γ-radiolysis in zeolites. In polar ZSM-5, only one radical cation is initially observed below 100K. Increasing the temperature above 200K gives rise to the cyclopentadiene radical cation. Higher temperatures (>360K) give rise to the cyclopenten-4-yl radical. The observation of cyclopentadiene radical cation implies the occurrence of the reverse Diels-Alder reaction. This is a thermally forbidden, photochemically allowed, process, which is made possible by the interaction of the polar zeolite matrix sites with parent NBD and Q radical cations

  18. PBCDD/F formation from radical/radical cross-condensation of 2-Chlorophenoxy with 2-Bromophenoxy, 2,4-Dichlorophenoxy with 2,4-Dibromophenoxy, and 2,4,6-Trichlorophenoxy with 2,4,6-Tribromophenoxy

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Xiangli [Environment Research Institute, Shandong University, Jinan 250100 (China); Yu, Wanni [Environment Research Institute, Shandong University, Jinan 250100 (China); College of Resources and Environment, Linyi University, Linyi 276000 (China); Xu, Fei [Environment Research Institute, Shandong University, Jinan 250100 (China); Zhang, Qingzhu, E-mail: zqz@sdu.edu.cn [Environment Research Institute, Shandong University, Jinan 250100 (China); Hu, Jingtian; Wang, Wenxing [Environment Research Institute, Shandong University, Jinan 250100 (China)

    2015-09-15

    Highlights: • We studied the formation of PBCDD/Fs from the reaction of three CPRs with BPRs. • The substitution pattern of halogenated phenols determines those of PBCDD/Fs. • The substitution of halogenated phenols influence the coupling of phenoxy radicals. • The rate constants of the crucial elementary steps were evaluated. - Abstract: Quantum chemical calculations were carried out to investigate the homogeneous gas-phase formation of mixed polybrominated/chlorinated dibenzo-p-dioxins/benzofurans (PBCDD/Fs) from the cross-condensation of 2-chlorophenoxy radical (2-CPR) with 2-bromophenoxy radical (2-BPR), 2,4-dichlorophenoxy radical (2,4-DCPR) with 2,4-dibromophenoxy radical (2,4-DBPR), and 2,4,6-trichlorophenoxy radical (2,4,6-TCPR) with 2,4,6-tribromophenoxy radical (2,4,6-TBPR). The geometrical parameters and vibrational frequencies were calculated at the MPWB1K/6-31+G(d,p) level, and single-point energy calculations were performed at the MPWB1K/6-311+G(3df,2p) level of theory. The rate constants of the crucial elementary reactions were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction over a wide temperature range of 600–1200 K. Studies show that the substitution pattern of halogenated phenols not only determines the substitution pattern of the resulting PBCDD/Fs, but also has a significant influence on the formation mechanism of PBCDD/Fs, especially on the coupling of the halogenated phenoxy radicals.

  19. 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)

  20. [Transanal laparoscopic radical resection with telescopic anastomosis for low rectal cancer].

    Science.gov (United States)

    Li, Shiyong; Chen, Gang; Du, Junfeng; Chen, Guang; Wei, Xiaojun; Cui, Wei; Yuan, Qiang; Sun, Liang; Bai, Xue; Zuo, Fuyi; Yu, Bo; Dong, Xing; Ji, Xiqing

    2015-06-01

    To assess the safety, feasibility and clinical outcome of laparoscopic radical resection for low rectal cancer with telescopic anastomosis or with colostomy by stapler through transanal resection without abdominal incisions. From January 2010 to September 2014, 37 patients underwent laparoscopic radical resection for low rectal cancer through transanal resection without abdominal incisions. The tumors were 4-7 cm above the anal verge. On preoperative assessment, 26 cases were T1N0M0 and 11 were T2N0M0. For all cases, successful surgery was performed. In telescopic anastomosis group, the mean operative time was (178±21) min, with average blood loss of (76±11) ml and (13±7) lymph nodes harvested. Return of bowel function was (3.0±1.2) d and the hospital stay was (12.0±4.2) d without postoperative complications. Patients were followed up for 3-45 months. Twelve months after surgery, 94.6%(35/37) patients achieved anal function Kirwan grade 1, indicating that their anal function returned to normal. Laparoscopic radical resection for low rectal cancer with telescopic anastomosis or colostomy by stapler through transanal resection without abdominal incisions is safe and feasible. Satisfactory clinical outcome can be achieved mini-invasively.

  1. Studies of combustion kinetics and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Gutman, D. [Catholic Univ. of America, Washington, DC (United States)

    1993-12-01

    The objective of the current research is to gain new quantitative knowledge of the kinetics and mechanisms of polyatomic free radicals which are important in hydrocarbon combustion processes. The special facility designed and built for these (which includes a heatable tubular reactor coupled to a photoionization mass spectrometer) is continually being improved. Where possible, these experimental studies are coupled with theoretical ones, sometimes conducted in collaboration with others, to obtain an improved understanding of the factors determining reactivity. The decomposition of acetyl radicals, isopropyl radicals, and n-propyl radicals have been studied as well as the oxidation of methylpropargyl radicals.

  2. Study of OH● Radicals in Human Serum Blood of Healthy Individuals and Those with Pathological Schizophrenia

    Directory of Open Access Journals (Sweden)

    Wolfgang Linert

    2011-01-01

    Full Text Available The human body is constantly under attack from free radicals that occur as part of normal cell metabolism, and by exposure to environmental factors such as UV light, cigarette smoke, environmental pollutants and gamma radiation. The resulting “Reactive Oxygen Species” (ROS circulate freely in the body with access to all organs and tissues, which can have serious repercussions throughout the body. The body possesses a number of mechanisms both to control the production of ROS and to cope with free radicals in order to limit or repair damage to tissues. Overproduction of ROS or insufficient defense mechanisms leads to a dangerous disbalance in the organism. Thereby several pathomechanisms implicated in over 100 human diseases, e.g., cardiovascular disease, cancer, diabetes mellitus, physiological disease, aging, etc., can be induced. Thus, a detailed investigation on the quantity of oxygen radicals, such as hydroxyl radicals (OH● in human serum blood, and its possible correlation with antioxidant therapy effects, is highly topical. The subject of this study was the influence of schizophrenia on the amount of OH● in human serum blood. The radicals were detected by fluorimetry, using terephthalic acid as a chemical trap. For all experiments the serum blood of healthy people was used as a control group.

  3. Free radicals and lipid peroxidation mediated injury in burn trauma: the role of antioxidant therapy

    International Nuclear Information System (INIS)

    Horton, Jureta W.

    2003-01-01

    Burn trauma produces significant fluid shifts that, in turn, reduce cardiac output and tissue perfusion. Treatment approaches to major burn injury include administration of crystalloid solutions to correct hypovolemia and to restore peripheral perfusion. While this aggressive postburn volume replacement increases oxygen delivery to previously ischemic tissue, this restoration of oxygen delivery is thought to initiate a series of deleterious events that exacerbate ischemia-related tissue injury. While persistent hypoperfusion after burn trauma would produce cell death, volume resuscitation may exacerbate the tissue injury that occurred during low flow state. It is clear that after burn trauma, tissue adenosine triphosphate (ATP) levels gradually fall, and increased adenosine monophosphate (AMP) is converted to hypoxanthine, providing substrate for xanthine oxidase. These complicated reactions produce hydrogen peroxide and superoxide, clearly recognized deleterious free radicals. In addition to xanthine oxidase related free radical generation in burn trauma, adherent-activated neutrophils produce additional free radicals. Enhanced free radical production is paralleled by impaired antioxidant mechanisms; as indicated by burn-related decreases in superoxide dismutase, catalase, glutathione, alpha tocopherol, and ascorbic acid levels. Burn related upregulation of inducible nitric oxide synthase (iNOS) may produce peripheral vasodilatation, upregulate the transcription factor nuclear factor kappa B (NF-κB), and promote transcription and translation of numerous inflammatory cytokines. NO may also interact with the superoxide radical to yield peroxynitrite, a highly reactive mediator of tissue injury. Free radical mediated cell injury has been supported by postburn increases in systemic and tissue levels of lipid peroxidation products such as conjugated dienes, thiobarbituric acid reaction products, or malondialdehyde (MDA) levels. Antioxidant therapy in burn therapy

  4. Reaction of hypochlorite with amino acids and peptides : EPR evidence for rapid rearrangement and fragmentation of nitrogen-centred radicals

    International Nuclear Information System (INIS)

    Hawkins, C.L.; Davies, M.J.

    1998-01-01

    Various amino acid side chains have been shown to be particularly susceptible to attack and modification by hypochlorite (HOCl). It is known that tyrosine is readily chlorinated by HOCl to give 3-chlorotyrosine and this product has been employed as a marker of HOCl-mediated damage to proteins. Cysteine and methionine react rapidly with HOCl to give oxy acids and cystine (from cysteine) and sulphoxides (from methionine). Lysine and amino acids which lack the above functional groups also react with HOCl via the free amino group which results in the generation of unstable chloramine intermediates; subsequent decomposition of these species gives NH 3 , CO 2 and aldehydes. While the products of reaction of HOCl with amino acids and peptides are reasonably well characterised, the mechanism(s) by which these products arise is less well understood. Electron paramagnetic resonance (EPR) spectroscopy with spin trapping and UV/visible spectroscopy has been employed to examine the reaction of HOCl with amino acids and some small peptides. Reaction of HOCl with N-acetyl amino acids or small peptides gives radicals predominantly at α-carbon sites via reaction at N-terminal free amino groups or amide (peptide) bonds. It is proposed that these carbon-centred radicals are produced as a result of the rearrangement of initial nitrogen-centred radicals formed on cleavage of the N-CI bond of the chloramine/chloramide species by a 1,2-shift reaction

  5. Ab initio study of the Si(CH3)2O double free radical under external electric field

    International Nuclear Information System (INIS)

    Chen Xiaojun; Luo Sunzhong; Jiang Shubing; Huang Wei; Gao Xiaoling; Ma Meizhong; Zhu Zhenghe

    2004-01-01

    Infrared spectrum and NMR chemical shifts of Si(CH 3 ) 2 O double free radical were calculated employing density functional theory (DFT) with the basis sets 6-311 + G(2d, p). Excited states, dipole moment and energy of Si(CH 3 ) 2 O double free radical were also calculated using time dependent density function theory (TD-DFT) with the same basis sets. It is found that the external electric field along the X, Y and Z axis affect differently on the excited states and other properties of Si(CH 3 ) 2 O double free radical. (author)

  6. DFT Study on Molecular Structures and ROS Scavenging Mechanisms of Novel Antioxidants from Lespedeza Virgata

    Science.gov (United States)

    Li, Min-jie; Zhang, Liang-miao; Liu, Wei-xia; Lu, Wen-cong

    2011-04-01

    The molecular structure and radical scavenging activity of three novel antioxidants from Lespedeza Virgata, lespedezavirgatol, lespedezavirgatal, and lespedezacoumestan, have been studied using density functional theory with the B3LYP and BhandHLYP methods. The optimized geometries of neutral, radical cation, radical and anion forms were obtained at the B3LYP/6-31G(d) level, in which it was found that all the most stable conformations contain intramolecular hydrogen bonds. The same results were obtained from the MP2 method. The homolytic O—H bond dissociation enthalpy and the adiabatic ionization potential of neutral and anion forms for the three new antioxidants and adiabatic electron affinity and H-atom affinity for hydroxyl radical, superoxide anion radical, and hydrogen peroxide radical were determined both in gas phase and in aqueous solution using IEF-PCM and CPCM model with UAHF or Bondi cavity. The antioxidant activities and reactive oxygen species scavenging mechanisms were then discussed, and the results obtained from different methods are consistent. Furthermore, the antioxidant activities are consistent with the experimental findings of the compounds under investigation.

  7. Monte Carlo simulation of non-linear free radical polymerization using a percolation kinetic gelation model (I): free radical homo polymerization

    International Nuclear Information System (INIS)

    Ghiass, M.; Dabir, B.; Nikazar, M.; Rey, A.D.; Mirzadeh, H.

    2001-01-01

    A kinetic gelation model that incorporates the kinetics of free radical homo polymerization is implemented to determine the effects of kinetics on polymerization statistics and microstructures. The simulation is performed on a simple cubic lattice that has 100 sites in each direction. A new algorithm for random selecting of the next step in a self-avoiding random walk and very efficient mechanisms of mobility of components are introduced to improve the generality of the predictions by removing commonly accruing deficiencies due to early trapping of radicals. A first order kinetics is considered for decomposition of initiator that enables us to consider the effect of temperature on polymerization reaction. Better understanding of microstructural evolution during polymerization and providing a framework to produce a realistic system of highly packed random chains within polymer network are among the benefits of model

  8. Youth De-Radicalization: A Canadian Framework

    Directory of Open Access Journals (Sweden)

    Hafal (Haval Ahmad

    2017-09-01

    Full Text Available Youth radicalization leading to violence has become a growing fear among Canadians, as terrorist attacks are carried out in Western states. Although Canada has suffered relatively fewer acts of violence, this fear has intensified and a de-radicalization strategy is needed in the Canadian context. In a qualitative case study methodology, interviews were conducted with school counsellors, religious leaders, and academics to explore solutions to youth radicalization. Youth de-radicalization approaches from the United Kingdom were analyzed and found that community-based initiatives were missing from programming. Social identity theory is used to explain that youth join radicalized groups to feel a sense of belonging and have to be provided an alternative and moderate group identity to de-radicalize. This study found youth de-radicalization in Canada is best served through a community collaboration approach.

  9. Diffusion of 1,4-butanedithiol radicals on Au(111) and Au(100): A DFT-based comparison

    Energy Technology Data Exchange (ETDEWEB)

    Franke, Andreas; Pehlke, Eckhard [Institut fuer Theoretische Physik und Astrophysik, Universitaet Kiel, 24098 Kiel (Germany)

    2010-07-01

    Organic molecules chemisorbed on surfaces hold the perspective of surface functionalization. The 1,4-butanedithiol radical chemisorbed at the Au(111) or Au(100) surface serves as a model system for the S-Au molecule-substrate bond. Density functional total-energy calculations have been carried out for the chemisorption of the radical on the unreconstructed Au surfaces, which are both known to be stabilized under electrochemical conditions. Local minima with close-by energies indicate multi-valley potential-energy surfaces, which originate from the interplay between the two S-Au adsorbate-substrate bonds and the internal degrees of freedom of the butanedithiol radical. Diffusion paths of the radical on both Au surfaces have been calculated within DFT using VASP. The diffusion barriers for translation and rotation of the radical differ. They can be fine-tuned by varying the applied potential in the electrochemical cell. This is considered theoretically by inspecting the variation of the dipole moment along the reaction paths. Consequences for the dynamics of succeeding diffusion hops are discussed.

  10. Remembering Dutch-Moluccan radicalism

    DEFF Research Database (Denmark)

    Marselis, Randi Lorenz

    2016-01-01

    This article examines memory politics in relation to radical actions of young Dutch-Moluccans, more specifically a train hijacking in 1977 at the village of De Punt in the Netherlands. The article examines how these historical events were remembered in the drama-documentary television film, De Punt...... of the web debate examines how viewers reacted to this interpretation. The web debate functioned as a participatory forum, where collective and national memories and postcolonial history were intensely discussed, and the debate made room for some degree of reconciliation between viewers of Dutch......-Moluccan and of Dutch majority background...

  11. Predicting an optimal outcome after radical prostatectomy: the trifecta nomogram.

    Science.gov (United States)

    Eastham, James A; Scardino, Peter T; Kattan, Michael W

    2008-06-01

    The optimal outcome after radical prostatectomy for clinically localized prostate cancer is freedom from biochemical recurrence along with the recovery of continence and erectile function, a so-called trifecta. We evaluated our series of open radical prostatectomy cases to determine the likelihood of this outcome and develop a nomogram predicting the trifecta. We reviewed the records of patients undergoing open radical prostatectomy for clinical stage T1c-T3a prostate cancer at our center during 2000 to 2006. Men were excluded if they received preoperative hormonal therapy, chemotherapy or radiation therapy, if pretreatment prostate specific antigen was more than 50 ng/ml, or if they were impotent or incontinent before radical prostatectomy. A total of 1,577 men were included in the study. Freedom from biochemical recurrence was defined as post-radical prostatectomy prostate specific antigen less than 0.2 ng/ml. Continence was defined as not having to wear any protective pads. Potency was defined as erection adequate for intercourse upon most attempts with or without phosphodiesterase-5 inhibitor. Mean patient age was 58 years and mean pretreatment prostate specific antigen was 6.4 ng/ml. A trifecta outcome (cancer-free status with recovery of continence and potency) was achieved in 62% of patients. In a nomogram developed to predict the likelihood of the trifecta baseline prostate specific antigen was the major predictive factor. Area under the ROC curve for the nomogram was 0.773 and calibration appeared excellent. A trifecta (optimal) outcome can be achieved in most men undergoing radical prostatectomy. The nomogram permits patients to estimate preoperatively their likelihood of an optimal outcome after radical prostatectomy.

  12. Formation and fragmentation of radical peptide anions: insights from vacuum ultra violet spectroscopy.

    Science.gov (United States)

    Brunet, Claire; Antoine, Rodolphe; Dugourd, Philippe; Canon, Francis; Giuliani, Alexandre; Nahon, Laurent

    2012-02-01

    We have studied the photodissociation of gas-phase deprotonated caerulein anions by vacuum ultraviolet (VUV) photons in the 4.5 to 20 eV range, as provided by the DESIRS beamline at the synchrotron radiation facility SOLEIL (France). Caerulein is a sulphated peptide with three aromatic residues and nine amide bonds. Electron loss is found to be the major relaxation channel at every photon energy. However, an increase in the fragmentation efficiency (neutral losses and peptide backbone cleavages) as a function of the energy is also observed. The oxidized ions, generated by electron photodetachment were further isolated and activated by collision (CID) in a MS(3) scheme. The branching ratios of the different fragments observed by CID as a function of the initial VUV photon energy are found to be independent of the initial photon energy. Thus, there is no memory effect of the initial excitation energy on the fragmentation channels of the oxidized species on the time scale of our tandem MS experiment. We also report photofragment yields as a function of photon energy for doubly deprotonated caerulein ions, for both closed-shell ([M-2H](2-)) non-radical ions and open-shell ([M-3H](2-•)) radical ions. These latter ions are generated by electron photodetachment from [M-3H](3-) precursor ions. The detachment yield increases monotonically with the energy with the appearance of several absorption bands. Spectra for radical and non-radical ions are quite similar in terms of observed bands; however, the VUV fragmentation yield is enhanced by the presence of a radical in caerulein peptides. © American Society for Mass Spectrometry, 2011

  13. Synchrotron-based valence shell photoionization of CH radical

    Energy Technology Data Exchange (ETDEWEB)

    Gans, B., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr; Falvo, C. [Institut des Sciences Moléculaires d’Orsay (ISMO), CNRS, Univ. Paris-Sud, Université Paris-Saclay, F-91405 Orsay (France); Holzmeier, F.; Röder, A. [Institut of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg (Germany); Krüger, J.; Garcia, G. A. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin BP 48, F-91192 Gif sur Yvette Cedex (France); Lopes, A.; Alcaraz, C., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr [Laboratoire de Chimie Physique, UMR 8000 CNRS—Univ. Paris-Sud, Univ. Paris-Saclay, Bât. 350, Centre Universitaire Paris-Sud, F-91405 Orsay Cedex (France); Fittschen, C. [Université Lille, CNRS, UMR 8522–PC2A–Physicochimie des Processus de Combustion et de l’Atmosphère, F-59000 Lille (France); Loison, J.-C. [Institut des Sciences Moléculaires, UMR 5255 CNRS—Université de Bordeaux, Bât. A12, 351 cours de la Libération, F-33405 Talence Cedex (France)

    2016-05-28

    We report the first experimental observations of X{sup +} {sup 1}Σ{sup +}←X {sup 2}Π and a{sup +} {sup 3}Π←X {sup 2}Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.

  14. The Phenalenyl Free Radical - a Jahn-Teller D3H PAH

    Science.gov (United States)

    O'Connor, G. D.; Troy, T. P.; Roberts, D. A.; Chalyavi, N.; Fückel, B.; Crossley, M. J.; Nauta, K.; Schmidt, T. W.; Stanton, J. F.

    2012-06-01

    After benzene and naphthalene, the smallest polycyclic aromatic hydrocarbon bearing six-membered rings is the threefold-symmetric phenalenyl radical. Despite the fact that it is so fundamental, its electronic spectroscopy has not been rigorously scrutinized, in spite of growing interest in graphene fragments for molecular electronic applications. Here we used complementary laser spectroscopic techniques to probe the jet-cooled phenalenyl radical in vacuo. Its spectrum reveals the interplay between four electronic states that exhibit Jahn-Teller and pseudo-Jahn-Teller (Herzberg-Teller) vibronic coupling. The coupling mechanism has been elucidated by the application of various ab initio quantum-chemical techniques.

  15. Thermal- and pH-Dependent Size Variable Radical Nanoparticles and Its Water Proton Relaxivity for Metal-Free MRI Functional Contrast Agents.

    Science.gov (United States)

    Morishita, Kosuke; Murayama, Shuhei; Araki, Takeru; Aoki, Ichio; Karasawa, Satoru

    2016-09-16

    For development of the metal-free MRI contrast agents, we prepared the supra-molecular organic radical, TEMPO-UBD, carrying TEMPO radical, as well as the urea, alkyl group, and phenyl ring, which demonstrate self-assembly behaviors using noncovalent bonds in an aqueous solution. In addition, TEMPO-UBD has the tertiary amine and the oligoethylene glycol chains (OEGs) for the function of pH and thermal responsiveness. By dynamic light scattering and transmission electron microscopy imaging, the resulting self-assembly was seen to form the spherical nanoparticles 10-150 nm in size. On heating, interestingly, the nanoparticles showed a lower critical solution temperature (LCST) behavior having two-step variation. This double-LCST behavior is the first such example among the supra-molecules. To evaluate of the ability as MRI contrast agents, the values of proton ((1)H) longitudinal relaxivity (r1) were determined using MRI apparatus. In conditions below and above CAC at pH 7.0, the distinguishable r1 values were estimated to be 0.17 and 0.21 mM(-1) s(1), indicating the suppression of fast tumbling motion of TEMPO moiety in a nanoparticle. Furthermore, r1 values became larger in the order of pH 7.0 > 9.0 > 5.0. Those thermal and pH dependencies indicated the possibility of metal-fee MRI functional contrast agents in the future.

  16. The first radical-based spintronic memristors: Towards resistive RAMs made of organic magnets

    Science.gov (United States)

    Goss, Karin; Krist, Florian; Seyfferle, Simon; Hoefel, Udo; Paretzki, Alexa; Dressel, Martin; Bogani, Lapo; Institut Fuer Anorganische Chemie, University of Stuttgart Collaboration; 1. Physikalisches Institut, University of Stuttgart Team

    2014-03-01

    Using molecules as building blocks for electronic devices offers ample possibilities for new device functionalities due to a chemical tunability much higher than that of standard inorganic materials, and at the same time offers a decrease in the size of the electronic component down to the single-molecule level. Purely organic molecules containing no metallic centers such as organic radicals can serve as an electronic component with magnetic properties due to the unpaired electron in the radical state. Here we present memristive logic units based on organic radicals of the nitronyl-nitroxide kind. Integrating these purely molecular units as a spin coated layer into crossbar arrays, electrically induced unipolar resistive switching is observed with a change in resistance of up to 100%. We introduce a model based on filamentary reorganization of molecules of different oxidation state revealing the importance of the molecular nature for the switching properties. The major role of the oxidation state of these paramagnetic molecules introduces a magnetic field dependence to the device functionality, which goes along with magnetoresistive charactistics observed for the material. These are the first steps towards a spintronic implementation of organic radicals in electronic devices.

  17. 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

  18. Taking a radical position: Evidence for position specific radical representations in Chinese character recognition using masked priming ERP

    Directory of Open Access Journals (Sweden)

    I-Fan eSu

    2012-09-01

    Full Text Available In the investigation of orthographic representation of Chinese characters, one question that has stimulated much research is whether radicals (character components are specified for spatial position in a character (e.g. Ding, Peng, & Taft, 2004; Tsang & Chen, 2009. Differing from previous work, component or radical position information in this study is conceived in terms of relative frequency across different positions of characters containing it. A lexical decision task in a masked priming paradigm focusing on radicals with preferred position of occurrence was conducted. A radical position that encompasses more characters than other positions was identified to be the preferred position of a particular radical. The prime that was exposed for 96ms might share a radical with the target in the same or different positions. Moreover, the shared radical appeared either in its preferred or non-preferred position in the target. While response latencies only revealed the effect of graphical similarity, both effects of graphical similarity and radical position preference were found in the ERP results. The former effect was reflected in greater positivity in occipital P1 and greater negativity in N400 for radicals in different positions in prime and target characters. The latter effect manifested as greater negativity in occipital N170 and greater positivity in frontal P200 in the same time window elicited by radicals in their non-preferred position. Equally interesting was the reversal of the effect of radical position preference in N400 with greater negativity associated with radicals in preferred position. These findings identify the early ERP components associated with activation of position-specific radical representations in the orthographic lexicon, and reveal the change in the nature of competition from processing at the radical level to the lexical level.

  19. Effects of Solvent and Temperature on Free Radical Formation in Electronic Cigarette Aerosols.

    Science.gov (United States)

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

    2018-01-16

    The ever-evolving market of electronic cigarettes (e-cigarettes) presents a challenge for analyzing and characterizing the harmful products they can produce. Earlier we reported that e-cigarette aerosols can deliver high levels of reactive free radicals; however, there are few data characterizing the production of these potentially harmful oxidants. Thus, we have performed a detailed analysis of the different parameters affecting the production of free radical by e-cigarettes. Using a temperature-controlled e-cigarette device and a novel mechanism for reliably simulating e-cigarette usage conditions, including coil activation and puff flow, we analyzed the effects of temperature, wattage, and e-liquid solvent composition of propylene glycol (PG) and glycerol (GLY) on radical production. Free radicals in e-cigarette aerosols were spin-trapped and analyzed using electron paramagnetic resonance. Free radical production increased in a temperature-dependent manner, showing a nearly 2-fold increase between 100 and 300 °C under constant-temperature conditions. Free radical production under constant wattage showed an even greater increase when going from 10 to 50 W due, in part, to higher coil temperatures compared to constant-temperature conditions. The e-liquid PG content also heavily influenced free radical production, showing a nearly 3-fold increase upon comparison of ratios of 0:100 (PG:GLY) and 100:0 (PG:GLY). Increases in PG content were also associated with increases in aerosol-induced oxidation of biologically relevant lipids. These results demonstrate that the production of reactive free radicals in e-cigarette aerosols is highly solvent dependent and increases with an increase in temperature. Radical production was somewhat dependent on aerosol production at higher temperatures; however, disproportionately high levels of free radicals were observed at ≥100 °C despite limited aerosol production. Overall, these findings suggest that e-cigarettes can be

  20. Suppression of Raman electron spin relaxation of radicals in crystals. Comparison of Cu2+ and free radical relaxation in triglycine sulfate and Tutton salt single crystals.

    Science.gov (United States)

    Hoffmann, S K; Goslar, J; Lijewski, S

    2011-08-31

    Electron spin-lattice relaxation was measured by the electron spin echo method in a broad temperature range above 4.2 K for Cu(2+) ions and free radicals produced by ionizing radiation in triglycine sulfate (TGS) and Tutton salt (NH4)(2)Zn(SO4)2 ⋅ 6H2O crystals. Localization of the paramagnetic centres in the crystal unit cells was determined from continuous wave electron paramagnetic resonance spectra. Various spin relaxation processes and mechanisms are outlined. Cu(2+) ions relax fast via two-phonon Raman processes in both crystals involving the whole phonon spectrum of the host lattice. This relaxation is slightly slower for TGS where Cu(2+) ions are in the interstitial position. The ordinary Raman processes do not contribute to the radical relaxation which relaxes via the local phonon mode. The local mode lies within the acoustic phonon band for radicals in TGS but within the optical phonon range in (NH4)(2)Zn(SO4)2 ⋅ 6H2O. In the latter the cross-relaxation was considered. A lack of phonons around the radical molecules suggested a local crystal amorphisation produced by x- or γ-rays.

  1. Radical production in biological systems

    International Nuclear Information System (INIS)

    Johnson, J.R.; Akabani, G.

    1994-10-01

    This paper describes our effort to develop a metric for radiation exposure that is more fundamental than adsorbed dose and upon which a metric for exposure to chemicals could be based. This metric is based on the production of radicals by the two agents. Radicals produced by radiation in biological systems commonly assumed to be the same as those produced in water despite the presence of a variety of complex molecules. This may explain why the extensive efforts to describe the relationship between energy deposition (track structure) and molecular damage to DNA, based on the spectrum of radicals produced, have not been successful in explaining simple biological effects such as cell killing. Current models assume that DNA and its basic elements are immersed in water-like media and only model the production and diffusion of water-based radicals and their interaction with DNA structures; these models lack the cross sections associated with each macro-component of DNA and only treat water-based radicals. It has been found that such models are not realistic because DNA is not immersed in pure water. A computer code capable of simulating electron tracks, low-energy electrons, energy deposition in small molecules, and radical production and diffusion in water like media has been developed. This code is still in at a primitive stage and development is continuing. It is being used to study radical production by radiation, and radical diffusion and interactions in simple molecular systems following their production. We are extending the code to radical production by chemicals to complement our PBPK modeling efforts. It therefore has been developed primarily for use with radionuclides that are in biological materials, and not for radiation fields

  2. Selective degradation of lignin and elimination of HO radicals in pulps by O3 and UV laser flash irradiation

    Institute of Scientific and Technical Information of China (English)

    林鹿; 周贤涛; 邱玉桂

    2002-01-01

    HO radical is an aggressive reagent to abstract hydrogen from diverse substitutes and lead them to degradation, however, in reaction of active oxygen species with lignins, complex phenolic polymers, in dispersed lignocellulose such as pulp for environment-benign delignification, HO radicals should be eliminated as more as possible to prevent cellulose from unfavorably concomitant degradation. A reaction system of O3 is constructed under UV laser flash irradiation, and HO radicals are controlled efficiently by it. A new mechanism is proposed, for the first time, that O radicals generated from reaction of O3 with UV laser flash irradiation might be the contributor to scavenge HO radicals.

  3. Mechanistic Insights into Radical-Mediated Oxidation of Tryptophan from ab Initio Quantum Chemistry Calculations and QM/MM Molecular Dynamics Simulations.

    Science.gov (United States)

    Wood, Geoffrey P F; Sreedhara, Alavattam; Moore, Jamie M; Wang, John; Trout, Bernhardt L

    2016-05-12

    An assessment of the mechanisms of (•)OH and (•)OOH radical-mediated oxidation of tryptophan was performed using density functional theory calculations and ab initio plane-wave Quantum Mechanics/Molecular Mechanics (QM/MM) molecular dynamics simulations. For the (•)OH reactions, addition to the pyrrole ring at position 2 is the most favored site with a barrierless reaction in the gas phase. The subsequent degradation of this adduct through a H atom transfer to water was intermittently observed in aqueous-phase molecular dynamics simulations. For the (•)OOH reactions, addition to the pyrrole ring at position 2 is the most favored pathway, in contrast to the situation in the model system ethylene, where concerted addition to the double bond is preferred. From the (•)OOH position 2 adduct QM/MM simulations show that formation of oxy-3-indolanaline occurs readily in an aqueous environment. The observed transformation starts from an initial rupture of the O-O bond followed by a H atom transfer with the accompanying loss of an (•)OH radical to solution. Finally, classical molecular dynamics simulations were performed to equate observed differential oxidation rates of various tryptophan residues in monoclonal antibody fragments. It was found that simple parameters derived from simulation correlate well with the experimental data.

  4. A computational study on Lewis acid-catalyzed diastereoselective acyclic radical allylation reactions with unusual selectivity dependence on temperature and epimer precursor.

    Science.gov (United States)

    Georgieva, Miglena K; Santos, A Gil

    2014-12-05

    In stereoselective radical reactions, it is accepted that the configuration of the radical precursor has no impact on the levels of stereoinduction, as a prochiral radical intermediate is planar, with two identical faces, independently of its origin. However, Sibi and Rheault (J. Am. Chem. Soc. 2000, 122, 8873-8879) remarkably obtained different selectivities in the trapping of radicals originated from two epimeric bromides, catalyzed by chelating Lewis acids. The selectivity rationalization was made on the basis of different conformational properties of each epimer. However, in this paper we show that the two epimers have similar conformational properties, which implies that the literature proposal is unable to explain the experimental results. We propose an alternative mechanism, in which the final selectivity is dependent on different reaction rates for radical formation from each epimer. By introducing a different perspective of the reaction mechanism, our model also allows the rationalization of different chemical yields obtained from each epimer, a result not rationalized by the previous model. Adaptation to other radical systems, under different reaction conditions, is also possible.

  5. Multiscale QM/MM molecular dynamics study on the first steps of guanine damage by free hydroxyl radicals in solution.

    Science.gov (United States)

    Abolfath, Ramin M; Biswas, P K; Rajnarayanam, R; Brabec, Thomas; Kodym, Reinhard; Papiez, Lech

    2012-04-19

    Understanding the damage of DNA bases from hydrogen abstraction by free OH radicals is of particular importance to understanding the indirect effect of ionizing radiation. Previous studies address the problem with truncated DNA bases as ab initio quantum simulations required to study such electronic-spin-dependent processes are computationally expensive. Here, for the first time, we employ a multiscale and hybrid quantum mechanical-molecular mechanical simulation to study the interaction of OH radicals with a guanine-deoxyribose-phosphate DNA molecular unit in the presence of water, where all of the water molecules and the deoxyribose-phosphate fragment are treated with the simplistic classical molecular mechanical scheme. Our result illustrates that the presence of water strongly alters the hydrogen-abstraction reaction as the hydrogen bonding of OH radicals with water restricts the relative orientation of the OH radicals with respect to the DNA base (here, guanine). This results in an angular anisotropy in the chemical pathway and a lower efficiency in the hydrogen-abstraction mechanisms than previously anticipated for identical systems in vacuum. The method can easily be extended to single- and double-stranded DNA without any appreciable computational cost as these molecular units can be treated in the classical subsystem, as has been demonstrated here. © 2012 American Chemical Society

  6. Stepwise radical cation Diels-Alder reaction via multiple pathways.

    Science.gov (United States)

    Shimizu, Ryo; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Herein we disclose the radical cation Diels-Alder reaction of aryl vinyl ethers by electrocatalysis, which is triggered by an oxidative SET process. The reaction clearly proceeds in a stepwise fashion, which is a rare mechanism in this class. We also found that two distinctive pathways, including "direct" and "indirect", are possible to construct the Diels-Alder adduct.

  7. Quantum mechanics with non-negative quantum distribution function

    International Nuclear Information System (INIS)

    Zorin, A.V.; Sevastianov, L.A.

    2010-01-01

    Full text: (author)Among numerous approaches to probabilistic interpretation of the conventional quantum mechanics the most close to the N. Bohr idea of the correspondence principle is the D.I. Blokhintzev - Ya.P. Terletsky approach using the quantum distribution function on the coordinate- momentum space. The detailed investigation of this approach has lead to the correspondence rule of V.V. Kuryshkin. Quantum mechanics of Kuryshkin (QMK) embody the program proposed by Yu.M. Shirokov for unifying classical and quantum mechanics in similar mathematical models. QMK develops and enhances Wigner's proposal concerning the calculation of quantum corrections to classical thermodynamic parameters using a phase distribution function. The main result of QMK is the possibility of description by mean of a positively-valued distribution function. This represents an important step towards a completely statistical model of quantum phenomena, compared with the quasi-probabilistic nature of Wigner distribution. Wigner's model does not permit to perform correctly the classical limit in quantum mechanics as well. On the other hand, QMK has a much more complex structure of operators of observables. One of the unsolved problems of QMK is the absence of a priori rules for establishing of auxiliary functions. Nevertheless, while it is impossible to overcome the complex form of operators, we find it quite possible to derive some methods of filing sets of auxiliary functions

  8. Functions and Mechanisms of Sleep

    Directory of Open Access Journals (Sweden)

    Mark R. Zielinski

    2016-04-01

    Full Text Available Sleep is a complex physiological process that is regulated globally, regionally, and locally by both cellular and molecular mechanisms. It occurs to some extent in all animals, although sleep expression in lower animals may be co-extensive with rest. Sleep regulation plays an intrinsic part in many behavioral and physiological functions. Currently, all researchers agree there is no single physiological role sleep serves. Nevertheless, it is quite evident that sleep is essential for many vital functions including development, energy conservation, brain waste clearance, modulation of immune responses, cognition, performance, vigilance, disease, and psychological state. This review details the physiological processes involved in sleep regulation and the possible functions that sleep may serve. This description of the brain circuitry, cell types, and molecules involved in sleep regulation is intended to further the reader’s understanding of the functions of sleep.

  9. Simultaneous electrochemical-electron spin resonance studies of carotenoid cation radicals and dications

    International Nuclear Information System (INIS)

    Khaled, M.; Hadjipetrou, A.; Xinhai Chen; Kispert, L.

    1989-01-01

    Carotenoids are present in the chloroplasts of photosynthetic green plants and serve as photoprotect devices and antenna pigments, and active role in the photosynthetic electron-transport chain with the carotenoid cation radical as an integral part of the electron-transfer process. The research reported herein has confirmed that carotenoid cation radicals have a lifetime that is sensitive to solvent, being longest in CH 2 Cl 2 and are best prepared electrochemically. Semiempirical AM1 and INDO calculations of the trans and cis isomers of β-carotene, canthaxanthin and β-apo-8'-carotenal cation radicals predicted the unresolved EPR line whose linewidth varies to a measurable degree with carotenoid, which subsequent experimental observations affirmed. Simultaneous electrochemical - electron spin resonance studies of carotenoid cation radicals and dications have shown the radicals detected by EPR are formed by the one electron oxidation of the carotenoid, that dimers are not formed upon decay of the radical cations and an estimate of the rate of comproportionation as a function of carotenoid can be given. The formal rate constant K' for heterogenous electron transfer rate at the electrode surface has been deduced from rotating disc experiments. Upon deuteration, and in the presence of excess β-carotene, the half-life for decay of the carotenoid radical cation increased an order of magnitude due to the reaction between diffusion carotenoid dications and carotenoids to form additional radical cations. The carotenoid diffusion coefficients deduced by chronocoulometry substantiates this measurement. The produces formed upon electrochemical studies are being studied by HPLC and the isomers formed thermally are being separated. Additional radical reactions are currently being studied by EPR and electrochemical methods

  10. Involvement of active oxygen in lipid peroxide radical reaction of epidermal homogenate following ultraviolet light exposure

    International Nuclear Information System (INIS)

    Nishi, J.; Ogura, R.; Sugiyama, M.; Hidaka, T.; Kohno, M.

    1991-01-01

    To elucidate the radical mechanism of lipid peroxidation induced by ultraviolet light (UV) irradiation, an electron spin resonance (ESR) study was made on epidermal homogenate prepared from albino rat skin. The exposure of the homogenate to UV light resulted in an increase in lipid peroxide content, which was proportional to the time of UV exposure. Using ESR spin trapping (dimethyl-1-pyrroline-N-oxide, DMPO), the DMPO spin adduct spectrum of lipid radicals (L.) was measured following UV exposure (DMPO-L.:aN = 15.5 G, aH = 22.7 G), as was the spectrum of DMPO-hydroxyl radical (DMPO-OH, aN = aH = 15.5 G). In the presence of superoxide dismutase, the DMPO spin adduct spectrum of lipid radicals was found to be reduced remarkably. Therefore, it was shown that the generation of the lipid radicals partially involves superoxide anion radicals, in addition to hydroxyl radicals. In the ESR free-radical experiment, an ESR signal appeared at g = 2.0064 when the ESR tube filled with homogenate was exposed to UV light at -150 degrees C. The temperature-dependent change in the ESR free radical signal of homogenate exposed to UV light was observed at temperatures varying from -150 degrees C to room temperature. By using degassed samples, it was confirmed that oxygen is involved in the formation of the lipid peroxide radicals (LOO.) from the lipid radicals (L.)

  11. Hyperfine interactions of a muoniated ethyl radical in supercritical CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Cormier, Philip; Taylor, Becky [Department of Chemistry, Mount Allison University, Sackville, New Brunswick, E4L 1G8 (Canada); Ghandi, Khashayar, E-mail: kghandi@mta.c [Department of Chemistry, Mount Allison University, Sackville, New Brunswick, E4L 1G8 (Canada)

    2009-04-15

    A muoniated ethyl radical was studied in supercritical carbon dioxide. The muon and the proton hyperfine coupling constants were measured over temperatures ranging from 305 to 475 K, and a density range from 0.2 to 0.7 (g cm{sup -3}). A decrease was found in the muon hyperfine coupling constants as a function of the density, which can be attributed to the interaction between the CO{sub 2} molecule and the p-orbital of the ethyl radical. The changes to the alpha-proton and beta-proton hyperfine coupling constants with density are attributed to changes in the overall geometry in the formed radical. This system was modeled using quantum calculations.

  12. Gnosticism and Radical Feminism

    DEFF Research Database (Denmark)

    Cahana, Jonathan

    2016-01-01

    and radical feminism would easily fall under this definition. There is, however, one major difference: since radical feminism is a relatively recent phenomenon which also benefited from modern modes of text production and preservation, almost all of the sources are still with us. This, in turn, may allow us...... to use radical feminism to make certain aspects of ancient Gnosticism re-emerge from their long submersion, provided that enough similarities can be independently drawn between the two phenomena to merit such a comparison. This paper therefore presents a comparison between concepts and positions...

  13. Inactivation of catalase by free radicals derived from oxygen via gamma radiolysis

    International Nuclear Information System (INIS)

    Malhaire, J.P.; Gardes-Albert, M.; Ferradini, C.; Sabourault, D.; Ribiere, C.

    1991-01-01

    The inactivation of catalase (10 -5 mol/l) by OH· or OH·/O 2 - · free radicals, at pH 7.4, has been investigated using γ radiolysis with doses up to 9000 Gy. Maxima initial G-values of catalase inactivation have been determined. These values are inferior to those of the free radicals OH· and O 2 - · produced by water radiolysis. Nevertheless, the presence of O 2 /O 2 - · enhances the inactivation due to OH· radicals. The general shape of the inactivation curves as a function of the radiation dose is biphasic: an initial rapid phase (from 0 to ∼ 500 Gy) followed by a slow phase (from ∼ 500 to 9000 Gy). The addition of H 2 O 2 at the beginning of irradiation decreases the inactivation yield by OH· radicals. This phenomenon could be due to the formation of compound-I (catalase-H 2 O 2 ) which would be less sensitive towards OH· radicals than catalase. In the presence of 0.1 mol/l ethanol, catalase (5 x 10 -6 mol/l) is not inactived by O 2 - · and RO 2 · (from ethanol) radicals for an irradiation dose of 2000 Gy, implying a complete protecting effect by ethanol [fr

  14. EPR spin trapping of protein radicals

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, Clare Louise

    2004-01-01

    Electron paramagnetic resonance (EPR) spin trapping was originally developed to aid the detection of low-molecular-mass radicals formed in chemical systems. It has subsequently found widespread use in biology and medicine for the direct detection of radical species formed during oxidative stress...... tumbling radicals are often broad and relatively poor in distinctive features, a number of techniques have been developed that allow a wealth of information to be obtained about the nature, site, and reactions of such radicals. This article summarizes recent developments in this area and reviews selected...... examples of radical formation on proteins....

  15. Reactions of clofibric acid with oxidative and reductive radicals-Products, mechanisms, efficiency and toxic effects

    Science.gov (United States)

    Csay, Tamás; Rácz, Gergely; Salik, Ádám; Takács, Erzsébet; Wojnárovits, László

    2014-09-01

    The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O2-•/HO2• reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O2-•/HO2•. Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC-MS method was developed based on 18O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid.

  16. Free radical formation in DNA: Some new aspects of an old problem

    International Nuclear Information System (INIS)

    Huettermann, J.; Gatzweiler, W.; Lange, M.; Weiland, B.

    1995-01-01

    Despite extensive efforts over the past three decades or more, there is a continuing debate about the number of different free radicals and their detailed chemical structure obtained from DNA irradiated under various conditions concerning, among others, hydration state, temperature of irradiation or measurement, base composition, and radiation dose or quality. The only proposal accepted unanimously is the 5-yl radical on the base thymine involving net H-gain at carbon C 6 denoted T(C 6 + H). Its octet spectrum which usually appears, after irradiation at e.g. 77 K, at elevated temperatures (ca. 200 K) provides for an unmistakable fingerprint in Electron Spin Resonance (ESR) spectroscopy, the method of choice for investigating free radicals in general. All other proposals of radical structures, nothing to say about details of their mechanism of formation or their subsequent reactions, have been challenged and are under debate. This apparently disturbing situation can, in the authors view, be traced back to several fundamental reasons which result from inherent limitations of both the sample itself and of the method of investigation

  17. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    Science.gov (United States)

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-02

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

  18. Measurement of J/{psi} production in pp collisions at {radical}(s)=7 TeV

    Energy Technology Data Exchange (ETDEWEB)

    Aaij, R.; Amoraal, J.; Bauer, T.; Beuzekom, M. van; Bos, E.; Carvalho Akiba, K.; Coco, V.; Eijk, D. van; Farinelli, C.; Hulsbergen, W.; Jans, E.; Jansen, F.; Koppenburg, P.; Kozlinskiy, A.; Leerdam, J. van; Merk, M.; Mous, I.; Oggero, S.; Pellegrino, A.; Pree, T. du; Serra, N.; Storaci, B.; Terrier, H.; Tuning, N.; Wiggers, L.; Ybeles Smit, G. [Nikhef National Institute for Subatomic Physics, Amsterdam (Netherlands); Adeva, B.; Cartelle, P.A.; Carson, L.; Cid Vidal, X.; Esperante Pereira, D.; Albor, V.F.; Fungueirino Pazos, J.L.; Gallas Torreira, A.; Morata, J.A.H.; Iglesias Escudero, C.; Pazos Alvarez, A.; Trigo, E.P.; Plo Casasus, M.; Cobo, C.R.; Perez, P.R.; Saborido Silva, J.J.; Seco, M.; Vazquez Regueiro, P.; Visniakov, J. [Universidad de Santiago de Compostela, Santiago de Compostela (Spain); Adinolfi, M.; Brook, N.H.; Coombes, M.; Hampson, T.; Imong, J.; Naik, P.; Rademacker, J.H.; Solomin, A.; Velthuis, J.J.; Voong, D. [University of Bristol, H.H. Wills Physics Laboratory, Bristol (United Kingdom); Adrover, C.; Aslanides, E.; Cogan, J.; Khanji, B.; Le Gac, R.; Leroy, O.; Mancinelli, G.; Maurice, E.; Sapunov, M.; Serrano, J.; Tsaregorodtsev, A. [Aix-Marseille Universite, CNRS/IN2P3, CPPM, Marseille (France); Affolder, A.; Bowcock, T.J.V.; Brown, H.; Casse, G.; Donleavy, S.; Hennessy, K.; Hicks, E.; Huse, T.; Hutchcroft, D.; Liles, M.; Mylroie-Smith, J.; Patel, G.D.; Rinnert, K.; Shears, T. [University of Liverpool, Oliver Lodge Lab., Liverpool (United Kingdom); Ajaltouni, Z.; Deschamps, O.; Henrard, P.; Jahjah Hussein, M.; Lefevre, R.; Gioi, L. Li; Monteil, S.; Niess, V.; Perret, P.; Roa Romero, D.A.; Sobczak, K. [Univ. Blaise Pascal, CNRS/IN2P3, LPC, Clermont Univ., Clermont-Ferrand (France); Albrecht, J.; Barschel, C.; Buytaert, J.; Caicedo Carvajal, J.M.; Cattaneo, M.; Charpentier, P.; Clemencic, M.; Closier, J.; Collins, P.; Corti, G.; D' Ambrosio, C.; Dijkstra, H.; Ferro-Luzzi, M.; Forty, R.; Frank, M.; Frei, C.; Garnier, J.C. [and others

    2011-05-15

    The production of J/{psi} mesons in proton-proton collisions at {radical}(s)=7 {proportional_to} TeV is studied with the LHCb detector at the LHC. The differential cross-section for prompt J/{psi} production is measured as a function of the J/{psi} transverse momentum p{sub T} and rapidity y in the fiducial region p{sub T} in[0;14]{proportional_to}GeV mskip-2{mu} mskip-1mu c and y element of [2.0;4.5]. The differential cross-section and fraction of J/{psi} from b-hadron decays are also measured in the same p{sub T} and y ranges. The analysis is based on a data sample corresponding to an integrated luminosity of 5.2 pb{sup -1}. The measured cross-sections integrated over the fiducial region are for prompt J/{psi} production and for J/{psi} from b-hadron decays, where the first uncertainty is statistical and the second systematic. The prompt J/{psi} production cross-section is obtained assuming no J/{psi} polarisation and the third error indicates the acceptance uncertainty due to this assumption. (orig.)

  19. 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.

  20. The role of technological innovation in creating radically new product meanings

    DEFF Research Database (Denmark)

    Krabbe, Anders Dahl

    2015-01-01

    This paper explores the concept of technological epiphanies from the literature on design driven innovation. A technological epiphany is defined as a product innovation that can be considered radical, both in terms of technology as well as the meaning and experiences it creates through its design....... Three cases of technological epiphanies from the hearing aid industry are analyzed and discussed in terms of how they represent a radical innovation in technology as well as in product meaning and which role the technological aspect has played in the radical innovation of the meaning of the product....... Three different ways in which technology can function as an enabler for the innovation of product meanings are explored and a fourth is found is found during the analysis. The paper concludes by suggesting directions for future research....

  1. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    Science.gov (United States)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  2. Sensitization of microorganisms and enzymes by radiation-induced selective inorganic radical anions

    International Nuclear Information System (INIS)

    Schubert, J.; Stegeman, H.

    1981-01-01

    Bacterial survival and enzymatic inactivation were examined following exposure to radiolytically-generated radical anions, X - 2 , where X=Cl, Br, I or CNS - . Depending on pH, radical anions react selectively or specifically with cysteine, tryptophan, tyrosine and histidine. Consequently, when one or more of these amino acids is crucial for enzymatic activity or bacterial survival and is attacked by a radical anion, a high degree or radiosensitization may be realized. Halide radical anions can form free chlorine, bromine or iodine. However, these bactericidal halogens are destroyed by reaction with the hydrated electron, e - sub(aq), or at pHs>9, as occurs, for example, when a medium saturated with nitrous oxide, N 2 O, and e - sub(aq) scavenger, is replaced by nitrogen or oxygen. Increasing concentration of other e - sub(aq) scavengers, such as phosphate buffer, promotes formation of halogen from halides. The conditions producing formation and elimination of halogens in irradiated media must be appreciated to avoid confusing radiosensitization by X 2 to X - 2 . Radiosensitization by radical anions of several microorganisms: S. faecalis, S. typhimurium, E. coli, and M. radiodurens is described. A crucial amino acid for survival of S. faecalis appears to be tyrosine, while both tyrosine and tryptophan seem essential for recovery of S. typhimurium from effects of ionizing radiation. It is postulated that the radiosensitizing action of radical anions involves inhibition of DNA repair of strand-breaks by depriving the cells of energy. In view of the high OH scavenging power of foods, it is concluded that the radiosensitization of bacteria and enzymes in foods by radical anions, except for special cases, is not practical. Rather, radical anions serve to identify crucial amino acids to radiosensitization mechanisms in model systems, and possibly in radiotherapy. (author)

  3. Robot-assisted radical prostatectomy in Brazil: preliminary results

    Directory of Open Access Journals (Sweden)

    Jose Roberto Colombo Junior

    2009-12-01

    Full Text Available Purpose: To report the initial experience on robot-assisted radical prostatectomy in Brazil. Methods: From March 2008 to March 2009, a hundred patients were treated with robot-assisted radical prostatectomy. Patient’s demographic data, as well as perioperative results of the procedures, are described in this study. Rresults: Patients’ mean age and mean PSA were 58 years and 7.58 ng/ml, respectively. All procedures were performed through transperitoneal approach, with a mean bleeding of 480 mL and surgical time of 298 minutes. A surgical margin affected by cancer was present in 16% of the cases. There were four complications: bleeding requiring transfusion (two cases, rectal perforation corrected on the spot and inadequate functioning of the robot. There was no conversion to another access or obit occurrences in this caseload. Cconclusions: Robot-assisted prostatectomy is a reality in Brazil and the results herein presented demonstrate that this procedure can be safely performed. Long-term follow-up is still necessary to assess the oncological and functional outcomes.

  4. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

    Østdal, H.; Davies, M.J.; Andersen, Henrik Jørgen

    2002-01-01

    The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2....... Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid...

  5. Search for high mass dilepton resonances in pp collisions at {radical}(s)=7 TeV with the ATLAS experiment

    Energy Technology Data Exchange (ETDEWEB)

    Aad, G [Fakultaet fuer Mathematik und Physik, Albert-Ludwigs-Universitaet, Freiburg i.Br. (Germany); Abbott, B [Homer L. Dodge Department of Physics and Astronomy, University of Oklahoma, Norman, OK (United States); Abdallah, J [Institut de Fisica d' Altes Energies and Universitat Autonoma de Barcelona and ICREA, Barcelona (Spain); Abdelalim, A A [Section de Physique, Universite de Geneve, Geneva (Switzerland); Abdesselam, A [Department of Physics, Oxford University, Oxford (United Kingdom); Abdinov, O [Institute of Physics, Azerbaijan Academy of Sciences, Baku (Azerbaijan); Abi, B [Department of Physics, Oklahoma State University, Stillwater, OK (United States); Abolins, M [Department of Physics and Astronomy, Michigan State University, East Lansing, MI (United States); Abramowicz, H [Raymond and Beverly Sackler School of Physics and Astronomy, Tel Aviv University, Tel Aviv (Israel); Abreu, H [LAL, Univ. Paris-Sud and CNRS/IN2P3, Orsay (France); Acerbi, E [INFN Sezione di Milano (Italy); Dipartimento di Fisica, Universita di Milano, Milano (Italy); Acharya, B S [INFN Gruppo Collegato di Udine (Italy); ICTP, Trieste [Italy; Adams, D L [Physics Department, Brookhaven National Laboratory, Upton, NY (United States); Addy, T N [Department of Physics, Hampton University, Hampton, VA (United States); Adelman, J [Department of Physics, Yale University, New Haven, CT (United States); Aderholz, M [Max-Planck-Institut fuer Physik (Werner-Heisenberg-Institut), Muenchen (Germany); Adomeit, S [Fakultaet fuer Physik, Ludwig-Maximilians-Universitaet Muenchen, Muenchen (Germany); Adragna, P [Department of Physics, Queen Mary University of London, London (United Kingdom); Adye, T [Particle Physics Department, Rutherford Appleton Laboratory, Didcot (United Kingdom); Aefsky, S [Department of Physics, Brandeis University, Waltham, MA (United States)

    2011-06-13

    This Letter presents a search for high mass e{sup +}e{sup -} or {mu}{sup +}{mu}{sup -} resonances in pp collisions at {radical}(s)=7 TeV at the LHC. The data were recorded by the ATLAS experiment during 2010 and correspond to a total integrated luminosity of {approx}40 pb{sup -1}. No statistically significant excess above the Standard Model expectation is observed in the search region of dilepton invariant mass above 110 GeV. Upper limits at the 95% confidence level are set on the cross section times branching ratio of Z{sup '} resonances decaying to dielectrons and dimuons as a function of the resonance mass. A lower mass limit of 1.048 TeV on the Sequential Standard Model Z{sup '} boson is derived, as well as mass limits on Z{sup *} and E{sub 6}-motivated Z{sup '} models.

  6. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  7. Microfluidics as a functional tool for cell mechanics.

    Science.gov (United States)

    Vanapalli, Siva A; Duits, Michel H G; Mugele, Frieder

    2009-01-05

    Living cells are a fascinating demonstration of nature's most intricate and well-coordinated micromechanical objects. They crawl, spread, contract, and relax-thus performing a multitude of complex mechanical functions. Alternatively, they also respond to physical and chemical cues that lead to remodeling of the cytoskeleton. To understand this intricate coupling between mechanical properties, mechanical function and force-induced biochemical signaling requires tools that are capable of both controlling and manipulating the cell microenvironment and measuring the resulting mechanical response. In this review, the power of microfluidics as a functional tool for research in cell mechanics is highlighted. In particular, current literature is discussed to show that microfluidics powered by soft lithographic techniques offers the following capabilities that are of significance for understanding the mechanical behavior of cells: (i) Microfluidics enables the creation of in vitro models of physiological environments in which cell mechanics can be probed. (ii) Microfluidics is an excellent means to deliver physical cues that affect cell mechanics, such as cell shape, fluid flow, substrate topography, and stiffness. (iii) Microfluidics can also expose cells to chemical cues, such as growth factors and drugs, which alter their mechanical behavior. Moreover, these chemical cues can be delivered either at the whole cell or subcellular level. (iv) Microfluidic devices offer the possibility of measuring the intrinsic mechanical properties of cells in a high throughput fashion. (v) Finally, microfluidic methods provide exquisite control over drop size, generation, and manipulation. As a result, droplets are being increasingly used to control the physicochemical environment of cells and as biomimetic analogs of living cells. These powerful attributes of microfluidics should further stimulate novel means of investigating the link between physicochemical cues and the biomechanical

  8. Formation of long-lived radicals on proteins by radical transfer from heme enzymes--a common process?

    DEFF Research Database (Denmark)

    Ostdal, H; Andersen, H J; Davies, Michael Jonathan

    1999-01-01

    concentrations were observed after limited digestion, although this effect was less marked with the HRP/H2O2/BSA system than with Fe(III)Mb/H2O2/BSA, consistent with different modes of radical transfer. More extensive digestion of BSA decreased the radical concentration to levels below those detected with native...... investigated using horseradish peroxidase (HRP)/H2O2, in the presence and absence of added tyrosine. Incubation of HRP with H2O2 and bovine or human serum albumins, in the presence and absence of tyrosine, gave long-lived albumin-derived radicals as detected by EPR spectroscopy. Evidence has been obtained...... for these albumin radicals being located on buried tyrosine residues on the basis of blocking experiments. The effect of protein conformation on radical transfer has been investigated using partial proteolytic digestion prior to protein oxidation. With HRP/H2O2/BSA and Fe(III)Mb/H2O2/BSA increased radical...

  9. Abstraction of iodine from aromatic iodides by alkyl radicals: steric and electronic effects.

    Science.gov (United States)

    Dolenc, Darko; Plesnicar, Bozo

    2006-10-13

    Abstraction of the iodine atom from aryl iodides by alkyl radicals takes place in some cases very efficiently despite the unfavorable difference in bond dissociation energies of C-I bonds in alkyl and aryl iodides. The abstraction is most efficient in iodobenzenes, ortho-substituted with bulky groups. The ease of abstraction can be explained by the release of steric strain during the elimination of the iodine atom. The rate of abstraction correlates fairly well with the strain energy, calculated by density functional theory (DFT) and Hartree-Fock (HF) methods as a difference in the total energy of ortho and para isomers. However, besides the steric bulk, the presence of some other functional groups in an ortho substituent also influences the rate. The stabilization of the transition state, resembling a 9-I-2 iodanyl radical, by electron-withdrawing groups seems to explain a positive sign of the Hammett rho value in the radical abstraction of halogen atoms.

  10. Formation of radical anions of radiosensitizers and related model compounds via electrospray ionization

    DEFF Research Database (Denmark)

    Feketeová, Linda; Albright, Abigail L; Sørensen, Brita Singers

    2014-01-01

    Radiosensitizers are used in radiotherapy to enhance tumour control of radioresistant hypoxic tumours. While the detailed mechanism of radiosensitization is still unknown, the formation of radical anions is believed to be a key step. Thus understanding the ionization reactions of radiosensitizers......, misonidazole and related compounds using a hybrid linear ion trap – Fourier Transform Ion Cyclotron Resonance mass spectrometer (Finnigan-LTQ-FT). A key finding is that negative electrospray ionization of these radiosensitizers leads to the formation of radical anions, allowing their fragmentation reactions...

  11. Structure reactivity relationship in the reaction of DNA guanyl radicals with hydroxybenzoates

    Energy Technology Data Exchange (ETDEWEB)

    Do, Trinh T.; Tang, Vicky J.; Aguilera, Joseph A. [Department of Radiology University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States); Milligan, Jamie R., E-mail: jmilligan@ucsd.ed [Department of Radiology University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States)

    2010-11-15

    In DNA, guanine bases are the sites from which electrons are most easily removed. As a result of hole migration to this stable location on guanine, guanyl radicals are major intermediates in DNA damage produced by the direct effect of ionizing radiation (ionization of the DNA itself and not through the intermediacy of water radicals). We have modeled this process by employing gamma irradiation in the presence of thiocyanate ions, a method which also produces single electron oxidized guanyl radicals in plasmid DNA in aqueous solution. The stable products formed in DNA from these radicals are detected as strand breaks after incubation with the FPG protein. When a phenolic compound is present in the solution during gamma irradiation, the formation of guanyl radical species is decreased by electron donation from the phenol to the guanyl radical. We have quantified the rate of this reaction for four different phenolic compounds bearing carboxylate substituents as proton acceptors. A comparison of the rates of these reactions with the redox strengths of the phenolic compounds reveals that salicylate reacts ca. 10-fold faster than its structural analogs. This observation is consistent with a reaction mechanism involving a proton coupled electron transfer, because intra-molecular transfer of a proton from the phenolic hydroxyl group to the carboxylate group is possible only in salicylate, and is favored by the strong 6-membered ring intra-molecular hydrogen bond in this compound.

  12. Effect of radical species density and ion bombardment during ashing of extreme ultralow-κ interlevel dielectric materials

    International Nuclear Information System (INIS)

    Worsley, M. A.; Bent, S. F.; Fuller, N. C. M.; Tai, T. L.; Doyle, J.; Rothwell, M.; Dalton, T.

    2007-01-01

    The significance of ion impact and radical species density on ash-induced modification of an extreme ultralow-κ interlevel dielectric (ILD) material (κ 2 and Ar/N 2 dual frequency capacitive discharges is determined by combining plasma diagnostics, modeling of the ion angular distribution function, and material characterization such as angle resolved x-ray photoelectron spectroscopy. Radical species density was determined by optical emission actinometry under the same conditions and in the same reactor in a previous study by the present authors. ILD modification is observed and correlated with changes in the plasma for a range of pressures (5-60 mTorr), bias powers (0-350 W), and percent Ar in the source gas (0%, 85%). For the Ar/O 2 discharge, extensive modification of the ILD sidewall was observed for significant ion scattering conditions, whereas minimal modification of the ILD sidewall was observed under conditions of minimal or no ion scattering. Further, for an identical increase in the O-radical density (∼ an order of magnitude), a different degree of modification was induced at the ILD trench bottom surface depending on whether pressure or percent Ar was used to increase the radical density. The different degrees of modification seemingly correlated with the relative changes in the ion current for increasing pressure or percent Ar. For the Ar/N 2 discharge, reduced damage of the ILD sidewall and trench bottom surfaces was observed for increasing pressure (increasing N-radical density) and decreasing ion current to both surfaces. It is, thus, proposed that the mechanism for modification of the porous ILD is dominated by the creation of reactive sites by ion impact under the present conditions. A detailed discussion of the results which support this proposal is presented

  13. Novel Profluorescent Nitroxides for Monitoring Alkyl Radical Reactions During Radiation Degradation

    International Nuclear Information System (INIS)

    George, G.

    2006-01-01

    Hindered amine stabilizers (HAS) are effective at retarding the photo-oxidative and high energy radiation degradation of PP and in certain circumstances, also thermo-oxidative degradation. The effectiveness of HAS as retarders of oxidation relies on the oxidation of the N-C bond by polymer hydroperoxide, ROOH, to form the nitroxyl group -NO which is the scavenger of polymer alkyl radicals, R. This reaction, which produces the alkoxy amine: -NO-R, must be competitive with the reaction of R with oxygen (which gives the chain-carrying peroxy radical, RO 2 ) if this stabilization mechanism is to be important in the inhibition of radiation-induced oxidative degradation of polyolefins by HAS. The rate of this reaction is high and in solution the rate coefficient is from 1 to 9x10 8 l mol - 1 s - 1. The efficient radical trapping by nitroxides has been widely employed in spin-trapping studies by electron spin resonance (esr) spectroscopy]. In addition to the hindered piperidine structure of commercial HAS, more rigid aromatic systems have been studied that are more stable to oxidative degradation and are more efficient at scavenging alkyl radicals. One such family is the iso-indoline nitroxide system, TMDBIO, shown below which, as it contains the phenanthrene fluorophore, is termed phenanthrene nitroxide. This nitroxide only becomes fluorescent when it reacts with alkyl radicals or is reduced and is termed profluorescent. TMDBIO has a vanishingly small fluorescence quantum yield (φ∼10 - 4) due to the enhanced intersystem crossing from the first excited singlet state to the ground state due to electron exchange interactions of the nitroxyl radical. When the nitroxide traps an alkyl radical, R, the resulting alkoxy amine is fluorescent (φ∼10 - 1) and the emission intensity is a measure of the number of reactions that have occurred. This property may be exploited by using quantitative fluorescence spectroscopy to follow the reaction of the nitroxide with alkyl radicals

  14. Nitrate radicals and biogenic volatile organic compounds ...

    Science.gov (United States)

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in

  15. Dimethylzinc-Initiated Radical Coupling of β-Bromostyrenes with Ethers and Amines

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Ahlburg, Andreas; Madsen, Robert

    2015-01-01

    A new coupling reaction has been developed in which β-bromostyrenes react with ethers and tertiary amines to introduce the styryl group in the α-position. The transformation is mediated by Me2Zn/O2 with 10 % MnCl2 and is believed to proceed by a radical addition-elimination mechanism. The ether...... and the amine are employed as solvent and the coupling takes place through the most stable α radical for unsymmetrical substrates. The products are obtained in moderate to good yields as the pure E isomers. The coupling can be achieved with a range of smaller cyclic and acyclic ethers/amines as well as various...

  16. Free radicals in an Adamantane matrix. XI. Electron paramagnetic resonance study of conformations in the β-halo-tert-butyl radicals

    International Nuclear Information System (INIS)

    Lloyd, R.V.; Wood, D.E.

    1975-01-01

    The β-halo-tert-butyl radicals were prepared by x-irradiation of the corresponding isobutyl halides in an adamantane matrix at 77 0 K and their conformations were determined by analysis of their EPR spectra. The radicals are nonplanar at the radical site, the fluoro and chloro radicals trans eclipsed and the bromo and iodo radicals gauche staggered with respect to the relative orientation of the carbon halogen bond and the direction of the singly occupied orbital. Vibration-rotation motions about the favored conformation are much larger for the fluoro radical than for the others. The rate of interconversion of the inequivalent methylene protons is approximately 1.5 x 10 9 sec -1 for the bromo radical at 202 0 K while it is too slow to measure for the iodo radical at the same temperature. The barrier to interconversion has a lower limit of 3 kcal/mol for the bromo radical and higher than that for the iodo radical. The halogen and proton hfsc in gauss and the g values for the XCH 2 C(CH 3 ) 2 radicals are: 19 F = 103.7, CH 2 = 10.4, CH 3 = 23.3, g = 2.0030 at 214 K; 35 Cl = 19.5, CH 2 = 6.3, CH 3 = 21.1, g = 2.0042 at 215 K; 81 Br = 6.7, CH 2 = 21.4, 42.7, CH 3 = 21.4, g = 2.0010 at 202 K; 127 I = 7.0, CH 2 = 21.9, 43.8, CH 3 = 21.9, g = 2.0009 at 208 K. The fluoro radical decays to nonradical products above 318 0 K, the chloro radical converts to 2-methyl allyl radical above 306 0 K, the bromo radical converts to tert-butyl radical by exchange with a matrix proton (or deuteron) at 209 0 K as does the iodo radical above 225 0 K. Photolysis with a Xe lamp converts the bromo and iodo radicals to nonradical products in less than the experimental time constant of 0.3 sec. The hypothesis is put forward that the nonplanarity and high barrier to rotation observed explain the retention of stereochemical configuration in reactions involving β-chloro, β-bromo, and β-iodo alkyl radicals. (auth)

  17. Magnetic Resonance Studies of Proton Loss from Carotenoid Radical Cations

    International Nuclear Information System (INIS)

    Kispert, Lowell D.; Focsan, A. Ligia; Konovalova, Tatyana A.; Lawrence, Jesse; Bowman, Michael K.; Dixon, David A.; Molnar, Peter; Deli, Jozsef

    2007-01-01

    Carotenoids, intrinsic components of reaction centers and pigment-protein complexes in photosynthetic membranes, play a photoprotective role and serve as a secondary electron donor. Before optimum use of carotenoids can be made in artificial photosynthetic systems, their robust nature in living materials requires extensive characterization of their electron transfer, radical trapping ability, stability, structure in and on various hosts, and photochemical behavior. Pulsed ENDOR and 2D-HYSCORE studies combined with DFT calculations reveal that photo-oxidation of natural zeaxanthin (I) and violaxanthin (II) on silica-alumina produces not only the carotenoid radical cations (Car ·+ ) but also neutral radicals ((number s ign)Car · ) by proton loss from the methyl groups at positions 5 or 5(prime), and possibly 9 or 9(prime) and 13 or 13(prime). Notably, the proton loss favored in I at the 5 position by DFT calculations, is unfavorable in II due to the epoxide at the 5, 6 position. DFT calculations predict the isotropic methyl proton couplings of 8-10 MHz for Car # center d ot# + which agree with the ENDOR for carotenoid π-conjugated radical cations. Large α-proton hyperfine coupling constants (>10 MHz) determined from HYSCORE are assigned from the DFT calculations to neutral carotenoid radicals. Proton loss upon photolysis was also examined as a function of carotenoid polarity (Lycopene (III) versus 8(prime)-apo-β-caroten-8(prime)-al (IV)); hydrogen bonding (Lutein (V) versus III); host (silica-alumina versus MCM-41 molecular sieve); and substituted metal in MCM-41. Loss of H + from the 5(5(prime)), 9(9(prime)) or 13(13(prime)) methyl positions has importance in photoprotection. Photoprotection involves nonphotochemical quenching (NPQ) in which 1 Ch1* decays via energy transfer to the carotenoid which returns to the ground state by thermal dissipation; or via electron transfer to form a charge transfer state (I # center d ot# + ...Chl # center d ot# - ), lower in

  18. 17.9.3 Radical cations of diazo compounds

    Science.gov (United States)

    Davies, A. G.

    This document is part of Subvolume E2 `Phosphorus-Centered Radicals, Radicals Centered on Other Heteroatoms, Organic Radical Ions' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  19. Hydrogen adsorption and storage on Palladium – functionalized graphene with NH-dopant: A first principles calculation

    Energy Technology Data Exchange (ETDEWEB)

    Faye, Omar, E-mail: omf071@mail.usask.ca [Department of Mechanical Engineering, College of Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, S7N 5A9 Saskatchewan (Canada); Department of Condensed Matter Physics, Cheikh Anta Diop University, Dakar (Senegal); Szpunar, Jerzy A; Szpunar, Barbara [Department of Mechanical Engineering, College of Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, S7N 5A9 Saskatchewan (Canada); Beye, Aboubaker Chedikh [Department of Condensed Matter Physics, Cheikh Anta Diop University, Dakar (Senegal)

    2017-01-15

    Highlights: • H{sub 2} adsorption in single and double-sided Pd-G(3x3) and the effect of NH radical on graphene were studied. • Strong interaction of Pd and graphene in double-sided Pd-G(3x3) than that in the single-sided Pd-G(3x3). • The storage capacity was 3.622 wt% with a binding energy of 0.658 eV/H2. • The increase of NH radicals on Pd-G(3x3) enhanced the binding of Pd atoms on the graphene sheet. • We predicted that 2NH-dopant at the opposite site of Pd atoms prevents the desorption of Pd atom from graphene sheet. - Abstract: We conducted a detailed theoretical investigation of the structural and electronic properties of single and double sided Pd-functionalized graphene and NH-doped Pd-functionalized graphene, which are shown to be efficient materials for hydrogen storage. Nitrene radical dopant was an effective addition required for enhancing the Pd binding on the graphene sheet as well as the storage of hydrogen. We found that up to eight H{sub 2} molecules could be adsorbed by double-sided Pd-functionalized graphene at 0 K with an average binding energy in the range 1.315–0.567 eVA gravimetric hydrogen density of 3.622 wt% was reached in the Pd-functionalized graphene on both sides. The binding mechanism of H{sub 2} molecules came not only the polarization mechanism between Pd and H atoms but also from the binding of the Pd atoms on the graphene sheet and the orbital hybridization. The most crucial part of our work is measuring the effect of nitrene radical on the H{sub 2} adsorption on Pd-functionalized graphene. Our calculations predicted that the addition of NH radicals on Pd-functionalized graphene enhance the binding of H{sub 2} molecules, which helps also to avoid the desorption of Pd(H{sub 2}){sub n} (n = 1–5) complexes from graphene sheet. Our results also predict Pd-functionalized NH-doped graphene is a potential hydrogen storage medium for on-board applications.

  20. Hydrogen adsorption and storage on Palladium – functionalized graphene with NH-dopant: A first principles calculation

    International Nuclear Information System (INIS)

    Faye, Omar; Szpunar, Jerzy A; Szpunar, Barbara; Beye, Aboubaker Chedikh

    2017-01-01

    Highlights: • H_2 adsorption in single and double-sided Pd-G(3x3) and the effect of NH radical on graphene were studied. • Strong interaction of Pd and graphene in double-sided Pd-G(3x3) than that in the single-sided Pd-G(3x3). • The storage capacity was 3.622 wt% with a binding energy of 0.658 eV/H2. • The increase of NH radicals on Pd-G(3x3) enhanced the binding of Pd atoms on the graphene sheet. • We predicted that 2NH-dopant at the opposite site of Pd atoms prevents the desorption of Pd atom from graphene sheet. - Abstract: We conducted a detailed theoretical investigation of the structural and electronic properties of single and double sided Pd-functionalized graphene and NH-doped Pd-functionalized graphene, which are shown to be efficient materials for hydrogen storage. Nitrene radical dopant was an effective addition required for enhancing the Pd binding on the graphene sheet as well as the storage of hydrogen. We found that up to eight H_2 molecules could be adsorbed by double-sided Pd-functionalized graphene at 0 K with an average binding energy in the range 1.315–0.567 eVA gravimetric hydrogen density of 3.622 wt% was reached in the Pd-functionalized graphene on both sides. The binding mechanism of H_2 molecules came not only the polarization mechanism between Pd and H atoms but also from the binding of the Pd atoms on the graphene sheet and the orbital hybridization. The most crucial part of our work is measuring the effect of nitrene radical on the H_2 adsorption on Pd-functionalized graphene. Our calculations predicted that the addition of NH radicals on Pd-functionalized graphene enhance the binding of H_2 molecules, which helps also to avoid the desorption of Pd(H_2)_n (n = 1–5) complexes from graphene sheet. Our results also predict Pd-functionalized NH-doped graphene is a potential hydrogen storage medium for on-board applications.

  1. 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.)

  2. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

    Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded in the l......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...... radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem...

  3. Electronic structure of Co islands grown on the {radical}3 x {radical}3-Ag/Ge(111) surface

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xiao-Lan; Chou, Chi-Hao; Lin, Chun-Liang; Tomaszewska, Agnieszka; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

    2011-09-30

    By means of room temperature scanning tunneling spectroscopy (RT STS), we have studied the electronic structure of two different Ag/Ge(111) phases as well as Co islands grown on the {radical}3 x {radical}3-Ag/Ge (111) forming either {radical}13 x {radical}13 or 2 x 2 patterns. The spectrum obtained from 4 x 4-Ag/Ge(111) structure shows the existence of a shoulder at 0.7 V which is also present in the electronic structure of the Ge(111)-c2 x 8 and indicates donation of Ge electrons to electronic states of the Ag-driven phase. However, this fact is not supported by the electronic spectrum taken from the {radical}3 x {radical}3-Ag/Ge (111). The complexity of the Co-{radical}13 x {radical}13 islands bonding with the substrate is mirrored by a large number of peaks in their electronic spectra. The spectra obtained from the Co-2 x 2 islands which had grown on the step differ from those taken from Co-2 x 2 islands located along the edge of the terrace by a number of peaks at negative sample bias. This discrepancy is elucidated in terms of dissimilarities of Co-substrate interaction accompanying Co islands growth on different areas of the stepped surface.

  4. Understanding political radicalization: The two-pyramids model.

    Science.gov (United States)

    McCauley, Clark; Moskalenko, Sophia

    2017-04-01

    This article reviews some of the milestones of thinking about political radicalization, as scholars and security officials struggled after 9/11 to discern the precursors of terrorist violence. Recent criticism of the concept of radicalization has been recognized, leading to a 2-pyramids model that responds to the criticism by separating radicalization of opinion from radicalization of action. Security and research implications of the 2-pyramids model are briefly described, ending with a call for more attention to emotional experience in understanding both radicalization of opinion and radicalization of action. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

  5. Orgasm after radical prostatectomy

    NARCIS (Netherlands)

    Koeman, M; VanDriel, MF; Schultz, WCMW; Mensink, HJA

    Objective To evaluate the ability to obtain and the quality of orgasm after radical prostatectomy, Patients and methods The orgasms experienced after undergoing radical prostatectomy were evaluated in 20 men (median age 65 years, range 56-76) using a semi-structured interview and a self-administered

  6. O Behaviorismo Radical como filosofia da mente Radical Behaviorism as philosophy of mind

    Directory of Open Access Journals (Sweden)

    Carlos Eduardo Lopes

    2003-01-01

    Full Text Available O Behaviorismo Radical de B. F. Skinner é constantemente acusado de eliminar a mente de sua explicação do comportamento humano. Uma análise do livro The Concept of Mind, de Gilbert Ryle, sugere a possibilidade de defender a existência de uma mente relacional, diferente da categoria de existência da mente defendida em interpretações cartesianas (mente substancial. A análise de alguns textos de Skinner sugere que o conceito de uma mente relacional também pode ser defendido no Behaviorismo Radical. Esse fato, culminaria na possibilidade de que, além de filosofia da Ciência do Comportamento, o Behaviorismo Radical, também pode ser uma filosofia da mente, o que traria conseqüências ao estudo e à aplicação da Análise do Comportamento.B. F. Skinner's Radical Behaviorism has been repeatedly accused of eliminating the mind from its explanation of human behavior. An analysis of Gilbert Ryle's book, The Concept of Mind, suggests the possibility of defending the existence of a relational mind, different from the category of existence of mind defended in Cartesian interpretations (substantial mind. The analysis of some texts of Skinner suggests that the concept of a relational mind can also be defended in Radical Behaviorism. This fact would lead to the possibility that, beyond a philosophy of Behavior Science, Radical Behaviorism may also be a philosophy of mind, which would bring consequences to the study and application of Analysis of Behavior.

  7. Systematic evaluation of skeletal mechanical function.

    Science.gov (United States)

    Smith, Lauren; Bigelow, Erin M R; Jepsen, Karl J

    2013-06-01

    Many genetic and environmental perturbations lead to measurable changes in bone morphology, matrix composition, and matrix organization. The skeletal system is highly adaptive, such that genetic and environmental perturbations affecting one trait are often accompanied by compensatory changes in other traits. This adaptation should be considered when attempting to draw meaningful conclusions about the role of a gene, for example. The challenge is to figure out which alterations can be attributed to the perturbation and which result from adaptive changes associated with establishing mechanical function. The goal of this chapter is to describe straight-forward biomechanical methods that can be used to determine whether a genetic or environmental perturbation affected bone strength. We introduce a systematic method for evaluating how bone strength was altered in the context of morphology and tissue-level mechanical properties, which are determined in large part from matrix composition, matrix organization, and porosity. We present this work as a first step toward screening mice for a phenotypic effect and for establishing the associated biomechanical mechanism by which function was altered. The outcome of these analyses generally provides insight into the next set of experiments required to further connect the cellular perturbation with the functional changes. The protocols were written to enable researchers without a background in engineering to conduct the assays or to enable researchers to better understand the outcomes of similar assays conducted by colleagues knowledgeable in engineering.

  8. On quantum mechanical phase-space wave functions

    DEFF Research Database (Denmark)

    Wlodarz, Joachim J.

    1994-01-01

    An approach to quantum mechanics based on the notion of a phase-space wave function is proposed within the Weyl-Wigner-Moyal representation. It is shown that the Schrodinger equation for the phase-space wave function is equivalent to the quantum Liouville equation for the Wigner distribution...... function. The relationship to the recent results by Torres-Vega and Frederick [J. Chem. Phys. 98, 3103 (1993)] is also discussed....

  9. Muonium radicals in benzene-styrene mixtures

    International Nuclear Information System (INIS)

    Ng, B.W.; Stadlbauer, J.W.; Walker, D.C.

    1984-01-01

    Muonium radicals were observed through their μ + SR precession frequencies in high transverse magnetic fields in pure benzene, pure styrene and their mixtures, all as liquids at room temperature. In benzene-styrene mixtures, the radicals obtained in each pure liquid are both present, so no slow (10 -9 -10 -5 s) intermolecular exchange occurs; but strong selectivity was found with the formation of the radical from styrene being about eight-times more probable than the radical from benzene. (Auth.)

  10. The properties and Roles of Resonance-Stabilized Radicals in Photochemical Pathways in Titan's Atmosphere

    Science.gov (United States)

    Sebree, Joshua A.; Kidwell, Nathan; Zwier, Timothy

    2010-11-01

    In recent years, the Cassini satellite has been providing details about the composition of Titan's atmosphere. Recent data has shown the existence of polycyclic aromatic hydrocarbons (PAHs) at higher altitudes than previously expected including masses tentatively ascribed to naphthalene and anthracene. The formation of indene (C9H9) and naphthalene (C10H8), the simplest PAHs, and their derivatives are of great interest as similar mechanisms may lead to the formation of larger fused-ring systems. In recent years it has been proposed that resonance-stabilized radicals (RSRs) may play an important role as intermediates along these pathways. RSRs gain extra stability by delocalizing the unpaired electron through a neighboring conjugated π-system. Because of this extra stability, RSRs are able to build up in concentration, allowing for the creation of larger, more complex systems through their recombination with other RSRs. Mass-selective UV-visible spectra of two RSRs, phenylallyl and benzylallenyl radicals, have been recorded under jet-cooled conditions. These two radicals, while sharing the same radical conjugation, have unique properties. The roles these radicals may play in the formation of fused ring systems will be discussed along with recent photochemical results on reaction pathways starting from benzylallene through the benzylallenyl radical.

  11. 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.

  12. Laparoscopic radical cystectomy: key points

    Directory of Open Access Journals (Sweden)

    D. V. Perlin

    2018-01-01

    Full Text Available Background. Radical cystectomy remains the golden standard for treatment of muscle invasive bladder cancer. Objective: to duplicate with highest accuracy the open radical cystectomy procedure, which we successfully utilized earlier in our clinic, in the of laparoscopic conditions in order to preserve the advantages of minimally invasive procedures and retain the reliability of the tried and tested open surgery.Materials and methods. In the report were included 35 patients (27 men and 8 women with bladder cancer, who underwent laparoscopic radical cystectomy in Volgograd Regional Center of Urology and Nephrology between April 2013 and March 2016. Only the patients who had been submitted to full intracorporal ileal conduits were included.Results. The mean operative time was 378 minutes, the mean blood loss was 285 millilitres, the mean length of hospital stay was 12.4 days, only 20 % of patients required the narcotic anesthetics. The postoperative complication rate was 11.4 %. However, the majority of the patients were successfully treated with minimally invasive procedures. Generally, our results were similar to other reported studies.Conclusion. Laparoscopic radical cystectomy is a safe and efficient modality of treatment of bladder cancer. However, it needs more procedures and longer observation period to establish laparoscopic radical cystectomy as an alternative to open radical cystectomy.

  13. Muslim Education, Celebrating Islam and Having Fun As Counter-Radicalization Strategies in Indonesia

    Directory of Open Access Journals (Sweden)

    Mark Woodward

    2010-11-01

    Full Text Available The paper refutes the linkage of Muslim education in Indonesia with radicalization, and addresses the commonly held, if incorrect, perception that theological conservatism has a causal relationship with violent extremism. Rather than a causal agent for extremism, Muslim education in Indonesia tends to operate as a protective mechanism against radicalization, as does participation in vibrant religious and cultural celebrations. Students attending the secular universities are most susceptible to extremist discourse, through the process of re-Islamization and the development of a stark and detached rational understanding of Islam. 

  14. Sulfate radical-induced degradation of Acid Orange 7 by a new magnetic composite catalyzed peroxymonosulfate oxidation process

    International Nuclear Information System (INIS)

    Chen, Dan; Ma, Xiaolong; Zhou, Jizhi; Chen, Xi; Qian, Guangren

    2014-01-01

    Graphical abstract: Organic dyes could be absorbed on the surface of the composite or dispersed in the solution. Sulfate radicals (SO 4 · − ) generated by the synergistic reaction between peroxymonosulfate (PMS) and the composite, attacked the organic functional groups of the dyes molecules both adsorbed on the composite surface and dispersed in the solution, which resulted in the degradation of AO7 dye. - Highlights: • A new composite was synthesized successfully via microwave hydrothermal method. • The complete degradation in the system of FLCN and PMS can be achieved. • The catalytic behavior of FLCN can be reused at least for five times. • The AO7 degradation mechanism in the system of FLCN and PMS was demonstrated. - Abstract: We synthesized a novel magnetic composite, Fe 3 O 4 /Cu(Ni)Cr-LDH, as a heterogeneous catalyst for the degradation of organic dyes in the solution using sulfate radical-based advanced oxidation processes. The physicochemical properties of the composite synthesized via two-step microwave hydrothermal method were characterized by several techniques, such as X-ray diffraction (XRD), inductively coupled plasma (ICP), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The degradation tests were performed at 25 °C with Acid Orange 7 (AO7) initial concentration of 25 mg/L and AO7/peroxymonosulfate (PMS) molar ratio of 1:10, which showed that the complete degradation by Fe 3 O 4 /Cu 1.5 Ni 0.5 Cr-LDH could be achieved and the mineralization rate could reach 46%. PMS was activated by Cu (II) and Fe (II/III) of Fe 3 O 4 /Cu(Ni)Cr-LDH to generate sulfate radicals (SO 4 · − ). Subsequently, the organic functional groups of AO7 molecules were destroyed by sulfate radicals (SO 4 · − ), inducing the degradation of AO7. Moreover, the catalytic behavior of the catalysts could be reused five times. Therefore, our work suggested that the Fe 3 O 4 /Cu(Ni)Cr-LDH composite could be applied widely for the

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Free radicals in health and disease

    International Nuclear Information System (INIS)

    Gonet, B.

    1993-01-01

    Free radicals appear in the cells as the result of exogenic factors (ionizing radiation, UV) or reactions naturally occurring in the cell. Free radical reactions may cause destruction of macromolecules (DNA, lipids, proteins). Free radical pathology is important in many diseases and aging processes in organisms

  20. Kinetics of several oxygenated carbon-centered free radical reactions with NO2.

    Science.gov (United States)

    Rissanen, Matti P; Arppe, Suula L; Timonen, Raimo S

    2013-05-16

    Five oxygenated carbon-centered free radical reactions with nitrogen dioxide (NO2) have been studied in direct time-resolved measurements. Experiments were conducted in a temperature-controlled flow tube reactor coupled to a 193 nm exciplex laser photolysis and a resonance gas lamp photoionization mass spectrometer. Reactions were investigated under pseudofirst-order conditions, with the NO2 concentrations of the experiments in great excess over the initial radical concentrations ([R]0 CH3CO radical reactions with NO2 and, hence, includes the three smallest hydroxyalkyl radical species (CH2OH, CH2CH2OH, and CH3CHOH). The obtained rate coefficients are high with the temperature-dependent rate coefficients given by a formula k(T) = k300K × (T/300 K)(-n) as (in units of cm(3) molecule(-1) s(-1)): k(CH2OH + NO2) = (8.95 ± 2.70) × 10(-11) × (T/300 K)(-0.54±0.27) (T = 298-363 K), k(CH2CH2OH + NO2) = (5.99 ± 1.80) × 10(-11) × (T/300 K)(-1.49±0.45)(T = 241-363 K), k(CH3CHOH + NO2) = (7.48 ± 2.24) × 10(-11) × (T/300 K)(-1.36±0.41) (T = 266-363 K), k(CH3OCH2 + NO2) = (7.85 ± 2.36) × 10(-11) × (T/300 K)(-0.93±0.28) (T = 243-363 K), and k(CH3CO + NO2) = (2.87 ± 0.57) × 10(-11) × (T/300 K)(-2.45±0.49) (T = 241-363 K), where the uncertainties refer to the estimated overall uncertainties of the values obtained. The determined rate coefficients show negative temperature dependence with no apparent bath gas pressure dependence under the current experimental conditions (241-363 K and about 1-3 Torr helium). This behavior is typical for a radical-radical addition mechanism with no potential energy barrier above the energy of the separated reactants in the entrance channel of the reaction. Unfortunately the absence of detected product signals prevented gaining deeper insight into the reaction mechanism.

  1. Damage of polyesters by the atmospheric free radical oxidant NO3 •: a product study involving model systems

    Science.gov (United States)

    Goeschen, Catrin

    2013-01-01

    Summary Manufactured polymer materials are used in increasingly demanding applications, but their lifetime is strongly influenced by environmental conditions. In particular, weathering and ageing leads to dramatic changes in the properties of the polymers, which results in decreased service life and limited usage. Despite the heavy reliance of our society on polymers, the mechanism of their degradation upon exposure to environmental oxidants is barely understood. In this work, model systems of important structural motifs in commercial high-performing polyesters were used to study the reaction with the night-time free radical oxidant NO3 • in the absence and presence of other radical and non-radical oxidants. Identification of the products revealed ‘hot spots’ in polyesters that are particularly vulnerable to attack by NO3 • and insight into the mechanism of oxidative damage by this environmentally important radical. It is suggested that both intermediates as well as products of these reactions are potentially capable of promoting further degradation processes in polyesters under environmental conditions. PMID:24204400

  2. Watson-Crick Base Pair Radical Cation as a Model for Oxidative Damage in DNA.

    Science.gov (United States)

    Feketeová, Linda; Chan, Bun; Khairallah, George N; Steinmetz, Vincent; Maitre, Philippe; Radom, Leo; O'Hair, Richard A J

    2017-07-06

    The deleterious cellular effects of ionizing radiation are well-known, but the mechanisms causing DNA damage are poorly understood. The accepted molecular events involve initial oxidation and deprotonation at guanine sites, triggering hydrogen atom abstraction reactions from the sugar moieties, causing DNA strand breaks. Probing the chemistry of the initially formed radical cation has been challenging. Here, we generate, spectroscopically characterize, and examine the reactivity of the Watson-Crick nucleobase pair radical cation in the gas phase. We observe rich chemistry, including proton transfer between the bases and propagation of the radical site in deoxyguanosine from the base to the sugar, thus rupturing the sugar. This first example of a gas-phase model system providing molecular-level details on the chemistry of an ionized DNA base pair paves the way toward a more complete understanding of molecular processes induced by radiation. It also highlights the role of radical propagation in chemistry, biology, and nanotechnology.

  3. EPR studies of free radicals decay and survival in gamma irradiated aminoglycoside antibiotics: sisomicin, tobramycin and paromomycin.

    Science.gov (United States)

    Wilczyński, Sławomir; Pilawa, Barbara; Koprowski, Robert; Wróbel, Zygmunt; Ptaszkiewicz, Marta; Swakoń, Jan; Olko, Paweł

    2012-02-14

    Radiation sterilization technology is more actively used now that any time because of its many advantages. Gamma radiation has high penetrating power, relatively low chemical reactivity and causes small temperature rise. But on the other hand radiosterilization can lead to radiolytic products appearing, in example free radicals. Free radicals in radiative sterilized sisomicin, tobramycin and paromomycin were studied by electron paramagnetic resonance (EPR) spectroscopy. Dose of gamma irradiation of 25kGy was used. Concentrations and properties of free radicals in irradiated antibiotics were studied. EPR spectra were recorded for samples stored in air and argon. For gamma irradiated antibiotics strong EPR lines were recorded. One- and two-exponential functions were fitted to experimental points during testing and researching of time influence of the antibiotics storage to studied parameters of EPR lines. Our study of free radicals in radiosterilized antibiotics indicates the need for characterization of medicinal substances prior to sterilization process using EPR values. We propose the concentration of free radicals and other spectroscopic parameters as useful factors to select the optimal type of sterilization for the individual drug. The important parameters are i.a. the τ time constants and K constants of exponential functions. Time constants τ give us information about the speed of free radicals concentration decrease in radiated medicinal substances. The constant K(0) shows the free radicals concentration in irradiated medicament after long time of storage. Copyright © 2011 Elsevier B.V. All rights reserved.

  4. Scavenging performance and antioxidant activity of γ-alumina nanoparticles towards DPPH free radical: Spectroscopic and DFT-D studies.

    Science.gov (United States)

    Zamani, Mehdi; Moradi Delfani, Ali; Jabbari, Morteza

    2018-05-03

    The radical scavenging performance and antioxidant activity of γ-alumina nanoparticles towards 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical were investigated by spectroscopic and computational methods. The radical scavenging ability of γ-alumina nanoparticles in the media with different polarity (i.e. i-propanol and n-hexane) was evaluated by measuring the DPPH absorbance in UV-Vis absorption spectra. The structure and morphology of γ-alumina nanoparticles before and after adsorption of DPPH were studied using XRD, FT-IR and UV-Vis spectroscopic techniques. The adsorption of DPPH free radical on the clean and hydrated γ-alumina (1 1 0) surface was examined by dispersion corrected density functional theory (DFT-D) and natural bond orbital (NBO) calculations. Also, time-dependent density functional theory (TD-DFT) was used to predict the absorption spectra. The adsorption was occurred through the interaction of radical nitrogen N and NO 2 groups of DPPH with the acidic and basic sites of γ-alumina surface. The high potential for the adsorption of DPPH radical on γ-alumina nanoparticles was investigated. Interaction of DPPH with Brønsted and Lewis acidic sites of γ-alumina was more favored than Brønsted basic sites. The following order for the adsorption of DPPH over the different active sites of γ-alumina was predicted: Brønsted base free radicals. Copyright © 2018. Published by Elsevier B.V.

  5. Effects of exercise training on pulmonary mechanics and functional status in patients with prolonged mechanical ventilation.

    Science.gov (United States)

    Chen, Yen-Huey; Lin, Hui-Ling; Hsiao, Hsiu-Feng; Chou, Lan-Ti; Kao, Kuo-Chin; Huang, Chung-Chi; Tsai, Ying-Huang

    2012-05-01

    The functional status and outcomes in patients with prolonged mechanical ventilation (PMV) are often limited by poor endurance and pulmonary mechanics, which result from the primary diseases or prolonged time bedridden. We evaluate the impact of exercise training on pulmonary mechanics, physical functional status, and hospitalization outcomes in PMV patients. Twenty-seven subjects with PMV in our respiratory care center (RCC) were divided randomly into an exercise training group (n = 12) and a control group (n = 15). The exercise program comprised 10 sessions of exercise training. The measurement of pulmonary mechanics and physical functional status (Functional Independence Measurement and Barthel index) were performed pre-study and post-study. The hospitalization outcomes included: days of mechanical ventilation, hospitalization days, and weaning and mortality rates during RCC stay. The training group had significant improvement in tidal volume (143.6 mL vs 192.5 mL, P = .02) and rapid shallow breathing index after training (162.2 vs 110.6, P = .009). No significant change was found in the control group except respiratory rate. Both groups had significant improvement in functional status during the study. However, the training group had greater changes in FIM score than the control group (44.6 vs 34.2, P = .024). The training group also had shorter RCC stay and higher weaning and survival rates than the control group, although no statistical difference was found. Subjects with PMV in our RCC demonstrated significant improvement in pulmonary mechanics and functional status after exercise training. The application of exercise training may be helpful for PMV patients to improve hospitalization outcomes.

  6. Radical-Local Teaching and Learning

    DEFF Research Database (Denmark)

    Hedegaard, Mariane; Chaiklin, Seth

    radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...

  7. What is Radical Behaviorism? A Review of Jay Moore's Conceptual Foundations of Radical Behaviorism

    Science.gov (United States)

    Baum, William M

    2011-01-01

    B. F. Skinner founded both radical behaviorism and behavior analysis. His founding innovations included: a versatile preparation for studying behavior; explicating the generic nature of stimulus and response; a pragmatic criterion for defining behavioral units; response rate as a datum; the concept of stimulus control; the concept of verbal behavior; and explicating the explanatory power of contingencies. Besides these achievements, however, Skinner also made some mistakes. Subsequent developments in radical behaviorist thought have attempted to remedy these mistakes. Moore's book presents a “party line” version of radical behaviorism. It focuses narrowly on a few of Skinner's concepts (mostly mentalism and verbal behavior) and contains no criticism of his mistakes. In fact, Moore adds a few mistakes of his own manufacture; for example, he insists that the mental realm does not exist—an unprovable and distracting assertion. The book's portrayal of behavior analysis would have been current around 1960; it mentions almost none of the developments since then. It also includes almost no developments in radical behaviorism since Skinner. Moore's book would give an unwary reader a highly distorted picture of contemporary behavior analysis and radical behaviorism.

  8. Sign of the electron exchange coupling in random radical encounter pairs in solution

    International Nuclear Information System (INIS)

    Thurnauer, M.C.; Chiu, T.M.; Trifunac, A.D.

    1985-01-01

    An important parameter in the study of reacting radical systems is the electron exchange interaction, J. The properties of interest are the sign and magnitude of J, and its functional dependence on distance between radicals. One source of information about J is from understanding the Chemically Induced Dynamic Electron Polarization (CIDEP) which is observed in the EPR spectra of reactive radical systems. For radicals reacting in solution to form new covalent bonds, it has generally been found that J O. It is suggested that F-pairs react at a separation greater than that at which spin correlated (geminate) pairs of the same radicals are formed, so that the intervening solvent molecules become involved in the exchange interaction giving rise to J>O via some sort of superexchange process. This is an interesting proposition since superexchange via solvent molecules may play a role in rates of long-distance electron transfer reactions and in the electron transfer reactions of photosynthesis. However, the model suggested runs contrary to all F-air radicals are produced. In order to clarify this important point, the authors present here a definitive study in which we examine several systems of radgenerated independently (exclusive F-pairs) by pulsed laser photolysis and pulsed radiolicals generatedysis in aqueous, alcoholic and hydrocarbon solvents

  9. Applications of tensor functions in creep mechanics

    International Nuclear Information System (INIS)

    Betten, J.

    1991-01-01

    Within this contribution a short survey is given of some recent advances in the mathematical modelling of materials behaviour under creep conditions. The mechanical behaviour of anisotropic solids requires a suitable mathematical modelling. The properties of tensor functions with several argument tensors constitute a rational basis for a consistent mathematical modelling of complex material behaviour. This paper presents certain principles, methods, and recent successfull applications of tensor functions in solid mechanics. The rules for specifying irreducible sets of tensor invariants and tensor generators for material tensors of rank two and four are also discussed. Furthermore, it is very important that the scalar coefficients in constitutive and evolutional equations are determined as functions of the integrity basis and experimental data. It is explained in detail that these coefficients can be determined by using tensorial interpolation methods. Some examples for practical use are discussed. (orig./RHM)

  10. Ultraviolet photodissociation dynamics of the benzyl radical.

    Science.gov (United States)

    Song, Yu; Zheng, Xianfeng; Lucas, Michael; Zhang, Jingsong

    2011-05-14

    Ultraviolet (UV) photodissociation dynamics of jet-cooled benzyl radical via the 4(2)B(2) electronically excited state is studied in the photolysis wavelength region of 228 to 270 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance enhanced multiphoton ionization (REMPI) techniques. In this wavelength region, H-atom photofragment yield (PFY) spectra are obtained using ethylbenzene and benzyl chloride as the precursors of benzyl radical, and they have a broad peak centered around 254 nm and are in a good agreement with the previous UV absorption spectra of benzyl. The H + C(7)H(6) product translational energy distributions, P(E(T))s, are derived from the H-atom TOF spectra. The P(E(T)) distributions peak near 5.5 kcal mol(-1), and the fraction of average translational energy in the total excess energy, , is ∼0.3. The P(E(T))s indicate the production of fulvenallene + H, which was suggested by recent theoretical studies. The H-atom product angular distribution is isotropic, with the anisotropy parameter β ≈ 0. The H/D product ratios from isotope labeling studies using C(6)H(5)CD(2) and C(6)D(5)CH(2) are reasonably close to the statistical H/D ratios, suggesting that the H/D atoms are scrambled in the photodissociation of benzyl. The dissociation mechanism is consistent with internal conversion of the electronically excited benzyl followed by unimolecular decomposition of the hot benzyl radical on the ground state.

  11. Novel technique to enhance bladder neck dissection with traction of Foley catheter during extraperitoneal laparoscopic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Henry Y. Lin

    2015-03-01

    Conclusion: Improved bladder neck enhancement provides a clearer vision during bladder neck dissection. Similar functional results and cancer control rates were also encountered during modified extraperitoneal radical prostatectomy. This novel technique is a feasible method for performing endoscopic radical prostatectomy using four ports instead of five.

  12. The Games Radicals Play: Special Issue on Free Radicals and Radical Ions

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2015-02-01

    Full Text Available 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 arrangements appearing on the scene are even more interesting. Some of these are ephemeral and enjoy only a brief appearance, others are retro-types reappearing in new guises, still others are genuinely new and “go viral” in the scientific world. This Special Issue of Molecules contains the observations and reflections of a select group of chemists and physicists fascinated by this spectacle. It contains an eclectic mix reflecting on new modes and advances as well as on permutations and combinations that revive mature themes. [...

  13. Numerical simulation for production of O and N radicals in an atmospheric-pressure streamer discharge

    International Nuclear Information System (INIS)

    Komuro, Atsushi; Ono, Ryo; Oda, Tetsuji

    2012-01-01

    A streamer discharge model is developed to analyse the characteristics of a pulsed positive streamer discharge in point-to-plane electrodes filled with oxygen-nitrogen mixed gas at room temperature and atmospheric pressure. In this paper we study the mechanisms of O and N radical production in an atmospheric-pressure streamer discharge. To confirm the validity of the simulation model, the discharge emission of light and the discharge current are compared with experimental data at several voltages in gas mixtures with 2-20% oxygen concentrations. The calculated streak picture and the axial distribution of streamer luminous intensity are in good agreement with our previous experimental results. After demonstrating the reliability of the model, we performed a numerical study on radical production by the streamer discharge. The experimentally obtained axial distributions of oxygen radical production in O 2 (20%)/N 2 and nitrogen radical production in O 2 (2%)/N 2 are successfully reproduced in our simulation. For the production of nitrogen radicals, two-step dissociation through the vibrationally excited states is predominant. (paper)

  14. A novel theory: biological processes mostly involve two types of mediators, namely general and specific mediators Endogenous small radicals such as superoxide and nitric oxide may play a role of general mediator in biological processes.

    Science.gov (United States)

    Mo, Jian

    2005-01-01

    A great number of papers have shown that free radicals as well as bioactive molecules can play a role of mediator in a wide spectrum of biological processes, but the biological actions and chemical reactivity of the free radicals are quite different from that of the bioactive molecules, and that a wide variety of bioactive molecules can be easily modified by free radicals due to having functional groups sensitive to redox, and the significance of the interaction between the free radicals and the bioactive molecules in biological processes has been confirmed by the results of some in vitro and in vivo studies. Based on these evidence, this article presented a novel theory about the mediators of biological processes. The essentials of the theory are: (a) mediators of biological processes can be classified into general and specific mediators; the general mediators include two types of free radicals, namely superoxide and nitric oxide; the specific mediators include a wide variety of bioactive molecules, such as specific enzymes, transcription factors, cytokines and eicosanoids; (b) a general mediator can modify almost any class of the biomolecules, and thus play a role of mediator in nearly every biological process via diverse mechanisms; a specific mediator always acts selectively on certain classes of the biomolecules, and may play a role of mediator in different biological processes via a same mechanism; (c) biological processes are mostly controlled by networks of their mediators, so the free radicals can regulate the last consequence of a biological process by modifying some types of the bioactive molecules, or in cooperation with these bioactive molecules; the biological actions of superoxide and nitric oxide may be synergistic or antagonistic. According to this theory, keeping the integrity of these networks and the balance between the free radicals and the bioactive molecules as well as the balance between the free radicals and the free radical scavengers

  15. 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.

  16. Pyrones to pyrans: enantioselective radical additions to acyloxy pyrones.

    Science.gov (United States)

    Sibi, Mukund P; Zimmerman, Jake

    2006-10-18

    This paper describes a highly site-, diastereo-, and enantioselective intermolecular radical addition/hydrogen atom transfer to hydroxypyrone pyromeconic and kojic acids. The methodology can be extended to the formation of chiral quaternary centers. The products obtained are densely functionalized pyran moieties. The products contain structural features amenable for the introduction of additional substituents.

  17. Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

    Science.gov (United States)

    Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

    2017-12-01

    In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Enantioselective radical reactions. Evaluation of nitrogen protecting groups in the synthesis of beta-amino acids.

    Science.gov (United States)

    Sibi, Mukund P; Patil, Kalyani

    2006-02-20

    We have investigated the effect of nitrogen protecting groups in radical addition trapping experiments leading to beta(2)-amino acids. Of the three N-protecting groups examined, the phthalimido group was optimal with respect to both yields and enantioselectivity. Additionally, radical additions to more complex acrylates were also investigated, which provided access to functionalized beta(2)-amino acids in modest selectivity.

  19. Use of a cocktail of spin traps for fingerprinting large range of free radicals in biological systems.

    Science.gov (United States)

    Marchand, Valérie; Charlier, Nicolas; Verrax, Julien; Buc-Calderon, Pedro; Levêque, Philippe; Gallez, Bernard

    2017-01-01

    It is well established that the formation of radical species centered on various atoms is involved in the mechanism leading to the development of several diseases or to the appearance of deleterious effects of toxic molecules. The detection of free radical is possible using Electron Paramagnetic Resonance (EPR) spectroscopy and the spin trapping technique. The classical EPR spin-trapping technique can be considered as a "hypothesis-driven" approach because it requires an a priori assumption regarding the nature of the free radical in order to select the most appropriate spin-trap. We here describe a "data-driven" approach using EPR and a cocktail of spin-traps. The rationale for using this cocktail was that it would cover a wide range of biologically relevant free radicals and have a large range of hydrophilicity and lipophilicity in order to trap free radicals produced in different cellular compartments. As a proof-of-concept, we validated the ability of the system to measure a large variety of free radicals (O-, N-, C-, or S- centered) in well characterized conditions, and we illustrated the ability of the technique to unambiguously detect free radical production in cells exposed to chemicals known to be radical-mediated toxic agents.

  20. 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...