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Sample records for peroxyl radicals derived

  1. 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...

  2. 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

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

    International Nuclear Information System (INIS)

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

    1987-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1987-09-01

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

  5. Pulse radiolysis investigations on the oxidation of bilirubin by chlorinated peroxyl radicals (Preprint No. RC.18)

    International Nuclear Information System (INIS)

    Mohan, Hari; Gopinathan, C.

    1989-01-01

    Chlorinated peroxyl radicals were observed to oxidize bilirubin. The rate constants, estimated from the formation kinetics of bilirubin cation, were observed to decrease with decrease in the chlorine substitution of various chlorinated peroxyl radicals. (author)

  6. 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

  7. 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

  8. 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...

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

    Science.gov (United States)

    Masood, Nusrat; Fatima, Kaneez; Luqman, Suaib

    2014-01-01

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

  10. Beta-carotene encapsulated in food protein nanoparticles reduces peroxyl radical oxidation in Caco-2 cells

    Science.gov (United States)

    Beta-carotene (BC) was encapsulated by sodium caseinate (SC), whey protein isolate (WPI), and soybean protein isolate (SPI) by the homogenization-evaporation method forming nanoparticles of 78, 90 and 370 nm diameter. Indices of the chemical antioxidant assays, the reducing power, DPPH radical scave...

  11. 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.

  12. Iron and iron derived radicals

    International Nuclear Information System (INIS)

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fast! Think small! In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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...

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

    DEFF Research Database (Denmark)

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

    2017-01-01

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

  19. Radicals derived from acetaldehyde and vinyl alcohol.

    Science.gov (United States)

    Estep, Marissa L; Morgan, W James; Winkles, Alexander T; Abbott, Adam S; Villegas-Escobar, Nery; Mullinax, J Wayne; Turner, Walter E; Wang, Xiao; Turney, Justin M; Schaefer, Henry F

    2017-10-18

    Vinyl alcohol and acetaldehyde are isoelectronic products of incomplete butanol combustion. Along with the radicals resulting from the removal of atomic hydrogen or the hydroxyl radical, these species are studied here using ab initio methods as complete as coupled cluster theory with single, double, triple, and perturbative quadruple excitations [CCSDT(Q)], with basis sets as large as cc-pV5Z. The relative energies provided herein are further refined by including corrections for relativistic effects, the frozen core approximation, and the Born-Oppenheimer approximation. The effects of anharmonic zero-point vibrational energies are also treated. The syn conformer of vinyl alcohol is predicted to be lower in energy than the anti conformer by 1.1 kcal mol -1 . The alcoholic hydrogen of syn-vinyl alcohol is found to be the easiest to remove, requiring 84.4 kcal mol -1 . Five other radicals are also carefully considered, with four conformers investigated for the 1-hydroxyvinyl radical. Beyond energetics, we have conducted an overhaul of the spectroscopic literature for these species. Our results also provide predictions for fundamental modes yet to be reported experimentally. To our knowledge, the ν 3 (3076 cm -1 ) and ν 4 (2999 cm -1 ) C-H stretches for syn-vinyl alcohol and all but one of the vibrational modes for anti-vinyl alcohol (ν 1 -ν 14 ) are yet to be observed experimentally. For the acetyl radical, ν 6 (1035 cm -1 ), ν 11 (944 cm -1 ), ν 12 (97 cm -1 ), and accounting for our changes to the assignment of the 1419.9 cm -1 experimental mode, ν 10 (1441 cm -1 ), are yet to be observed. We have predicted these unobserved fundamentals and reassigned the experimental 1419.9 cm -1 frequency in the acetyl radical to ν 4 rather than to ν 10 . Our work also strongly supports reassignment of the ν 10 and ν 11 fundamentals of the vinoxy radical. We suggest that the bands assigned to the overtones of these fundamentals were in fact combination bands. Our

  20. Tyrosine-lipid peroxide adducts from radical termination: para coupling and intramolecular Diels-Alder cyclization.

    Science.gov (United States)

    Shchepin, Roman; Möller, Matias N; Kim, Hye-young H; Hatch, Duane M; Bartesaghi, Silvina; Kalyanaraman, Balaraman; Radi, Rafael; Porter, Ned A

    2010-12-15

    Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogues of tyrosine gave rise to lipid peroxide-tyrosine (phenol) adducts in both aqueous micellar and organic solutions. The novel adducts were isolated and characterized by 1D and 2D NMR spectroscopy as well as by mass spectrometry (MS). The spectral data suggest that the polyunsaturated lipid peroxyl radicals give stable peroxide coupling products exclusively at the para position of the tyrosyl (phenoxy) radicals. These adducts have characteristic (13)C chemical shifts at 185 ppm due to the cross-conjugated carbonyl of the phenol-derived cyclohexadienone. The primary peroxide adducts subsequently undergo intramolecular Diels-Alder (IMDA) cyclization, affording a number of diastereomeric tricyclic adducts that have characteristic carbonyl (13)C chemical shifts at ~198 ppm. All of the NMR HMBC and HSQC correlations support the structure assignments of the primary and Diels-Alder adducts, as does MS collision-induced dissociation data. Kinetic rate constants and activation parameters for the IMDA reaction were determined, and the primary adducts were reduced with cuprous ion to give a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found in either the primary or cuprous reduction product mixtures. These studies provide a framework for understanding the nature of lipid-protein adducts formed by peroxyl-tyrosyl radical-radical termination processes. Coupling of lipid peroxyl radicals with tyrosyl radicals leads to cyclohexenone and cyclohexadienone adducts, which are of interest in and of themselves since, as electrophiles, they are likely targets for protein nucleophiles. One consequence of lipid peroxyl reactions with tyrosyls may therefore be protein-protein cross-links via interprotein Michael adducts.

  1. Protection of myocytes against free radical-induced damage by accelerated turnover of the glutathione redox cycle

    NARCIS (Netherlands)

    Le, C. T.; Hollaar, L.; van der Valk, E. J.; Franken, N. A.; van Ravels, F. J.; Wondergem, J.; van der Laarse, A.

    1995-01-01

    The primary defence mechanism of myocytes against peroxides and peroxide-derived peroxyl and alkoxyl radicals is the glutathione redox cycle. The purpose of the present study was to increase the turnover rate of this cycle by stimulating the glutathione peroxidase catalysed reaction (2GSH-->GSSG),

  2. In vitro evaluation of peroxyl radical scavenging capacity of water ...

    African Journals Online (AJOL)

    STORAGESEVER

    2009-04-06

    Apr 6, 2009 ... ... phenolics viz. condensed tannin and phlobatannin, gallic acid, protocatechuic acid pyrocatechol, (+)- ... Lipid peroxidation by thiobarbituric acid assay (TBA). TBA reacts with .... Antifungal activity of polyphenolic complex of ...

  3. Molecular Dynamics Simulations of the Hydrogen Peroxyl Radical

    Science.gov (United States)

    2014-05-01

    Pasta , and Ulam10 (FPU) on the equipartion of energy in a one-dimensional anharmonic chain of oscillators yielded results that surprised the...gas collision frequency. The energy transference probability is typically based on gas-phase results, and the collision frequency is taken from a...schemes are based on finite steps along the function or system of functions that is being integrated. These finite steps are used to extrapolate to the

  4. Antioxidant activity of the new thiosulfinate derivative, S-benzyl phenylmethanethiosulfinate, from Petiveria alliacea L.

    Science.gov (United States)

    Okada, Youji; Tanaka, Kaoru; Sato, Eisuke; Okajima, Haruo

    2008-03-21

    The antioxidant effects of the new thiosulfinate derivative, S-benzyl phenylmethanethiosulfinate (BPT), against the oxidation of cumene and methyl linoleate (ML) in chlorobenzene were studied in detail using HPLC. The results showed that BPT provided effective inhibition with a well-defined induction period under these oxidation conditions, and it was found that the stoichiometric factor (n), the number of peroxyl radicals trapped by one antioxidant molecule, of BPT is about 2. We then undertook a thorough investigation aimed at elucidating the active structural site of BPT. Various model compounds, such as diphenyl disulfide, dibenzyl disulfide, S-phenyl benzenethiosulfinate and S-ethyl phenylmethanethiosulfinate, were used which provided evidence that the benzylic hydrogen of BPT is mainly associated with the peroxyl radical scavenging. Moreover, we measured the rate constant for the reaction of BPT with peroxyl radicals derived from cumene and ML in chlorobenzene, and based on these measurements, BPT reacts with these peroxyl radicals with a rate constant of k(inh) = 8.6 x 10(3) and 6.2 x 10(4) M(-1) s(-1), respectively.

  5. Analysis of electron spin resonance spectra of irradiated gingers: Organic radical components derived from carbohydrates

    International Nuclear Information System (INIS)

    Yamaoki, Rumi; Kimura, Shojiro; Ohta, Masatoshi

    2010-01-01

    Electron spin resonance (ESR) spectral characterizations of gingers irradiated with electron beam were studied. Complex asymmetrical spectra (near g=2.005) with major spectral components (line width=2.4 mT) and minor signals (at 6 mT apart) were observed in irradiated gingers. The spectral intensity decreased considerably 30 days after irradiation, and continued to decrease steadily thereafter. The spectra simulated on the basis of characteristics of free radical components derived from carbohydrates in gingers are in good agreement with the observed spectra. Analysis showed that shortly after irradiation the major radical components of gingers were composed of radical species derived from amylose and cellulose, and the amylose radicals subsequently decreased considerably. At 30 days after irradiation, the major radical components of gingers were composed of radical species derived from cellulose, glucose, fructose or sucrose.

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

    Science.gov (United States)

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

    2015-10-01

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

  7. Photostability enhancement of the pentacene derivative having two nitronyl nitroxide radical substituents.

    Science.gov (United States)

    Shimizu, Akihiro; Ito, Akitaka; Teki, Yoshio

    2016-02-18

    Pentacene derivatives possessing nitronyl nitroxide radical substituents (1a and 1b) were synthesized, and their photochemical properties were evaluated. 1a with two radical substituents showed a remarkable enhancement of photostability compared with pentacene, 6,13-bis(triisopropylsilylethynyl)pentacene and the monoradical, 1b. This is understood due to the presence of the multiple deactivation pathways in the photoexcited states.

  8. Atmospherically Relevant Radicals Derived from the Oxidation of Dimethyl Sulfide.

    Science.gov (United States)

    Mardyukov, Artur; Schreiner, Peter R

    2018-02-20

    The large number and amounts of volatile organosulfur compounds emitted to the atmosphere and the enormous variety of their reactions in various oxidation states make experimental measurements of even a small fraction of them a daunting task. Dimethyl sulfide (DMS) is a product of biological processes involving marine phytoplankton, and it is estimated to account for approximately 60% of the total natural sulfur gases released to the atmosphere. Ocean-emitted DMS has been suggested to play a role in atmospheric aerosol formation and thereby cloud formation. The reaction of ·OH with DMS is known to proceed by two independent channels: abstraction and addition. The oxidation of DMS is believed to be initiated by the reaction with ·OH and NO 3 · radicals, which eventually leads to the formation of sulfuric acid (H 2 SO 4 ) and methanesulfonic acid (CH 3 SO 3 H). The reaction of DMS with NO 3 · appears to proceed exclusively by hydrogen abstraction. The oxidation of DMS consists of a complex sequence of reactions. Depending on the time of the day or altitude, it may take a variety of pathways. In general, however, the oxidation proceeds via chains of radical reactions. Dimethyl sulfoxide (DMSO) has been reported to be a major product of the addition channel. Dimethyl sulfone (DMSO 2 ), SO 2 , CH 3 SO 3 H, and methanesulfinic acid (CH 3 S(O)OH) have been observed as products of further oxidation of DMSO. Understanding the details of DMS oxidation requires in-depth knowledge of the elementary steps of this seemingly simple transformation, which in turn requires a combination of experimental and theoretical methods. The methylthiyl (CH 3 S·), methylsulfinyl (CH 3 SO·), methylsulfonyl (CH 3 SO 2 ·), and methylsulfonyloxyl (CH 3 SO 3 ·) radicals have been postulated as intermediates in the oxidation of DMS. Therefore, studying the chemistry of sulfur-containing free radicals in the laboratory also is the basis for understanding the mechanism of DMS oxidation in the

  9. Synthesis of heterocyclic chalcone derivatives and their radical scavenging ability toward 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radicals

    International Nuclear Information System (INIS)

    Hwang, Kijun; Kim, Hoseok; Kim, Beomtae; Han, Incheol

    2012-01-01

    A series of heterocyclic chalcone derivatives bearing heterocycles such as thiophene or furan ring as an isostere of benzene ring were carefully prepared, and the influence of heterocycles on 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activities was systematically investigated. Structure-activity relationships (SAR) analysis showed that the activities of thiophene ring-containing chalcones were higher than those of furan ring containing chalcones, and the presence of methyl substituent of heterocyclic ring distinctly affected the activities compared with non-substituted heterocycles in an opposite manner, with the 4'-methyl group of thiophene ring increasing activity and the 3'-methyl group of the furan ring decreasing activity. The distinct isosteric effect of heterocycles (i.e., thiophene or furan ring) on radical scavenging activities of heterocyclic chalcones was distinctly demonstrated in our work

  10. 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.

  11. Study of atmospheric photo-oxidation mechanisms by concentration measurements of peroxy radicals by chemical amplification in the laboratory and in the atmosphere; Etudes des mecanismes de photooxydation atmospherique par mesure des radicaux peroxyles par amplification chimique au laboratoire et dans l'atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Pinceloup, St.

    2002-10-01

    In this thesis, we have continued to develop and to automate a chemical amplifier, with which measurements of peroxy radicals (RO{sub 2}) under real and simulated atmosphere can be made in order to better understand the atmospheric oxidation processes. Firstly, some experiments in laboratory have confirmed the inhibitory effect of water vapour on the chain length of the chemical amplifier, which is a technique of measuring peroxy radicals used by the LCSR. We have shown that the decrease in the chain length is primarily due to the increase of the HO{sub 2} loss to the wall of the amplifier in presence of H2{sub O} and to the HO{sub 2} loss in the gas phase by a minority way of the reaction NO + HO{sub 2} producing HNO{sub 3}. This reaction was studied using a turbulent flow reactor coupled to an ion molecule reactor with mass spectrometric detection. Secondly, the photo-oxidation of formaldehyde has been studied in the atmospheric simulation chamber of the LISA at Creteil coupled with the chemical amplifier. This study has allowed us to determine realistic values of the photolysis constants of radical and molecular ways of formaldehyde and the thermal decomposition constant at 298 K of the adduct HOCH{sub 2}O{sub 2} formed by reaction of HO{sub 2} with HCHO, thanks to the peroxy radicals measurements effectuated. Finally, we have participated in the field campaign, ESCOMPTE, during which concentrations of RO{sub 2}, NO, NO{sub 2} and ozone were measured continuously at the Dupail site. The measured concentrations were typical of a rural site. Using these measurements and those accomplished by other teams, we have determined the production rate of ozone by the radical budget method. The results show that the local photochemical production was important on the Dupail site and controlled essentially by the nitrogen oxides (NO, NO{sub 2}) characterizing a site free of emissions. (author)

  12. 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

  13. Radicals derived from histone hydroperoxides damage nucleobases in RNA and DNA

    DEFF Research Database (Denmark)

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

    2000-01-01

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

  14. 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

  15. Pulse radiolysis studies of bergenin, an isocoumarin polyphenolic derivative

    International Nuclear Information System (INIS)

    Singh, Umang; Srinivasan, R.; Barik, A.; Priyadarsini, K.I.

    2008-01-01

    Bergenin, a polyphenolic isocoumarin derivative, isolated from medicinal plant Caesalpinia digynae, has been subjected for OH and oxidizing radical reactions using pulse radiolysis technique coupled with absorption detection. OH radicals cause multiple reactions, producing transients absorbing with maxima at 440 nm and 500 nm. By comparing the spectra and decay kinetics with that produced by N 3 radicals, the species absorbing at 440 nm is assigned to phenoxyl type radical and the one absorbing at 500 nm to be a hydroxyl-radical adduct, which has been found to be reducing in nature. Bergenin also reacts with peroxyl radicals, with rate constants of 4.2 x 10 6 M -1 s -1 . (author)

  16. Pulse radiolysis studies of bergenin, an isocoumarin polyphenolic derivative

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Umang; Srinivasan, R; Barik, A; Priyadarsini, K I [Radiation and Photochemistry Div., Bhabha Atomic Research Centre, Mumbai (India)

    2008-01-15

    Bergenin, a polyphenolic isocoumarin derivative, isolated from medicinal plant Caesalpinia digynae, has been subjected for OH and oxidizing radical reactions using pulse radiolysis technique coupled with absorption detection. OH radicals cause multiple reactions, producing transients absorbing with maxima at 440 nm and 500 nm. By comparing the spectra and decay kinetics with that produced by N{sub 3} radicals, the species absorbing at 440 nm is assigned to phenoxyl type radical and the one absorbing at 500 nm to be a hydroxyl-radical adduct, which has been found to be reducing in nature. Bergenin also reacts with peroxyl radicals, with rate constants of 4.2 x 10{sup 6} M{sup -1}s{sup -1}. (author)

  17. p53 Mutagenesis by Benzo[a]pyrene derived Radical Cations

    Science.gov (United States)

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

    2013-01-01

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

  18. 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

  19. Excited-state dynamics of pentacene derivatives with stable radical substituents.

    Science.gov (United States)

    Ito, Akitaka; Shimizu, Akihiro; Kishida, Noriaki; Kawanaka, Yusuke; Kosumi, Daisuke; Hashimoto, Hideki; Teki, Yoshio

    2014-06-23

    The excited-state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited-state characteristics of the derivatives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Effects of hydroxylated benzaldehyde derivatives on radiation-induced reactions involving various organic radicals

    Science.gov (United States)

    Ksendzova, G. A.; Samovich, S. N.; Sorokin, V. L.; Shadyro, O. I.

    2018-05-01

    In the present paper, the effects of hydroxylated benzaldehyde derivatives and gossypol - the known natural occurring compound - on formation of decomposition products resulting from radiolysis of ethanol and hexane in deaerated and oxygenated solutions were studied. The obtained data enabled the authors to make conclusions about the effects produced by the structure of the compounds under study on their reactivity towards oxygen- and carbon-centered radicals. It has been found that 2,3-dihydroxybenzaldehyde, 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde and 4,6-di-tert-butyl-3-(1,3-dioxane-2-yl)-1,2-dihydroxybenzene are not inferior in efficiency to butylated hydroxytoluene - the industrial antioxidant - as regards suppression of the radiation-induced oxidation processes occurring in hexane. The derivatives of hydroxylated benzaldehydes were shown to have a significant influence on radiation-induced reactions involving α-hydroxyalkyl radicals.

  1. Novel Water Soluble Chitosan Derivatives with 1,2,3-Triazolium and Their Free Radical-Scavenging Activity.

    Science.gov (United States)

    Li, Qing; Sun, Xueqi; Gu, Guodong; Guo, Zhanyong

    2018-03-28

    Chitosan is an abundant and renewable polysaccharide, which exhibits attractive bioactivities and natural properties. Improvement such as chemical modification of chitosan is often performed for its potential of providing high bioactivity and good water solubility. A new class of chitosan derivatives possessing 1,2,3-triazolium charged units by associating "click reaction" with efficient 1,2,3-triazole quaternization were designed and synthesized. Their free radical-scavenging activity against three free radicals was tested. The inhibitory property and water solubility of the synthesized chitosan derivatives exhibited a remarkable improvement over chitosan. It is hypothesized that triazole or triazolium groups enable the synthesized chitosan to possess obviously better radical-scavenging activity. Moreover, the scavenging activity against superoxide radical of chitosan derivatives with triazolium (IC 50 radical-scavenging assay, the same pattern were observed, which should be related to the triazolium grafted at the periphery of molecular chains.

  2. Multihydroxy-Anthraquinone Derivatives as Free Radical and Cationic Photoinitiators of Various Photopolymerizations under Green LED.

    Science.gov (United States)

    Zhang, Jing; Hill, NicholasS; Lalevée, Jacques; Fouassier, Jean-Pierre; Zhao, Jiacheng; Graff, Bernadette; Schmidt, Timothy W; Kable, Scott H; Stenzel, Martina H; Coote, Michelle L; Xiao, Pu

    2018-04-20

    Multihydroxy-anthraquinone derivatives [i.e., 1,2,4-trihydroxyanthraquinone (124-THAQ), 1,2,7-trihydroxyanthraquinone (127-THAQ), and 1,2,5,8-tetrahydroxyanthraquinone (1258-THAQ)] can interact with various additives [e.g., iodonium salt, tertiary amine, N-vinylcarbazole, and 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine] under household green LED irradiation to generate active species (cations and radicals). The relevant photochemical mechanism is investigated using quantum chemistry, fluorescence, cyclic voltammetry, laser flash photolysis, steady state photolysis, and electron spin resonance spin-trapping techniques. Furthermore, the multihydroxy-anthraquinone derivative-based photoinitiating systems are capable of initiating cationic photopolymerization of epoxides or divinyl ethers under green LED, and the relevant photoinitiation ability is consistent with the photochemical reactivity (i.e., 124-THAQ-based photoinitiating system exhibits highest reactivity and photoinitiation ability). More interestingly, multihydroxy-anthraquinone derivative-based photoinitiating systems can initiate free radical crosslinking or controlled (i.e., reversible addition-fragmentation chain transfer) photopolymerization of methacrylates under green LED. It reveals that multihydroxy-anthraquinone derivatives can be used as versatile photoinitiators for various types of photopolymerization reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Electrochemical behavior of free-radical derivatives of tetra(4hydroxyl-3,5-di-tert-butylphenyl) porphyrin

    Energy Technology Data Exchange (ETDEWEB)

    Pokhodenko, V.D.; Melezhik, A.V.; Platonova, E.P.; Vovk, D.N.

    1984-08-01

    The electrochemical behavior of free-radical derivatives of tetra(4hydroxyl-3,5-di-tert-butylphenyl) porphyrins and their complexes with Mg(II), Zn(II), Ni(II), CU(II), and Pd(II) ions was studied by the methods of voltamperometry, ESR, and spectrophotometry. It was shown that the introduction of free-radical substituents into the porphin macrocycle leads to a substantial decrease in the oxidation and reduction potentials of the complexes. The degree of conjunction of substituents with the porphin macrocycle is estimated according to the difference of the redox potentials of free-radical and quinoid derivatives of metalloporphyrins.

  4. Cut-off effect of radical TEMPO derivatives in olive oil-in-water emulsions.

    Science.gov (United States)

    Lopez de Arbina, Amaia; Rezende, Marcos Caroli; Aliaga, Carolina

    2017-06-01

    Three oil-in-water emulsions were prepared from mixtures of olive oil and Tween 20 in water. The effectiveness of a series of radical 2,2,6,6-tetramethylpiperidinoxyl (TEMPO) derivatives of variable lipophilicity in reactions with antioxidant Trolox, and as pyrene-fluorescence quenchers, was compared in the three emulsions. A "cut-off" effect was observed for the pyrene quenching by the probes, but not for their reaction with Trolox. The results were rationalized in terms of the amphiphobic nature of the probes, and the different locations of probe, pyrene and Trolox in the three-phase microheterogeneous systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Theoretical insights on the antioxidant activity of edaravone free radical scavengers derivatives

    Science.gov (United States)

    Cerón-Carrasco, José P.; Roy, Hélène M.; Cerezo, Javier; Jacquemin, Denis; Laurent, Adèle D.

    2014-04-01

    The prediction of antioxidant properties is not straightforward due to the complexity of the in vivo systems. Here, we use theoretical descriptors, including the potential of ionization, the electrodonating power and the spin density distribution, to characterize the antioxidant capacity of edaravone (EDV) derivatives. Our computations reveal the relationship between these parameters and their potential bioactivity as free radical scavengers. We conclude that more efficient antioxidants could be synthesized by tuning the R1 and R2 positions of the EDV structure, rather than modifying the R3 group. Such modifications might improve the antioxidant activity in neutral and deprotonated forms.

  6. Spectral and Kinetic Properties of Radicals Derived from Oxidation of Quinoxalin-2-One and Its Methyl Derivative

    Directory of Open Access Journals (Sweden)

    Konrad Skotnicki

    2014-11-01

    Full Text Available The kinetics and spectral characteristics of the transients formed in the reactions of •OH and •N3 with quinoxalin-2(1H-one (Q, its methyl derivative, 3-methylquinoxalin-2(1H-one (3-MeQ and pyrazin-2-one (Pyr were studied by pulse radiolysis in aqueous solutions at pH 7. The transient absorption spectra recorded in the reactions of •OH with Q and 3-MeQ consisted of an absorption band with λmax = 470 nm assigned to the OH-adducts on the benzene ring, and a second band with λmax = 390 nm (for Q and 370 nm (for 3-MeQ assigned, inter alia, to the N-centered radicals on a pyrazin-2-one ring. The rate constants of the reactions of •OH with Q and 3-MeQ were found to be in the interval (5.9–9.7 × 109 M–1·s–1 and were assigned to their addition to benzene and pyrazin-2-one rings and H-abstraction from the pyrazin-2-one nitrogen. In turn, the transient absorption spectrum observed in the reaction of •N3 exhibits an absorption band with λmax = 350 nm. This absorption was assigned to the N-centered radical on the Pyr ring formed after deprotonation of the respective radical cation resulting from one-electron oxidation of 3-MeQ. The rate constant of the reaction of •N3 with 3 MeQ was found to be (6.0 ± 0.5 × 109 M–1·s–1. Oxidation of 3-MeQ by •N3 and Pyr by •OH and •N3 confirms earlier spectral assignments. With the rate constant of the •OH radical with Pyr (k = 9.2 ± 0.2 × 109 M–1·s‒1, a primary distribution of the •OH attack was estimated nearly equal between benzene and pyrazin-2-one rings.

  7. Spectral and kinetic properties of radicals derived from oxidation of quinoxalin-2-one and its methyl derivative.

    Science.gov (United States)

    Skotnicki, Konrad; De la Fuente, Julio R; Cañete, Alvaro; Bobrowski, Krzysztof

    2014-11-19

    The kinetics and spectral characteristics of the transients formed in the reactions of •OH and •N3 with quinoxalin-2(1H)-one (Q), its methyl derivative, 3-methylquinoxalin-2(1H)-one (3-MeQ) and pyrazin-2-one (Pyr) were studied by pulse radiolysis in aqueous solutions at pH 7. The transient absorption spectra recorded in the reactions of •OH with Q and 3-MeQ consisted of an absorption band with λmax = 470 nm assigned to the OH-adducts on the benzene ring, and a second band with λmax = 390 nm (for Q) and 370 nm (for 3-MeQ) assigned, inter alia, to the N-centered radicals on a pyrazin-2-one ring. The rate constants of the reactions of •OH with Q and 3-MeQ were found to be in the interval (5.9-9.7) × 109 M-1·s-1 and were assigned to their addition to benzene and pyrazin-2-one rings and H-abstraction from the pyrazin-2-one nitrogen. In turn, the transient absorption spectrum observed in the reaction of •N3 exhibits an absorption band with λmax = 350 nm. This absorption was assigned to the N-centered radical on the Pyr ring formed after deprotonation of the respective radical cation resulting from one-electron oxidation of 3-MeQ. The rate constant of the reaction of •N3 with 3 MeQ was found to be (6.0 ± 0.5) × 109 M-1·s-1. Oxidation of 3-MeQ by •N3 and Pyr by •OH and •N3 confirms earlier spectral assignments. With the rate constant of the •OH radical with Pyr (k = 9.2 ± 0.2) × 109 M-1·s‒1, a primary distribution of the •OH attack was estimated nearly equal between benzene and pyrazin-2-one rings.

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

    KAUST Repository

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

    2016-01-01

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

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

    KAUST Repository

    Fava, Eleonora

    2016-05-02

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

  10. Reconstruction of radical prostatectomy-induced urethral damage using skeletal muscle-derived multipotent stem cells.

    Science.gov (United States)

    Hoshi, Akio; Tamaki, Tetsuro; Tono, Kayoko; Okada, Yoshinori; Akatsuka, Akira; Usui, Yukio; Terachi, Toshiro

    2008-06-15

    Postoperative damage of the urethral rhabdosphincter (URS) and neurovascular bundle (NVB) is a major operative complication of radical prostatectomy. It is generally recognized to be caused by unavoidable surgical damage to the muscle-nerve-blood vessel units around the urethra. We attempted to treat this damage using skeletal muscle-derived stem cells, which are able to reconstitute muscle-nerve-blood vessel units. Cells were enzymatically extracted and sorted by flow cytometry as CD34/45 (Sk-34) and CD34/45 (Sk-DN) cells from green fluorescent protein transgenic mice and rats. URS-NVB damage was induced by manually removing one-third of the total URS and unilateral invasion of NVB in wild-type Sprague-Dawley and node rats. Freshly isolated Sk-34, Sk-34+Sk-DN cells, and cultured Sk-DN cells were directly transplanted into the damaged portion. At 4 and 12 weeks after transplantation, urethral pressure profile by electrical stimulation through the sacral surface (L6-S1) was evaluated as functional recovery. The recovery ratio in the control and transplanted groups was 37.6% and 72.9%, at 4 weeks, and 41.6% and 78.4% at 12 weeks, respectively (Pcells differentiated into numerous skeletal muscle fibers having neuromuscular junctions (innervation) and nerve bundle-related Schwann cells and perineurium, and blood vessel-related endothelial cells and pericyte around the urethra. Thus, we conclude that transplantation of skeletal muscle-derived multipotent Sk-34 and Sk-DN cells is potentially useful for the reconstitution of postoperative damage of URS and NVB after radical prostatectomy.

  11. Novel Water Soluble Chitosan Derivatives with 1,2,3-Triazolium and Their Free Radical-Scavenging Activity

    Directory of Open Access Journals (Sweden)

    Qing Li

    2018-03-01

    Full Text Available Chitosan is an abundant and renewable polysaccharide, which exhibits attractive bioactivities and natural properties. Improvement such as chemical modification of chitosan is often performed for its potential of providing high bioactivity and good water solubility. A new class of chitosan derivatives possessing 1,2,3-triazolium charged units by associating “click reaction” with efficient 1,2,3-triazole quaternization were designed and synthesized. Their free radical-scavenging activity against three free radicals was tested. The inhibitory property and water solubility of the synthesized chitosan derivatives exhibited a remarkable improvement over chitosan. It is hypothesized that triazole or triazolium groups enable the synthesized chitosan to possess obviously better radical-scavenging activity. Moreover, the scavenging activity against superoxide radical of chitosan derivatives with triazolium (IC50 < 0.01 mg mL−1 was more efficient than that of derivatives with triazole and Vitamin C. In the 1,1-diphenyl-2-picrylhydrazyl (DPPH and hydroxyl radical-scavenging assay, the same pattern were observed, which should be related to the triazolium grafted at the periphery of molecular chains.

  12. 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.

  13. Using a Radical-Derived Character E-Learning Platform to Increase Learner Knowledge of Chinese Characters

    Science.gov (United States)

    Chen, Hsueh-Chih; Hsu, Chih-Chun; Chang, Li-Yun; Lin, Yu-Chi; Chang, Kuo-En; Sung, Yao-Ting

    2013-01-01

    The present study is aimed at investigating the effect of a radical-derived Chinese character teaching strategy on enhancing Chinese as a Foreign Language (CFL) learners' Chinese orthographic awareness. An e-learning teaching platform, based on statistical data from the Chinese Orthography Database Explorer (Chen, Chang, Chou, Sung, & Chang,…

  14. New fluorescent probes of the hydroxyl radical: characterisation and modelization of the reactivity of coumarin derivatives with HO

    International Nuclear Information System (INIS)

    Louit, G.

    2005-10-01

    The hydroxyl radical is involved in a wide range of different fields, from oxidative stress to atmospheric chemistry. In addition to the study of oxidative damage in biological media, the hydroxyl radical detection allows to perform a dosimetry when it is produced by ionising radiation. The aims of this work have been double: - to improve the detection of the hydroxyl radical by the design of new probes - to improve knowledge on the reactive pathways in which the hydroxyl radical is involved. We have studied the coumarin molecule, as well as 6 derivatives that we have synthesised, as fluorescent probes of the hydroxyl radical. Firstly, fluorescence spectroscopy and HPLC chromatography have allowed the evaluation of the sensibility and selectivity of detection of the probes. Consequently to this study, two applications have been developed, concerning the determination of rate constants by competition kinetics and bidimensional dosimetry. Secondly, we have studied the reactivity of the hydroxyl radical through the regioselectivity of its addition on the aromatic cycle. This problem was addressed by the combined use of experimental methods such as time resolved kinetics and HPLC along with interpretation from classical and ab initio modelization. (author)

  15. EPR study of gamma induced radicals in amino and iminodiacetic acid derivatives

    International Nuclear Information System (INIS)

    Aydin, Murat; Baskan, M. Halim; Osmanoglu, Y. Emre

    2009-01-01

    In this study, electron paramagnetic resonance spectroscopy was used to investigate free radicals formed in gamma irradiated L-glutamine hydrochloride, iminodiacetic acid hydrochloride and N-(2-hydroxyethyl) iminodiacetic acid powders. The free radicals produced in L-glutamine hydrochloride powders were attributed to the CH 2 CHCOOH radical; and those in iminodiacetic acid hydrochloride and N-(2-hydroxyethyl) iminodiacetic acid powders to the HNCHCH 2 (CO OH) 2 and HOCH 2 CH 2 NCHCH 2 (CO OH) 2 , respectively. The g-values of the radicals and the hyperfine structure constants of the free electron with the environmental protons and 14 N nucleus were determined. The samples were not displayed before they were not irradiated. The free radicals were found stable at room temperature for more than six months. Some spectroscopic properties and suggestions concerning possible structure of the radicals are discussed in this paper. (author)

  16. Adriamycin and derivatives interaction with the mitochondrial membrane: O2 consumption and free radicals formation

    NARCIS (Netherlands)

    Pollakis, G.; Goormaghtigh, E.; Delmelle, M.; Lion, Y.; Ruysschaert, J. M.

    1984-01-01

    Adriamycin induces the formation of semiquinone free radicals, O(2) and OH. species, in beef heart intact mitochondria, submitochondrial particles and complex I-III containing proteoliposomes. Free radicals were detected by the use of Electron Spin Resonance (ESR) spectroscopy with the spin trapping

  17. Effect of concentration and molecular weight of chitosan and its derivative on the free radical scavenging ability.

    Science.gov (United States)

    Li, Huili; Xu, Qing; Chen, Yun; Wan, Ajun

    2014-03-01

    Chitosan is a biodegradable and biocompatible natural scaffold material, which has numerous applications in biomedical sciences. In this study, the in vitro antioxidant activity of chitosan scaffold material was investigated by the chemiluminescence signal generated from the hydroxyl radical (•OH) scavenging assay. The scavenging mechanism was also discussed. The results indicated that the free radical scavenging ability of chitosan scaffold material significantly depends on the chitosan concentration and shows interesting kinetic change. Within the experimental concentration range, the optimal concentration of chitosan was 0.2 mg/mL. The molecular weight of chitosan also attributed to the free radical scavenging ability. Comparison between chitosan and its derivative found that carboxymethyl chitosan possessed higher scavenging ability. Copyright © 2013 Society of Plastics Engineers.

  18. 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

  19. 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 •- .

  20. Synthesis and Biological Evaluation of 3-Benzylidene-4-chromanone Derivatives as Free Radical Scavengers and α-Glucosidase Inhibitors.

    Science.gov (United States)

    Takao, Koichi; Yamashita, Marimo; Yashiro, Aruki; Sugita, Yoshiaki

    2016-01-01

    A series of 3-benzylidene-4-chromanone derivatives (3-20) were synthesized and the structure-activity relationships for antioxidant and α-glucosidase inhibitory activities were evaluated. Among synthesized compounds, compounds 5, 13, 18, which contain catechol moiety, showed the potent 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity (5: EC50 13 µM; 13: EC50 14 µM; 18: EC50 13 µM). The compounds 12, 14, 18 showed higher α-glucosidase inhibitory activity (12: IC50 15 µM; 14: IC50 25 µM; 18: IC50 28 µM). The compound 18 showed both of potent DPPH radical scavenging and α-glucosidase inhibitory activities. These data suggest that 3-benzylidene-4-chromanone derivatives, such as compound 18, may serve as the lead compound for the development of novel α-glucosidase inhibitors with antioxidant activity.

  1. 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

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

    Science.gov (United States)

    Osmanoğlu, Y. Emre; Sütçü, Kerem

    2017-10-01

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

  3. Identification of the substrate radical intermediate derived from ethanolamine during catalysis by ethanolamine ammonia-lyase.

    Science.gov (United States)

    Bender, Güneş; Poyner, Russell R; Reed, George H

    2008-10-28

    Rapid-mix freeze-quench (RMFQ) methods and electron paramagnetic resonance (EPR) spectroscopy have been used to characterize the steady-state radical in the deamination of ethanolamine catalyzed by adenosylcobalamin (AdoCbl)-dependent ethanolamine ammonia-lyase (EAL). EPR spectra of the radical intermediates formed with the substrates, [1-13C]ethanolamine, [2-13C]ethanolamine, and unlabeled ethanolamine were acquired using RMFQ trapping methods from 10 ms to completion of the reaction. Resolved 13C hyperfine splitting in EPR spectra of samples prepared with [1-13C]ethanolamine and the absence of such splitting in spectra of samples prepared with [2-13C]ethanolamine show that the unpaired electron is localized on C1 (the carbinol carbon) of the substrate. The 13C splitting from C1 persists from 10 ms throughout the time course of substrate turnover, and there was no evidence of a detectable amount of a product like radical having unpaired spin on C2. These results correct an earlier assignment for this radical intermediate [Warncke, K., et al. (1999) J. Am. Chem. Soc. 121, 10522-10528]. The EPR signals of the substrate radical intermediate are altered by electron spin coupling to the other paramagnetic species, cob(II)alamin, in the active site. The dipole-dipole and exchange interactions as well as the 1-13C hyperfine splitting tensor were analyzed via spectral simulations. The sign of the isotropic exchange interaction indicates a weak ferromagnetic coupling of the two unpaired electrons. A Co2+-radical distance of 8.7 A was obtained from the magnitude of the dipole-dipole interaction. The orientation of the principal axes of the 13C hyperfine splitting tensor shows that the long axis of the spin-bearing p orbital on C1 of the substrate radical makes an angle of approximately 98 degrees with the unique axis of the d(z2) orbital of Co2+.

  4. New derivatives of 3,4-dihydroisoquinoline-3-carboxylic acid with free-radical scavenging, D-amino acid oxidase, acetylcholinesterase and butyrylcholinesterase inhibitory activity.

    Science.gov (United States)

    Solecka, Jolanta; Guśpiel, Adam; Postek, Magdalena; Ziemska, Joanna; Kawęcki, Robert; Lęczycka, Katarzyna; Osior, Agnieszka; Pietrzak, Bartłomiej; Pypowski, Krzysztof; Wyrzykowska, Agata

    2014-09-30

    A series of 3,4-dihydroisoquinoline-3-carboxylic acid derivatives were synthesised and tested for their free-radical scavenging activity using 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·), 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radical (ABTS·+), superoxide anion radical (O2·-) and nitric oxide radical (·NO) assays. We also studied d-amino acid oxidase (DAAO), acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) inhibitory activity. Almost each of newly synthesised compounds exhibited radical scavenging capabilities. Moreover, several compounds showed moderate inhibitory activities against DAAO, AChE and BuChE. Compounds with significant free-radical scavenging activity may be potential candidates for therapeutics used in oxidative-stress-related diseases.

  5. Radical-Scavenging Activity of Thiols, Thiobarbituric Acid Derivatives and Phenolic Antioxidants Determined Using the Induction Period Method for Radical Polymerization of Methyl Methacrylate

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa

    2012-04-01

    Full Text Available The radical-scavenging activities of two thiols, eight (thiobarbituric acid derivatives and six chain-breaking phenolic antioxidants were investigated using the induction period method for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2’-azobisisobutyronitrile (AIBN and monitored by differential scanning calorimetry (DSC. The induction period (IP for the thiols 2-mercaptoethanol (ME and 2-mercapto-1-methylimidazole (MMI was about half that for phenolic antioxidants. Except for the potent inhibitor 5,5-dimethyl-2-thiobarbituric acid (3, the IP for thiobarbituric acid derivatives was about one tenth of that for phenolic antioxidants. The IP for 1,3,5-trimethyl-2-thiobarbituric acid (1 and 5-allyl-1, 3-dimethyl-2-thiobarbituric acid (7 was less than that of the control, possibly due to inhibition by a small amount of atmospheric oxygen in the DSC container. The ratio of the chain inhibition to that of chain propagation (CI/CP for the thiols and thiobarbituric acid compounds except for 1, 3 and 7 was about 10 times greater or greater than that for phenolic compounds. A kinetic chain length (KCL about 10% greater than that of the control was observed for 1, suggesting that 1 had chain transfer reactivity in the polymerization of MMA. The average molecular weight of polymers formed from thiobarbituric acid derivatives is discussed.

  6. Conformational analysis of the EPR spectra of cyclohexenyl radical and some of its alkyl derivatives

    International Nuclear Information System (INIS)

    de Tannoux, N.M.

    1975-01-01

    Electron paramagnetic resonance spectra have been obtained for radicals produced by x-irradiation of cyclohexene and various alkyl-substituted cyclohexenes trapped in an adamantane matrix. Temperature variations of these spectra permits determination of the enthalpy and entropy of activation for interconversion between the conformations. For cyclohexenyl radical, the enthalpy of activation is 6.81 +- 0.58 kcal/mole and the entropy of activation is -0.04 +- 2.38 e.u. Methyl substitution on C 1 gives a radical with activation parameters similar to the parent radical. Methyl groups attached to C 5 increase the activation parameters significantly. On the basis of these observations, it is suggested the cyclohexenyl radicals exist in two conformations of the same energy which are of the ''envelope'' type, with C 1 , C 2 , C 3 , C 4 , and C 6 coplanar. A model involving a planar transition state for the interconversion process is proposed which accounts for most of the experimental results

  7. Synthesis and in Vitro Antioxidant Activity Evaluation of 3-Carboxycoumarin Derivatives and QSAR Study of Their DPPH• Radical Scavenging Activity

    Directory of Open Access Journals (Sweden)

    Maria Teresa Sumaya-Martínez

    2012-12-01

    Full Text Available The in vitro antioxidant activities of eight 3-carboxycoumarin derivatives were assayed by the quantitative 1,1-diphenyl-2-picrylhydrazil (DPPH• radical scavenging activity method. 3-Acetyl-6-hydroxy-2H-1-benzopyran-2-one (C1 and ethyl 6-hydroxy-2-oxo-2H-1-benzopyran-3-carboxylate (C2 presented the best radical-scavenging activity. A quantitative structure-activity relationship (QSAR study was performed and correlated with the experimental DPPH• scavenging data. We used structural, geometrical, topological and quantum-chemical descriptors selected with Genetic Algorithms in order to determine which of these parameters are responsible of the observed DPPH• radical scavenging activity. We constructed a back propagation neural network with the hydrophilic factor (Hy descriptor to generate an adequate architecture of neurons for the system description. The mathematical model showed a multiple determination coefficient of 0.9196 and a root mean squared error of 0.0851. Our results shows that the presence of hydroxyl groups on the ring structure of 3-carboxy-coumarins are correlated with the observed DPPH• radical scavenging activity effects.

  8. 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

  9. Effects of exogenous oxygen derived free radicals on myocardial capillary permeability, vascular tone, and incidence of ventricular arrhythmias in the canine heart

    DEFF Research Database (Denmark)

    Svendsen, Jesper Hastrup; Bjerrum, P J

    1992-01-01

    The aim was to examine the effects of exogenous oxygen derived free radicals on myocardial capillary permeability for a small hydrophilic indicator, postischaemic vascular tone, and the occurrence of arrhythmias in the canine heart in vivo.......The aim was to examine the effects of exogenous oxygen derived free radicals on myocardial capillary permeability for a small hydrophilic indicator, postischaemic vascular tone, and the occurrence of arrhythmias in the canine heart in vivo....

  10. Inactivation of alcohol dehydrogenase (ADH) by ferryl derivatives of human hemoglobin.

    Science.gov (United States)

    Kowalczyk, Aleksandra; Puchała, Mieczysław; Wesołowska, Katarzyna; Serafin, Eligiusz

    2007-01-01

    In this paper, inactivation of alcohol dehydrogenase (ADH) by products of reactions of H2O2 with metHb has been studied. Inactivation of the enzyme was studied in two systems corresponding to two kinetic stages of the reaction. In the first system H2O2 was added to the mixture of metHb and ADH [the (metHb+ADH)+H2O2] system (ADH was present in the system since the moment of addition of H2O2 i. e. since the very beginning of the reaction of metHb with H2O2). In the second system ADH was added to the system 5 min after the initiation of the reaction of H2O2 with metHb [the (metHb+H2O2)5 min+ADH] system. In the first case all the products of reaction of H2O2 with metHb (non-peroxyl and peroxyl radicals and non-radical products, viz. hydroperoxides and *HbFe(IV)=O) could react with the enzyme causing its inactivation. In the second system, enzyme reacted almost exclusively with non-radical products (though a small contribution of reactions with peroxyl radicals cannot be excluded). ADH inactivation was observed in both system. Hydrogen peroxide alone did not inactivate ADH at the concentrations employed evidencing that enzyme inactivation was due exclusively to products of reaction of H2O2 with metHb. The rate and extent of ADH inactivation were much higher in the first than in the second system. The dependence of ADH activity on the time of incubation with ferryl derivatives of Hb can be described by a sum of three exponentials in the first system and two exponentials in the second system. Reactions of appropriate forms of the ferryl derivatives of hemoglobin have been tentatively ascribed to these exponentials. The extent of the enzyme inactivation in the second system was dependent on the proton concentration, being at the highest at pH 7.4 and negligible at pH 6.0. The reaction of H2O2 with metHb resulted in the formation of cross-links of Hb subunits (dimers and trimers). The amount of the dimers formed was much lower in the first system i. e. when the radical

  11. Radical Ions of 3-Styryl-quinoxalin-2-one Derivatives Studied by Pulse Radiolysis in Organic Solvents.

    Science.gov (United States)

    Skotnicki, Konrad; De la Fuente, Julio R; Cañete, Álvaro; Berrios, Eduardo; Bobrowski, Krzysztof

    2018-04-12

    The absorption-spectral and kinetic behaviors of radical ions and neutral hydrogenated radicals of seven 3-styryl-quinoxalin-2(1 H)-one (3-SQ) derivatives, one without substituents in the styryl moiety, four others with electron-donating (R = -CH 3 , -OCH 3 , and -N(CH 3 ) 2 ) or electron-withdrawing (R = -OCF 3 ) substituents in the para position in their benzene ring, and remaining two with double methoxy substituents (-OCH 3 ), however, at different positions (meta/para and ortho/meta) have been studied by UV-vis spectrophotometric pulse radiolysis in neat acetonitrile saturated with argon (Ar) and oxygen (O 2 ) and in 2-propanol saturated with Ar, at room temperature. In acetonitrile solutions, the radical anions (4R-SQ •- ) are characterized by two absorption maxima located at λ max = 470-490 nm and λ max = 510-540 nm, with the respective molar absorption coefficients ε 470-490 = 8500-13 100 M -1 cm -1 and ε 510-540 = 6100-10 300 M -1 cm -1 , depending on the substituent (R). All 4R-SQ •- decay in acetonitrile via first-order kinetics, with the rate constants in the range (1.2-1.5) × 10 6 s -1 . In 2-propanol solutions, they decay predominantly through protonation by the solvent, forming neutral hydrogenated radicals (4R-SQH • ), which are characterized by weak absorption bands with λ max = 480-490 nm. Being oxygen-insensitive, the radical cations (4R-SQ •+ ) are characterized by a strong absorption with λ max = 450-630 nm, depending on the substituent (R). They are formed in a charge-transfer reaction between a radical cation derived from acetonitrile (ACN •+ ) and substituted 3-styryl-quinoxalin-2-one derivatives (4R-SQ) with a pseudo-first-order rate constant k = (2.7-4.7) × 10 5 s -1 measured in solutions containing 0.1 mM 4R-3-SQ. The Hammett equation plot gave a very small negative slope (ρ = -0.08), indicating a very weak influence of the substituents in the benzene ring on the rate of charge-transfer reaction. The decay of 4R

  12. Cone Beam Computed Tomography-Derived Adaptive Radiotherapy for Radical Treatment of Esophageal Cancer

    International Nuclear Information System (INIS)

    Hawkins, Maria A.; Brooks, Corrinne; Hansen, Vibeke N.; Aitken, Alexandra; Tait, Diana M.

    2010-01-01

    Purpose: To investigate the potential for reduction in normal tissue irradiation by creating a patient specific planning target volume (PTV) using cone beam computed tomography (CBCT) imaging acquired in the first week of radiotherapy for patients receiving radical radiotherapy. Methods and materials: Patients receiving radical RT for carcinoma of the esophagus were investigated. The PTV is defined as CTV(tumor, nodes) plus esophagus outlined 3 to 5 cm cranio-caudally and a 1.5-cm circumferential margin is added (clinical plan). Prefraction CBCT are acquired on Days 1 to 4, then weekly. No correction for setup error made. The images are imported into the planning system. The tumor and esophagus for the length of the PTV are contoured on each CBCT and 5 mm margin is added. A composite volume (PTV1) is created using Week 1 composite CBCT volumes. The same process is repeated using CBCT Week 2 to 6 (PTV2). A new plan is created using PTV1 (adaptive plan). The coverage of the 95% isodose of PTV1 is evaluated on PTV2. Dose-volume histograms (DVH) for lungs, heart, and cord for two plans are compared. Results: A total of 139 CBCT for 14 cases were analyzed. For the adaptive plan the coverage of the 95% prescription isodose for PTV1 = 95.6% ± 4% and the PTV2 = 96.8% ± 4.1% (t test, 0.19). Lungs V20 (15.6 Gy vs. 10.2 Gy) and heart mean dose (26.9 Gy vs. 20.7 Gy) were significantly smaller for the adaptive plan. Conclusions: A reduced planning volume can be constructed within the first week of treatment using CBCT. A single plan modification can be performed within the second week of treatment with considerable reduction in organ at risk dose.

  13. 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.

  14. Spectral and Kinetic Properties of Radicals Derived from Oxidation of Quinoxalin-2-One and Its Methyl Derivative

    OpenAIRE

    Konrad Skotnicki; Julio R. De la Fuente; Alvaro Cañete; Krzysztof Bobrowski

    2014-01-01

    The kinetics and spectral characteristics of the transients formed in the reactions of •OH and •N3 with quinoxalin-2(1H)-one (Q), its methyl derivative, 3-methylquinoxalin-2(1H)-one (3-MeQ) and pyrazin-2-one (Pyr) were studied by pulse radiolysis in aqueous solutions at pH 7. The transient absorption spectra recorded in the reactions of •OH with Q and 3-MeQ consisted of an absorption band with λmax = 470 nm assigned to the OH-adducts on the benzene ring, and a second band with λmax = 390 nm (...

  15. Protein capped nanosilver free radical oxidation: role of biomolecule capping on nanoparticle colloidal stability and protein oxidation.

    Science.gov (United States)

    Ahumada, Manuel; Bohne, Cornelia; Oake, Jessy; Alarcon, Emilio I

    2018-05-03

    We studied the effect of human serum albumin protein capped spherical nanosilver on the nanoparticle stability upon peroxyl radical oxidation. The nanoparticle-protein composite is less prone to oxidation compared to the individual components. However, higher concentrations of hydrogen peroxide were formed in the nanoparticle-protein system.

  16. 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.

  17. Theoretical investigation of the hydrogen shift reactions in peroxy radicals derived from the atmospheric decomposition of 3-methyl-3-buten-1-ol (MBO331)

    DEFF Research Database (Denmark)

    Knap, Hasse Christian; Jørgensen, Solvejg; Kjærgaard, Henrik Grum

    2015-01-01

    The hydroxy peroxy radical derived from the oxidation of 3-methyl-3-buten-1-ol (MBO331), can undergo four different hydrogen shift (H-shift) reactions. We have compared optimized geometries, barrier heights and reaction rate constants obtained with five different DFT functionals (BLYP, B3LYP, BHand...

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

    Science.gov (United States)

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

    2015-01-01

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

  19. Migration of methyl and phenyl radicals, oxygen and sulphur atoms in certain diphenylthiophosphorane derivatives under electron impact

    International Nuclear Information System (INIS)

    Cauquis, G.; Divisia, B.; Ulrich, J.

    The fragmentation of various diphenylthiophosphoranes (Ph 2 P(S)R) subjected to electron impact gives rise to rearrangements dependent on the nature of the radical R. Migrations of phenyl or methyl radicals from phosphorus towards sulphur were thus observed for R=Ph, CH 3 , CH 2 Ph and NH 2 . When an electrophilic centre is formed, during a fragmentation, on a carbon in the α-position of the diphenylthiophosphoranyl radical, migrations of sulphur atoms and phenyl radicals take place from the phosphorus towards the carbon. This is found to be the case with certain fragmentations of diazo 5 and 6 compounds [fr

  20. Free radical derivatives formed from cyclooxygenase-catalyzed dihomo-γ-linolenic acid peroxidation can attenuate colon cancer cell growth and enhance 5-fluorouracil's cytotoxicity.

    Science.gov (United States)

    Xu, Yi; Qi, Jin; Yang, Xiaoyu; Wu, Erxi; Qian, Steven Y

    2014-01-01

    Dihomo-γ-linolenic acid (DGLA) and its downstream fatty acid arachidonic acid (AA) are both nutritionally important ω-6 polyunsaturated fatty acids (ω-6s). Evidence shows that, via COX-mediated peroxidation, DGLA and its metabolites (1-series prostaglandins) are associated with anti-tumor activity, while AA and its metabolites (2-series prostaglandins) could be tightly implicated in various cancer diseases. However, it still remains a mystery why DGLA and AA possess contrasting bioactivities. Our previous studies showed that DGLA could go through an exclusive C-8 oxygenation pathway during COX-catalyzed lipid peroxidation in addition to a C-15 oxygenation pathway shared by both DGLA and AA, and that the exclusive C-8 oxygenation could lead to the production of distinct DGLA׳s free radical derivatives that may be correlated with DGLA׳s anti-proliferation activity. In the present work, we further investigate the anti-cancer effect of DGLA׳s free radical derivatives and their associated molecular mechanisms. Our study shows that the exclusive DGLA׳s free radical derivatives from C-8 oxygenation lead to cell growth inhibition, cell cycle arrest and apoptosis in the human colon cancer cell line HCA-7 colony 29, probably by up-regulating the cancer suppressor p53 and the cell cycle inhibitor p27. In addition, these exclusive radical derivatives were also able to enhance the efficacy of 5-Fluorouracil (5-FU), a widely used chemo-drug for colon cancer. For the first time, we show how DGLA׳s radical pathway and metabolites are associated with DGLA׳s anti-cancer activities and able to sensitize colon cancer cells to chemo-drugs such as 5-FU. Our findings could be used to guide future development of a combined chemotherapy and dietary care strategy for colon cancer treatment.

  1. Structure of Radicals from X-irradiated Guanine Derivatives: An Experimental and Computational Study of Sodium Guanosine Dihydrate Single Crystals

    Science.gov (United States)

    Jayatilaka, Nayana; Nelson, William H.

    2008-01-01

    In sodium guanosine dihydrate single crystals, the guanine moiety is deprotonated at N1 due to growth from high-pH (>12) solutions. EPR and ENDOR study of crystals x-irradiated at 10 K detected evidence for three radical forms. Radical R1,characterized by two proton and two nitrogen hyperfine interactions, was identified as the product of net hydrogenation at N7 of the N1-deprotonated guanine unit. R1 exhibited an unusually distorted structure leading to net positive isotropic components of the hydrogen couplings. Radical R2, characterized by one proton and one nitrogen hyperfine coupling was identified as the primary electron loss product. This product is equivalent to that of deprotonation at N1 by the guanine cation and represents the first ENDOR characterization of that product. Radical R3, characterized by a single hydrogen hyperfine coupling, was identified as the product of net dehydrogenation at C1 of the ribose moiety. The identification of radicals R1-R3 was supported by DFT calculations on several possible structures using the B3LYP/6-311G(2df,p)//6-31G(d,p) approach. Radical R4, detected after warming the crystals to room temperature, was identified as the well-known product of net hydrogenation of C8 of the (N1-deprotonated) guanine component. Radical R1, evidently formed by protonation of the primary electron addition product, was present as roughly 60% of the total radicals detected at 10 K. Radical R2 was present as roughly 27% of the total yield, and the concentration of R3 contributed the remaining 13%. R3 is evidently the product of oneelectron oxidation followed by deprotonation; thus, the balance of oxidation and reduction products is approximately equal within experimental uncertainty. PMID:17249824

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

    Science.gov (United States)

    Caldwell, Charles R

    2003-07-30

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

  3. Antioxidant and DPPH (1,1-diphenyl-2-picrylhydrazyl Free Radical Scavenging Activities of Boniger Acid and Calix[4]arene Derivative

    Directory of Open Access Journals (Sweden)

    E. ERDEM

    2014-07-01

    Full Text Available Diazonium derivative of calix[4]arene has been synthesized using three different synthetic steps. Initially p-tert-butylcalix[4]arene was synthesized with the condensation reaction of p-tert-butylphenol and formaldehyde in basic conditions. Calix[4]arene was obtained after the debutylation reaction of p-tert-butylcalix[4]arene with AlCl3. Calix[4]arene reacted with diazonium salt of Böniger acid to yield the 5,17-[(Bis(azo-bis(5-hydroxy-2,7-naphthalenedisulfonicacid]-25,26,27,28-tetrahydroxy calix[4]arene which has eight free phenolic hydroxyl group. Reaction steps were shown in Fig.1.2,7-naphthalenedisulfonicacid]-25,26,27,28-tetrahydroxy calix[4]arene The antioxidant activity of the Böniger acid and calix[4]aren derivative were determined using β-karotene-linoleic acid system. Moreover, the free radical scavenging activity values were tested with DPPH free radical. The two compounds showed strong antioxidant activity. Total antioxidant activity of Böniger acid and calix[4]aren derivative was determined using β–carotenelinoleic acid model system and was found the antioxidant activity of 84.00% and 85.60 % respectively. The free radical scavenging activities were determined as 83.05% and 84.69 %. Results show that, two compounds has the antioxidant activity. The calix[4]aren derivaties has more higher activity then Boniger acid because of calix[4]aren derivative has much hydroxl groups.

  4. l-Tryptophan Radical Cation Electron Spin Resonance Studies: Connecting Solution-derived Hyperfine Coupling Constants with Protein Spectral Interpretations

    Science.gov (United States)

    Connor, Henry D.; Sturgeon, Bradley E.; Mottley, Carolyn; Sipe, Herbert J.; Mason, Ronald P.

    2009-01-01

    Fast-flow electron spin resonance (ESR) spectroscopy has been used to detect a free radical formed from the reaction of l-tryptophan with Ce4+ in an acidic aqueous environment. Computer simulations of the ESR spectra from l-tryptophan and several isotopically modified forms strongly support the conclusion that the l-tryptophan radical cation has been detected by ESR for the first time. The hyperfine coupling constants (HFCs) determined from the well-resolved isotropic ESR spectra support experimental and computational efforts to understand l-tryptophan's role in protein catalysis of oxidation-reduction processes. l-tryptophan HFCs facilitated the simulation of fast-flow ESR spectra of free radicals from two related compounds, tryptamine and 3-methylindole. Analysis of these three compounds' β-methylene hydrogen HFC data along with equivalent l-tyrosine data has led to a new computational method that can distinguish between these two amino acid free radicals in proteins without dependence on isotope labeling, electron nuclear double resonance or high-field ESR. This approach also produces geometric parameters (dihedral angles for the β-methylene hydrogens) which should facilitate protein site assignment of observed l-tryptophan radicals as has been done for l-tyrosine radicals. PMID:18433127

  5. Synthesis and properties of novel TEMPO-contained polypyrrole derivatives as the cathode material of organic radical battery

    International Nuclear Information System (INIS)

    Xu, Lihuan; Yang, Fang; Su, Chang; Ji, Lvlv; Zhang, Cheng

    2014-01-01

    Two 2,2,6,6-tetramethylpiperidinyl-N-oxy (TEMPO) contained polypyrrole (PPy) derivatives with the different side-chain length were synthesized by esterification of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radial with pyrrole butyric acid and pyrrole caproic acid. Then the homopolymers of 4-(3-(Pyrrol-1-yl)butyryloxy)-2,2,6,6-tetramethylpiperidin-1-yloxy (PPy-B-TEMPO) and 4-(3-(Pyrrol-1-yl)hexanoyloxy)-2,2,6,6-tetramethylpiperidin-1-yloxy (PPy-C-TEMPO) were prepared by chemical oxidative polymerization. The structure, morphology, electrochemical properties of prepared polymers were characterized by fourier transform infrared spectroscopy (FTIR), ultraviolet visible spectroscopy (UV-vis), scanning electron microscopy (SEM), cyclic voltammograms (CV) and electrochemical impedance spectra (EIS), respectively. Also, the charge-discharge properties of the prepared polymers were studied by galvanostatic charge-discharge testing. The results demonstrated that the as-synthesized nitroxide radical polymers showed a reversible two-electron redox reaction process in the potential limits of 2.5–3.0 V and 3.4–3.8 V vs Li/Li + , respectively. Under our experimental conditions, PPy only presented the discharge capacity of 16.5 mAh·g −1 at 20 mA·g −1 between 2.5 and 4.2 V, while PPy-B-TEMPO with the short side-chain linked to TEMPO groups exhibited an initial discharge capacity of up to 86.5 mAh·g −1 with two well-defined plateaus. Furthermore, the PPy-C-TEMPO with the longer linking side-chain even displayed a discharge capacity of 115 mAh·g −1 . These superior electrochemical performances were ascribed to the flexible linking side-chain and the introduction of stable conductive PPy main chain, which benefits the improvement of charge carrier transportation in the aggregated polymer bulk

  6. MRI-derived Restriction Spectrum Imaging Cellularity Index is Associated with High Grade Prostate Cancer on Radical Prostatectomy Specimens

    Directory of Open Access Journals (Sweden)

    Michael Andre Liss

    2015-02-01

    Full Text Available Objectives: We evaluate a novel magnetic resonance imaging (MRI technique to improve detection of aggressive prostate cancer. Methods: We performed a retrospective analysis of presurgical prostate MRI scans using an advanced diffusion weighted imaging technique called Restriction Spectrum Imaging (RSI, which can be presented as a normalized z-score statistic (RSI z-score. Scans were acquired prior to radical prostatectomy. Prostatectomy specimens were processed using whole mount sectioning and regions of interest (ROIs were drawn around individual prostate cancer (PCa tumors. Corresponding ROIs were drawn on the MRI imaging and paired with ROIs in regions with no pathology. RSI z-score and conventional apparent diffusion coefficient (ADC values were recorded for each ROI. Paired t-test, ANOVA and logistic regression analyses were performed.Results: We evaluated 28 patients with 64 regions of interest (28 benign and 36 PCa. The mean difference in RSI z-score (PCa ROI – Benign ROI was 2.17 (SE = 0.11; p <0.001 and in ADC was 551 mm2/sec (SE = 80 mm2/sec; paired t-test, p <0.001. The differences in the means among all groups (benign, primary Gleason 3 and primary Gleason 4 was significant for both RSI z-score (F3,64 = 97.7, p <0.001 and ADC (F3,64 = 13.9, p <0.001. A t-test was performed on only PCa tumor ROIs (n=36 to determine prostate cancer aggressiveness (Gleason 3 vs. Gleason 4 revealing that RSI z-score was still significant (p = 0.03, whereas, ADC values were no longer significant (p = 0.08. In multivariable analysis adjusting for age and race, RSI z-score was associated with PCa aggressiveness (OR 10.3, 95%CI: 1.4-78.0, p=0.02 while ADC trended to significance (p=0.07. Conclusions: The RSI derived normalized cellularity index (RSI z-score is associated with aggressive prostate cancer as determined by pathologic Gleason scores. Further utilization of RSI techniques may serve to enhance standardized reporting systems.

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

    Science.gov (United States)

    Karthikeyan, S; Sekaran, G

    2014-03-07

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

  8. Electrografting of alkyl films at low driving force by diverting the reactivity of aryl radicals derived from diazonium salts.

    Science.gov (United States)

    Hetemi, Dardan; Kanoufi, Frédéric; Combellas, Catherine; Pinson, Jean; Podvorica, Fetah I

    2014-11-25

    Alkyl and partial perfluoroalkyl groups are strongly attached to carbon surfaces through (i) the abstraction of the iodine atom from an iodoalkane by the sterically hindered 2,6-dimethylphenyl radical and (ii) the reaction of the ensuing alkyl radical with the carbon surface. Since the 2,6-dimethylphenyl radical is obtained at -0.25 V/Ag/AgCl by reducing the corresponding diazonium salt, the electrografting reaction is facilitated by ∼1.7 V by comparison with the direct electrografting of the iodo compounds. Layers of various thicknesses, including monolayers, are obtained by controlling the time duration of the electrolysis. The grafted films are characterized by electrochemistry, IR, XPS, ellipsometry, and water contact angles.

  9. Antioxidant and DPPH (1,1-diphenyl-2-picrylhydrazyl Free Radical Scavenging Activities of New the Calix[4]arene-bodipy Derivative

    Directory of Open Access Journals (Sweden)

    E. ERDEM

    2014-07-01

    Full Text Available p-tert-butylcalix[4]arene was synthesized with the condesation reaction of p-tert-butylphenol and formaldehyde in basic conditions and then has derivatized from the both of two hydroxyl position with chloride which is containing donor oxygen atoms. BODIPY compound (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene was synthesized with appropriate pyrrole and aldehyde compounds and then was bonded p-tert-butylcalix[4]arene derivative via lower rim hydroxyl groups.The antioxidant activity of the calix[4]arene-BODIPY compound were determined using β-karotene-linoleic acid system. Moreover, the free radical scavenging activity values were tested with DPPH free radical. The compound showed strong antioxidant activity.Total antioxidant activity of the compound was determined using β–carotenelinoleic acid model system and was found the antioxidant activity of 72,50%. The free radical scavenging activities were determined as 75.19%. Results show that, calix[4]arene-BODIPY compound has the antioxidant activity. 

  10. Some aspects of radiation-induced free-radical chemistry of biologically important molecules

    International Nuclear Information System (INIS)

    Sonntag, C. von

    1992-01-01

    Biologically relevant material is usually associated with considerable amounts of water. When ionizing radiation interacts with such material one must consider two modes of energy deposition: the direct effect (ionizing radiation is absorbed by the biomolecules) and the indirect effect (ionizing radiation is absorbed by the surrounding water). In the direct effect, radical cations plus electrons, and excited states of the biomolecules are formed. In the indirect effect the water is decomposed resulting in the formation of the water radicals OH,H and e aq - . These reactive intermediates then interact with the biomolecules. When such systems are irradiated oxygen is often present. As a result of this, the radicals formed in the biomolecules by the various routes are converted into the corresponding peroxyl radicals. In certain cases, e.g. with the nucleobases of DNA, radical cations can be produced in dilute aqueous solutions by radiation-generated SO 4 - radicals, and the fate of these nucleobase radical cations studied by pulse radiolysis and product analysis. Attention will be drawn to the fact that frequently some of the reaction products of the radical cations with water are identical to those formed by OH radical attack, but that there are also marked differences. Similarly, protonation of radical anions (formed by the reaction of solvated electrons with the biomolecules) and the reaction of H-atoms with these molecules can lead to radical intermediates with considerably differing characteristics. Our present knowledge of the variety of reactions of the peroxyl radicals occurring in aqueous solutions will be briefly discussed, emphasizing the large variety of HO 2 /O 2 - elimination reactions and pointing to the reversibility of the oxygen addition (RO 2 →R + O 2 ) in some systems recently studied. (author)

  11. [Quality of life and overall survival in high risk patients after radical cystectomy with a simple urinary derivation].

    Science.gov (United States)

    Mucciardi, Giuseppe; Macchione, Luciano; Galì, Alessandro; di Benedetto, Antonina; Subba, Enrica; Pappalardo, Rosa; Mucciardi, Massimo; Butticè, Salvatore; Inferrera, Antonino; Magno, Carlo

    2015-01-01

    To evaluate quality of life (QoL) and overall survival after radical cystectomy with cutaneous ureterostomies for locally advanced bladder cancer in elderly patients with high surgical risk. Fifty eight patients older than 74 years (mean age 80,6±4,3) with locally advanced bladder cancer (group A), underwent radical cystectomy and ureterocutaneous diversion. Patients completed the EORTC QLQC30 before and six months after surgery to assess functional, clinical and QoL outcomes. The same evaluation was carried out in a control group (group B) of 29 patients (mean age 82,3±3,8 years), who had refused cystectomy. Questionnaires were also administered to patients of both groups who survived at least 20 months and 5 years. All patients presented with an ASA score ≥3. Mean hospital stay was 15.1 days (±4.8) in group A and 23.5 days (±4.1) in Group B. No intraoperative complications occurred in group A. Postoperative overall survival evaluated within 6 months in group A was 97% versus 79% in group B (pbladder cancer and high operative risk. Comparison between two groups showed a statistically significant difference for almost all the Qol related parameters and for short and medium term overall survival. Copyright © 2012 AEC. Publicado por Elsevier España, S.L.U. All rights reserved.

  12. Synthesis of Amide and Ester Derivatives of Cinnamic Acid and Its Analogs: Evaluation of Their Free Radical Scavenging and Monoamine Oxidase and Cholinesterase Inhibitory Activities.

    Science.gov (United States)

    Takao, Koichi; Toda, Kazuhiro; Saito, Takayuki; Sugita, Yoshiaki

    2017-01-01

    A series of cinnamic acid derivatives, amides (1-12) and esters (13-22), were synthesized, and structure-activity relationships for antioxidant activity, and monoamine oxidases (MAO) A and B, acetylcholinesterase, and butyrylcholinesterase (BChE) inhibitory activities were analyzed. Among the synthesized compounds, compounds 1-10, 12-18, and rosmarinic acid (23), which contained catechol, o-methoxyphenol or 5-hydroxyindole moieties, showed potent 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity. Compounds 9-11, 15, 17-22 showed potent and selective MAO-B inhibitory activity. Compound 20 was the most potent inhibitor of MAO-B. Compounds 18 and 21 showed moderate BChE inhibitory activity. In addition, compound 18 showed potent antioxidant activity and MAO-B inhibitory activity. In a comparison of the cinnamic acid amides and esters, the amides exhibited more potent DPPH free radical scavenging activity, while the esters showed stronger inhibitory activities against MAO-B and BChE. These results suggested that cinnamic acid derivatives such as compound 18, p-coumaric acid 3,4-dihydroxyphenethyl ester, and compound 20, p-coumaric acid phenethyl ester, may serve as lead compounds for the development of novel MAO-B inhibitors and candidate lead compounds for the prevention or treatment of Alzheimer's disease.

  13. Safety and Potential Effect of a Single Intracavernous Injection of Autologous Adipose-Derived Regenerative Cells in Patients with Erectile Dysfunction Following Radical Prostatectomy

    DEFF Research Database (Denmark)

    Haahr, Martha Kirstine; Jensen, Charlotte Harken; Toyserkani, Navid Mohamadpour

    2016-01-01

    BACKGROUND: Prostate cancer is the most common cancer in men, and radical prostatectomy (RP) often results in erectile dysfunction (ED) and a substantially reduced quality of life. The efficacy of current interventions, principal treatment with PDE-5 inhibitors, is not satisfactory and this condi......BACKGROUND: Prostate cancer is the most common cancer in men, and radical prostatectomy (RP) often results in erectile dysfunction (ED) and a substantially reduced quality of life. The efficacy of current interventions, principal treatment with PDE-5 inhibitors, is not satisfactory...... and this condition presents an unmet medical need. Preclinical studies using adipose-derived stem cells to treat ED have shown promising results. Herein, we report the results of a human phase 1 trial with autologous adipose-derived regenerative cells (ADRCs) freshly isolated after a liposuction. METHODS: Seventeen...... men suffering from post RP ED, with no recovery using conventional therapy, were enrolled in a prospective phase 1 open-label and single-arm study. All subjects had RP performed 5-18 months before enrolment, and were followed for 6 months after intracavernosal transplantation. ADRCs were analyzed...

  14. ESR studies of radiation induced radical products from linoleic acid and linolenic acid and the radioprotective effect by α-tocopherol

    International Nuclear Information System (INIS)

    Zhu Younan; Tu Tiecheng; Dong Jirong; Zhang Jiashan; Li Nianyun

    1993-01-01

    Primary radicals from the γ-radiolysis of air-saturated linoleic acid and linolenic acid at 77 K, and the subsequent secondary radicals appeared during the course of variable temperature elevation were investigated by ESR. The ESR spectrum from samples irradiated and observed at 77 K shows the presence of the radical anion doublet arise from the electron adducts of the carboxy groups and the poorly resolved broad singlet results from some carbon-centered radicals. Annealing to approximately 125 K which allows for molecular oxygen migration results in the formation of peroxyl radicals. At 247 K, the ESR spectrum is a multi-line pattern which is attributable to structure of the α-carbon radical superimposed on the pentadienyl radicals. The ESR spectra from linoleic acid-α-tocopherol and linolenic acid-α-tocopherol binary systems irradiated at 77 K and recorded at 140 K or 215 K revealed the characteristic similarity to that from α-tocopherol alone, no trace of ESR signal from either peroxyl or the composite pattern from superposition of pentadienyl radical and α-carbon radicals can be found out. Therefore α-tocopherol has exerted radioprotection effect on peroxidation of linoleic acid and linolenic acid

  15. Comparative biomarker expression and RNA integrity in biospecimens derived from radical retropubic and robot-assisted laparoscopic prostatectomies.

    Science.gov (United States)

    Ricciardelli, Carmela; Bianco-Miotto, Tina; Jindal, Shalini; Dodd, Thomas J; Cohen, Penelope A; Marshall, Villis R; Sutherland, Peter D; Samaratunga, Hemamali; Kench, James G; Dong, Ying; Wang, Hong; Clements, Judith A; Risbridger, Gail P; Sutherland, Robert L; Tilley, Wayne D; Horsfall, David J

    2010-07-01

    Knowledge of preanalytic conditions that biospecimens are subjected to is critically important because novel surgical procedures, tissue sampling, handling, and storage might affect biomarker expression or invalidate tissue samples as analytes for some technologies. We investigated differences in RNA quality, gene expression by quantitative real-time PCR, and immunoreactive protein expression of selected prostate cancer biomarkers between tissues from retropubic radical prostatectomy (RRP) and robot-assisted laparoscopic prostatectomy (RALP). Sections of tissue microarray of 23 RALP and 22 RRP samples were stained with antibodies to androgen receptor (AR) and prostate-specific antigen (PSA) as intersite controls, and 14 other candidate biomarkers of research interest to three laboratories within the Australian Prostate Cancer BioResource tissue banking network. Quantitative real-time PCR was done for AR, PSA (KLK3), KLK2, KLK4, and HIF1A on RNA extracted from five RALP and five RRP frozen tissue cores. No histologic differences were observed between RALP and RRP tissue. Biomarker staining grouped these samples into those with increased (PSA, CK8/18, CKHMW, KLK4), decreased (KLK2, KLK14), or no change in expression (AR, ghrelin, Ki67, PCNA, VEGF-C, PAR2, YB1, p63, versican, and chondroitin 0-sulfate) in RALP compared with RRP tissue. No difference in RNA quality or gene expression was detected between RALP and RRP tissue. Changes in biomarker expression between RALP and RRP tissue exist at the immunoreactive protein level, but the etiology is unclear. Future studies should account for changes in biomarker expression when using RALP tissues, and mixed cohorts of RALP and RRP tissue should be avoided.

  16. Spin Trapping Radicals from Lipid Oxidation in Liposomes in the Presence of Flavonoids

    International Nuclear Information System (INIS)

    Arshad, N.

    2013-01-01

    Interactions of four structurally related flavonoids - quercetin, rutin, morin and catechin with peroxyl radicals using liposome/N-tert-butyl-alpha-phenylnitrone (PBN) and liposome -(4-pyridyl-N-oxide)-N-tert-butylnitrone (POBN)-spin trap systems have been studied through spin trapping ESR. Results obtained were different from that of conjugated diene analysis experiments, where lag phases indicated radical scavenging activity of all the flavonoids. No clear lag phase was observed in ESR experiments under same conditions. In the presence of flavonoids decreasing ESR signals of spin adducts in PBN, while no or negligibly smaller spin adducts with POBN system were observed which may be attributed to the possibility that spin traps interacted with free radicals. Experiments with buffer/spin trap systems without liposome revealed that spin adducts were only stable with catechin and destroyed by quercetin, rutin and morin in buffer/spin trap systems. These results further assured that quercetin, rutin and morin not only interacted with peroxyl radicals but also with spin adducts. (author)

  17. Edaravone, a potent free radical scavenger, reacts with peroxynitrite to produce predominantly 4-NO-edaravone.

    Science.gov (United States)

    Fujisawa, Akio; Yamamoto, Yorihiro

    2016-05-01

    3-Methyl-1-phenyl-2-pyrazolin-5-one (edaravone) is used in clinical treatment of acute brain infarction to rescue the penumbra, based on its ability to prevent lipid peroxidation by scavenging lipid peroxyl radicals. Here, we show that edaravone also reacts with peroxynitrite to yield 4-NO-edaravone as the major product and 4-NO2-edaravone as a minor product. We observed little formation of 3-methyl-1-phenyl-2-pyrazolin-4,5-dione (4-oxoedaravone) and its hydrate, 2-oxo-3-(phenylhydrazono)butanoic acid, which are the major free radical-induced oxidation products of edaravone, suggesting that free radicals are not involved in the reaction with peroxynitrite. The reaction of peroxynitrite with edaravone is approximately 30-fold greater than with uric acid, a physiological peroxynitrite scavenger (reaction rate k = 1.5 × 10 (4)  M(-1) s(-1) vs. 480 M(-1) s(-1)). These results suggest that edaravone functions therapeutically as a scavenger of peroxynitrite as well as lipid peroxyl radicals, which is consistent with a report that edaravone treatment reduced levels of 3-nitrotyrosine in the cerebrospinal fluid of patients with amyotrophic lateral sclerosis.

  18. The chemistry of separations ligand degradation by organic radical cations

    International Nuclear Information System (INIS)

    Mezyk, S.P.; Horne, G.P.; Mincher, B.J.; Zalupski, P.R.; Cook, A.R.; Wishart, J.F.

    2016-01-01

    Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexing agents and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normal alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R"."+), carbon-centered radicals (R".), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R"."+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with 2 ligands: CMPO and TODGA. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved. (authors)

  19. 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.

  20. The chemistry of separations ligand degradation by organic radical cations

    Energy Technology Data Exchange (ETDEWEB)

    Mezyk, S.P.; Horne, G.P. [California State University at Long Beach, Long Beach, CA 90840 (United States); Mincher, B.J.; Zalupski, P.R. [Idaho National Laboratory, Idaho Falls, ID 83415 (United States); Cook, A.R.; Wishart, J.F. [Chemistry Department, Brookhaven National Laboratory, New York, 11973 (United States)

    2016-07-01

    Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexing agents and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normal alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R{sup .+}), carbon-centered radicals (R{sup .}), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R{sup .+} as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with 2 ligands: CMPO and TODGA. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved. (authors)

  1. Free radical scavenging activity and neuroprotective potentials of D138, one Cu(II)/Zn(II) Schiff-base complex derived from N,N'-bis(2-hydroxynaphthylmethylidene)-1,3-propanediamine.

    Science.gov (United States)

    Wang, Che; Cai, Zheng-Xu; You, Zhong-Lu; Guo, Hui-Shu; Shang, De-Jing; Wang, Xiao-Ling; Zhang, Liang; Ma, Li-Jie; Tan, Jun; Le, Wei-Dong; Li, Song

    2014-09-01

    There is increasing evidence that free radicals play an important role in neuronal damages induced by diabetes mellitus or cerebral ischemia insults. Antioxidants with free radical scavenging activities have been shown to be beneficial and neuroprotective for these pathological conditions. Here, we report free radical scavenging activity and neuroprotective potential of D138, one copper(II)/zinc(II) Schiff-base complex derived from N,N'-2(2-hydroxynaphthylmethylidene)-1,3-propanediamine. The data from three in vitro assays, 2,2-diphenyl-1-picrylhydrazyl assay, nitro blue tetrazolium assay and hydroxyl radical scavenging assay, indicated that D138 presented a potent free radical scavenging activity. The neuroprotective and antioxidative effects of D138 were further evaluated in vivo using bilateral common carotid artery occlusion (BCCAO) mouse model and streptozotocin (STZ) diabetic mouse model. Our results indicated that treatment of D138 significantly ameliorated the hippocampal neuronal damage and the oxidative stress levels in these animal models. Moreover, D138 also reversed the behavioral deficiencies induced by BCCAO or STZ, as assessed by Y-maze test and fear conditioning test. In conclusion, all these findings support that D138 exerts free radical scavenging and neuroprotective activities and has the potentials to be a potent therapeutic candidate for brain oxidative damage induced by cerebral ischemia or diabetes mellitus.

  2. ESR investigation of the reactions of glutathione, cysteine and penicillamine thiyl radicals: competitive formation of RSOcenter dot, Rcenter dot, RSSRcenter dot-. , and RSScenter dot

    Energy Technology Data Exchange (ETDEWEB)

    Becker, David; Swarts, Steven; Champagne, Mark; Sevilla, M D

    1988-05-01

    The reactions of cysteine, glutathione and penicillamine thiyl radicals with oxygen and their parent thiols in frozen solutions have been elucidated with e.s.r. The major sulfur radicals observed are: (1) thiyl radicals, RS center dot; (2) disulfide radical anions, RSSR anion radicals; (3) perthiyl radicals, RSS center dot and upon introduction of oxygen; (4) sulfinyl radicals, RSO center dot, where R represents the remainder of the cysteine, glutathione or penicillamine moiety. The radical product observed depends on pH, concentration of thiol, and presence or absence of molecular oxygen. The sulfinyl radical is a ubiquitous intermediate, peroxyl radical attack on thiols may lead to sulfinyl radicals. The authors elaborate the observed reaction sequences that lead to sulfinyl radicals and, using /sup 17/O isotopic substitution studies, demonstrate the oxygen atom in sulfinyl radicals originates from dissolved molecular oxygen. The glutathione radical is found to abstract hydrogen from the ..cap alpha..-carbon position on the cysteine residue of glutathione to form a carbon-centred radical.

  3. Superoxide dismutase 1-mediated production of ethanol- and DNA-derived radicals in yeasts challenged with hydrogen peroxide: molecular insights into the genome instability of peroxiredoxin-null strains.

    Science.gov (United States)

    Ogusucu, Renata; Rettori, Daniel; Netto, Luis E S; Augusto, Ohara

    2009-02-27

    Peroxiredoxins are receiving increasing attention as defenders against oxidative damage and sensors of hydrogen peroxide-mediated signaling events. In the yeast Saccharomyces cerevisiae, deletion of one or more isoforms of the peroxiredoxins is not lethal but compromises genome stability by mechanisms that remain under scrutiny. Here, we show that cytosolic peroxiredoxin-null cells (tsa1Deltatsa2Delta) are more resistant to hydrogen peroxide than wild-type (WT) cells and consume it faster under fermentative conditions. Also, tsa1Deltatsa2Delta cells produced higher yields of the 1-hydroxyethyl radical from oxidation of the glucose metabolite ethanol, as proved by spin-trapping experiments. A major role for Fenton chemistry in radical formation was excluded by comparing WT and tsa1Deltatsa2Delta cells with respect to their levels of total and chelatable metal ions and of radical produced in the presence of chelators. The main route for 1-hydroxyethyl radical formation was ascribed to the peroxidase activity of Cu,Zn-superoxide dismutase (Sod1), whose expression and activity increased approximately 5- and 2-fold, respectively, in tsa1Deltatsa2Delta compared with WT cells. Accordingly, overexpression of human Sod1 in WT yeasts led to increased 1-hydroxyethyl radical production. Relevantly, tsa1Deltatsa2Delta cells challenged with hydrogen peroxide contained higher levels of DNA-derived radicals and adducts as monitored by immuno-spin trapping and incorporation of (14)C from glucose into DNA, respectively. The results indicate that part of hydrogen peroxide consumption by tsa1Deltatsa2Delta cells is mediated by induced Sod1, which oxidizes ethanol to the 1-hydroxyethyl radical, which, in turn, leads to increased DNA damage. Overall, our studies provide a pathway to account for the hypermutability of peroxiredoxin-null strains.

  4. Pulse radiolysis study on free radical scavenger edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one). 2: A comparative study on edaravone derivatives

    International Nuclear Information System (INIS)

    Hata, Kuniki; Katsumura, Yosuke; Lin, M.; Yamashita, Shinichi; Muroya, Yusa; Fu Haiying; Nakagawa, Hidehiko

    2011-01-01

    A comparative study using the pulse radiolysis technique was carried out to investigate transient absorption spectra and rate constants for the reactions of OH radical and N 3 radical with edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) and its four analogue compounds, 1,3-dimethyl-2-pyrazolin-5-one, 3-methyl-1-(pyridin-2-yl)-2-pyrazolin-5-one, 1-phenyl-3-trifluoromethyl-2-pyrazolin-5-one and 1-(4-chlorophenyl)-3-methyl-2-pyrazolin-5-one. The results showed that, unlike reaction mechanisms previously proposed, the phenyl group of edaravone played an important role in the reaction with OH radical and OH adducts to the phenyl group were formed. Quantum chemical calculations also strongly supported this attribution and suggested that the most favorable site for attacks by OH radical is the ortho position of the phenyl group. Moreover, the rate constants for the reactions of edaravone and its analogues towards OH radical and N 3 radical were about 8.0 x 10 9 , and 4.0 x 10 9 dm 3 mol -1 s -1 , respectively. Edaravone displayed higher reactivity compared to the others, in contrast to a previous report in which 3-methyl-1-(pyridin-2-yl)-2-pyrazolin-5-one showed the highest reactivity towards Hydroxyl radical OH. (author)

  5. Pulse radiolysis study on free radical scavenger edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one). 2: A comparative study on edaravone derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Hata, Kuniki; Katsumura, Yosuke [Tokyo Univ., School of Engineering, Tokyo (Japan); Lin, M; Yamashita, Shinichi [Japan Atomic Energy Agency, Advanced Science Research Center, Tokai, Ibaraki (Japan); Muroya, Yusa [Tokyo Univ., Nuclear Professional School, Tokai, Ibaraki (Japan); Haiying, Fu [Chinese Academy of Sciences, Shanghai (China); Nakagawa, Hidehiko [Nagoya City Univ., Graduate School of Pharmaceutical Sciences, Nagoya, Aichi (Japan)

    2011-01-15

    A comparative study using the pulse radiolysis technique was carried out to investigate transient absorption spectra and rate constants for the reactions of OH radical and N{sub 3} radical with edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) and its four analogue compounds, 1,3-dimethyl-2-pyrazolin-5-one, 3-methyl-1-(pyridin-2-yl)-2-pyrazolin-5-one, 1-phenyl-3-trifluoromethyl-2-pyrazolin-5-one and 1-(4-chlorophenyl)-3-methyl-2-pyrazolin-5-one. The results showed that, unlike reaction mechanisms previously proposed, the phenyl group of edaravone played an important role in the reaction with OH radical and OH adducts to the phenyl group were formed. Quantum chemical calculations also strongly supported this attribution and suggested that the most favorable site for attacks by OH radical is the ortho position of the phenyl group. Moreover, the rate constants for the reactions of edaravone and its analogues towards OH radical and N{sub 3} radical were about 8.0 x 10{sup 9}, and 4.0 x 10{sup 9} dm{sup 3} mol{sup -1} s{sup -1}, respectively. Edaravone displayed higher reactivity compared to the others, in contrast to a previous report in which 3-methyl-1-(pyridin-2-yl)-2-pyrazolin-5-one showed the highest reactivity towards Hydroxyl radical OH. (author)

  6. Secondary radicals derived from chloramines of apolipoprotein B-100 contribute to HOCl-induced lipid peroxidation of low-density lipoproteins

    DEFF Research Database (Denmark)

    Hazell, L J; Davies, Michael Jonathan; Stocker, R

    1999-01-01

    component to be the major site of attack, whereas others describe extensive lipid peroxidation. The present study addresses this controversy. The results obtained are consistent with the hypothesis that radical-induced oxidation of LDL's lipids by HOCl is a secondary reaction, with most HOCl consumed via...... by an extended period of lipid peroxidation during which further protein oxidation does not occur. The secondary lipid peroxidation process involves EPR-detectable radicals, is attenuated by a radical trap or treatment of HOCl-oxidized LDL with methionine, and occurs less rapidly when the lipoprotein...

  7. Alkoxyl- and carbon-centered radicals as primary agents for degrading non-phenolic lignin-substructure model compounds.

    Science.gov (United States)

    Ohashi, Yasunori; Uno, Yukiko; Amirta, Rudianto; Watanabe, Takahito; Honda, Yoichi; Watanabe, Takashi

    2011-04-07

    Lignin degradation by white-rot fungi proceeds via free radical reaction catalyzed by oxidative enzymes and metabolites. Basidiomycetes called selective white-rot fungi degrade both phenolic and non-phenolic lignin substructures without penetration of extracellular enzymes into the cell wall. Extracellular lipid peroxidation has been proposed as a possible ligninolytic mechanism, and radical species degrading the recalcitrant non-phenolic lignin substructures have been discussed. Reactions between the non-phenolic lignin model compounds and radicals produced from azo compounds in air have previously been analysed, and peroxyl radical (PR) is postulated to be responsible for lignin degradation (Kapich et al., FEBS Lett., 1999, 461, 115-119). However, because the thermolysis of azo compounds in air generates both a carbon-centred radical (CR) and a peroxyl radical (PR), we re-examined the reactivity of the three radicals alkoxyl radical (AR), CR and PR towards non-phenolic monomeric and dimeric lignin model compounds. The dimeric lignin model compound is degraded by CR produced by reaction of 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH), which under N(2) atmosphere cleaves the α-β bond in 1-(4-ethoxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol to yield 4-ethoxy-3-methoxybenzaldehyde. However, it is not degraded by the PR produced by reaction of Ce(4+)/tert-BuOOH. In addition, it is degraded by AR produced by reaction of Ti(3+)/tert-BuOOH. PR and AR are generated in the presence and absence of veratryl alcohol, respectively. Rapid-flow ESR analysis of the radical species demonstrates that AR but not PR reacts with the lignin model compound. Thus, AR and CR are primary agents for the degradation of non-phenolic lignin substructures.

  8. 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.

  9. 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.

  10. Key role of chemical hardness to compare 2,2-diphenyl-1-picrylhydrazyl radical scavenging power of flavone and flavonol O-glycoside and C-glycoside derivatives.

    Science.gov (United States)

    Waki, Tsukasa; Nakanishi, Ikuo; Matsumoto, Ken-ichiro; Kitajima, Junichi; Chikuma, Toshiyuki; Kobayashi, Shigeki

    2012-01-01

    The antioxidant activities of flavonoids and their glycosides were measured with the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH radical, DPPH(·)) scavenging method. The results show that free hydroxyl flavonoids are not necessarily more active than O-glycoside. Quercetin and kaempferol showed higher activity than apigenin. The C- and O-glycosides of flavonoids generally showed higher radical scavenging activity than aglycones; however, kaempferol C3-O-glycoside (astragalin) showed higher activity than kaempferol. In the radical scavenging activity of flavonoids, it was expected that OH substitutions at C3 and C5 and catechol substitution at C2 of B ring and intramolecular hydrogen bonding between OH at C5 and ketone at C3 would increase the activity; however, the reasons have yet to be clarified. We here show that the radical scavenging activities of flavonoids are controlled by their absolute hardness (η) and absolute electronegativity (χ) as a electronic state. Kaempferol and quercetin provide high radical scavenging activity since (i) OH substitutions at C3 and C5 strikingly decrease η of flavones, (ii) OH substitutions at C3 and C7 decrease χ and η of flavones, and (iii) phenol or o-catechol substitution at C2 of B ring decrease χ of flavones. The coordinate r(χ, η) as the electron state must be small to increase the radical scavenging activity of flavonoids. The results show that chemically soft kaempferol and quercetin have higher DPPH radical scavenging activity than chemically hard genistein and daidzein.

  11. Synchrotron radiation structure analyses of the light-induced radical pair of a hexaarylbiimidazolyl derivative. Origin of the spin-multiplicity change

    CERN Document Server

    Kawano, M; Matsubara, K; Imabayashi, H; Mitsumi, M; Toriumi, K; Ohashi, Y

    2002-01-01

    In situ synchrotron radiation structure analyses of a light-induced radical pair from o-Cl-HABI were performed by using an X-ray vacuum camera at 23-70K at the BL02B1 station of SPring-8. The combined results of X-ray analysis with theoretical calculation, IR, and UV-vis spectroscopy reveal that a slight conformational change of the radical pair causes the drastic spin-multiplicity change during 2-140K. (author)

  12. Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins

    KAUST Repository

    Millet, Anthony; Lefebvre, Quentin; Rueping, Magnus

    2016-01-01

    A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary and secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts of an iridium photocatalyst. The reactivity of the α-amino radicals has been evaluated for the functionalization of a variety of activated olefins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  13. Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins

    KAUST Repository

    Millet, Anthony

    2016-06-20

    A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary and secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts of an iridium photocatalyst. The reactivity of the α-amino radicals has been evaluated for the functionalization of a variety of activated olefins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  14. 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.

  15. 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.

  16. The role of proteins in damage induced by free radicals

    International Nuclear Information System (INIS)

    Gebicki, J.M.

    1996-01-01

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

  17. The role of proteins in damage induced by free radicals

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-12-31

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

  18. Putative anticancer potential of novel 4-thiazolidinone derivatives: cytotoxicity toward rat C6 glioma in vitro and correlation of general toxicity with the balance of free radical oxidation in rats.

    Science.gov (United States)

    Коbylinska, Lesya I; Boiko, Nataliya M; Panchuk, Rostyslav R; Grytsyna, Iryna I; Klyuchivska, Olga Yu; Biletska, Liliya P; Lesyk, Roman B; Zіmenkovsky, Borys S; Stoika, Rostyslav S

    2016-04-23

    To evaluate the cytotoxic action of 4-thiazolidinone derivatives (ID 3288, ID 3882, and ID 3833) toward rat glioma C6 cells and to compare the effects of these compounds and doxorubicin on the balance of free radical oxidation (FRO) and antioxidant activity (AOA) in the serum of rats. Glioma cells were treated with ID 3882, ID 3288, ID 3833, and doxorubicin, and their cytotoxicity was studied using MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay and Trypan blue exclusion test, light and fluorescent microscopy, and flow cytometric study of cell cycling and apoptosis, including measuring of Annexin V-positive cells. The contents of superoxide radical, hydrogen peroxide, hydroxyl radical, malonic dialdehyde, and hydrogen sulfide were measured in the serum of rats. Enzymatic activity of superoxide dismutase (SOD), catalase (Cat), and glutathione peroxydase (GPO) was determined. Among novel 4-thiazolidinone derivatives, ID 3288 was most toxic toward rat glioma C6 cells, even compared with doxorubicin. All applied derivatives were less active than doxorubicin in inducing reactive oxygen species-related indicators in the serum of rats. A similar effect was observed when enzymatic indicators of AOA processes were measured. While doxorubicin inhibited the activity of SOD, GPO, and Cat, the effects of 4-thiazolidinone derivatives were less prominent. Novel 4-thiazolidinone derivatives differ in their antineoplastic action toward rat glioma C6 cells, and ID 3288 possesses the highest activity compared to doxorubicin. Measurement of indicators of FRO and AOA in the serum of rats treated with these compounds showed their lower general toxicity compared with doxorubicin's toxicity.

  19. Highly Functionalized and Potent Antiviral Cyclopentane Derivatives Formed by a Tandem Process Consisting of Organometallic, Transition-Metal-Catalyzed, and Radical Reaction Steps

    Czech Academy of Sciences Publication Activity Database

    Jagtap, Pratap; Ford, Leigh Robert; Deister, E.; Pohl, Radek; Císařová, I.; Hodek, Jan; Weber, Jan; Mackman, R.; Bahador, G.; Jahn, Ullrich

    2014-01-01

    Roč. 20, č. 33 (2014), s. 10298-10304 ISSN 0947-6539 R&D Projects: GA ČR GA203/09/1936 Institutional support: RVO:61388963 Keywords : antiviral activity * cyclopentanes * isomerization * organic synthesis * radicals Subject RIV: CC - Organic Chemistry Impact factor: 5.731, year: 2014

  20. 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

  1. 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)

  2. 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)

  3. 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

  4. DPPH RADICAL SCAVENGING ACTIVITY, TOTAL PHENOLICS AND FLAVONOIDS OF WATER SOLUBLE EXTRACTS DERIVED FROM LEAVES AND FRUIT OF Ficus carica L. AND Ficus parietalis Bl.

    Directory of Open Access Journals (Sweden)

    Oktavia Tri Wahyuni

    2016-08-01

    Full Text Available Ficus carica L and Ficus parietalis Bl. (Moraceae are closely related plants which also known in Indonesia as Figs L. Considering the wide therapeutic value of Figs, this research was aimed to evaluate the DPPH-radical scavenging activity of both plants as well as their total phenolic and flavonoids. Extracts were produced by using boiled water and diluted to gain the desired concentration. Analyses were performed by using UV-vis spectrophotometer. Radical scavenging activity testing was done by using radical of DPPH (2,2-diphenyl-1-pycrylhydrazyl to determine the IC50s. The determination of total phenolic was conducted by using Folin-Ciocalteau method and calculated as Gallic Acid Equivalence (GAE. The total flavonoid was measured by using AlCl3-reagents, and calculated as Rutin Equivalence (RE. Afterwards, the radical scavenging activity was correlated to the total phenolic and flavonoids contents. The results showed that the water soluble extract of F. carica fruit had the best IC50 value of 33.38 mg/mL, followed successively by the F. parietalis fruit (35.69 mg/mL, F. parietalis leaves (44.01 mg/mL and the F. carica leaves (76.38 mg/mL. The highest content of total phenolic was shown by the leaves of F. parietalis (1.46% w/w GAE and the lowest was in the fruit or F. carica (0.36% w/w GAE. The highest flavonoid content was detected in the leaves of F. carica (1.42% w/w RE and the lowest was in the F. parietalis fruit (0.20% w/w RE. Correlation analyses of the IC50 values vs. the total phenolic and the flavonoids contents resulted in a positive slope having R2 values as 0.5362 and 0.9895, respectively. As a conclusion, the total flavonoid content influenced the DPPH radical scavenging activity by 98.95%, while the total phenolic content influence was only 53.62%.

  5. Radio reduction of the vitamin K in ethanolic solution: Contribution to radical oxidation study of a glutamic residue

    International Nuclear Information System (INIS)

    Fackir, L.

    1995-01-01

    The biological action of vitamin K may involve mono electronic exchanges. Therefore, in this work we achieved a radiolytical study on one land, of mono electronic reduction of vitamin K hydroquinone symbolized by KHsubn pp. We also studied the vitamin K2 model of glutamic residue( B - Glu ) by radiolytic mean. The study of radical mechanisms of vitamin K1 reduction in ethanolic solution showed that vitamin K1 is a good sensor of free radicals alpha - hydroxyethyles ( R sup . ) issued from the radiolysis of vitamin K1 ethanolic solutions, saturated with N sub2 O. The final product is hydroquinone K sub 1 H sub 2. It has been demonstrated that mono electronic reduction can be also initiated by solvated electrons. The mono electronic oxidation of K H sub p has been studied in ethanolic solution.The results showed that K H sub p is a good sensor of peroxyl radicals model (RO sub2) sup . issues from ethanol. The oxidation leads to the formation a dimeric from of the quinone K. All these results showed that the free radicals R sup . centred on carbon are efficient reducing agents of vitamin K1, and that the peroxyl radicals R Osub2 centred on oxygen are possible oxidants of KH sub p. At the end and for modeling the eventual interaction of semi quinonic radical with glutamic acid. We have irradiated mixture of vitamin K1 and a compound having a glutamic residue, the concentration ratio (B-Glu) sub 0/ (K sub 1) sub 0 varying for 0,03 to 1. The obtained results showed that the yield of vitamin K sub 1 disappearance is superior to G (R sup .)/R for low concentration of B-Glu. 80 figs., 5 tabs., 105 refs. (F. M.)

  6. Kinetics and structure-activity relationship of dendritic bridged hindered phenol antioxidants to protect styrene against free radical induced peroxidation

    Science.gov (United States)

    Li, Cui-Qin; Guo, Su-Yue; Wang, Jun; Shi, Wei-Guang; Zhang, Zhi-Qiu; Wang, Peng-Xiang

    2017-12-01

    A series of dendritic poly(amido-amine) (PAMAM) bridged hindered phenols antioxidants were synthesized. The active antioxidant group (3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionic acid) was attached to two generations of PAMAM dendrimers, and their structure was verified by nuclear magnetic resonance (NMR) and fourier transform infrared spectra (FT-IR). The antioxidant abilities of the dendritic phenols to inhibit the oxidation of styrene were evaluated and the relationships between the length of core, the generation of dendrimers and the antioxidant activities were established. The reaction kinetics of scavenging peroxyl radicals was followed by oxygen consumption. The inhibition time ( t inh) values showed the dendritic phenols had the ability of scavenging peroxyl radicals, and that the antioxidant ability increased with the increasing length of the core and the generation. The kinetic analysis demonstrated that dendritic phenols could slow the rate of styrene peroxidation induced by AIBN, as shown by the number of trapping ROO· ( n), and this role was in accordance with that of the t inh values.

  7. Thermochemical properties of exo-tricyclo[5.2.1.0(2,6)]decane (JP-10 jet fuel) and derived tricyclodecyl radicals.

    Science.gov (United States)

    Hudzik, Jason M; Asatryan, Rubik; Bozzelli, Joseph W

    2010-09-09

    exo-Tricyclo[5.2.1.0(2,6)]decane (TCD) or exo-tetrahydrodicyclopentadiene is the principal component of the high-energy density hydrocarbon fuel commonly identified as JP-10. Thermodynamic parameters for the parent TCD molecule and of all the tricyclodecyl radicals corresponding to the loss of hydrogen atoms from different carbons sites (TCD-Ri with i indicating the given carbon center) are determined using several density functional theory and G3MP2B3 and CBS-QB3 higher level composite computational chemistry methods. Five isodesmic work reactions, three involving bridged hydrocarbon reference molecules with similar ring strains, are employed to produce a cancelation of systematic calculation errors in evaluation of standard, gas-phase formation enthalpies at 298 K. Delta(f)H degrees (298) for TCD is found to be -19.5 +/- 1.3 kcal mol(-1), which is several kcal mol(-1) lower than the commonly used values. C(i)-H bond energies for corresponding TCD carbon sites are evaluated as follows: TCD-R1, 107.2; TCD-R2, 100.1; TCD-R3, 98.0; TCD-R4, 98.5; TCD-R9, 98.7; TCD-R10, 104.1 kcal mol(-1). Results from use of five different DFT methods are in very good agreement with composite level values for all work reactions used for the radicals. The exo and endo isomers of TCD are both determined to have chair and boat conformers.

  8. Development of 2-(Substituted Benzylamino)-4-Methyl-1, 3-Thiazole-5-Carboxylic Acid Derivatives as Xanthine Oxidase Inhibitors and Free Radical Scavengers.

    Science.gov (United States)

    Ali, Md Rahmat; Kumar, Suresh; Afzal, Obaid; Shalmali, Nishtha; Sharma, Manju; Bawa, Sandhya

    2016-04-01

    A series of 2-(substituted benzylamino)-4-methylthiazole-5-carboxylic acid was designed and synthesized as structural analogue of febuxostat. A methylene amine spacer was incorporated between the phenyl ring and thiazole ring in contrast to febuxostat in which the phenyl ring was directly linked with the thiazole moiety. The purpose of incorporating methylene amine was to provide a heteroatom which is expected to favour hydrogen bonding within the active site residues of the enzyme xanthine oxidase. The structure of all the compounds was established by the combined use of FT-IR, NMR and MS spectral data. All the compounds were screened in vitro for their ability to inhibit the enzyme xanthine oxidase as per the reported procedure along with DPPH free radical scavenging assay. Compounds 5j, 5k and 5l demonstrated satisfactory potent xanthine oxidase inhibitory activities with IC50 values, 3.6, 8.1 and 9.9 μm, respectively, whereas compounds 5k, 5n and 5p demonstrated moderate antioxidant activities having IC50 15.3, 17.6 and 19.6 μm, respectively, along with xanthine oxidase inhibitory activity. Compound 5k showed moderate xanthine oxidase inhibitory activity as compared with febuxostat along with antioxidant activity. All the compounds were also studied for their binding affinity in active site of enzyme (PDB ID-1N5X). © 2015 John Wiley & Sons A/S.

  9. HPLC-ESR techniques for detection of complex trapped radicals

    International Nuclear Information System (INIS)

    Tu Tiecheng; Dong Jirong; Lin Nianyun; Xie Leidong; Liu Rengzhong

    1992-01-01

    High performance liquid chromatography (HPLC) and ESR combined examination of radical species is an advanced techniques for separation and identification of complex radical species. At SRCL, Waters 990 HPLC has been used to separate the complex trapped radicals and Varian E-112 ESR spectrometer to record the spectra of single trapped radicals after HPLC separation. The advantages of the combined techniques are described as bellow: HPLC is used to separate the long-lived complex trapped radicals derived from reaction of short-lived radicals with spin trap. ESR spectra from single trapped radicals, obtained following HPLC separation of complex trapped radicals, are recorded one by one and well resolved. The structures of short-lived radicals can be inferred from the ESR spectra of the long-lived trapped radicals

  10. 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

  11. 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...

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

    Science.gov (United States)

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

    2011-09-01

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

  13. 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?

  14. 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)

  15. 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

  16. Generation of carotenoid radical cation in the vicinity of a chlorophyll derivative bound to titanium oxide, upon excitation of the chlorophyll derivative to the Q y state, as identified by time-resolved absorption spectroscopy

    Science.gov (United States)

    Wang, Xiao-Feng; Kakitani, Yoshinori; Xiang, Junfeng; Koyama, Yasushi; Rondonuwu, Ferdy S.; Nagae, Hiroyoshi; Sasaki, Shin-ichi; Tamiaki, Hitoshi

    2005-12-01

    Electron injection from a chlorophyll derivative (methyl 3-carboxy-3-devinylpyropheophorobide a, abbreviated as PPB a) to TiO 2 nanoparticle took place in ≈30 fs following the decay of an excimer that was generated immediately after excitation to the Q y state (681 nm). Then, electron transfer from carotenoids (Cars) to PPB arad + took place in ≈200-240 ps. The latter observation supports the electron-transfer mechanism proposed in a previous investigation, in which Cars were added as redox spacers to the PPB a-sensitized TiO 2 solar cells to enhance their performance (X.-F. Wang, J. Xiang, P. Wang, Y. Koyama, S. Yanagida, Y. Wada, K. Hamada, S. Sasaki, H. Tamiaki, Chem. Phys. Lett. 408 (2005) 409).

  17. 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

  18. 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

  19. Antioxidant multi-walled carbon nanotubes by free radical grafting of gallic acid: new materials for biomedical applications.

    Science.gov (United States)

    Cirillo, Giuseppe; Hampel, Silke; Klingeler, Rüdiger; Puoci, Francesco; Iemma, Francesca; Curcio, Manuela; Parisi, Ortensia Ilaria; Spizzirri, Umile Gianfranco; Picci, Nevio; Leonhardt, Albrecht; Ritschel, Manfred; Büchner, Bernd

    2011-02-01

    To prove the possibility of covalently functionalizing multi-walled carbon nanotubes (CNTs) by free radical grafting of gallic acid on their surface with the subsequent synthesis of materials with improved biological properties evaluated by specific in-vitro assays. Antioxidant CNTs were synthesized by radical grafting of gallic acid onto pristine CNTs. The synthesis of carbon nanotubes was carried out in a fixed-bed reactor and, after the removal of the amorphous carbon, the grafting process was performed. The obtained materials were characterized by fluorescence and Fourier transform infrared spectroscopy (FT-IR) analyses. After assessment of the biocompatibility and determination of the disposable phenolic group content, the antioxidant properties were evaluated in terms of total antioxidant activity and scavenger ability against 2,2'-diphenyl-1-picrylhydrazyl (DPPH), hydroxyl and peroxyl radicals. Finally the inhibition activity on acetylcholinesterase was evaluated.   The covalent functionalization of CNTs with gallic acid was confirmed and the amount of gallic acid bound per g of CNTs was found to be 2.1±0.2 mg. Good antioxidant and scavenging properties were recorded in the functionalized CNTs, which were found to be able to inhibit the acetylcholinesterase with potential improved activity for biomedical and pharmaceutical applications. For the first time, a free radical grafting procedure was proposed as a synthetic approach for the covalent functionalization of CNTs with an antioxidant polyphenol. © 2010 The Authors. JPP © 2010 Royal Pharmaceutical Society.

  20. 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.

  1. Psychopathology according to behaviorism: a radical restatement.

    Science.gov (United States)

    Pérez-Alvarez, Marino

    2004-11-01

    This article is a radical restatement of the predominant psychopathology, which is characterized by nosological systems and by its approach towards a neurobiological conception of the so-called mental disorders. The "radical" sense of this restatement is that of radical behaviorism itself. As readers will recall, "radical" applied to behaviorism means total (not ignoring anything that interests psychology), pragmatic (referring to the practical sense of knowledge), and it also derives from the Latin word for "root" (and thus implies change beginning at a system's roots or getting to the root of things, in this case, of psychological disorders). Based on this, I introduce the Aristotelian distinction of material and form, which, besides being behaviorist avant la lettre, is used here as a critical instrument to unmask the hoax of psychopathology as it is presented. The implications of this restatement are discussed, some of them already prepared for clinical practice.

  2. 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

  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. 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

  5. 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.)

  6. 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.

  7. 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...

  8. 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...

  9. 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

  10. Crotylations of alpha-carbonyl radicals with crotylstannane.

    Science.gov (United States)

    Sibi, Mukund P; Miyabe, Hideto

    2002-10-03

    Electrophilic radicals undergo crotylation with crotylstannane with moderate to good efficiency. The reaction provides the syn isomer as the major product. The present methodology is complementary to Claisen protocols for the synthesis of gamma,delta-unsaturated carboxylic acid derivatives. Details of the new radical methodology are presented. [reaction: see text

  11. Moderate and Radical Islam

    National Research Council Canada - National Science Library

    Rabasa, Angel

    2005-01-01

    This report presents the statement of Angel Rabasa, PhD, Senior Policy Analyst, The RAND Corporation, to the Committee on Armed Services, Defense Review Terrorism and Radical Islam Gap Panel, United...

  12. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks...... within this field and to answer the question: From an empirical point of view, what is known and what is not known about radicalization connected to militant Islamism in Europe?...

  13. 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)

  14. Ex-vivo and in vitro protective effects of kolaviron against oxygen-derived radical-induced DNA damage and oxidative stress in human lymphocytes and rat liver cells

    DEFF Research Database (Denmark)

    Farombi, E.O.; Moller, P.; Dragsted, L.O.

    2004-01-01

    at concentrations between 30-90 mumol/L and decreased H2O2-induced DNA strand breaks and oxidized bases. Neither alpha-tocopherol nor curcumin decreased H2O2-induced DNA damage in this assay. In lymphocytes incubated with Fe3+ /GSH, Fe3+ was reduced to Fe2+ by GSH initiating a free radical generating reaction which...

  15. 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.

  16. Radical dematerialization and degrowth

    Science.gov (United States)

    Kallis, Giorgos

    2017-05-01

    The emission targets agreed in Paris require a radical reduction of material extraction, use and disposal. The core claim of this article is that a radical dematerialization can only be part and parcel of degrowth. Given that capitalist economies are designed to grow, this raises the question of whether, and under what circumstances, the inevitable `degrowth' can become socially sustainable. Three economic policies are discussed in this direction: work-sharing, green taxes and public money. This article is part of the themed issue 'Material demand reduction'.

  17. Muon substituted free radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

    1984-01-01

    Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

  18. Photoionisation of the tropyl radical

    Directory of Open Access Journals (Sweden)

    Kathrin H. Fischer

    2013-04-01

    Full Text Available We present a study on the photoionisation of the cycloheptatrienyl (tropyl radical, C7H7, using tunable vacuum ultraviolet synchrotron radiation. Tropyl is generated by flash pyrolysis from bitropyl. Ions and electrons are detected in coincidence, permitting us to record mass-selected photoelectron spectra. The threshold photoelectron spectrum of tropyl, corresponding to the X+ 1A1’ ← X 2E2” transition, reveals an ionisation energy of 6.23 ± 0.02 eV, in good agreement with Rydberg extrapolations, but slightly lower than the value derived from earlier photoelectron spectra. Several vibrations can be resolved and are reassigned to the C–C stretch mode ν16+ and to a combination of ν16+ with the ring breathing mode ν2+. Above 10.55 eV dissociative photoionisation of tropyl is observed, leading to the formation of C5H5+ and C2H2.

  19. Counter radicalization development assistance

    OpenAIRE

    van Hippel, Karin

    2006-01-01

    The paper reviews current research and practice and recommends strategies for development agencies working in the Arab and Muslim world. It builds on the basic assumption that the realization of the Millennium Development Goals will be vital to reduce support for terrorism in the long term. Within this overall framework, emphasis is placed on particular programs that could be specifically applied to counter radicalization.

  20. 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.

  1. Sexuality Following Radical Prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Serefoglu, Ege C; Albersen, Maarten

    2017-01-01

    incontinence in relation to sexual activity after surgery. This can present at the time of orgasm (ie, climacturia) or arise during arousal. In general, the problem subsides with time and pelvic floor training and tension penile loops can be used as treatments. Orgasmic disturbances after radical prostatectomy...

  2. 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.

  3. Online Radicalization: Bangladesh Perspective

    Science.gov (United States)

    2017-06-09

    radicalization through cyberspace, Bangladesh mostly implements hard powers such as removing contents and restricting access to the internet. However, freedom...cyberspace, Bangladesh mostly implements hard powers such as removing contents and restricting access to the internet. However, freedom of speech...67 An Organizational Approach to Implement the Measures........................................ 69 Formation of

  4. Cation radicals of xanthophylls.

    Science.gov (United States)

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

    2007-10-01

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

  5. 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

  6. 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)

  7. Reactions of inorganic free radicals with liver protecting drugs

    International Nuclear Information System (INIS)

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

    1990-01-01

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

  8. 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.

  9. 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.

  10. Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

    International Nuclear Information System (INIS)

    Dzeba, I.; Mihaljevic, B.

    2011-01-01

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

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

    DEFF Research Database (Denmark)

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

    2001-01-01

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

  12. 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...

  13. New homo- and heteroleptic derivatives of trivalent ytterbium containing anion-radical 1,4-diazadiene ligands. Synthesis, properties and crystal structure of (C9H7)2Yb[2-MeC6H4NC(Me)C(Me)NC6H4Me-2] and [PhNC(Ph)C(Ph)NPh]3Yb complexes

    International Nuclear Information System (INIS)

    Gudilenkov, I.D.; Fukin, G.K.; Cherkasov, A.V.; Shavyrin, A.S.; Trifonov, A.A.; Larionova, Yu.E.

    2008-01-01

    Reaction of ytterbium bisindenyl complex (C 9 H 7 ) 2 Yb II (THF) 2 (1) with 1,4-diazabutadiene 2-MeC 6 H 4 N=C(Me)-C(Me)=NC 6 H 4 Me-2 ( Me DAD) is accompanied by the oxidation of metal atom until trivalent state and results in the formation of paramagnetic compound of metallocenes type (C 9 H 7 ) 2 Yb III ( Me DAD -. ) (3) containing 1,4-diazabutadiene anion-radical. Structure of complex 3 is ascertained by the X-ray structure analysis. Reactions of bisindenyl (1) and bisfluorenyl (C 13 H 9 ) 2 Yb II (THF) 2 (2) derivatives of bivalent ytterbium with 1,4-diazabutadiene PhN=C(Ph)-C(Ph)=NPh ( Ph DAD) (at 1:2 molar ratio of reagents) proceed with the complete break of Yb-C bonds, oxidation of ytterbium atom until trivalent state, and result in the formation of homoligand complex ( Ph DAD -. ) 3 Yb (6) containing three anion-radical 1,4-diazadiene ligands. Complex 6 was also prepared by the exchange reaction of YbCl 3 with Ph DAD -. K + (1:3) in THF. Complex 6 is characterized by the X-ray structure analysis [ru

  14. Redox potentials of free radicals. III. Reevaluation of the method

    International Nuclear Information System (INIS)

    Rao, P.S.; Hayon, E.

    1974-01-01

    A reevaluation of the method described in ref 1 and 2 to determine the redox potentials of free radicals (.RH) in water using the techniques of pulse radiolysis and absorption spectrophotometry is presented. This method is based on the dependence of the percentage efficiency for the one-electron oxidation (or reduction) of .RH radicals on the redox potentials E 01 of the electron acceptors, A. The reaction .RH + A → .A - + R + H + (kappa/sub ox/) is not reversible for most radicals under the experimental conditions used, and the derived potentials are, therefore, not thermodynamic values. A reinterpretation of the results is made on the basis of the kinetic competition between the above reaction and .RH + A → .RHA (kappa/sub add/) (radical adducts). Based on kappa/ sub ox/ and kappa/sub add/, it is concluded that the observed experimental ''titration'' curves do represent a measure of the redox property of the free radicals. From the midpoint on the curves, the kinetic potential, E/sub kappa/ 01 : of the free radicals can be derived based on the known two-electron redox potentials of the electron acceptors. These and other questions are discussed. (U.S.)

  15. 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

  16. 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

  17. 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.

  18. Evaluation of radical scavenging activity, intestinal cell viability and antifungal activity of Brazilian propolis by-product.

    Science.gov (United States)

    de Francisco, Lizziane; Pinto, Diana; Rosseto, Hélen; Toledo, Lucas; Santos, Rafaela; Tobaldini-Valério, Flávia; Svidzinski, Terezinha; Bruschi, Marcos; Sarmento, Bruno; Oliveira, M Beatriz P P; Rodrigues, Francisca

    2018-03-01

    Propolis is a natural adhesive resinous compound produced by honeybees to protect hives from bacteria and fungi, being extremely expensive for food industry. During propolis production, a resinous by-product is formed. This resinous waste is currently undervalued and underexploited. Accordingly, in this study the proximate physical and chemical quality, as well as the antioxidant activity, radical scavenging activity and cell viability of this by-product were evaluated and compared with propolis in order to boost new applications in food and pharmaceutical industries. The results revealed that the by-product meets the physical and chemical quality standards expected and showed that the propolis waste contains similar amounts of total phenolic content (TPC) and total flavonoid content (TFC) to propolis. Also, a good scavenging activity against reactive oxygen and nitrogen species (ROS and RNS, respectively) determined by the assays of superoxide anion radical (O 2 - ), hydrogen peroxide (H 2 O 2 ), hypochlorous acid (HOCl), nitric oxide (NO) and peroxyl radical (ROO) were determined. Linear positive correlations were established between the TPC of both samples and the antioxidant activity evaluated by three different methods (DPPH, ABTS and FRAP assays). The extracts were also screened for cell viability assays in two different intestinal cell lines (HT29-MTX and Caco-2), showing a viability concentration-dependent. Similarly, the Artemia salina assay, used to assess toxicity, demonstrated the concentration influence on results. Finally, the antifungal activity against ATCC species of Candida was demonstrated. These results suggest that propolis by-product can be used as a new rich source of bioactive compounds for different areas, such as food or pharmaceutical. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Reactivity of OH radicals with chlorobenzoic acids-A pulse radiolysis and steady-state radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Zona, Robert [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Solar, Sonja, E-mail: sonja.solar@univie.ac.a [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Getoff, Nikola [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology, UZAII, Althanstrasse 14, A-1090 Vienna (Austria); Sehested, Knud; Holcman, Jerzy [RISO National Laboratory Environmental Science and Technology Department, DK-4000, Roskilde (Denmark)

    2010-05-15

    The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k({sup c}entre dotOH+substrates)=(4.5-6.2)x10{sup 9} dm{sup 3} mol{sup -1} s{sup -1}, have been studied by pulse radiolysis in N{sub 2}O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320-340 nm. Their decay was according to a second-order reaction, 2k=(1-9)x10{sup 8} dm{sup 3} mol{sup -1} s{sup -1}. In the presence of N{sub 2}O/O{sub 2} the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O{sub 2})=(2-4)x10{sup 7} dm{sup 3} mol{sup -1} s{sup -1}, while this reaction for 3-ClBzA was too slow to be registered. In the presence of N{sub 2}O the degradation rates induced by gamma radiation were very similar for all chlorobenzoic acids, yet the chloride formation was distinctly higher for 3-ClBzA. In the presence of oxygen the initial degradation of 2-and 4-ClBzA equaled the OH-radical concentration, whereas in case of 3-ClBzA only approx60% of {sup c}entre dotOH led to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out.

  20. Radical cystectomy: Analysis of postoperative course

    Directory of Open Access Journals (Sweden)

    Jeremić Dimitrije

    2010-01-01

    Full Text Available Background/Aim. Radical cystectomy is a method of choice in the therapy of infiltrative bladder cancer. The aim of this research was to analyze postoperative course after radical cystectomy (length of hospitalization, most frequent complications and utilization of antibiotics and transfusions. Methods. We analyzed the records of 82 patients operated on in the Department of Urology, Clinical Center of Vojvodina, in a three-year period. In order to aquire data World Health Organization (WHO has developed Anatomical Therapeutic Chemical/Defined Daily Dose (ATC/DDD methodology. Defined daily dose (DDD is the assumed average maintenance dose per day for a drug use for its main indication. Results. Continent urinary derivation was preformed in 23.15% cases. Postoperative complications occurred in 18.29% of patients. Average blood utilization was 2.19 units. Blood utilization for continent derivations (n = 48 was 4.6 units, and incontinent ones 3.36 units. Totally 159.33 DDD/100 bed days were used. Conclusion. When preforming continent derivation there is a significant increase in blood utilization. Frequency of postoperative complications correlates to those reported in the literature.

  1. Peroxy Radical Measurements via Laser Induced Fluorescence

    Science.gov (United States)

    Trawny, Katrin; Tatum Ernest, Cheryl; Novelli, Anna; Elste, Thomas; Plaß-Dülmer, Christian; Rudolf, Markus; Martinez, Monica; Harder, Hartwig; Lelieveld, Jos

    2013-04-01

    We present a newly built Laser Induced Fluorescence (LIF) system to measure the sum of all peroxy radicals (RO2) utilizing chemical conversion to OH. This instrument operates in two different modes: the ROx mode (sum of OH, HO2, and RO2) and the HOx mode (sum of OH and HO2). The HOx mode is used to derive the RO2 data from the ROx measurements. A model approach was used during instrumental development to identify the key parameters needed for the conversion process in front of the detection area and to optimize sensitivity. The instrument was then carefully characterized in various lab experiments, where it could be shown that the wall losses for HO2 are negligible and that nearly all HO2 is converted to OH in front of the detection zone. The pressure and temperature dependencies were also analyzed and assured that the instrument does not show any photolytical interference. As the instrument is calibrated with only one kind of peroxy radicals it was very important that the differences in sensitivity for different peroxy radicals are acceptable. Lab experiments as well as first results from the HOPE 2012 intensive field campaign, which took place in summer 2012 at the Global Atmosphere Watch (GAW) station of the German Weather Service, will be discussed.

  2. 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

  3. 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.

  4. Hot wire radicals and reactions

    International Nuclear Information System (INIS)

    Zheng Wengang; Gallagher, Alan

    2006-01-01

    Threshold ionization mass spectroscopy is used to measure radical (and stable gas) densities at the substrate of a tungsten hot wire (HW) reactor. We report measurements of the silane reaction probability on the HW and the probability of Si and H release from the HW. We describe a model for the atomic H release, based on the H 2 dissociation model. We note major variations in silicon-release, with dependence on prior silane exposure. Measured radical densities versus silane pressure yield silicon-silane and H-silane reaction rate coefficients, and the dominant radical fluxes to the substrate

  5. 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

  6. Geminate free radical processes and magnetic field effects

    International Nuclear Information System (INIS)

    Eveson, Robert W.

    2000-01-01

    introduction to the physical properties of simple micelles, the media for the all the magnetic field effect work. Low field effect measurements are then presented as function of micelle size for both anionic and non-ionic micelles, radical pair type and temperature for the benzophenone-surfactant derived radical pair. These are accounted for quantitatively by a simple model for the radical pair motion inside of the micelle. Completing the thesis is a brief comparison of the results with current theories of the low field effect and a discussion on their relevance to biological systems. (author)

  7. Lanthanide Lewis acid-mediated enantioselective conjugate radical additions.

    Science.gov (United States)

    Sibi, Mukund P; Manyem, Shankar

    2002-08-22

    [reaction: see text] Lanthanide triflates along with proline-derived ligands have been found to be efficient catalysts for enantioselective conjugate addition of nucleophilic radicals to enoates. N-Acyl oxazolidinones, when used as achiral additives, gave meaningful enhancements in the ees for the product.

  8. CONTINENT RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak

    2013-01-01

    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.

  9. CONTINENT RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak

    2014-07-01

    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.

  10. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    .... Radical change by entrepreneurial design then becomes the focal point, in order to acquaint the reader with the strategies and tactics of well-known entrepreneurs who have been successful in molding...

  11. Penile rehabilitation after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Ohl, Dana A; Ralph, David

    2013-01-01

    The pathophysiology of erectile dysfunction after radical prostatectomy (RP) is believed to include neuropraxia, which leads to temporarily reduced oxygenation and subsequent structural changes in penile tissue. This results in veno-occlusive dysfunction, therefore, penile rehabilitation programmes...

  12. β-diketones containing oxygen atom in fluorinated radical

    International Nuclear Information System (INIS)

    Shivanyuk, A.F.; Kudryavtseva, L.S.; Lozinskij, M.O.; Neplyuev, V.M.; Fialkov, Yu.A.; Bratolyubova, A.G.

    1981-01-01

    The synthesis of a number of new aliphatic fluorinated β- diketones containing oxygen atom in fluorinated radical of linear or cyclic structure is described. The reaction of combination with aryldiazonium salts resulting in the formation of corresponding arylhydrazones of fluorinated triketones is studied. It is shown that as a result of arylhydrazone condensation with hydroxylamine, hydrazine and its substituted derivatives the fluorine-containing derivatives of isoxazol and pyrazol are formed [ru

  13. beta. -diketones containing oxygen atom in fluorinated radical

    Energy Technology Data Exchange (ETDEWEB)

    Shivanyuk, A.F.; Kudryavtseva, L.S.; Lozinskij, M.O.; Neplyuev, V.M.; Fialkov, Yu.A.; Bratolyubova, A.G. (AN Ukrainskoj SSR, Kiev. Inst. Organicheskoj Khimii)

    1981-10-01

    The synthesis of a number of new aliphatic fluorinated ..beta..-diketones containing oxygen atom in fluorinated radical of linear or cyclic structure is described. The reaction of combination with aryldiazonium salts resulting in the formation of corresponding arylhydrazones of fluorinated triketones is studied. It is shown that as a result of arylhydrazone condensation with hydroxylamine, hydrazine and its substituted derivatives the fluorine-containing derivatives of isoxazol and pyrazol are formed.

  14. Radical prostatectomy. Results and indications

    International Nuclear Information System (INIS)

    Jacqmin, D.

    1997-01-01

    Radical prostatectomy is the surgical curative treatment of localized prostate cancer. The survival is good in young patients (<70) with T2 N0M0 tumors and more than 10 year's life expectancy. Side-effects are urinary incontinence, impotence and anastomosis stricture. Quality of life should be considered as an important factor for the choice of the patient between radical prostatectomy, radiotherapy and follow-up. (author)

  15. Radical Islamism and Failed Developmentalism

    OpenAIRE

    Rahnema, Saeed

    2008-01-01

    The rise of radical Islamism in recent years does not limit the applicability of the concept of cultural nationalism. Rather the two are intertwined in ways which this article will attempt to highlight. Islam took specific national forms as modern nation-states arose and the contemporary resurgence of radical Islamism also follows that modern pattern. I examine the emergence of the three most important movements in the Islamic world, namely, the Muslim Brotherhood in Egypt, Jama'at-e Islami i...

  16. 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

  17. 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.

  18. 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...

  19. 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...

  20. Asymptotic aspect of derivations in Banach algebras

    Directory of Open Access Journals (Sweden)

    Jaiok Roh

    2017-02-01

    Full Text Available Abstract We prove that every approximate linear left derivation on a semisimple Banach algebra is continuous. Also, we consider linear derivations on Banach algebras and we first study the conditions for a linear derivation on a Banach algebra. Then we examine the functional inequalities related to a linear derivation and their stability. We finally take central linear derivations with radical ranges on semiprime Banach algebras and a continuous linear generalized left derivation on a semisimple Banach algebra.

  1. Theory of solvent effects on the hyperfine splitting constants in ESR spectra of free radicals

    International Nuclear Information System (INIS)

    Abe, T.; Tero-Kubota, S.; Ikegami, Y.

    1982-01-01

    An expression for the effects of solvation and hydrogen bonding on the hyperfine splitting constants of a free radical has been derived by obtaining π-electron spin densities of the radical in solution by perturbation theory. When no hydrogen bonding occurs between the radical and a solvent molecule, the splitting constant is approximately proportional to the Block and Walker parameter of theta(epsilon/sub r/) identical with 3 epsilon/sub r/ (ln epsilon/sub r/)/(epsilon/sub r/ ln epsilon/sub r/ - epsilon/sub r/ + 1) - 6/(ln epsilon/sub r/) - 2, where epsilon/sub r/ is the relative permittivity of the solvent. The expression is successfully applied to the di-tert-butyl nitroxide radical, the 1-methyl-4-(methoxycarbonyl)pyridinyl radical, and other free radicals. The effects of hydrogen bonding are discussed

  2. 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.

  3. 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)

  4. 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'.

  5. Radical-scavenging Activity of Natural Methoxyphenols vs. Synthetic Ones using the Induction Period Method

    Directory of Open Access Journals (Sweden)

    Seiichiro Fujisawa

    2007-02-01

    Full Text Available The radical-scavenging activities of the synthetic antioxidants 2-allyl-4-X-phenol (X=NO2, Cl, Br, OCH3, COCH3, CH3, t-(CH33, C6H5 and 2,4-dimethoxyphenol, and the natural antioxidants eugenol and isoeugenol, were investigated using differential scanning calorimetry (DSC by measuring their anti-1,1-diphenyl-2-picrylhydrazyl (DPPH radical activity and the induction period for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN and benzoyl peroxide (BPO. 2-Allyl-4-methoxyphenol and 2,4-dimethoxy-phenol scavenged not only oxygen-centered radicals (PhCOO. derived from BPO, but also carbon-centered radicals (R. derived from the AIBN and DPPH radical much more efficiently, in comparison with eugenol and isoeugenol. 2-Allyl-4-methoxyphenol may be useful for its lower prooxidative activity.

  6. 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.

  7. Photoionization of the OH radical

    International Nuclear Information System (INIS)

    Dehmer, P.M.

    1985-01-01

    The hydroxyl radical (OH) is one of the most thoroughly studied free radicals because of its importance in atmospheric chemistry, combustion processes, and the interstellar medium. Detailed experimental and theoretical studies have been performed on the ground electronic state (X 2 PI/sub i/) and on the four lowest bound excited electronic states (A 2 Σ + , B 2 Σ + , D 2 Σ - , and C 2 Σ + ). However, because it is difficult to distinguish the spectrum of OH from the spectra of the various radical precursors, the absorption spectrum in the wavelength region below 1200 A has not been well characterized. In the present work, the spectrum of OH has been determined in the wavelength region from 750 to 950 A using the technique of photoionization mass spectrometry. This technique allows complete separation of the spectrum of OH from that of the other components of the discharge and permits the unambiguous determination of the spectrum of OH

  8. 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

  9. Influence of anoxia on the induction of mutations by phenylalanine radicals during gamma-irradiation of plasmid DNA in aqueous solution.

    NARCIS (Netherlands)

    Kuipers, G.K.; Slotman, B.J.; Reitsma-Wijker, CA; Andel, R.J.; Poldervaart, H.A.; Lafleur, M.V.M.

    2004-01-01

    When DNA is irradiated in aqueous solution, most of the damage is inflicted by water-derived radicals. This is called the indirect effect of ionizing radiation. However in whole cells not only the primary formed water radicals play a role, because some cellular compounds form secondary radicals

  10. 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.

  11. Radical feminists & trans activists truce

    OpenAIRE

    Mackay, F.

    2014-01-01

    #GenderWeek: Truce! When radical feminists and trans feminists empathise\\ud Feminist Times\\ud By Finn Mackay \\ud read all #GenderWeek articles.\\ud We wanted to explore the ground between the polarised, entrenched positions in the so-called “TERF-war”. Radical feminists on one pole, trans-inclusionary feminists and trans activists on the other. The disputed territory being women-only space, language and the ever changing legal framework surrounding gender.\\ud Entrenchment leads to stalemate. S...

  12. 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.)

  13. Hydroxyl radical induced degradation of ibuprofen

    Energy Technology Data Exchange (ETDEWEB)

    Illés, Erzsébet, E-mail: erzsebet.illes@chem.u-szeged.hu [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Takács, Erzsébet [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Dombi, András [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Gajda-Schrantz, Krisztina [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Department of Inorganic and Analytical Chemistry, University of Szeged, Szeged (Hungary); EMPA, Laboratory for High Performance Ceramics, Duebendorf (Switzerland); Rácz, Gergely; Gonter, Katalin; Wojnárovits, László [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary)

    2013-03-01

    Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm{sup −3}. For end product characterization {sup 60}Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of {sup ·}OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation.

  14. Hydroxyl radical induced degradation of ibuprofen

    International Nuclear Information System (INIS)

    Illés, Erzsébet; Takács, Erzsébet; Dombi, András; Gajda-Schrantz, Krisztina; Rácz, Gergely; Gonter, Katalin; Wojnárovits, László

    2013-01-01

    Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm −3 . For end product characterization 60 Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of · OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation

  15. Radiolytic studies of the cumyloxyl radical in aqueous solutions

    International Nuclear Information System (INIS)

    Neta, P.; Dizdaroglu, M.; Simic, M.G.

    1984-01-01

    Formation and reactions of the cumyloxyl radical in aqueous solutions were studied by steady-state and pulse radiolytic techniques. Cumene hydroperoxide reacts with esub(aq)sup(-) (k = 4.4x10 9 M -1 s -1 ) to yield the cumyloxyl radical. The spectrum recorded after the pulse indicates formation of a species absorbing at 250 nm. This product was identified as acetophenone, which is formed by the fragmentation of the cumyloxyl radical. By comparison of the pseudo-first-order rates of esub(aq)sup(-) decay at 600 nm with the rate of production of acetophenone at 245 nm at increasing concentrations of cumene hydroperoxide, it was possible to derive a rate constant of 1.0x10 7 s -1 for the cleavage of cumyloxyl to acetophenone and methyl radical. This value is higher than that measured previously in organic solvents (1x10 6 s -1 ), as expected. HPLC analysis of the radiation products acetophenone and cumyl alcohol permitted determination of rate constants for hydrogen abstraction by the cumyloxyl radical, in competition with the fragmentation. The rate constants for H abstraction from i-PrOH, EtOH, and MeOH by CmO were found to be 9.9x10 6 , 3.8x10 6 , and 8.5x10 5 M -1 s -1 , respectively

  16. Quenching of nucleotide-derived radicals by bisbenzimidazole ...

    Indian Academy of Sciences (India)

    Unknown

    aRadiation Chemistry and Chemical Dynamics Division, Bhabha Atomic ... reaction of DNA-minor-groove ligand bisbenzimidazole Hoechst 33258 with ... flights, nuclear industries and management of radiation-induced accidents 1,2.

  17. 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...

  18. Laparoscopically assisted vaginal radical trachelectomy

    International Nuclear Information System (INIS)

    Bielik, T.; Karovic, M.; Trska, R.

    2013-01-01

    Purpose: Radical trachelectomy is a fertility-sparing procedure with the aim to provide adequate oncological safety to patients with cervical cancer while preserving their fertility. The purpose of this study was to retrospectively evaluate, in a series of 3 patients, the feasibility, morbidity, and safety of laparoscopically assisted vaginal radical trachelectomy for early cervical cancer. Patients and Methods: Three non consecutive patients with FIGO stage IA1 and IB1 cervical cancer was evaluated in a period of years 2008 - 2011. The patients underwent a laparoscopic pelvic lymphadenectomy and radical parametrectomy class II procedure according to the Piver classification. The section of vaginal cuff, trachelectomy, permanent cerclage and isthmo-vaginal anastomosis ware realised by vaginal approach. Results: The median operative time, the median blood loss and the mean number of resected pelvic nodes was comparable with published data. Major intraoperative complications did not occur and no patient required a blood transfusion. The median follow-up time was 33 (38-59) months. One vaginal recurrence occurred in 7 months after primary surgery. The patient was underwent a radicalisation procedure and adjuvant oncologic therapy and now is free of disease. Conclusions: Laparoscopically assisted vaginal radical trachelectomy (LAVRT)may be an alternative in fertility-preserving surgery for early cervical cancer. The procedure offers patients potential benefits of minimally invasive surgery with adequate oncological safety, but it should be reserved for oncologic surgeons trained in advanced laparoscopic procedures. (author)

  19. Is Radical Innovation Management Misunderstood?

    DEFF Research Database (Denmark)

    Kristiansen, Jimmi Normann; Gertsen, Frank

    2015-01-01

    This paper poses a critical view on radical innovation (RI) management research and practice. The study investigates how expected RI performance influences firms’ under- standing of their RI capability. RI performance is often based on output measures such as market shares or fiscal return...

  20. Exploring the Theories of Radicalization

    Directory of Open Access Journals (Sweden)

    Maskaliūnaitė Asta

    2015-12-01

    Full Text Available After the London bombings in July 2005, the concern of terrorism scholars and policy makers has turned to “home-grown” terrorism and potential for political violence from within the states. “Radicalization” became a new buzz word. This article follows a number of reviews of the literature on radicalization and offers another angle for looking at this research. First, it discusses the term “radicalization” and suggests the use of the following definition of radicalization as a process by which a person adopts belief systems which justify the use of violence to effect social change and comes to actively support as well as employ violent means for political purposes. Next, it proposes to see the theories of radicalization focusing on the individual and the two dimensions of his/her motivation: whether that motivation is internal or external and whether it is due to personal choice or either internal (due to some psychological traits or external compulsion. Though not all theories fall neatly within these categories, they make it possible to make comparisons of contributions from a variety of different areas thus reflecting on the interdisciplinary nature of the study of terrorism in general and radicalization as a part of it.

  1. Ultrasound-induced radical polymerization

    NARCIS (Netherlands)

    Kuijpers, M.W.A.; Kemmere, M.F.; Keurentjes, J.T.F.

    2004-01-01

    Sonochemistry comprises all chemical effects that are induced by ultrasound. Most of these effects are caused by cavitations, ie, the collapse of microscopic bubbles in a liquid. The chemical effects of ultrasound include the formation of radicals and the enhancement of reaction rates at ambient

  2. 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...

  3. On radicalizing behaviorism: A call for cultural analysis

    Science.gov (United States)

    Malagodi, E. F.

    1986-01-01

    Our culture at large continues many practices that work against the well-being of its members and its chances for survival. Our discipline has failed to realize its potential for contributing to the understanding of these practices and to the generation of solutions. This failure of realization is in part a consequence of the general failure of behavior analysts to view social and cultural analysis as a fundamental component of radical behaviorism. This omission is related to three prevailing practices of our discipline. First, radical behaviorism is characteristically defined as a “philosophy of science,” and its concerns are ordinarily restricted to certain epistemological issues. Second, theoretical extensions to social and cultural phenomena too often depend solely upon principles derived from the analysis of behavior. Third, little attention has been directed at examining the relationships that do, or that should, exist between our discipline and related sciences. These practices themselves are attributed to certain features of the history of our field. Two general remedies for this situation are suggested: first, that radical behaviorism be treated as a comprehensive world view in which epistemological, psychological, and cultural analyses constitute interdependent components; second, that principles derived from compatible social-science disciplines be incorporated into radical behaviorism. PMID:22478643

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

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

    Directory of Open Access Journals (Sweden)

    Cohn Corey A

    2008-02-01

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

  6. 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.

  7. First examples of intramolecular addition of primary amidyl radicals to olefins

    Energy Technology Data Exchange (ETDEWEB)

    Gaudreault, P.; Drouin, C.; Lessard, J. [Sherbrooke Univ., PQ (Canada). Dept. de Chimie

    2005-07-01

    This paper presents the first examples of radical cyclization involving a primary amidyl radical and a pendant olefin. Amidyl radicals have attracted interest in terms of their structure, reactivity, and ways to generate them. The intramolecular addition of an amidyl radical on a pendant olefin appears to be a powerful synthetic tool for creating nitrogen-containing heterocycles. Although several examples of cyclization involving secondary amidyl radicals are cited in the the literature, there are no examples of a successful cyclization involving a primary amidyl radical. This is because all attempts to prepare the usual radical precursors have failed when applied to olefinic primary amides. This study reveals that N-(phenylthio) derivatives of olefinic primary amides can be easily prepared and that nitrogen heterocycles resulting from their radical cyclization can be obtained in good to very good yields. Four olefinic primary amides were chosen as models for radical cyclization of primary amidyl radicals. They were prepared from the corresponding carboxylic acids via the acid chlorides. Conversion of primary amides into suitable amidyl radical precursors was also examined. The study showed that N-(phenylthio) amides could be easily prepared by following a slightly modified protocol developed by Esker and Newcomb, by reacting the anion of the amide with phenylsulfenyl chloride. In particular, olefinic N-(phenylthio) amides were prepared and used as primary amidyl radical precursors in a reaction with a solution of 2,2'-azobis(isobutyronitrile) in catalytic quantities and tributyltin hydride in benzene. The resulting yields of cyclic products ranged from 63 to 85 per cent. The intent of the study was to demonstrate that it is no longer necessary to prepare an N-protected precursor and then remove the protecting group after cyclization. Further studies are currently underway. 10 refs., 1 tab.

  8. Flavonoids as scavengers of nitric oxide radical.

    NARCIS (Netherlands)

    van Acker, S.A.B.E.; Tromp, M.N.J.L.; Haenen, G.R.M.M.; van der Vijgh, W.J.F.; Bast, A.

    1995-01-01

    Flavonoids are a group of naturally occurring compounds used, e.g., in the treatment of vascular endothelial damage. They are known to be excellent scavengers of oxygen free radicals. Since the nitric oxide radical (

  9. O conceito de mal radical The concept of radical evil

    Directory of Open Access Journals (Sweden)

    Adriano Correia

    2005-01-01

    Full Text Available A noção de mal radical aparece em Kant no contexto da discussão da religião nos limites da simples razão e busca dar conta da complexa relação entre o respeito pela lei moral e o amor-próprio na definição do móbil para a ação. Na busca por identificar o fundamento da propensão para o mal no homem, Kant se vê diante da dificuldade de ter de articular natureza e liberdade, e ainda que a noção de mal radical possa conservar algumas ambigüidades, permite conceber uma noção de responsabilidade compatível com uma inata propensão para o mal. Neste texto busco explicitar alguns passos fundamentais na construção do conceito por Kant.The concept of radical evil appears in Kant's theory when he discusses the religion in the limits of the mere reason and aims explain the complex relationship between respect for the moral law and the self-love, for establish the motive of the action. By aiming identify the basis of human inclination to evil, Kant is faced with the trouble of have to put nature and freedom in connection. Despite of the concept of radical evil retain some ambiguity, it allows conceive a notion of responsibility suitable to an inherent inclination to evil. In this paper is my purpose to explain some basic moments of Kantian formulation of that notion.

  10. 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.)

  11. Cation Radical Accelerated Nucleophilic Aromatic Substitution via Organic Photoredox Catalysis.

    Science.gov (United States)

    Tay, Nicholas E S; Nicewicz, David A

    2017-11-15

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

  12. 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

  13. 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

  14. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

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

    DEFF Research Database (Denmark)

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

    1998-01-01

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

  16. 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.

  17. A muoniated radical in selenium

    International Nuclear Information System (INIS)

    Reid, I.D.; Cox, S.F.J.; Jayasooriya, U.A.; Zimmermann, U.

    2003-01-01

    We report new 0.3 T transverse-field μSR experiments in crystalline Se which show only a small, slowly relaxing muon signal at 300 K, accounting for about 30% of the incoming muon polarization. However, at 90 K signals are observed around 74 and 157 MHz, characteristic of a radical with a hyperfine coupling of 231 MHz. Very fast relaxation which increases with temperature makes these signals impossible to follow beyond 200 K. Above 400 K a quickly relaxing diamagnetic signal becomes visible, its relaxation falling with increasing temperature. In the melt (>490 K) just a single non-relaxing diamagnetic signal is seen. These observations may be explained by electron spin-exchange with a muoniated radical

  18. 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.

  19. Structure and dynamics of olefin radical cation aggregates. Time-resolved fluorescence detected magnetic resonance

    International Nuclear Information System (INIS)

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

    1986-01-01

    The time-resolved EPR spectra and thus the structure and dynamics of transient hydrocarbon radical cations are obtained by the pulse radiolysis-fluorescence detected magnetic resonance (FDMR) technique. Here the authors report the observation of short-lived radical cations from olefins. FDMR-EPR spectra of radical cations from tetramethylethylene and cyclohexadiene are illustrated. The olefin radical cations, FDMR spectra are concentration-dependent, since dimerization with neutral molecules takes place at higher (>10 -2 M) olefin concentration. Rate constants for the dimerization reaction are derived and the effect of solvent viscosity on aggregate formation is demonstrated. By monitoring the further reactions of dimer cations the authors have obtained EPR evidence for previously unobserved higher-order (multimer) radical cation aggregates of olefins. 16 references, 5 figures

  20. DNA Binding Hydroxyl Radical Probes

    OpenAIRE

    Tang, Vicky J; Konigsfeld, Katie M; Aguilera, Joe A; Milligan, Jamie R

    2012-01-01

    The hydroxyl radical is the primary mediator of DNA damage by the indirect effect of ionizing radiation. It is a powerful oxidizing agent produced by the radiolysis of water and is responsible for a significant fraction of the DNA damage associated with ionizing radiation. There is therefore an interest in the development of sensitive assays for its detection. The hydroxylation of aromatic groups to produce fluorescent products has been used for this purpose. We have examined four different c...

  1. 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.

  2. Radical Smiles Rearrangement: An Update

    Directory of Open Access Journals (Sweden)

    Ingrid Allart-Simon

    2016-07-01

    Full Text Available Over the decades the Smiles rearrangement and its variants have become essential synthetic tools in modern synthetic organic chemistry. In this mini-review we summarized some very recent results of the radical version of these rearrangements. The selected examples illustrate the synthetic power of this approach, especially if it is incorporated into a domino process, for the preparation of polyfunctionalized complex molecules.

  3. 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

  4. Geoscientists and the Radical Middle

    Science.gov (United States)

    Tinker, S. W.

    2015-12-01

    Addressing the great challenges facing society requires industry, government, and academia to work together. I call this overlap space, where compromises are made and real solutions determined, the Radical Middle. Radical because it can appear at times as if the loudest and most publicly influential voices lie outside of the actual solution space, content to provoke but not problem-solve. One key area where geoscientists can play a lead role in the Radical Middle is in the overlap between energy, the environment, and the economy. Globally, fossil fuels still represent 85% of the aggregate energy mix. As existing conventional oil and natural-gas reservoir production continues to slowly decline, unconventional reservoirs, led today by shale and other more expensive resources, will represent a growing part of the oil and gas production mix. Many of these unconventional reservoirs require hydraulic fracturing. The positive economic impact of hydraulic fracturing and associated natural gas and oil production on the United States economy is well documented and undeniable. Yet there are environmental concerns about fracking, and some states and nations have imposed moratoria. This energy-environment-economy space is ideal for leadership from the geosciences. Another such overlap space is the potential for geoscience leadership in relations with China, whose economy and global presence continue to expand. Although China is building major hydropower and natural-gas power plants, as well as nuclear reactors, coal is still king—with the associated environmental impacts. Carbon sequestration—onshore in brine and to enhance oil recovery, as well as offshore—could prove viable. It is vital that educated and objective geoscientists from industry, government, and academia leave their corners and work together in the Radical Middle to educate the public and develop and deliver balanced, economically sensible energy and environmental strategies.

  5. 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....

  6. Antioxidant properties of a radical-scavenging peptide purified from enzymatically prepared fish skin gelatin hydrolysate.

    Science.gov (United States)

    Mendis, Eresha; Rajapakse, Niranjan; Kim, Se-Kwon

    2005-02-09

    Hoki (Johnius belengerii) skin gelatin was hydrolyzed with three commercial enzymes to identify radical-scavenging potencies of derived peptides. Peptides derived from tryptic hydrolysate exhibited the highest scavenging activities on superoxide, carbon-centered 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals assessed by ESR spectroscopy. Following consecutive chromatographic separations of tryptic hydroolysate, the peptide sequence His-Gly-Pro-Leu-Gly-Pro-Leu (797 Da) acted as a strong radical scavenger under studied conditions. Further, this peptide could act as an antioxidant against linoleic acid peroxidation and the activity was closer to the highly active synthetic antioxidant butylated hydroxytoluene (BHT). In addition, antioxidative enzyme levels in cultured human hepatoma cells were increased in the presence of this peptide and it was presumed to be the peptide involved in maintaining the redox balance in the cell environment. Present data indicate that free-radical-scavenging activities of hoki skin gelatin peptides substantially contribute to their antioxidant properties measured in different oxidative systems.

  7. Peroxy radical measurements during HOPE 2012

    Science.gov (United States)

    Trawny, K.; Tatum Ernest, C.; Novelli, A.; Elste, T.; Werner, A.; Englert, J.; Plass-Duelmer, C.; Rudolf, M.; Martinez, M.; Harder, H. D.; Lelieveld, J.

    2012-12-01

    We present the first ambient air measurements of a newly built Laser Induced Fluorescence (LIF) system to measure the sum of all peroxy radicals (RO2) utilizing chemical conversion to OH. This instrument operates in two different modes: the ROx mode (sum of OH, HO2, and RO2) and the HOx mode (sum of OH and HO2). The HOx mode is used to derive the RO2 data from the ROx measurements and is also compared to HOx measurements of a second LIF system. The HOPE 2012 intensive field campaign took place in summer 2012 at the Global Atmosphere Watch (GAW) station of the German Weather Service located approximately 60 km south-west of Munich and approximately 20 km away from the Alps at Hohenpeissenberg (988 m, 47° 48‧ N, 11° 0‧ E). Simultaneous side-by-side measurements of ROx were conducted on the roof platform of the observatory with two instruments using Chemical Ionization Mass Spectrometry (CIMS) and LIF. The RO2 measurements are compared to modeled data derived from the constrained box model CAABA/MECCA.

  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. FAR RIGHT RADICALIZATION AND SOCIALIST RADICALIZATION IN INTERWAR ROMANIA

    Directory of Open Access Journals (Sweden)

    IONUŢ BUTOI

    2017-03-01

    Full Text Available In his comments on Mircea Vulcănescu. O microistorie a interbelicului românesc (Eikon, 2015, Emanuel Copilaş states that, regarding the cause of the far right radicalization manifested in the interwar Romania, I share the same historical explanation about fascism as Ernst Nolte. In this concise answer, I explain why this is an unsuitable comparison by summarizing the historiographical perspective I use in the cited volume. Nevertheless, Copilaş’s comments are reopening a debate about how to explain the Romanian fascism

  10. 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

  11. Evidence for radical-oxidation of plasma proteins in humans

    International Nuclear Information System (INIS)

    Wang, D.; Davies, M.; Dean, R.; Fu, S.; Taurins, A.; Sullivans, D.

    1998-01-01

    Oxidation of proteins by radicals has been implicated in many pathological processes. The hydroxyl radical is known to generate protein-bound hydroxylated derivatives of amino acids, for example hydroxyvaline (from Val), hydroxyleucine (from Leu), o-tyrosine (from Phe), and DOPA (from Tyr). In this study, we have investigated the occurrence of these oxidised amino acids in human plasma proteins from both normal subjects and dialysis patients. By employing previously established HPLC methods [Fu et al. Biochemical Journal, 330, 233-239, 1998], we have found that oxidised amino acids exist in normal human plasma proteins (n=32). The level of these oxidised amino acids is not correlated to age. Similar levels of oxidised amino acids are found in the plasma proteins of the dialysis patients (n=6), but a more detailed survey is underway. The relative abundance of the oxidised amino acids is similar to that resulting from oxidation of BSA by hydroxy radicals or Fenton systems [Fu et al. Biochemical Journal, 333, 519-525, 1998]. The results suggest that metal-ion catalysed oxyl-radical chemistry may be a key contributor to the oxidative damage in plasma proteins in vivo in humans

  12. Radical-mediated reduction of the dithiocarbamate group under tin-free conditions.

    Science.gov (United States)

    McMaster, Claire; Bream, Robert N; Grainger, Richard S

    2012-06-28

    Reductive desulfurisation of dithiocarbamates is conveniently achieved using H(3)PO(2)-Et(3)N-ACCN in refluxing dioxane. Fused and spirocyclic β-lactams, prepared through 4-exo trig carbamoyl radical cyclisation-dithiocarbamate group transfer reactions, are reduced without fragmentation of the strained 4-membered ring. Diethyl tetraacetyl-d-glucopyranosyl dithiocarbamate is selectively reduced with or without acyloxy group migration depending on reaction conditions and choice of reductant. Deuterium incorporation from D(3)PO(2)-Et(3)N is observed for a system involving a nucleophilic radical intermediate, but not in the case of the electrophilic radical obtained through acyloxy group migration on a glucose derivative.

  13. 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)

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

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2016-01-01

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

  15. Radical probing of spliceosome assembly.

    Science.gov (United States)

    Grewal, Charnpal S; Kent, Oliver A; MacMillan, Andrew M

    2017-08-01

    Here we describe the synthesis and use of a directed hydroxyl radical probe, tethered to a pre-mRNA substrate, to map the structure of this substrate during the spliceosome assembly process. These studies indicate an early organization and proximation of conserved pre-mRNA sequences during spliceosome assembly. This methodology may be adapted to the synthesis of a wide variety of modified RNAs for use as probes of RNA structure and RNA-protein interaction. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. 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...

  17. Laser spectroscopy of hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Chen, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    The author reports the application of supersonic jet flash pyrolysis to the specific preparation of a range of organic radicals, biradicals, and carbenes in a skimmed molecular beam. Each species was produced cleanly and specifically, with little or no secondary reactions by the thermal dissociation of appropriately designed and synthesized organic precursors. Photoelectron spectra of the three isomeric C{sub 3}H{sub 2} carbenes, ortho-benzyne, and the {alpha},3-dehydrotoluene biradical, were used to establish adiabatic ionization potentials for use in thermochemical determinations.

  18. 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.

  19. 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.

  20. On Functional Inequalities Originating from Module Jordan Left Derivations

    OpenAIRE

    Kang Sheon-Young; Chang Ick-Soon; Kim Hark-Mahn

    2008-01-01

    Abstract We first examine the generalized Hyers-Ulam stability of functional inequality associated with module Jordan left derivation (resp., module Jordan derivation). Secondly, we study the functional inequality with linear Jordan left derivation (resp., linear Jordan derivation) mapping into the Jacobson radical.

  1. On Functional Inequalities Originating from Module Jordan Left Derivations

    Directory of Open Access Journals (Sweden)

    Kang Sheon-Young

    2008-01-01

    Full Text Available Abstract We first examine the generalized Hyers-Ulam stability of functional inequality associated with module Jordan left derivation (resp., module Jordan derivation. Secondly, we study the functional inequality with linear Jordan left derivation (resp., linear Jordan derivation mapping into the Jacobson radical.

  2. Radical-trapping and preventive antioxidant effects of 2-hydroxymelatonin and 4-hydroxymelatonin: Contributions to the melatonin protection against oxidative stress.

    Science.gov (United States)

    Pérez-González, Adriana; Galano, Annia; Alvarez-Idaboy, J Raúl; Tan, Dun Xian; Reiter, Russel J

    2017-09-01

    Melatonin is well known for its antioxidant capacity, which has been attributed to the combined protective effects of the parent molecule and its metabolites. However, the potential role of 2-hydroxymelatonin (2OHM) and 4-hydroxymelatonin (4OHM) in such protection has not been previously investigated. The calculations were performed using the Density Functional Theory, with the M05-2X and M05 functionals, the 6-311+G(d,p) basis set and the solvation model based on density (SMD). 4OHM shows excellent antioxidant activity via radical-trapping, reacting with peroxyl radicals faster than Trolox and melatonin. 4OHM can be moderately efficient as a preventing antioxidant by inhibiting Cu(II). This effect would lower the Cu(I) availability, which is the redox state required for the OH to be formed, via Fenton-like reactions. 4OHM turns off the oxidant effects of copper-ascorbate mixtures. The presence of a phenolic group was identified as the key structural feature in the antioxidant activity of 4OHM. On the other hand, 2OHM does not present a phenolic group, despite its formal name. Its keto tautomer was identified as the most abundant one (~100%). This may explain the relative low antioxidant protection of 2OHM. 4OHM significantly contributes to the overall antioxidant activity exhibited by melatonin, while the effects of 2OHM in this context are predicted to be only minor. This low reactivity might justify the relatively large abundance of 2OHM in biological systems. Hydroxylated melatonin metabolites, such as 4OHM, may play an important role in the protective effects of melatonin against oxidative stress. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. 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)

  4. Measurement of antioxidant activity with trifluoperazine dihydrochloride radical cation

    Directory of Open Access Journals (Sweden)

    M.N. Asghar

    2008-06-01

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

  5. 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.

  6. Redox reactions of tocopherol monoglucoside in aqueous solutions. A pulse radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, S.; Mukherjee, T.; Nair, C.K.K. [Bhabha Atomic Research Centre, Mumbai (India); Kagiya, Tsutomu V. [Health Research Foundation, Kyoto (Japan)

    2002-03-01

    The reactions between tocopherol monoglucoside (TMG), a water-soluble vitamin-E derivative, with Br{sub 2}{sup {center_dot}}{sup -}, N{sub 3}{sup {center_dot}}, (SCN){sub 2}{sup {center_dot}}{sup -}, NO{sub 2}{sup {center_dot}}, OH{sup {center_dot}} and various halogenated peroxyl radicals were examined using a pulse radiolysis technique. The results demonstrate that TMG forms a stable phenoxyl radical at pH>6.8. The thus-formed phenoxyl radical shows pH-dependent decay kinetics and is disproportionated by 2nd order kinetics at pH2.3. It was observed that the TMG reactivity towards a halogenated peroxyl radical increases with the number of halogen atoms at the carbon atom having a peroxyl group. The reaction between the TMG phenoxyl radical and ascorbic acid was also examined using a pulse radiolysis technique. The results indicate that the TMG phenoxyl radical is repaired by ascorbate. Kinetic studies indicate that TMG may act as an antioxidant to repair free-radical damage to some biologically importnat compounds. The one-electron reduction potential for TMG was found to be 0.522 V{+-}0.06 vs. NHE. (author)

  7. Fluorescence lifetime measurement of radical ions

    International Nuclear Information System (INIS)

    Ichinose, Nobuyuki; Kinugasa, Jun-ichiro; Hagiri, Masahide; Nakayama, Toshihiro; Murakami, Hiroshi; Kishimoto, Maki; Daido, Hiroyuki

    2004-01-01

    One-photonic excitation of a charge transfer complex of hexamethoxybenzene (HMB) and nitrosonium tetrafluoroborate (NO + BF 4 - ) in acetonitrile afforded fluorescences emission from excited radical cation of HMB (HMB + *). Lifetime of the excited radical ion species was measured to be 7 ps by the pump-probe transient absorption technique. The lifetime was much shorter than that of free radical ion (63 ps), indicating the presence of an interaction between HMB + * and NO in the excited complex. (author)

  8. Reorientation dynamics of cyclohexadienyl radicals in zeolites

    International Nuclear Information System (INIS)

    Stolmar, M.; Roduner, E.; Dilger, H.; Himmer, U.; Shelley, M.; Reid, I.D.

    1997-01-01

    The dynamics of the muonium substituted cyclohexadienyl radical adsorbed on silicalite and NaZSM-5 is investigated by means of avoided level crossing muon spin resonance. The influence of benzene loading on the mobility of the radical is studied. At low loadings the radicals were found to be located on a single adsorption site where they undergo a wobbling type of motion. With increasing loading an additional species adsorbed on a different site is observed

  9. 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...

  10. Structure of radicals produced by γ radiolysis. Part 4. Adamantane matrices doped with various 5-membered heterocyclic molecules

    International Nuclear Information System (INIS)

    Winters, D.L.; Ling, A.C.

    1976-01-01

    The effects of γ-radiolysis at room temperature on adamantane and adamantane-d 16 matrices doped with 5-membered heterocyclic molecules has been examined by X-band electron spin resonance (esr) spectrometry. Radical structures formed from heterocyclic solute molecules are discussed and tentative assignments made. Discussion of possible radical structures derived from selected heterocyclic compounds is included, but unambiguous assignmens of structure cannot be made for these compounds from the esr data obtained. It was noted that perdeuterated adamantane matrices provided superior resolution for esr spectra derived from radicals with a delocalized spin center such as allyl or allenyl species. (author)

  11. Influence of anoxia on the induction of mutations by phenylalanine radicals during gamma-irradiation of plasmid DNA in aqueous solution.

    Science.gov (United States)

    Kuipers, Gitta K; Slotman, Ben J; Reitsma-Wijker, Carola A; van Andel, Rob J; Poldervaart, Hester A; Lafleur, M Vincent M

    2004-12-21

    When DNA is irradiated in aqueous solution, most of the damage is inflicted by water-derived radicals. This is called the indirect effect of ionizing radiation. However in whole cells not only the primary formed water radicals play a role, because some cellular compounds form secondary radicals which can also damage DNA. It is known that the amino acid phenylalanine is able to react with water radicals, resulting in the production of secondary phenylalanine radicals which can damage and inactivate DNA. In a previous study the influence of the presence of phenylalanine during gamma-irradiation of DNA in aqueous solution under oxic conditions was studied. Under anoxic irradiation conditions different amounts and types of reactive water-derived radicals are formed compared to oxic conditions and also different phenylalanine radicals are formed. Therefore, this study examines the influence of the presence of phenylalanine under anoxic conditions on the gamma-radiation-induced mutation spectrum. The results indicate that phenylalanine radicals are damaging to DNA, but less effective compared to primary water radicals. On the mutational level, in the presence of phenylalanine radicals under anoxic conditions, the amount of mutations on G:C base pairs was significantly decreased as compared to oxic conditions. Furthermore, the results of this study indicate that nucleotide excision repair is involved in repair of both inactivating and mutagenic damage induced by phenylalanine radicals under anoxic conditions.

  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. One-electron oxidation of BD84, an ellipticine antitumor derivative

    International Nuclear Information System (INIS)

    Sekaki, A.; Gardes-Albert, M.; Houee-Levin, C.; Ferradini, C.; Rivalle, C.; Bisagni, E.; Hickel, B.

    1991-01-01

    The one-electron oxidation of BD84, an ellipticine-related drug, has been studied by pulse radiolysis using OH· radicals as oxidizing agents. In the absence of oxygen, R· radicals are formed. They disappear by recombination. In the presence of oxygen, R· radicals react with O 2 to give peroxy radicals RO 2 ·, which decay by a second-order process. These results are compared to those obtained for other ellipticine derivatives [fr

  14. Students' Ideas and Radical Constructivism

    Science.gov (United States)

    Sánchez Gómez, Pedro J.

    2016-08-01

    In this article, I study, from the point of view of the analytic philosophy of mind, the compatibility of students' ideas studies (SIS) with radical constructivism (RC). I demonstrate that RC is based on a psychology of narrow mental states; that is, the idea that the mental content of an individual can be fully characterised without any reference external to her or him. I show that this fact imposes some severe restrictions to SIS to be incorporated into RC. In particular, I argue that only qualitative studies can comply with the requirement of narrowness. Nevertheless, I propose that quantitative works can be employed as sources of types in order to study token actual students. I use this type-token dichotomy to put forward an outline of a theory of the relation between school contents and mental contents. In this view, token mental contents regarding a given topic can be defined, and probed, only by resorting to typical school contents.

  15. DNA Binding Hydroxyl Radical Probes.

    Science.gov (United States)

    Tang, Vicky J; Konigsfeld, Katie M; Aguilera, Joe A; Milligan, Jamie R

    2012-01-01

    The hydroxyl radical is the primary mediator of DNA damage by the indirect effect of ionizing radiation. It is a powerful oxidizing agent produced by the radiolysis of water and is responsible for a significant fraction of the DNA damage associated with ionizing radiation. There is therefore an interest in the development of sensitive assays for its detection. The hydroxylation of aromatic groups to produce fluorescent products has been used for this purpose. We have examined four different chromophores which produce fluorescent products when hydroxylated. Of these, the coumarin system suffers from the fewest disadvantages. We have therefore examined its behavior when linked to a cationic peptide ligand designed to bind strongly to DNA.

  16. 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.

  17. Electron spin resonance characterization of radical components in irradiated black pepper skin and core

    International Nuclear Information System (INIS)

    Yamaoki, Rumi; Kimura, Shojiro; Ohta, Masatoshi

    2011-01-01

    Characteristics of free radical components of irradiated black pepper fruit (skin) and the pepper seed (core) were analyzed using electron spin resonance. A weak signal near g=2.005 was observed in black pepper before irradiation. Complex spectra near g=2.005 with three lines (the skin) or seven lines (the core) were observed in irradiated black pepper (both end line width; ca. 6.8 mT). The spectral intensities decreased considerably at 30 days after irradiation, and continued to decrease steadily thereafter. The spectra simulated on the basis of the content and the stability of radical components derived from plant constituents, including fiber, starch, polyphenol, mono- and disaccharide, were in good agreement with the observed spectra. Analysis showed that the signal intensities derived from fiber in the skin for an absorbed dose were higher, and the rates of decrease were lower, than that in the core. In particular, the cellulose radical component in the skin was highly stable. - Highlights: → We identified the radical components in irradiated black pepper skin and core. → The ESR spectra near g=2.005 with 3-7 lines were emerged after irradiation. → Spectra simulated basing on the content and the stability of radical from the plant constituents. → Cellulose radical component in black pepper skin was highly stable. → Single signal near g=2.005 was the most stable in black pepper core.

  18. 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.

  19. 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

  20. Allylthioketone Mediated Free Radical Polymerization of Methacrylates

    Directory of Open Access Journals (Sweden)

    Feng Zhong

    2017-11-01

    Full Text Available By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate (PMMA are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate (PGMA, and major component of the obtained polymer has the structure, (CH32(CNC-PGMA-C7H9O3. Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent.

  1. Moment matrices, border bases and radical computation

    NARCIS (Netherlands)

    B. Mourrain; J.B. Lasserre; M. Laurent (Monique); P. Rostalski; P. Trebuchet (Philippe)

    2013-01-01

    htmlabstractIn this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming it complex (resp. real) variety is nte. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and

  2. Moment matrices, border bases and radical computation

    NARCIS (Netherlands)

    Lasserre, J.B.; Laurent, M.; Mourrain, B.; Rostalski, P.; Trébuchet, P.

    2013-01-01

    In this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming its complex (resp. real) variety is finite. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and semi-definite

  3. Moment matrices, border bases and radical computation

    NARCIS (Netherlands)

    B. Mourrain; J.B. Lasserre; M. Laurent (Monique); P. Rostalski; P. Trebuchet (Philippe)

    2011-01-01

    htmlabstractIn this paper, we describe new methods to compute the radical (resp. real radical) of an ideal, assuming it complex (resp. real) variety is nte. The aim is to combine approaches for solving a system of polynomial equations with dual methods which involve moment matrices and

  4. Quantification of hydroxyl radical produced during phacoemulsification.

    Science.gov (United States)

    Gardner, Jonathan M; Aust, Steven D

    2009-12-01

    To quantitate hydroxyl radicals produced during phacoemulsification with various irrigating solutions and conditions used in cataract surgery. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. All experiments were performed using an Infiniti Vision System phacoemulsifier with irrigation and aspiration. Hydroxyl radicals were quantitated using electron spin resonance spectroscopy and a spectrophotometric assay for malondialdehyde, which is formed by the oxidation of deoxyribose by the hydroxyl radical. Hydroxyl radical production increased during longitudinal-stroking phacoemulsification as power levels were increased in a nonlinear, nonexponential fashion. The detection of hydroxyl radical was reduced in irrigating solutions containing organic molecules (eg, citrate, acetate, glutathione, dextrose) and further reduced in Navstel, an irrigating solution containing a viscosity-modifying agent, hydroxypropyl methylcellulose. Hydroxyl radicals produced in settings representative of those used in phacoemulsification cataract surgery were quantitated using the deoxyribose method. Hydroxyl radical production was dependent on the level of ultrasound power applied and the irrigating solution used. Oxidative stress on the eye during phacoemulsification may be minimized by using irrigating solutions that contain organic molecules, including the viscosity-modifying agent hydroxypropyl methylcellulose, that can compete for reaction with hydroxyl radicals.

  5. Self-Terminating, Oxidative Radical Cyclizations

    Directory of Open Access Journals (Sweden)

    Uta Wille

    2004-05-01

    Full Text Available The recently discovered novel concept of self-terminating, oxidative radical cyclizations, through which alkynes can be converted into carbonyl compounds under very mild reaction conditions using O-centered inorganic and organic radicals as oxidants, is described

  6. An Appreciation of Free Radical Chemistry

    Indian Academy of Sciences (India)

    ... Lecture Workshops · Refresher Courses · Symposia · Live Streaming. Home; Journals; Resonance – Journal of Science Education; Volume 10; Issue 9. An Appreciation of Free Radical Chemistry - 6. Experiments Involving Free Radicals. G Nagendrappa. Classroom Volume 10 Issue 9 September 2005 pp 79-84 ...

  7. Radical Behaviorism and Buddhism: Complementarities and Conflicts

    Science.gov (United States)

    Diller, James W.; Lattal, Kennon A.

    2008-01-01

    Comparisons have been made between Buddhism and the philosophy of science in general, but there have been only a few attempts to draw comparisons directly with the philosophy of radical behaviorism. The present review therefore considers heretofore unconsidered points of comparison between Buddhism and radical behaviorism in terms of their…

  8. Simultaneous quantification of ten constituents of Xanthoceras sorbifolia Bunge using UHPLC-MS methods and evaluation of their radical scavenging, DNA scission protective, and α-glucosidase inhibitory activities.

    Science.gov (United States)

    Zhang, Yu; Ma, Jian-Nan; Ma, Chun-Li; Qi, Zhi; Ma, Chao-Mei

    2015-11-01

    The present study was designed to investigate the bioactive constituents of Xanthoceras sorbifolia in terms of amounts and their antioxidant, DNA scission protection, and α-glucosidase inhibitory activities. Simultaneous quantification of 10 X. sorbifolia constituents was carried out by a newly established ultra-high performance liquid chromatography-quadrupole mass spectrometry method (UHPLC-MS). The antioxidant activities were evaluated by measuring DPPH radical scavenging and DNA scission protective activities. The α-glucosidase inhibitory activities were investigated by using an assay with α-glucosidase from Bacillus Stearothermophilus and disaccharidases from mouse intestine. We found that the wood of X. sorbifolia was rich in phenolic compounds with the contents of catechin, epicatechin, myricetin, and dihydromyricetin being 0.12-0.19, 1.94-2.16, 0.77-0.91, and 6.76-7.89 mg·g(-1), respectively. The four constituents strongly scavenged DPPH radicals (with EC50 being 4.2, 3.8 and 5.7 μg·mL(-1), respectively) and remarkably protected peroxyl radical-induced DNA strand scission (92.10%, 94.66%, 75.44% and 89.95% of protection, respectively, at a concentration of 10 μmol·L(-1)). A dimeric flavan 3-ol, epigallocatechin-(4β→8, 2β→O-7)-epicatechin potently inhibited α-glucosidase with an IC50 value being as low as 1.2 μg·mL(-1). The established UHPLC-MS method could serve as a quality control tool for X. sorbifolia. In conclusion, the high contents of antioxidant and α-glucosidase inhibitory constituents in X. sorbifolia support its use as complementation of other therapeutic agents for metabolic disorders, such as diabetes and hypertension. Copyright © 2015 China Pharmaceutical University. Published by Elsevier B.V. All rights reserved.

  9. Measurement of interferences associated with the detection of the hydroperoxy radical in the atmosphere using laser-induced fluorescence

    Science.gov (United States)

    Lew, Michelle M.; Dusanter, Sebastien; Stevens, Philip S.

    2018-01-01

    One technique used to measure concentrations of the hydroperoxy radical (HO2) in the atmosphere involves chemically converting it to OH by addition of NO and subsequent detection of OH. However, some organic peroxy radicals (RO2) can also be rapidly converted to HO2 (and subsequently OH) in the presence of NO, interfering with measurements of ambient HO2 radical concentrations. This interference must be characterized for each instrument to determine to what extent various RO2 radicals interfere with measurements of HO2 and to assess the impact of this interference on past measurements. The efficiency of RO2-to-HO2 conversion for the Indiana University laser-induced fluorescence-fluorescence assay by gas expansion (IU-FAGE) instrument was measured for a variety of RO2 radicals. Known quantities of OH and HO2 radicals were produced from the photolysis of water vapor at 184.9 nm, and RO2 radicals were produced by the reaction of several volatile organic compounds (VOCs) with OH. The conversion efficiency of RO2 radicals to HO2 was measured when NO was added to the sampling cell for conditions employed during several previous field campaigns. For these conditions, approximately 80 % of alkene-derived RO2 radicals and 20 % of alkane-derived RO2 radicals were converted to HO2. Based on these measurements, interferences from various RO2 radicals contributed to approximately 35 % of the measured HO2 signal during the Mexico City Metropolitan Area (MCMA) 2006 campaign (MCMA-2006), where the measured VOCs consisted of a mixture of saturated and unsaturated species. However, this interference can contribute more significantly to the measured HO2 signal in forested environments dominated by unsaturated biogenic emissions such as isoprene.

  10. Yields of hydrogen peroxide from the reaction of hydroxyl radical with organic compounds in solution and ice

    Directory of Open Access Journals (Sweden)

    T. Hullar

    2011-07-01

    Full Text Available Hydrogen peroxide (HOOH is a significant oxidant in atmospheric condensed phases (e.g., cloud and fog drops, aqueous particles, and snow that also photolyzes to form hydroxyl radical (OH. OH can react with organics in aqueous phases to form organic peroxyl radicals and ultimately reform HOOH, but the efficiency of this process in atmospheric aqueous phases, as well as snow and ice, is not well understood. We investigate HOOH formation from OH attack on 10 environmentally relevant organic compounds: formaldehyde, formate, glycine, phenylalanine, benzoic acid, octanol, octanal, octanoic acid, octanedioic acid, and 2-butoxyethanol. Liquid and ice samples with and without nitrate (as an OH source were illuminated using simulated solar light, and HOOH formation rates were measured as a function of pH and temperature. For most compounds, the formation rate of HOOH without nitrate was the same as the background formation rate in blank water (i.e., illumination of the organic species does not produce HOOH directly, while formation rates with nitrate were greater than the water control (i.e., reaction of OH with the organic species forms HOOH. Yields of HOOH, defined as the rate of HOOH production divided by the rate of OH production, ranged from essentially zero (glycine to 0.24 (octanal, with an average of 0.12 ± 0.05 (95 % CI. HOOH production rates and yields were higher at lower pH values. There was no temperature dependence of the HOOH yield for formaldehyde or octanedioic acid between −5 to 20 °C and ice samples had approximately the same HOOH yield as the aqueous solutions. In contrast, HOOH yields in formate solutions were higher at 5 and 10 °C compared to −5 and 20 °C. Yields of HOOH in ice for solutions containing nitrate and either phenylalanine, benzoate, octanal, or octanoic acid were indistinguishable from zero. Our HOOH yields were approximately

  11. 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.

  12. Investigation of free radicals in paprika with the ESR method

    International Nuclear Information System (INIS)

    Kispeter, J.; Szabo, I.; Horvath, L.J.

    1998-01-01

    Complete text of publication follows. The ESR method is the one of the most successfully applied method among the physical methods for the identification of radiation or ionising treatment of foods. The identification of free radicals having short and long lifetimes is the base of the measurement. The quantitative determination makes possible the determination of the absorbed dose deriving from 60 Co radiation treatment. It has to be noted that the treatment of the foods with ionising radiation and other treatments (milling, frying, baking) and the oxidative process result free radicals in paprika samples as a function of absorbed radiation dose (2.5; 5 and 10 kGy) on the different particle size and on storage time. The intensities of the samples given after each of the seven stages of the paprika milling increased till the fifth stage corresponding to the effect of a 2 kGy absorbed dose. After conditioning and increasing the water content by 5-8% the ESR intensity shows significant lowering. This value characterises the ESR intensity of not irradiated sample. As an effect of the irradiation the ESR intensities increased along with the increase of the absorbed dose. The samples having lower particle size are more sensible for the identification of the irradiation. Evaluating the art of the decline we concluded that there are free radicals having short and long shelf lifetimes in paprika samples at the same time

  13. 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.

  14. 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

  15. Orgasmic Dysfunction after Radical Prostatectomy

    Directory of Open Access Journals (Sweden)

    Paolo Capogrosso

    2017-04-01

    Full Text Available In addition to urinary incontinence and erectile dysfunction, several other impairments of sexual function potentially occurring after radical prostatectomy (RP have been described; as a whole, these less frequently assessed disorders are referred to as neglected side effects. In particular, orgasmic dysfunctions (ODs have been reported in a non-negligible number of cases, with detrimental impacts on patients’ overall sexual life. This review aimed to comprehensively discuss the prevalence and physiopathology of post-RP ODs, as well as potential treatment options. Orgasm-associated incontinence (climacturia has been reported to occur in between 20% and 93% of patients after RP. Similarly, up to 19% of patients complain of postoperative orgasm-associated pain, mainly referred pain at the level of the penis. Moreover, impairment in the sensation of orgasm or even complete anorgasmia has been reported in 33% to 77% of patients after surgery. Clinical and surgical factors including age, the use of a nerve-sparing technique, and robotic surgery have been variably associated with the risk of ODs after RP, although robust and reliable data allowing for a proper estimation of the risk of postoperative orgasmic function impairment are still lacking. Likewise, little evidence regarding the management of postoperative ODs is currently available. In general, physicians should be aware of the prevalence of ODs after RP, in order to properly counsel all patients both preoperatively and immediately post-RP about the potential occurrence of bothersome and distressful changes in their overall sexual function.

  16. Orgasmic Dysfunction after Radical Prostatectomy

    Science.gov (United States)

    Ventimiglia, Eugenio; Cazzaniga, Walter; Montorsi, Francesco; Salonia, Andrea

    2017-01-01

    In addition to urinary incontinence and erectile dysfunction, several other impairments of sexual function potentially occurring after radical prostatectomy (RP) have been described; as a whole, these less frequently assessed disorders are referred to as neglected side effects. In particular, orgasmic dysfunctions (ODs) have been reported in a non-negligible number of cases, with detrimental impacts on patients' overall sexual life. This review aimed to comprehensively discuss the prevalence and physiopathology of post-RP ODs, as well as potential treatment options. Orgasm-associated incontinence (climacturia) has been reported to occur in between 20% and 93% of patients after RP. Similarly, up to 19% of patients complain of postoperative orgasm-associated pain, mainly referred pain at the level of the penis. Moreover, impairment in the sensation of orgasm or even complete anorgasmia has been reported in 33% to 77% of patients after surgery. Clinical and surgical factors including age, the use of a nerve-sparing technique, and robotic surgery have been variably associated with the risk of ODs after RP, although robust and reliable data allowing for a proper estimation of the risk of postoperative orgasmic function impairment are still lacking. Likewise, little evidence regarding the management of postoperative ODs is currently available. In general, physicians should be aware of the prevalence of ODs after RP, in order to properly counsel all patients both preoperatively and immediately post-RP about the potential occurrence of bothersome and distressful changes in their overall sexual function. PMID:28459142

  17. 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.

  18. User involvement competence for radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher

    2007-01-01

    -assisted navigation systems. The case study analysis reveals that firms who closely interact with specific users benefit significantly for their radical innovation work. These users have a high motivation toward new solutions, are open to new technologies, possess diverse competencies, and are embedded into a very......One important market related capability for firms which seek to develop radical innovations is the competence to involve the 'right' users at the 'right' time in the 'right' form. While former studies have identified a rather passive role of users in the radical innovation process, this paper...

  19. User involvement competence for radical innovation

    DEFF Research Database (Denmark)

    Lettl, Christopher

    2007-01-01

    One important market related capability for firms which seek to develop radical innovations is the competence to involve the 'right' users at the 'right' time in the 'right' form. While former studies have identified a rather passive role of users in the radical innovation process, this paper......-assisted navigation systems. The case study analysis reveals that firms who closely interact with specific users benefit significantly for their radical innovation work. These users have a high motivation toward new solutions, are open to new technologies, possess diverse competencies, and are embedded into a very...

  20. 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.

  1. Some reactions of oxidizing radicals with enzymes in aqueous solution

    International Nuclear Information System (INIS)

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

    1979-01-01

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

  2. Pulsed-laser studies on the free-radical polymerization kinetics of styrene in microemulsion

    NARCIS (Netherlands)

    Manders, L.G.; Herk, van A.M.; German, A.L.; Sarnecki, J.; Schomäcker, R.; Schweer, J.

    1993-01-01

    A mean value of 339 L mol-1 s-1 was obtained for the propagation const. derived from pulsed-laser polymn. (PLP) of styrene in aq. AOT microemulsions. For accurate detns., simulations accounting for the esp. high radical concn. after the laser pulse in microemulsions were recommended. PLP with

  3. Radical pancreaticoduodenectomy for benign disease.

    LENUS (Irish Health Repository)

    Kavanagh, D O

    2008-01-01

    Whipple\\'s procedure is the treatment of choice for pancreatic and periampullary malignancies. Preoperative histological confirmation of malignancy is frequently unavailable and some patients will subsequently be found to have benign disease. Here, we review our experience with Whipple\\'s procedure for patients ultimately proven to have benign disease. The medical records of all patients who underwent Whipple\\'s procedure during a 15-year period (1987-2002) were reviewed; 112 patients underwent the procedure for suspected malignancy. In eight cases, the final histology was benign (7.1%). One additional patient was known to have benign disease at resection. The mean age was 50 years (range: 30-75). The major presenting features included jaundice (five), pain (two), gastric outlet obstruction (one), and recurrent gastrointestinal haemorrhage (one). Investigations included ultrasound (eight), computerised tomography (eight), endoscopic retrograde cholangiopancreatography (seven; of these, four patients had a stent inserted and three patients had sampling for cytology), and endoscopic ultrasound (two). The pathological diagnosis included benign biliary stricture (two), chronic pancreatitis (two), choledochal cyst (one), inflammatory pseudotumour (one), cystic duodenal wall dysplasia (one), duodenal angiodysplasia (one), and granular cell neoplasm (one). There was no operative mortality. Morbidity included intra-abdominal collection (one), anastomotic leak (one), liver abscess (one), and myocardial infarction (one). All patients remain alive and well at mean follow-up of 41 months. Despite recent advances in diagnostic imaging, 8% of the patients undergoing Whipple\\'s procedure had benign disease. A range of unusual pathological entities can mimic malignancy. Accurate preoperative histological diagnosis may have allowed a less radical operation to be performed. Endoscopic ultrasound-guided fine needle aspirate (EUS-FNA) may reduce the need for Whipple\\'s operation

  4. Radical Pancreaticoduodenectomy for Benign Disease

    Directory of Open Access Journals (Sweden)

    D. O. Kavanagh

    2008-01-01

    Full Text Available Whipple's procedure is the treatment of choice for pancreatic and periampullary malignancies. Preoperative histological confirmation of malignancy is frequently unavailable and some patients will subsequently be found to have benign disease. Here, we review our experience with Whipple's procedure for patients ultimately proven to have benign disease. The medical records of all patients who underwent Whipple's procedure during a 15-year period (1987–2002 were reviewed; 112 patients underwent the procedure for suspected malignancy. In eight cases, the final histology was benign (7.1%. One additional patient was known to have benign disease at resection. The mean age was 50 years (range: 30–75. The major presenting features included jaundice (five, pain (two, gastric outlet obstruction (one, and recurrent gastrointestinal haemorrhage (one. Investigations included ultrasound (eight, computerised tomography (eight, endoscopic retrograde cholangiopancreatography (seven; of these, four patients had a stent inserted and three patients had sampling for cytology, and endoscopic ultrasound (two. The pathological diagnosis included benign biliary stricture (two, chronic pancreatitis (two, choledochal cyst (one, inflammatory pseudotumour (one, cystic duodenal wall dysplasia (one, duodenal angiodysplasia (one, and granular cell neoplasm (one. There was no operative mortality. Morbidity included intra-abdominal collection (one, anastomotic leak (one, liver abscess (one, and myocardial infarction (one. All patients remain alive and well at mean follow-up of 41 months. Despite recent advances in diagnostic imaging, 8% of the patients undergoing Whipple'’s procedure had benign disease. A range of unusual pathological entities can mimic malignancy. Accurate preoperative histological diagnosis may have allowed a less radical operation to be performed. Endoscopic ultrasound–guided fine needle aspirate (EUS-FNA may reduce the need for Whipple's operation in

  5. 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.

  6. Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines

    Directory of Open Access Journals (Sweden)

    Andreas Gansäuer

    2013-08-01

    Full Text Available The intramolecular radical addition to aniline derivatives was investigated by DFT calculations. The computational methods were benchmarked by comparing the calculated values of the rate constant for the 5-exo cyclization of the hexenyl radical with the experimental values. The dispersion-corrected PW6B95-D3 functional provided very good results with deviations for the free activation barrier compared to the experimental values of only about 0.5 kcal mol−1 and was therefore employed in further calculations. Corrections for intramolecular London dispersion and solvation effects in the quantum chemical treatment are essential to obtain consistent and accurate theoretical data. For the investigated radical addition reaction it turned out that the polarity of the molecules is important and that a combination of electrophilic radicals with preferably nucleophilic arenes results in the highest rate constants. This is opposite to the Minisci reaction where the radical acts as nucleophile and the arene as electrophile. The substitution at the N-atom of the aniline is crucial. Methyl substitution leads to slower addition than phenyl substitution. Carbamates as substituents are suitable only when the radical center is not too electrophilic. No correlations between free reaction barriers and energies (ΔG‡ and ΔGR are found. Addition reactions leading to indanes or dihydrobenzofurans are too slow to be useful synthetically.

  7. Photodynamically generated bovine serum albumin radicals

    DEFF Research Database (Denmark)

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

    1998-01-01

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

  8. 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

  9. Radical Sustainable Innovation of office buildings

    DEFF Research Database (Denmark)

    Koch, Christian; Berker, Thomas; Koch-Ørvad, Nina

    2017-01-01

    by high degrees of newness in the entire life cycle. RSI should offer significant enhancements of known benefits, entirely new benefits, or substantial cost reductions, leading to the transformation of existing markets, the creation of sustainable growth, and global sustainability. Thus, if buildings were....../could be radically new. How to evaluate radicality is a major challenge. It is tentatively proposed, to use standards for sustainable office buildings. Standards are developed to accelerate the sustainable development but has to some extent come to constrain possibilities of radical innovation. As the criteria...... of newness is incorporated in standards, going beyond them, could be viewed as radical. Empirically a selection of international cases of office buildings with very high scores of BREEAM, LEED and DGNB are examined. Six selected cases were analysed more in detail, one of them, Geelens...

  10. Interactions between simple radicals and water

    International Nuclear Information System (INIS)

    Crespo-Otero, Rachel; Sanchez-Garcia, Elsa; Suardiaz, Reynier; Montero, Luis A.; Sander, Wolfram

    2008-01-01

    The interactions of the simple radicals CH 3 , NH 2 , OH, and F with water have been studied by DFT (UB3LYP/6-311++G(2d,2p)) and ab initio (RHF-UCCSD(T)/6-311++G(2d,2p)) methods. In this order the number of lone pairs (from zero to three), the electronegativity, and the strength of the X-H bonds increase (X = C, N, and O). The various minima of the radical-water complexes were located using the multiple minima hypersurface (MMH) approach which had previously been proven to be useful for closed-shell molecules. The role of the unpaired electron in hydrogen bonding was investigated using the natural bond orbital (NBO) analysis. A considerable contribution of the unpaired electron to the complex stabilization was only found for the methyl radical and the fluorine atom, whereas in the aminyl and the hydroxyl radical the role of the unpaired electron is negligible

  11. 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...

  12. Prison Radicalization: The New Extremist Training Grounds?

    National Research Council Canada - National Science Library

    Coffin, Jr., McKinley D

    2007-01-01

    As a nation with the largest prison population in the world, the United States has all the ingredients for criminals, extremists, and religious radicals to collaborate in producing a new breed of homegrown terrorist...

  13. Neo-liberal Governing of 'Radicals'

    DEFF Research Database (Denmark)

    Lindekilde, Lasse

    2012-01-01

    The Danish government’s counter-radicalization Action Plan of 2009 had intended and unintended effects. Primarily targeting Danish Muslims, it employs neoliberal governmentality approaches of governance through individual support and response, information and knowledge, empowerment, surveillance...

  14. 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.

  15. Spectroscopy and reaction dynamics of collision complexes containing hydroxyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Lester, M.I. [Univ. of Pennsylvania, Philadelphia (United States)

    1993-12-01

    The DOE supported work in this laboratory has focused on the spectroscopic characterization of the interaction potential between an argon atom and a hydroxyl radical in the ground X{sup 2}II and excited A {sup 2}{summation}{sup +} electronic states. The OH-Ar system has proven to be a test case for examining the interaction potential in an open-shell system since it is amenable to experimental investigation and theoretically tractable from first principles. Experimental identification of the bound states supported by the Ar + OH (X {sup 2}II) and Ar + OH(A {sup 2}{summation}{sup +}) potentials makes it feasible to derive realistic potential energy surfaces for these systems. The experimentally derived intermolecular potentials provide a rigorous test of ab initio theory and a basis for understanding the dramatically different collision dynamics taking place on the ground and excited electronic state surfaces.

  16. Analysis of radicals of irradiated garlic

    International Nuclear Information System (INIS)

    Kameya, Hiromi; Kaimori, Yoshihiko; Ukai, Mitsuko

    2010-01-01

    The detection method of gamma ray irradiated garlic using Electron Spin Resonance(ESR)spectroscopy was studied. The ESR spectrum was consisted of one singlet signal at g=2.00. This signal is due to an organic free radical. Upon irradiation, the intensity of the signal was increased. Also two signals due to cellulose radical were detected nearby the singlet. The intensity of the singlet signal was increased as depend on the increase of the irradiation dose level. (author)

  17. Western radicalization: rethinking the psychology of terrorism

    OpenAIRE

    Pierson, Vern

    2017-01-01

    Approved for public release; distribution is unlimited The U.S. strategy to counter violent extremism relies heavily on the expert consensus that terrorists are engaging in political group speak and are by nature psychologically normal. Thus, anyone is susceptible to radicalization. To counter radicalization, finding answers is like finding a needle in a haystack. However, in the psychologically similar phenomenon of arson by firefighter—when a firefighter deliberately sets and then exting...

  18. Free radicals trapped in polyethylene matrix

    International Nuclear Information System (INIS)

    Shimada, S.; Maeda, M.; Hori, Y.; Kashiwabara, H.

    1977-01-01

    Two types of alkyl radicals were found to be trapped in irradiated crystals grown from polyethylene solution. One of them corresponds to the broad sextet pattern of the e.s.r. spectrum and the other corresponds to the sharp sextet pattern. The free radicals attributed to the broad sextet began to disappear at a lower temperature than the temperature at which the free radicals attributed to the sharp sextet disappeared. When butadiene molecules were brought into contact with the specimen, the decay of the free radicals corresponding to the broad sextet was accelerated. When the specimen was subjected to fuming nitric acid treatment, no broad sextet was observed. The mat of the crystals was aligned so that the c-axes of its crystallites were perpendicular to its surface. The broad sextet showed no anisotropy when the angle between the direction of applied magnetic field and that of the c-axis of the crystallite was varied. On the other hand, the sharp component of the spectrum showed apparent anisotropy. It can be concluded that the broad component comes from the free radicals trapped in the lamellar surface and the sharp component is attributed to the free radicals trapped in the inner part of the crystallite. (author)

  19. OKN-007 decreases free radical levels in a preclinical F98 rat glioma model.

    Science.gov (United States)

    Coutinho de Souza, Patricia; Smith, Nataliya; Atolagbe, Oluwatomisin; Ziegler, Jadith; Njoku, Charity; Lerner, Megan; Ehrenshaft, Marilyn; Mason, Ronald P; Meek, Bill; Plafker, Scott M; Saunders, Debra; Mamedova, Nadezda; Towner, Rheal A

    2015-10-01

    Free radicals are associated with glioma tumors. Here, we report on the ability of an anticancer nitrone compound, OKN-007 [Oklahoma Nitrone 007; a disulfonyl derivative of α-phenyl-tert-butyl nitrone (PBN)] to decrease free radical levels in F98 rat gliomas using combined molecular magnetic resonance imaging (mMRI) and immunospin-trapping (IST) methodologies. Free radicals are trapped with the spin-trapping agent, 5,5-dimethyl-1-pyrroline N-oxide (DMPO), to form DMPO macromolecule radical adducts, and then further tagged by immunospin trapping by an antibody against DMPO adducts. In this study, we combined mMRI with a biotin-Gd-DTPA-albumin-based contrast agent for signal detection with the specificity of an antibody for DMPO nitrone adducts (anti-DMPO probe), to detect in vivo free radicals in OKN-007-treated rat F98 gliomas. OKN-007 was found to significantly decrease (P free radical levels detected with an anti-DMPO probe in treated animals compared to untreated rats. Immunoelectron microscopy was used with gold-labeled antibiotin to detect the anti-DMPO probe within the plasma membrane of F98 tumor cells from rats administered anti-DMPO in vivo. OKN-007 was also found to decrease nuclear factor erythroid 2-related factor 2, inducible nitric oxide synthase, 3-nitrotyrosine, and malondialdehyde in ex vivo F98 glioma tissues via immunohistochemistry, as well as decrease 3-nitrotyrosine and malondialdehyde adducts in vitro in F98 cells via ELISA. The results indicate that OKN-007 effectively decreases free radicals associated with glioma tumor growth. Furthermore, this method can potentially be applied toward other types of cancers for the in vivo detection of macromolecular free radicals and the assessment of antioxidants. Copyright © 2015. Published by Elsevier Inc.

  20. Sulfite-induced protein radical formation in LPS aerosol-challenged mice: Implications for sulfite sensitivity in human lung disease

    Directory of Open Access Journals (Sweden)

    Ashutosh Kumar

    2018-05-01

    Full Text Available Exposure to (bisulfite (HSO3– and sulfite (SO32– has been shown to induce a wide range of adverse reactions in sensitive individuals. Studies have shown that peroxidase-catalyzed oxidation of (bisulfite leads to formation of several reactive free radicals, such as sulfur trioxide anion (.SO3–, peroxymonosulfate (–O3SOO., and especially the sulfate (SO4. – anion radicals. One such peroxidase in neutrophils is myeloperoxidase (MPO, which has been shown to form protein radicals. Although formation of (bisulfite-derived protein radicals is documented in isolated neutrophils, its involvement and role in in vivo inflammatory processes, has not been demonstrated. Therefore, we aimed to investigate (bisulfite-derived protein radical formation and its mechanism in LPS aerosol-challenged mice, a model of non-atopic asthma. Using immuno-spin trapping to detect protein radical formation, we show that, in the presence of (bisulfite, neutrophils present in bronchoalveolar lavage and in the lung parenchyma exhibit, MPO-catalyzed oxidation of MPO to a protein radical. The absence of radical formation in LPS-challenged MPO- or NADPH oxidase-knockout mice indicates that sulfite-derived radical formation is dependent on both MPO and NADPH oxidase activity. In addition to its oxidation by the MPO-catalyzed pathway, (bisulfite is efficiently detoxified to sulfate by the sulfite oxidase (SOX pathway, which forms sulfate in a two-electron oxidation reaction. Since SOX activity in rodents is much higher than in humans, to better model sulfite toxicity in humans, we induced SOX deficiency in mice by feeding them a low molybdenum diet with tungstate. We found that mice treated with the SOX deficiency diet prior to exposure to (bisulfite had much higher protein radical formation than mice with normal SOX activity. Altogether, these results demonstrate the role of MPO and NADPH oxidase in (bisulfite-derived protein radical formation and show the involvement of

  1. Application of EPR spectroscopy to examine free radicals evolution during storage of the thermally sterilized Ungentum ophthalmicum.

    Science.gov (United States)

    Ramos, Paweł; Pilawa, Barbara

    2016-06-24

    Free radicals formed during thermal sterilization of the Ungentum ophthalmicum were examined by an X-band EPR spectroscopy. The influence of storage time (15 min; 1, 2 and 3 days after heating) on free radical properties and concentrations in this sample was determined. Thermal sterilization was done according to the pharmaceutical norms. The first-derivative EPR spectra with g-values about 2 were measured with magnetic modulation of 100 kHz in the range of microwave power 2.2-70 mW. The changes of amplitudes (A) and linewidths (ΔB pp ) with microwave powers were evaluated. Free radicals in concentration ∼10 17 spin/g were formed during heating of the tested Ungentum. Free radical concentration decreased with increase in storage time, and reached values ∼10 17 spin/g after 3 days from sterilization. The tested U. ophthalmicum should not be sterilized at a temperature of 160 °C because of the free radicals formation, or it should be used 3 days after heating, when free radicals were considerably quenched. Free radical properties remain unchanged during storage of the Ungentum. The EPR lines of the U. ophthalmicum were homogeneously broadened and their linewidths (ΔB pp ) increased with increase in microwave power. EPR spectroscopy is useful to examine free radicals to optimize sterilization process and storage conditions of ophthalmologic samples.

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

    International Nuclear Information System (INIS)

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

    1986-01-01

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

  3. Radical and Not So Radical Transgressions: Invading Backstage Domains

    Directory of Open Access Journals (Sweden)

    Lada Čale Feldman

    2012-06-01

    Full Text Available Featuring as one of the privileged metaphors in humanities and social sciences, theatre provides primarily an image of a circumscribed space whose spatial syntax and modes of human engagement take place within and with respect to the larger space of the city, the world, and, as in Calderon’s Gran teatro del mundo, the universe. It is precisely as a special organization of spatiality that theatre reached the status of Foucault’s radical hetero-topos, flexible as it proved to be as a model for not only counter-representing all the human dealings in the external space, but also of conceptualizing, as in Freud’s psychoanalysis, man’s inner world, his psychic topography. But theatre is above all a concrete place, a built form with its own spatial history, its changing social and ideological functions, and its ways of bestowing to the bodies that enter into it actual or phantasm identities, thoughts, sensations, feelings and memories.My intervention will deal with one of the ruling borders/dichotomies/barriers of theatrical space, the one dividing “front stage” from “backstage” regions. In his detailed analysis of the latter in an individual and concrete theatre building, Andrew Filmer relies among others on Edward Soja’s “trialectics of being”, and thus also on Lefebvre’s categories of perceptual, conceptual and lived aspects of spatiality which Soja evokes, which will here be of particular interest. In contrast to the repercussions of such an analytical triad for the ethnographic study of concrete theatrical sites, I will ask how it pertains to potential manipulations of the aforementioned division of front-stage and backstage within contemporary performance practice. The temporal aspect of this manipulation should also be emphasized, having in mind the historical provenance of a whole backstage mythology – evidenced in numerous novels, plays and films situated in the backstage world - in the elaborated architectural

  4. Original Research

    African Journals Online (AJOL)

    home

    2014-03-10

    Mar 10, 2014 ... energy, they are important for calcification of bone, blood coagulation, neuromuscular activity ... It is well known that reactive oxygen species (ROS) such as superoxide radical, hydroxyl radical, singlet oxygen, peroxyl radical ...

  5. 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.

  6. Differential radioprotection and free radical scavenging activity of Caesalpinia digyna extracts and the active constituent

    International Nuclear Information System (INIS)

    Singh, Umang; Kunwar, A.; Barik, A.; Priyadarsini, K.I.; Mula, S.; Srinivasan, R.

    2008-01-01

    Differential free radical activity of the fractionated extracts (F1: methanolic fraction, F2: acetone soluble fraction and F3: acetone insoluble fraction) of a medicinal plant Caesalpinia digyna, has been studied employing DPPH, superoxide radical and in vitro radioprotecting activity by following their effect on radiation induced protein carbonylation and DNA damage in pBR322. The activity for these fractions is in the order of F1>F2>F3. HPLC analysis indicated that all fractions contain high amount of bergenin, a polyhydroxy isocoumarin derivative and the fractions are more active than isolated bergenin. (author)

  7. Differential radioprotection and free radical scavenging activity of Caesalpinia digyna extracts and the active constituent

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Umang; Kunwar, A; Barik, A; Priyadarsini, K I [Radiation and Photochemistry Div., Bhabha Atomic Research Centre, Mumbai (India); Mula, S [Bio-Organic Div., Bhabha Atomic Research Centre, Mumbai (India); Srinivasan, R [JSS College of Pharmacy, Ootacamund (India)

    2008-01-15

    Differential free radical activity of the fractionated extracts (F1: methanolic fraction, F2: acetone soluble fraction and F3: acetone insoluble fraction) of a medicinal plant Caesalpinia digyna, has been studied employing DPPH, superoxide radical and in vitro radioprotecting activity by following their effect on radiation induced protein carbonylation and DNA damage in pBR322. The activity for these fractions is in the order of F1>F2>F3. HPLC analysis indicated that all fractions contain high amount of bergenin, a polyhydroxy isocoumarin derivative and the fractions are more active than isolated bergenin. (author)

  8. Activism and radical politics in the digital age: Towards a typology

    DEFF Research Database (Denmark)

    Neumayer, Christina; Jakob, Svensson

    2014-01-01

    This article aims to develop a typology for evaluating different types of activism in the digital age, based on the ideal of radical democracy. Departing from this ideal, activism is approached in terms of processes of identification by establishing conflictual frontiers to outside others as either...... in radical democracy concerning developing frontiers. The second axis, about readiness to engage in civil disobedience, is derived from a review of studies of different forms of online activism. The article concludes by suggesting that the different forms of political engagement online have to be taken...

  9. Global Derivatives

    DEFF Research Database (Denmark)

    Andersen, Torben Juul

    approaches to dealing in the global business environment." - Sharon Brown-Hruska, Commissioner, Commodity Futures Trading Commission, USA. "This comprehensive survey of modern risk management using derivative securities is a fine demonstration of the practical relevance of modern derivatives theory to risk......" provides comprehensive coverage of different types of derivatives, including exchange traded contracts and over-the-counter instruments as well as real options. There is an equal emphasis on the practical application of derivatives and their actual uses in business transactions and corporate risk...... management situations. Its key features include: derivatives are introduced in a global market perspective; describes major derivative pricing models for practical use, extending these principles to valuation of real options; practical applications of derivative instruments are richly illustrated...

  10. 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

  11. Free radical formation in deoxyguanosine-5'-monophosphate γ-irradiated in frozen solution. A computer-assisted analysis of temperature-dependent ESR spectra

    International Nuclear Information System (INIS)

    Gregoli, S.; Olast, M.; Bertinchamps, A.

    1977-01-01

    Deoxyguanosine-5'-monophosphate (dGMP) was γ-irradiated at 77 K in frozen aqueous solution and then annealed in a stepwise fashion up to the melting point. During this process, the primary radicals formed in DGMP at 77 K are progressively converted into secondary radical species. This is observed as changes in the spectrum intensity and conformation. Computer-assisted analysis of these temperature-dependent spectra permitted us to identify the transient radical species involved and to draw up single-radical concentration kinetics vs temperature. The radiation chemical behavior of dGMP was found to be quite similar to that of dAMP, investigated previously. In both these purine derivatives, radical anions are converted into radicals of H-addition to C-8, and radical cations are converted into radicals of OH-addition to the same position. In dGMP, however, the cationic channel is only induced under certain experimental conditions (alkaline pH, presence of electron scavengers). At neutral pH, G + radicals are quite stable and finally become deactivated without being converted into secondary GOH radicals. Specific deuterium substitution at carbon C-8, and irradiation in H 2 O or in D 2 O, confirmed that both H + and OH - attachments do occur at C-8, and that both the H + and OH - groups come from the aqueous medium

  12. Synthesis and Characterization of Ethylenedithio-MPTTF-PTM Radical Dyad as a Potential Neutral Radical Conductor

    DEFF Research Database (Denmark)

    Souto, Manuel; Bendixen, Dan; Jensen, Morten

    2016-01-01

    During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF...

  13. How to counter radical narratives: Dutch deradicalization policy in the case of Moluccan and Islamic radicals

    NARCIS (Netherlands)

    Demant, F.; de Graaf, B.

    2010-01-01

    This article deals with the role of government in encouraging the decline of radical movements. The question posed is: "Which story can the government tell to encourage the decline of radical groups and the disengagement of their members?" The article makes use of the survey of factors promoting

  14. Radical Transversal Lightlike Submanifolds of Indefinite Para-Sasakian Manifolds

    OpenAIRE

    Shukla S.S.; Yadav Akhilesh

    2014-01-01

    In this paper, we study radical transversal lightlike submanifolds and screen slant radical transversal lightlike submanifolds of indefinite para-Sasakian manifolds giving some non-trivial examples of these submanifolds. Integrability conditions of distributions D and RadTM on radical transversal lightlike submanifolds and screen slant radical transversal lightlike submanifolds of indefinite para-Sasakian manifolds, have been obtained. We also study totally contact umbilical radical transvers...

  15. 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...

  16. 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.

  17. Vibronic Spectroscopy of the Phenylcyanomethyl Radical

    Science.gov (United States)

    Mehta, Deepali N.; Kidwell, Nathanael M.; Zwier, Timothy S.

    2011-06-01

    Resonance stabilized radicals (RSRs) are thought to be key intermediates in the formation of larger molecules in planetary atmospheres. Given the nitrogen-rich atmosphere of Titan, and the prevalence of nitriles there, it is likely that nitrile and isonitrile RSRs could be especially important in pathways leading to the formation of more complex nitrogen-containing compounds and the aerosols ("tholins") that are ultimately produced. In this talk, the results of a gas phase, jet-cooled vibronic spectroscopy study of the phenylcyanomethyl radical (C_6H_5.{C}HCN), the nitrogen-containing analog of the 1-phenylpropargyl radical, will be presented. A resonant two color photon ionization spectrum over the range 21,350-22,200 Cm-1 (450.0-468.0 nm) has been recorded, and the D_0-D_1 origin band has been tentatively identified at 21,400 Cm-1. Studies identifying the ionization threshold, and characterizing the vibronic structure will also be presented. An analogous study of the phenylisocyanomethyl radical, C_6H_5.{C}HNC, is currently being pursued for comparison with that of phenylcyanomethyl radical.

  18. 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.

  19. Analysis of radicals induced in irradiated foods

    International Nuclear Information System (INIS)

    Kishida, Keigo; Kaimori, Yoshihiko; Kawamura, Shoei; Sakamoto, Yuhki; Nakamura, Hideo; Ukai, Mitsuko; Kikuchi, Masahiro; Shimoyama, Yuhei; Kobayashi, Yasuhiko

    2012-01-01

    By electron spin resonance (ESR) spectroscopy, we revealed free radicals in γ-ray irradiated foods; black pepper, green coffee bean and ginseng. We also analyzed the decay behavior of radiation induced free radicals during storage of irradiated foods. The ESR spectrum of experimental irradiated foods consists of a sextet signal centered at g=2.0 and a singlet signal at the same g-value position and a singlet signal at g=4.0. The singlet signal at g=2.0 is originated from organic free radicals and its peak intensity showed the dependence of γ-ray irradiation dose levels. The signal intensity was decreased during storage. Only after 3 hours of radiation treatment the peak intensity was decreased fast and after that the intensity was decreased slowly. The relaxation times, T 1 and T 2 , of radiation induced free radicals showed the variations before and after irradiation. During long time storage period it was shown that T 1 was increased and T 2 was decreased. By analysis of decay process using the simulation methods based on the theory of reaction speed, it is considered that at least two kinds of radicals were induced in irradiated foods during long time storage. (author)

  20. 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.

  1. Hydroxyl radical induced degradation of salicylates in aerated aqueous solution

    International Nuclear Information System (INIS)

    Szabó, László; Tóth, Tünde; Homlok, Renáta; Rácz, Gergely; Takács, Erzsébet; Wojnárovits, László

    2014-01-01

    Ionizing radiation induced degradation of acetylsalicylic acid, its hydrolysis product salicylic acid and a salicylic acid derivative 5-sulpho-salicylic acid, was investigated in dilute aqueous solutions by UV–vis spectrophotometry, HPLC separation and diode-array or MS/MS detection, chemical oxygen demand, total organic carbon content and by Vibrio fischeri toxicity measurements. Hydroxyl radicals were shown to degrade these molecules readily, and first degradation products were hydroxylated derivatives in all cases. Due to the by-products, among them hydrogen peroxide, the toxicity first increased and then decreased with the absorbed dose. With prolonged irradiation complete mineralization was achieved. - Highlights: • In OH induced reactions of salicylates first products are hydroxylated derivatives. • With prolonged irradiation dihydroxy derivatives also form. • In aerated solutions the one-electron oxidant OH induces 3–4 oxidations. • Toxicity first increases and then decreases with dose mainly due to H 2 O 2 formation. • The toxicity in tap water is smaller than in pure water

  2. Sphingosines Derived from Marine Sponge as Potential Multi-Target Drug Related to Disorders in Cancer Development

    Science.gov (United States)

    Biegelmeyer, Renata; Schröder, Rafael; Rambo, Douglas F.; Dresch, Roger R.; Carraro, João L. F.; Mothes, Beatriz; Moreira, José Cláudio F.; da Frota Junior, Mário L. C.; Henriques, Amélia T.

    2015-01-01

    Haliclona tubifera, marine sponge species abundant in Brazilian coastline, presents only a few papers published in the literature. Recently, we have reported the isolation of two modified C18 sphingoid bases: (2R,3R,6R,7Z)-2-aminooctadec-7-ene-1,3,6-triol and and (2R,3R,6R)-2-aminooctadec-1,3,6-triol. In order to continue our research, in this work aimed at the biological investigation of fractions that led to the isolation of these compounds. We evaluated the cytotoxic effect of marine sponge H. tubifera fractions in glioma (U87) and neuroblastoma (SH-SY5Y) human cell lines. In addition, considering the link between cancer, imbalance of reactive oxygen species and coagulation disorders, we also investigated the in vitro effects on blood coagulation and their redox properties. We showed that the ethyl acetate (EtOAc) fraction, rich in sphingoid bases, had important cytotoxic effects in both cancer cell lines with an IC50 < 15 μg/mL and also can inhibit the production of peroxyl radicals. Interestingly, this fraction increased the recalcification time of human blood, showing anticoagulant properties. The present study indicates the sphingosines fraction as a promising source of chemical prototypes, especially multifunctional drugs in cancer therapy. PMID:26308014

  3. 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

  4. Financial Derivatives

    DEFF Research Database (Denmark)

    Wigan, Duncan

    2013-01-01

    Contemporary derivatives mark the development of capital and constitute a novel form of ownership. By reconfiguring the temporal, spatial and legal character of ownership derivatives present a substantive challenge to the tax collecting state. While fiscal systems are nationally bounded...... and inherently static, capital itself is unprecedentedly mobile, fluid and fungible. As such derivatives raise the specter of ‘financial weapons of mass destruction’....

  5. Financial Derivatives

    OpenAIRE

    Janečková, Alena

    2011-01-01

    1 Abstract/ Financial derivatives The purpose of this thesis is to provide an introduction to financial derivatives which has been, from the legal perspective, described in a not satisfactory manner as quite little literature that can be found about this topic. The main objectives of this thesis are to define the term "financial derivatives" and its particular types and to analyse legal nature of these financial instruments. The last objective is to try to draft future law regulation of finan...

  6. 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)

  7. Increased cerebral output of free radicals during hypoxia: implications for acute mountain sickness?

    DEFF Research Database (Denmark)

    Bailey, Damian M; Taudorf, Sarah; Berg, Ronan M G

    2009-01-01

    This study examined whether hypoxia causes free radical-mediated disruption of the blood-brain barrier (BBB) and impaired cerebral oxidative metabolism and whether this has any bearing on neurological symptoms ascribed to acute mountain sickness (AMS). Ten men provided internal jugular vein...... paramagnetic resonance spectroscopy and ozone-based chemiluminescence were employed for direct detection of spin-trapped free radicals and nitric oxide metabolites. Neuron-specific enolase (NSE), S100beta, and 3-nitrotyrosine (3-NT) were determined by ELISA. Hypoxia increased the arterio-jugular venous...... concentration difference (a-v(D)) and net cerebral output of lipid-derived alkoxyl-alkyl free radicals and lipid hydroperoxides (P

  8. Formation of tryptophan radicals in irradiated aqueous solutions of hexachloroplatinate(IV): a flash photolysis study.

    Science.gov (United States)

    Zang, L; Rodgers, M A

    1999-10-01

    The oxidation of tryptophan photosensitized by PtCl6(2-) has been investigated in aqueous solutions at different pH using nanosecond laser flash photolysis. Cationic and neutral radicals of tryptophan were detected at pH 2.8 and 8.5, respectively. The generation of the radical was attributed to oxidation by Cl2- that was formed from the homolytic bond cleavage in the excited state of PtCl6(2-). The bimolecular rate constant derived from the kinetics analysis, 2.8 +/- 0.2 x 10(9) M-1 s-1, is in good agreement with the value obtained in earlier pulse radiolysis studies. Both the cationic and neutral radicals decayed by second-order kinetics, consistent with the dimerization process.

  9. Glutathione mediation of papain inactivation by hydrogen peroxide and hydroxyl radicals

    International Nuclear Information System (INIS)

    Lin, W.S.; Armstrong, D.A.

    1977-01-01

    Glutathione reacts with papainCys 25 SOH, formed by the reaction of papain with hydrogen peroxide, to give papainCys 25 SSG. Subsequent reaction of this mixed disulfide with glutathione is slow (k -1 sec -1 ). However, at 30 0 C it is readily cleaved by cysteine to form active papain, i.e., papainCys 25 SH. Glutathione resembles cysteine in protecting papain by the scavenging of .OH radicals, but, unlike cysteine, glutathione gave no evidence for the repair of enzyme radical lesions or for the conversion of papainCys 25 S. radicals to repairable derivatives. Its overall effectiveness for reducing the radiation inactivation of papain in aqueous solution is much less than that of cysteine

  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. Optimal pain management for radical prostatectomy surgery

    DEFF Research Database (Denmark)

    Joshi, Grish P; Jaschinski, Thomas; Bonnet, Francis

    2015-01-01

    BACKGROUND: Increase in the diagnosis of prostate cancer has increased the incidence of radical prostatectomy. However, the literature assessing pain therapy for this procedure has not been systematically evaluated. Thus, optimal pain therapy for patients undergoing radical prostatectomy remains...... controversial. METHODS: Medline, Embase, and Cochrane Central Register of Controlled Trials were searched for studies assessing the effects of analgesic and anesthetic interventions on pain after radical prostatectomy. All searches were conducted in October 2012 and updated in June 2015. RESULTS: Most...... treatments studied improved pain relief and/or reduced opioid requirements. However, there were significant differences in the study designs and the variables evaluated, precluding quantitative analysis and consensus recommendations. CONCLUSIONS: This systematic review reveals that there is a lack...

  12. Customers as Partners in Radical Service Innovation

    DEFF Research Database (Denmark)

    Scupola, Ada; Nicolajsen, Hanne Westh

    2009-01-01

      Purpose- The main purpose of this paper is to investigate customer involvement and related challenges in radical service innovations in engineering consulting services Design/methodology/approach - The paper uses a case study approach and so called rich descriptions to investigate customer...... involvement, roles and related challenges and conditions in radical service innovations.Findings- One main finding is that customers can engage in radical service innovations in engineering consultancy services and may play a decisive role. In doing this they most likely take on all the three user involvement...... roles defined in the literature of New Service and New Product Development. Also a number of conditions are found to be necessary in order for this collaboration to succeed. The conclusion is that another understanding and handling of the customer/supplier relation is needed along with a need...

  13. Radiation chemistry of aromatic dimer radical cations

    International Nuclear Information System (INIS)

    Okamoto, Kazumasa; Tagawa, Seiichi

    2009-01-01

    π-π Interactions of aromatic molecules are paid attention much in many fields, especially biology, chemistry, and applied physics, represented as protein, DNA, electron donor-accepter complexes, charge transfers, and self assembly molecules. Aromatic molecules including benzene rings are the simplest case to study the π-π interactions. To interpret the charge resonance (CR) structure in the dimer radical cations, spectroscopic and ESR methods have been carried out. The spectroscopic study on the dimer radical ion of molecules with two chromophores would be profitable to identify the electronic and configurational properties. In this article, dynamics of the dimer radical cation of benzenes, polystyrenes, and resist polymers is described on the basis of direct observation of CR band by the nanosecond pulse radiolysis and low temperature γ-radiolysis methods. (author)

  14. Formation of stable radicals during perfluoroalkane radiolysis

    International Nuclear Information System (INIS)

    Allayarov, S.R.; Demidov, S.V.; Kiryukhin, D.P.; Mikhajlov, A.I.; Barkalov, I.M.

    1984-01-01

    Accumulation and stabilization kinetics of perfluoroalkyls during α-radiolysis ( 60 Co) of perfluoralkanes (PFA) in a wide temperature range for different PFA fractions differing in the average molecular weight, is investigated. It is noted that low temperature (PFA) radiolysis (77 K) is of a linear nature of accumulation of stabilized radicals up to doses of approximately 700 KGy. In the case of PFA radiolysis at 300 K radiation yields of stable radicals are somewhat lower than at 47 K and at doses of 200-300 KGy, their accumulation ceases. It is shown that kinetics of formation and accumulation of stable radicals does not depend on molecular mass and PFA fraction viscosity. Perfluoroalkyl stability is explained by intra molecular conformation spheric insulation of the free valency. Perfluoroalkyl stability in different PFA fractions in a wide time range in different media is investigated

  15. 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.

  16. 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...

  17. Preparation and study of dialkyl nitroxide radicals

    International Nuclear Information System (INIS)

    Chenavas, P.

    1969-01-01

    These radicals are obtained by oxidation of N-hydroxy-imides with lead tetracetate or p-nitro-perbenzoic acid. These imides are prepared by heating dicarboxylic acids anhydrides with benzyloxy-amine followed by catalytic hydrogenation of N-benzyloxy-imides so obtained. Two series of radicals have mainly been studied, the first concerning five-membered cyclic imides, the second six-membered cyclic imides, these molecules having methyls substituents or no on the carbon ring. N. M. R. spectra of some O-benzyl-imides have been analysed. These different results have made it possible to study the conformation and stereochemistry of these imides. (author) [fr

  18. RADICAL. Radiation information centre with analysing logic

    International Nuclear Information System (INIS)

    Rantanen, H.

    1998-01-01

    in an emergency, the production of data is overwhelming and the need of accurate and up-to-date information is essential. In Finland a new system (RADICAL) has been developed in order to automatically collect and maintain an overall view of the radiation situation and to facilitate the analysis of the consequences of any radiation incident. The project was started in the beginning of 1992 and the system was operational in summer 1994. The main objectives of the development process and how they are being fulfilled with the RADICAL system are discussed. (author)

  19. Dibromine radical anion reactions with heme enzymes

    International Nuclear Information System (INIS)

    Gebicka, L.; Gebicki, J.L.

    1996-01-01

    Reactions of Br 2 radical anion with heme enzymes, catalase horseradish peroxidase, have been studied by pulse radiolysis. It has been found that Br 2 - does not react with the heme centre of investigated enzymes. Dibromine radical anion reacts with tryptophan residues of catalase without any influence on the activity of catalase. It is suggested that in pulse radiolysis studies, where horseradish peroxidase is at about tenfold excess toward Br 2 - , the enzyme is modified rather by Br 2 , than by Br 2 - . (author). 26 refs., 3 figs

  20. Radical Islamism and Migrant Integration in Denmark

    DEFF Research Database (Denmark)

    Goli, Marco; Rezaei, Shahamak

    2011-01-01

    It has been suggested that alienation and failed integration may be causes of “Homegrown Radical Islamism” in Western societies. Western countries often expect that migrants and their descendants residing there as citizens will embrace or support common democratic ideals as a predicate for – or c......It has been suggested that alienation and failed integration may be causes of “Homegrown Radical Islamism” in Western societies. Western countries often expect that migrants and their descendants residing there as citizens will embrace or support common democratic ideals as a predicate...

  1. Resonance ionization detection of combustion radicals

    Energy Technology Data Exchange (ETDEWEB)

    Cool, T.A. [Cornell Univ., Ithaca, NY (United States)

    1993-12-01

    Fundamental research on the combustion of halogenated organic compounds with emphasis on reaction pathways leading to the formation of chlorinated aromatic compounds and the development of continuous emission monitoring methods will assist in DOE efforts in the management and disposal of hazardous chemical wastes. Selective laser ionization techniques are used in this laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

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

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

    Science.gov (United States)

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

    2016-04-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-04-15

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

  5. Competing with the radical right: Distances between the European radical right and other parties on typical radical right issues

    NARCIS (Netherlands)

    Immerzeel, T.; Lubbers, M.; Coffé, H.

    2016-01-01

    The popularity of European Radical Right Populist parties (RRPs) has led to investigations into the distances between RRPs' and other parties' stances regarding immigration. This article adds to this literature by investigating the distance between RRPs and the other parties on a wider variety of

  6. Competing with the radical right. Distances between the European radical right and other parties on typical radical right issues

    NARCIS (Netherlands)

    Immerzeel, T.; Lubbers, M.; Coffe, H.R.

    2015-01-01

    The popularity of European Radical Right Populist parties (RRPs) has led to investigations into the distances between RRPs’ and other parties’ stances regarding immigration. This article adds to this literature by investigating the distance between RRPs and the other parties on a wider variety of

  7. Enhancement by platelets of oxygen radical responses of human neutrophils

    Energy Technology Data Exchange (ETDEWEB)

    McCulloch, K.K.; Powell, J.; Johnson, K.J.; Ward, P.A.

    1986-03-01

    When human blood neutrophils were incubated with immune complexes (consisting of IgG antibody) in the presence of platelets, there was a 2 to 10 fold enhancement in the generation of O-/sub 2/ and H/sub 2/O/sub 2/. This enhancement phenomenon was proportional to the dose of immune complex added and the number of platelets present. The response was not agonist specific since similar enhancement also occurred with the following agonists: phorbol myristate acetate, opsonized zymosan particles and the chemotactic peptide N-formyl-met-leu-phe. The platelet related phenomenon of enhanced O-/sub 2/ generation could not be reproduced by the addition of serotonin, histamine or platelet-derived growth factor and was not affected by prior treatment of platelets with cyclooxygenase inhibitors (indomethacin, piroxicam) or lipoxygenase inhibitors (nafazatrom, BW755C or nordihydroguaiaretic acid). However, activation of platelets by thrombin caused release into the platelet supernatant fluid of a factor that, only in the presence of immune complexes, caused enhanced O-/sub 2/ responses to neutrophils. These data indicate that platelets potentiate oxygen radical responses of human neutrophils and suggest a mechanisms by which platelets may participate in tissue injury which is mediated by oxygen radical products from activated neutrophils.

  8. Enhancement by platelets of oxygen radical responses of human neutrophils

    International Nuclear Information System (INIS)

    McCulloch, K.K.; Powell, J.; Johnson, K.J.; Ward, P.A.

    1986-01-01

    When human blood neutrophils were incubated with immune complexes (consisting of IgG antibody) in the presence of platelets, there was a 2 to 10 fold enhancement in the generation of O- 2 and H 2 O 2 . This enhancement phenomenon was proportional to the dose of immune complex added and the number of platelets present. The response was not agonist specific since similar enhancement also occurred with the following agonists: phorbol myristate acetate, opsonized zymosan particles and the chemotactic peptide N-formyl-met-leu-phe. The platelet related phenomenon of enhanced O- 2 generation could not be reproduced by the addition of serotonin, histamine or platelet-derived growth factor and was not affected by prior treatment of platelets with cyclooxygenase inhibitors (indomethacin, piroxicam) or lipoxygenase inhibitors (nafazatrom, BW755C or nordihydroguaiaretic acid). However, activation of platelets by thrombin caused release into the platelet supernatant fluid of a factor that, only in the presence of immune complexes, caused enhanced O- 2 responses to neutrophils. These data indicate that platelets potentiate oxygen radical responses of human neutrophils and suggest a mechanisms by which platelets may participate in tissue injury which is mediated by oxygen radical products from activated neutrophils

  9. Absolute photoionization cross-section of the propargyl radical

    Energy Technology Data Exchange (ETDEWEB)

    Savee, John D.; Welz, Oliver; Taatjes, Craig A.; Osborn, David L. [Sandia National Laboratories, Combustion Research Facility, Livermore, California 94551 (United States); Soorkia, Satchin [Institut des Sciences Moleculaires d' Orsay, Universite Paris-Sud 11, Orsay (France); Selby, Talitha M. [Department of Chemistry, University of Wisconsin, Washington County Campus, West Bend, Wisconsin 53095 (United States)

    2012-04-07

    Using synchrotron-generated vacuum-ultraviolet radiation and multiplexed time-resolved photoionization mass spectrometry we have measured the absolute photoionization cross-section for the propargyl (C{sub 3}H{sub 3}) radical, {sigma}{sub propargyl}{sup ion}(E), relative to the known absolute cross-section of the methyl (CH{sub 3}) radical. We generated a stoichiometric 1:1 ratio of C{sub 3}H{sub 3} : CH{sub 3} from 193 nm photolysis of two different C{sub 4}H{sub 6} isomers (1-butyne and 1,3-butadiene). Photolysis of 1-butyne yielded values of {sigma}{sub propargyl}{sup ion}(10.213 eV)=(26.1{+-}4.2) Mb and {sigma}{sub propargyl}{sup ion}(10.413 eV)=(23.4{+-}3.2) Mb, whereas photolysis of 1,3-butadiene yielded values of {sigma}{sub propargyl}{sup ion}(10.213 eV)=(23.6{+-}3.6) Mb and {sigma}{sub propargyl}{sup ion}(10.413 eV)=(25.1{+-}3.5) Mb. These measurements place our relative photoionization cross-section spectrum for propargyl on an absolute scale between 8.6 and 10.5 eV. The cross-section derived from our results is approximately a factor of three larger than previous determinations.

  10. Gastric injury induced by hemorrhage, local ischemia, and oxygen radical generation

    International Nuclear Information System (INIS)

    Wadhwa, S.S.; Perry, M.A.

    1987-01-01

    Gastric mucosal injury caused by local intra-arterial generation of oxygen-derived free radicals was compared with gastric injury caused by 30 min of hemorrhage-induced ischemia or local ischemia. The index of injury was the loss of 51 Cr-labeled red cells across the gastric mucosa. Generation of oxygen radicals in the celiac artery caused a rapid increase in mucosal blood loss during the period of radical generation, and this loss was maintained after radical production ceased. Local ischemia produced similar mucosal injury; however, this occurred after reperfusion of the stomach and not during the ischemic episode. Hemorrhage-induced ischemia produced a threefold greater mucosal blood loss than local ischemia. The results of this study indicate that (1) oxygen radicals generated enzymatically in the blood supply to the stomach cause mucosal bleeding of similar magnitude to that observed after local ischemia and (2) that gastric ischemia induced by systemic hypotension produces more severe gastric injury than the same level of local hypotension

  11. 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.

  12. 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

  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. Radical scavenging activity of crude polysaccharides from Camellia sinensis

    Directory of Open Access Journals (Sweden)

    Yang Fan

    2011-01-01

    Full Text Available A preparation of crude polysaccharides (TPS was isolated from Camellia sinensis by precipitation and ultrafiltration. TPS1, TPS2, and TPS3 had molecular weights of 240, 21.4, and 2.46 kDa, respectively. The radical scavenging activities of TPS were evaluated by DPPH free radical, hydroxyl radical and superoxide radical scavenging. These results revealed that TPS exhibited strong radical scavenging activity in a concentration-dependent manner. TPS3 with lowest molecular weight showed a higher radical scavenging activity.

  15. 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).

  16. The pentafluorostyrene endeavours with atom transfer radical polymerization - quo vadis?

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2014-01-01

    The versatility of the atom transfer radical polymerization (ATRP) of pentafluorostyrene (FS) is comprehensively evaluated. The ATRP of a wide range of monomers derived from FS is likewise discussed with emphasis on the potential polymer applications. A large number of block and star copolymers...... centred around polypentafluorostyrene (PFS) and prepared primarily using the bromomacroinitiator concept is surveyed. Here the main emphasis is on the feasibility of the polymer design, but also the very many different applications are highlighted. The potential grafting onto PFS and PFS block copolymers...... by exploitation of the very labile para-fluorine demonstrates new material architecture possibilities through very mild reaction conditions. Finally the utility of PFS in various conducting materials is elaborated. The amphiphilic nature of PFS in triblock copolymers with polyethers has been exploited for Li+ ion...

  17. Anti-social behaviour, community and radical moral communitarianism

    Directory of Open Access Journals (Sweden)

    Roger Hopkins-Burke

    2015-12-01

    Full Text Available This article offers an insight into the lives of individuals who are repeat victims of antisocial behaviour (ASB. Drawing on data derived from 15 case studies, the authors demonstrate the plight that such victims endure on a daily basis. The research reveals that a number of victims feel abandoned by their communities and the authorities and, how for many, there is an overwhelming sense of being “trapped” within their own homes. The article also offers evidence to support previous claims that police crime data only captures a small proportion of the actual number of incidents of ASB that occur. We conclude by proposing an emphasis on individual and community responsibility and suggest that by adopting a radical moral communitarian approach ASB could be reduced as part of rebuilding communities.

  18. Can the United States Defeat Radical Islam

    Science.gov (United States)

    2008-05-22

    It strongly disapproves of idolatry, the popular cult of saints and tomb visitation. 11...twentieth century, Sayyid Qutb (1906-1966), an Egyptian Islamic radical, referencing al-Wahhab, developed a modified concept of jahiliyya. In Qutb’s...It strongly disapproves of idolatry, the popular cult of saints and tomb visitation. When ibn Taymiyya was asked if the murderous. Mongols, who

  19. Identity and Islamic Radicalization in Western Europe

    NARCIS (Netherlands)

    S.M. Murshed (Syed); S. Pavan (Sara)

    2009-01-01

    textabstractThis paper argues that both socio-economic disadvantage and political factors, such as the West’s foreign policy with regard to the Muslim world, along with historical grievances, play a part in the development of Islamic radicalized collective action in Western Europe. We emphasise the

  20. Lipophilic fluorescent products of free radicals

    Czech Academy of Sciences Publication Activity Database

    Ivica, Josko; Wilhelm, Jiří

    2014-01-01

    Roč. 158, č. 3 (2014), s. 365-372 ISSN 1213-8118 R&D Projects: GA ČR(CZ) GAP303/11/0298 Institutional support: RVO:67985823 Keywords : lipofuscin-like pigments * lipid peroxidation * free radical s * fluorescence Subject RIV: CE - Biochemistry Impact factor: 1.200, year: 2014

  1. Radical Negativity: Music Education for Social Justice

    Science.gov (United States)

    McLaren, Peter

    2011-01-01

    According to Hedges (2010), the real enemies of the liberal class are radical thinkers such as Noam Chomsky and Ralph Nader, iconoclastic intellectuals who possess the moral autonomy to defy the power elite. While this author agrees with Hedges, he would take this argument even further. In this article, the author argues that the real enemy of…

  2. Unimolecular reaction dynamics of free radicals

    International Nuclear Information System (INIS)

    Terry A. Miller

    2006-01-01

    Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy

  3. Neglected Side Effects After Radical Prostatectomy

    DEFF Research Database (Denmark)

    Frey, Anders Ullmann; Sønksen, Jens; Fode, Mikkel

    2014-01-01

    INTRODUCTION: A series of previously neglected sexually related side effects to radical prostatectomy (RP) has been identified over the recent years. These include orgasm-associated incontinence (OAI), urinary incontinence in relation to sexual stimulation (UISS), altered perception of orgasm, or...

  4. Letter: OCCO*+, NNCO*+ and NNNN*+ radical cations.

    Science.gov (United States)

    Flammang, R; Srinivas, R; Nguyen, M T; Gerbaux, P

    2007-01-01

    Chemical ionization of a mixture of nitrogen and carbon monoxide produces three stable isobaric species at m/z 56: OCCO, OCNN and NNNN radical cations. Separated at increased resolution, these ions are readily identified by collisional activation. Neutralization-reionization experiments performed on two different mass spectrometers have not allowed the detection of any recovery signals for the corresponding neutrals.

  5. Antioxidant Capacity, Radical Scavenging Kinetics and Phenolic ...

    African Journals Online (AJOL)

    Antioxidant Capacity, Radical Scavenging Kinetics and Phenolic Profile of Methanol Extracts of Wild Plants of Southern Sonora, Mexico. EF Moran-Palacio, LA Zamora-Álvarez, NA Stephens-Camacho, GA Yáñez- Farías, A Virgen-Ortiz, O Martínez-Cruz, JA Rosas-Rodríguez ...

  6. Quantification of Radicals Generated in a Sonicator

    Directory of Open Access Journals (Sweden)

    Kassim Badmus

    2016-06-01

    Full Text Available The hydroxyl radical (OH• is a powerful oxidant produced as a consequence of cavitation in water. It can react nonspecifically in breaking down persistent organic pollutants in water into their mineral form. It can also recombine to form hydrogen peroxide which is very useful in water treatment. In this study, terephthalic acid (TA and potassium iodide dosimetry were used to quantify and investigate the behaviour of the generated OH radical in a laboratory scale sonicator. The 2-hydroxyl terephthalic acid (HTA formed during terephthalic acid dosimetry was determined by optical fibre spectrometer. The production rate of HTA served as a means of evaluating and characterizing the OH• generated over given time in a sonicator. The influence of sonicator power intensity, solution pH and irradiation time upon OH• generation were investigated. Approximately 2.2 ´ 10-9 M s-1 of OH radical was generated during the sonication process. The rate of generation of the OH radicals was established to be independent of the concentration of the initial reactant. Thus, the rate of generation of OH• can be predicted by zero order kinetics in a sonicator.

  7. Parents’ Perspectives on Radicalization: A Qualitative Study

    NARCIS (Netherlands)

    E. Sikkens (Elga); M.R.P.J.R.S. van San (Marion); S. Sieckelinck (Stijn); M. de Winter (Micha)

    2018-01-01

    textabstractAbstract: Radicalization of young people might be influenced by the way parents react towards the development of political or religious ideals. However, these reactions have hardly been explored. This study aimed to discover how parents reacted to the development of extreme ideals, and

  8. Radical Feminism and the Subject of Writing.

    Science.gov (United States)

    Rhodes, Jacqueline

    The radical feminists of the late 1960s and early 1970s, as well as their online counterparts today, offer provocative examples of networked textuality, a discourse dependent on the constant and visible contextualization of self and writing within the discourses of hegemony. Given its potential use for liberatory writing pedagogies, it seems…

  9. 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)

  10. Albert Einstein: Radical Pacifist and Democrat

    Science.gov (United States)

    Jayaraman, T.

    We draw attention here to the radical political grounding of Einstein's pacifism. We also drescribe some less commonly known aspects of his commitment to civil liberties, particularly in the context of the anti-l hysteria and anti-racism current in the United States of the late 1940s and 1950s. We also examine briefly his views on socialism.

  11. Phytochemical screening, free radical scavenging and antibacterial ...

    African Journals Online (AJOL)

    Cassia sieberiana is a tropical plant, widely distributed throughout Sudan and Guinea savannah. It is used in traditional medicine for the treatment of malarial, cancer and stomach ache. The study was conducted to screen for phytochemicals, free radical scavenging and antibacterial potentials of the root bark.

  12. 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)

  13. Flavonoids: hemisynthesis, reactivity, characterization and free radical scavenging activity.

    Science.gov (United States)

    Es-Safi, Nour-Eddine; Ghidouche, Souhila; Ducrot, Paul Henri

    2007-09-26

    Phenolic compounds form one of the main classes of secondary metabolites. They display a large range of structures and they are responsible for the major organoleptic characteristics of plant-derived-foods and beverages, particularly color and taste properties and they also contribute to the nutritional qualities of fruits and vegetables. Phenolic compounds are also highly unstable compounds which undergo numerous enzymatic and chemical reactions during postharvest food storage and processing thus adding to the complexity of plant polyphenol composition. Among these compounds flavonoids constitute one of the most ubiquitous groups of all plant phenolics. Owing to their importance in food organoleptic properties and in human health, a better understanding of their structures, their reactivity and chemical properties in addition to the mechanisms generating them appears essential to predict and control food quality. The purpose of this work is an overview of our findings concerning the hemisynthesis, the reactivity and the enzymatic oxidation of some flavonoids and shed light on the mechanisms involved in some of these processes and the structures of the resulting products. The free radical scavenging activity of some of the synthesized compounds is also presented and a structure-activity relationship is discussed. The first part of this review concerns the synthesis and structural characterization of modified monomeric flavanols. The use of these compounds as precursor for the preparation of natural and modified dimeric procyanidin derivatives was then explored through different coupling reactions. The full characterization of the synthesized compounds was achieved by concerted use of NMR and ESI-MS techniques. The free radical scavenging activity of some of the synthesized compounds was investigated. The second part of this review concerns the enzymatic oxidation of several flavonols by Trametes versicolor laccase. Most of the major oxidation products have been

  14. Flavonoids: Hemisynthesis, Reactivity, Characterization and Free Radical Scavenging Activity

    Directory of Open Access Journals (Sweden)

    Paul Henri Ducrot

    2007-09-01

    Full Text Available Phenolic compounds form one of the main classes of secondary metabolites. They display a large range of structures and they are responsible for the major organoleptic characteristics of plant-derived-foods and beverages, particularly color and taste properties and they also contribute to the nutritional qualities of fruits and vegetables. Phenolic compounds are also highly unstable compounds which undergo numerous enzymatic and chemical reactions during postharvest food storage and processing thus adding to the complexity of plant polyphenol composition. Among these compounds flavonoids constitute one of the most ubiquitous groups of all plant phenolics. Owing to their importance in food organoleptic properties and in human health, a better understanding of their structures, their reactivity and chemical properties in addition to the mechanisms generating them appears essential to predict and control food quality. The purpose of this work is an overview of our findings concerning the hemisynthesis, the reactivity and the enzymatic oxidation of some flavonoids and shed light on the mechanisms involved in some of these processes and the structures of the resulting products. The free radical scavenging activity of some of the synthesized compounds is also presented and a structure-activity relationship is discussed. The first part of this review concerns the synthesis and structural characterization of modified monomeric flavanols. The use of these compounds as precursor for the preparation of natural and modified dimeric procyanidin derivatives was then explored through different coupling reactions. The full characterization of the synthesized compounds was achieved by concerted use of NMR and ESI-MS techniques. The free radical scavenging activity of some of the synthesized compounds was investigated. The second part of this review concerns the enzymatic oxidation of several flavonols by Trametes versicolor laccase. Most of the major oxidation

  15. Laboratory measurements and astronomical search for the HSO radical.

    Science.gov (United States)

    Cazzoli, Gabriele; Lattanzi, Valerio; Kirsch, Till; Gauss, Jürgen; Tercero, Belén; Cernicharo, José; Puzzarini, Cristina

    2016-07-01

    Despite the fact that many sulfur-bearing molecules, ranging from simple diatomic species up to astronomical complex molecules, have been detected in the interstellar medium, the sulfur chemistry in space is largely unknown and a depletion in the abundance of S-containing species has been observed in the cold, dense interstellar medium (ISM). The chemical form of the missing sulfur has yet to be identified. For these reasons, in view of the fact that there is a large abundance of triatomic species harbouring sulfur, oxygen, and hydrogen, we decided to investigate the HSO radical in the laboratory to try its astronomical detection. High-resolution measurements of the rotational spectrum of the HSO radical were carried out within a frequency range well up into the THz region. Subsequently, a rigorous search for HSO in the two most studied high-mass star-forming regions, Orion KL and Sagittarius (Sgr) B2, and in the cold dark cloud Barnard 1 (B1-b) was performed. The frequency coverage and the spectral resolution of our measurements allowed us to improve and extend the existing dataset of spectroscopic parameters, thus enabling accurate frequency predictions up to the THz range. These were used to derive the synthetic spectrum of HSO, by means of the MADEX code, according to the physical parameters of the astronomical source under consideration. For all sources investigated, the lack of HSO lines above the confusion limit of the data is evident. The derived upper limit to the abundance of HSO clearly indicates that this molecule does not achieve significant abundances in either the gas phase or in the ice mantles of dust grains.

  16. Effect of metal complexation to anti-inflammatory over the action against oxidative and free radicals: ketoprofen action; Efeito da complexacao de metais aos antiinflamatorios na acao contra agentes oxidativos e radicais livres: acao do cetoprofeno

    Energy Technology Data Exchange (ETDEWEB)

    Manente, Francine Alessandra; Mello, Lucas Rosolen de Almeida; Vellosa, Jose Carlos Rebuglio [UEPG, Universidade Estadual de Ponta Grossa, Departamento de Analises Clinicas eToxicologicas, Ponta Grossa, PR (Brazil); Khalil, Omar Arafat Kdudsi [IFG, Instituto Federal de Goias, Campus de Formosa, Formosa - GO (Brazil); Carvalho, Claudio Teodoro de [UFGD, Universidade Federal da Grande Dourados, Faculdade de Ciencias Exatas e Tecnologias, Dourados-MS (Brazil); Bannach, Gilbert [UNESP, Universidade Estadual Paulista Julio de Mesquita Filho, Faculdade de Ciencias de Bauru, Bauru, SP (Brazil)

    2011-07-01

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

  17. 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.

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

    Directory of Open Access Journals (Sweden)

    Castellano, J. M.

    2016-09-01

    Full Text Available 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.Este trabajo estudia el papel del ácido oleanólico (OA, aislado de la hoja de olivo, como secuestrador de radicales libres e inhibidor de enzimas implicados en la hidrolisis de los carbohidratos de la dieta, dos mecanismos por los que el triterpeno podría mitigar la hiperglicemia postprandial y el estrés oxidativo. Se aportan nuevas evidencias que muestran que el OA puede capturar radicales ácido 2,2’-azino-bis-(3-etilbenzotiazolín-6-sulfónico y peroxilo, y que ejerce una potente inhibición no-competitiva de α-glucosidasa (IC50 10.11±0.30 μM. El análisis cinético y espectrométrico llevado a cabo indica que OA interacciona con este enzima en el interior de un bolsillo hidrofóbico, mediante un proceso endotérmico no espontáneo, de naturaleza hidrofóbica. Estos son dos posibles mecanismos por los cuales el OA puede facilitar un mejor control de la hiperglucemia postprandial y el estrés oxidativo

  19. 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

  20. Radical formation of irradiated α-alanine and N-acetyl alanine with heavy ion beams. Effects of the irradiation temperature

    International Nuclear Information System (INIS)

    Minegishi, Atsuko; Nagasaki, Jun; Mori, Wasuke; Amano, Chikara; Takagi, Shinji; Murakami, Takeshi; Kanai, Tatsuaki; Furusawa, Yoshiya; Iwata, Yoshiyuki

    2003-01-01

    The characteristics of irradiation with C290 MeV/u ion beams were investigated using X-band electron spin resonance (ESR) spectroscopy for a polycrystalline powder of L-α-alanine at from 77K to 310K. The formed main radicals at 190K∼310K were the deamino radical and the decarboxyl radical. Because of the first-derivative ESR, decarboxyl radical showed an expanded spectral width and a lower peak height because of its amino hydrogen and nitrogen than that of the same amount of deamino radical. The ESR of irradiated L-α-alanine predominantly indicates the spectrum of the deamino radical. On the irradiated, L-α-alanine at from 77K to 310K ESR showed 1:4:6:4:1 lines at 220K and at room temperature, which indicate that the methyl group of the radical was rotating. On the other hand, at 77K ESR the spectrum showed nearly 1:5:5:5:1 lines, like the teeth of a saw, on samples irradiated at 270K∼350K (range IV), and 1:4:6:4:1 lines for those irradiated at 180K∼260K (range II and III), respectively. It is considered that the radical conformation of the deamino radical is planar (most stable conformation) on an irradiated sample in range IV, and a pyramidal structure on the irradiated sample in ranges II and III. (author)

  1. 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...

  2. Multi-State Vibronic Interactions in Fluorinated Benzene Radical Cations.

    Science.gov (United States)

    Faraji, S.; Köppel, H.

    2009-06-01

    Conical intersections of potential energy surfaces have emerged as paradigms for signalling strong nonadiabatic coupling effects. An important class of systems where some of these effects have been analyzed in the literature, are the benzene and benzenoid cations, where the electronic structure, spectroscopy, and dynamics have received great attention in the literature. In the present work a brief overview is given over our theoretical treatments of multi-mode and multi-state vibronic interactions in the benzene radical cation and some of its fluorinated derivatives. The fluorobenzene derivatives are of systematic interest for at least two different reasons. (1) The reduction of symmetry by incomplete fluorination leads to a disappearance of the Jahn-Teller effect present in the parent cation. (2) A specific, more chemical effect of fluorination consists in the energetic increase of the lowest σ-type electronic states of the radical cations. The multi-mode multi-state vibronic interactions between the five lowest electronic states of the fluorobenzene radical cations are investigated theoretically, based on ab initio electronic structure data, and employing the well-established linear vibronic coupling model, augmented by quadratic coupling terms for the totally symmetric vibrational modes. Low-energy conical intersections, and strong vibronic couplings are found to prevail within the set of tilde{X}-tilde{A} and tilde{B}-tilde{C}-tilde{D} cationic states, while the interactions between these two sets of states are found to be weaker and depend on the particular isomer. This is attributed to the different location of the minima of the various conical intersections occurring in these systems. Wave-packet dynamical simulations for these coupled potential energy surfaces, utilizing the powerful multi-configuration time-dependent Hartree method are performed. Ultrafast internal conversion processes and the analysis of the MATI and photo-electron spectra shed new light

  3. 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

  4. Direct evidence of iNOS-mediated in vivo free radical production and protein oxidation in acetone-induced ketosis

    Science.gov (United States)

    Stadler, Krisztian; Bonini, Marcelo G.; Dallas, Shannon; Duma, Danielle; Mason, Ronald P.; Kadiiska, Maria B.

    2008-01-01

    Diabetic patients frequently encounter ketosis that is characterized by the breakdown of lipids with the consequent accumulation of ketone bodies. Several studies have demonstrated that reactive species are likely to induce tissue damage in diabetes, but the role of the ketone bodies in the process has not been fully investigated. In this study, electron paramagnetic resonance (EPR) spectroscopy combined with novel spin-trapping and immunological techniques has been used to investigate in vivo free radical formation in a murine model of acetone-induced ketosis. A six-line EPR spectrum consistent with the α-(4-pyridyl-1-oxide)-N-t-butylnitrone radical adduct of a carbon-centered lipid-derived radical was detected in the liver extracts. To investigate the possible enzymatic source of these radicals, inducible nitric oxide synthase (iNOS) and NADPH oxidase knockout mice were used. Free radical production was unchanged in the NADPH oxidase knockout but much decreased in the iNOS knockout mice, suggesting a role for iNOS in free radical production. Longer-term exposure to acetone revealed iNOS overexpression in the liver together with protein radical formation, which was detected by confocal microscopy and a novel immunospin-trapping method. Immunohistochemical analysis revealed enhanced lipid peroxidation and protein oxidation as a consequence of persistent free radical generation after 21 days of acetone treatment in control and NADPH oxidase knockout but not in iNOS knockout mice. Taken together, our data demonstrate that acetone administration, a model of ketosis, can lead to protein oxidation and lipid peroxidation through a free radical-dependent mechanism driven mainly by iNOS overexpression. PMID:18559982

  5. Free-radical-induced chain scission and cross-linking of polymers in aqueous solution. An overview

    International Nuclear Information System (INIS)

    Von Sonntag, C.

    2002-01-01

    Complete text of publication follows. In the radiolysis of N 2 O-saturated aqueous solutions OH are generated. In their reactions with polymers, they give rise to polymer-derived radicals. The kinetics of the formation and decay of these radicals are reviewed. The rate of reaction of a polymer with a reactive free radical is noticeably lower than that of an equivalent concentration of monomer due to the non-random distribution of the reaction sites. Once a larger number of radicals are formed on one polymer molecule, e.g. upon pulse radiolysis, close-by radicals recombine more rapidly while the more distant ones survive for much longer times than an equivalent concentration of freely diffusing radicals. Intermolecular cross-linking (between two polymer chains, increase in molecular weight) and intramolecular cross-linking (formation of small loops, no increase in polymer weight) are competing processes, and their relative yields thus depend on the dose rate and polymer concentration. Hydrogen-transfer reactions within the polymer, e.g. transformation of a secondary radical into a tertiary one, are common and facilitated by the high local density of reactive sites. Due to repulsive forces, the lifetime of radicals of charged polymers is substantially increased. This enables even relatively slow b-fragmentation reactions to become of importance. In the case of poly(methacrylic acid), where β-fragmentation is comparatively fast, this even leads to an unzipping, and as a consequence of the efficient release of methacrylic acid the situation of equilibrium polymerization is approached. Heterolytic β-fragmentation is possible when adequate leaving groups are available, e.g. in polynucleotides and DNA. In the presence of O 2 , chain scission occurs via oxyl radicals as intermediates. Some implications for technical applications are discussed

  6. 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

  7. 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).

  8. 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)

  9. Measurements of free radicals in a megacity during the Clean Air for London Project

    Science.gov (United States)

    Heard, Dwayne; Whalley, Lisa; Stone, Daniel; Clancy, Noel; Lee, James; Kleffman, Jorg; Laufs, Sebastian; Bandy, Brian

    2013-04-01

    Free radicals control the photo-oxidative chemistry of the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3, multifunctional species and particulates. Here we present measurements of OH, HO2 and RO2 radicals and OH reactivity recorded at North Kensington, Central London, during two Intensive Operational Periods (IOPs) of the Clear Air for London (Clearflo) project in the summer and winter of 2012. OH and HO2 were measured using laser-induced fluorescence (LIF) spectroscopy at low pressure (the FAGE technique), and RO2 was measured using the recently developed ROXLIF technique, which utilises an external flow-reactor interfaced to FAGE, and which is able to discriminate between HO2 and organic peroxy radicals. Through control of reagent gases we are further able to provide a separate measurement of those RO2 species which are known to give an interference for HO2 measurements (namely alkene, aromatic and large-chain alkane derived RO2). OH reactivity was measured using laser-flash photolysis combined with FAGE. Low concentrations of radicals were observed during the winter IOP, with mixing ratios of [OH] ~ 0.04 pptv, [HO2] ~ 0.4 pptv, and [RO2] ~ 1.6 pptv at noon, all displaying a negative correlation with NO. The photolysis of O3 and subsequent reaction of O(1D) with H2O vapour was only a minor contribution to radical production in winter, with photolysis of HONO a major radical source. The summer IOP coincided with the London Olympic Games, with a number of pollution events, with ozone peaking at 100 ppbv (exceeding EU air quality directives) and elevated radical concentrations (peak [OH] ~ 0.14 pptv, [HO2] ~ 4 pptv, [RO2] ~ 6.4 pptv) being observed. The net rate of ozone production was calculated from radical observations and agreed well with measured ozone production, suggesting that advection/dilution by continental air-masses was not playing a significant role in determining ozone

  10. Pyrimidine nucleobase radical reactivity in DNA and RNA

    Science.gov (United States)

    Greenberg, Marc M.

    2016-11-01

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

  11. Isoflurane preconditions myocardium against infarction via release of free radicals

    NARCIS (Netherlands)

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

    2002-01-01

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

  12. 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.

  13. Free radical injury in skin cultured fibroblasts from Alzheimer's disease patients.

    Science.gov (United States)

    Tesco, G; Latorraca, S; Piersanti, P; Sorbi, S; Piacentini, S; Amaducci, L

    1992-12-26

    Oxygen radical production is postulated to be a major cause of cell damage in aging. We have studied the response to toxic oxygen metabolites of fibroblast cell lines derived from skin biopsies of patients with familial and sporadic Alzheimer's disease compared with those derived from normal controls. Fibroblasts were damaged by the generation of oxygen metabolites during the enzymatic oxidation of acetaldehyde by 50 mU of xanthine-oxidase. To quantify cell damage we measured lactate dehydrogenase activity in the culture medium and cell viability in fibroblast cultures from four normal subjects, five FAD, and four AD patients after 2 hours of Xo incubation. We found a significant increase of LDH activity in FAD vs. controls and also in AD vs. controls, suggesting that AD cells are more susceptible to oxygen radical damage than are normal controls.

  14. Free Radical Scavenging Properties of Annona squamosa

    Science.gov (United States)

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

    2017-10-26

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

  15. Leadership Styles for the Five Stages of Radical Change

    Science.gov (United States)

    1998-04-01

    radical change. This article continues prior work on radical change with theory and research on leadership style. The result is a model of radical...every stage of that process. Leadership style and organiza- tional change theory and re- search have ex- isted for de- cades, but have rarely con...phase, inspire and en- ergize them to adopt the change after it Figure 3. Senior Manager Leadership Styles for the Five Phases of Radical Change Phase

  16. 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

  17. Derivative chameleons

    International Nuclear Information System (INIS)

    Noller, Johannes

    2012-01-01

    We consider generalized chameleon models where the conformal coupling between matter and gravitational geometries is not only a function of the chameleon field φ, but also of its derivatives via higher order co-ordinate invariants (such as ∂ μ φ∂ μ φ,□φ,...). Specifically we consider the first such non-trivial conformal factor A(φ,∂ μ φ∂ μ φ). The associated phenomenology is investigated and we show that such theories have a new generic mass-altering mechanism, potentially assisting the generation of a sufficiently large chameleon mass in dense environments. The most general effective potential is derived for such derivative chameleon setups and explicit examples are given. Interestingly this points us to the existence of a purely derivative chameleon protected by a shift symmetry for φ → φ+c. We also discuss potential ghost-like instabilities associated with mass-lifting mechanisms and find another, mass-lowering and instability-free, branch of solutions. This suggests that, barring fine-tuning, stable derivative models are in fact typically anti-chameleons that suppress the field's mass in dense environments. Furthermore we investigate modifications to the thin-shell regime and prove a no-go theorem for chameleon effects in non-conformal geometries of the disformal type

  18. Derivative chameleons

    Energy Technology Data Exchange (ETDEWEB)

    Noller, Johannes, E-mail: johannes.noller08@imperial.ac.uk [Theoretical Physics, Blackett Laboratory, Imperial College London, Prince Consort Road, London, SW7 2BZ (United Kingdom)

    2012-07-01

    We consider generalized chameleon models where the conformal coupling between matter and gravitational geometries is not only a function of the chameleon field φ, but also of its derivatives via higher order co-ordinate invariants (such as ∂{sub μ}φ∂{sup μ}φ,□φ,...). Specifically we consider the first such non-trivial conformal factor A(φ,∂{sub μ}φ∂{sup μ}φ). The associated phenomenology is investigated and we show that such theories have a new generic mass-altering mechanism, potentially assisting the generation of a sufficiently large chameleon mass in dense environments. The most general effective potential is derived for such derivative chameleon setups and explicit examples are given. Interestingly this points us to the existence of a purely derivative chameleon protected by a shift symmetry for φ → φ+c. We also discuss potential ghost-like instabilities associated with mass-lifting mechanisms and find another, mass-lowering and instability-free, branch of solutions. This suggests that, barring fine-tuning, stable derivative models are in fact typically anti-chameleons that suppress the field's mass in dense environments. Furthermore we investigate modifications to the thin-shell regime and prove a no-go theorem for chameleon effects in non-conformal geometries of the disformal type.

  19. Stereoselective conjugate radical additions: application of a fluorous oxazolidinone chiral auxiliary for efficient tin removal.

    Science.gov (United States)

    Hein, Jason E; Zimmerman, Jake; Sibi, Mukund P; Hultin, Philip G

    2005-06-23

    [reaction: see text] A series of asymmetric free-radical-mediated intermolecular conjugate additions using a fluorous oxazolidinone chiral auxiliary has been completed. The fluorous auxiliary facilitated product isolation using fluorous solid phase extractions (FSPE), effectively removing excess organic and organometallic reagents. Parallel reactions carried out with a similar but nonfluorous norephedrine-derived oxazolidinone demonstrated the superior stereoselectivity and purification obtainable with the fluorous chiral auxiliary.

  20. Dynamics of Peroxy and Alkenyl Radicals Undergoing Competing Rearrangements in Biodiesel Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Dibble, Theodore S. [State Univ. of New York (SUNY), Syracuse, NY (United States)

    2016-03-24

    Biodiesel fuel is increasingly being used worldwide. Although we have a fair understanding of the molecular details of the chemistry of peroxy radicals derived from alkanes, biodiesel fuels contain ester and olefin groups which significantly impact the thermodynamics and kinetics of biodiesel ignition. The broader goal of this research is to carry out systematic computational studies of the elementary kinetics of the chemistry of ROO•, QOOH and •OOQOOH compounds that are models for biodiesel ignition.

  1. Oxidation of spin-traps by chlorine dioxide (ClO2) radical in aqueous solutions: first ESR evidence of formation of new nitroxide radicals.

    Science.gov (United States)

    Ozawa, T; Miura, Y; Ueda, J

    1996-01-01

    The reactivities of the chlorine dioxide (ClO2), which is a stable free radical towards some water-soluble spin-traps were investigated in aqueous solutions by an electron spin resonance (ESR) spectroscopy. The ClO2 radical was generated from the redox reaction of Ti3+ with potassium chlorate (KClO3) in aqueous solutions. When one of the spin-traps, 5,5-dimethyl-1-pyrroline N-oxide (DMPO), was included in the Ti3+-KClO3 reaction system, ESR spectrum due to the ClO2 radical completely disappeared and a new ESR spectrum [aN(1) = 0.72 mT, aH(2) = 0.41 mT], which is different from that of DMPO-ClO2 adduct, was observed. The ESR parameters of this new ESR signal was identical to those of 5,5-dimethylpyrrolidone-(2)-oxyl-(1) (DMPOX), suggesting the radical species giving the new ESR spectrum is assignable to DMPOX. The similar ESR spectrum consisting of a triplet [aN(1) = 0.69 mT] was observed when the derivative of DMPO, 3,3,5,5-tetramethyl-1-pyrroline N-oxide (M4PO) was included in the Ti3+-KClO3 reaction system. This radical species is attributed to the oxidation product of M4PO, 3,3,5,5-tetramethylpyrrolidone-(2)-oxyl-(1) (M4POX). When another nitrone spin-trap, alpha-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN) was used as a spin-trap, the ESR signal intensity due to the ClO2 radical decreased and a new ESR signal consisting of a triplet [aN(1) = 0.76 mT] was observed. The similar ESR spectrum was observed when N-t-butyl-alpha- nitrone (PBN) was used as a spin-trap. This ESR parameter [a(N)(1) = 0.85 mT] was identical to the oxidation product of PBN, PBNX. Thus, the new ESR signal observed from POBN may be assigned to the oxidation product of POBN, POBNX. These results suggest that the ClO2, radical does not form the stable spin adducts with nitrone spin-traps, but oxidizes these spin-traps to give the corresponding nitroxyl radicals. On the other hand, nitroso spin-traps, 5,5-dibromo-4-nitrosobenzenesulfonate (DBNBS), and 2-methyl-2-nitrosopropane (MNP) did not trap

  2. Hybrid radical energy storage device and method of making

    Science.gov (United States)

    Gennett, Thomas; Ginley, David S; Braunecker, Wade; Ban, Chunmei; Owczarczyk, Zbyslaw

    2015-01-27

    Hybrid radical energy storage devices, such as batteries or electrochemical devices, and methods of use and making are disclosed. Also described herein are electrodes and electrolytes useful in energy storage devices, for example, radical polymer cathode materials and electrolytes for use in organic radical batteries.

  3. Responsibility for radical change in addressing climate change

    NARCIS (Netherlands)

    Bouvrie, des N.; Karlsson-Vinkhuyzen, S.I.S.E.; Jollands, N.

    2015-01-01

    To radically address the problem of climate change, it is not enough to modify specific attitudes and behaviors while upholding the present paradigms. This article aims to show why modifications will never bring about radical carbon emission reductions. We discuss what it implies to desire radical

  4. Biochemistry and pathology of radical-mediated protein oxidation

    DEFF Research Database (Denmark)

    Dean, R T; Fu, S; Stocker, R

    1997-01-01

    Radical-mediated damage to proteins may be initiated by electron leakage, metal-ion-dependent reactions and autoxidation of lipids and sugars. The consequent protein oxidation is O2-dependent, and involves several propagating radicals, notably alkoxyl radicals. Its products include several catego...

  5. Enhancing production through optimisation of DPPH and radical ...

    African Journals Online (AJOL)

    ... of dry matter for DPPH radical scavenging activity. Methanol had the lowest value (78 mg g-1 dry matter) for polyphenol extracts and 80 mg g-1 for the DPPH radical scavenging activity. The main extract compounds were gallic acid, catechin and epicatechin. Key Words: High density lipids, polyphenol, radical scavenging ...

  6. Synthesis, Characterization, Antimicrobial Screening and Free-Radical Scavenging Activity of Some Novel Substituted Pyrazoles

    Directory of Open Access Journals (Sweden)

    Nagwa Mohamed Mahrous Hamada

    2015-06-01

    Full Text Available The present work deals with the synthesis of acetoxysulfonamide pyrazole derivatives, substituted 4,5-dihydropyrazole-1-carbothioamide and 4,5-dihydropyrazole-1-isonicotinoyl derivatives starting from substituted vanillin chalcones. Acetoxysulfonamide pyrazole derivatives were prepared from the reaction of chalcones with p-sulfamylphenylhydrazine followed by treatment with acetic anhydride. At the same time 4,5-dihydropyrazole-1-carbothioamide and 4,5-dihydropyrazole-1-isonicotinoyl derivatives were prepared from the reaction of chalcones with either thiosemicarbazide or isonicotinic acid hydrazide, respectively. The synthesized compounds were structurally characterized on the basis of IR, 1H-NMR, 13C-NMR spectral data and microanalyses. All of the newly isolated compounds were tested for their antimicrobial activities. The antimicrobial screening using the agar well-diffusion method revealed that the chloro derivatives are the most active ones. Moreover, the antioxidant and anti-inflammatory activity of these chloro derivatives are also studied using the DPPH radical scavenging and NO radical scavenging methods, respectively.

  7. 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.

  8. Electricity derivatives

    CERN Document Server

    Aïd, René

    2015-01-01

    Offering a concise but complete survey of the common features of the microstructure of electricity markets, this book describes the state of the art in the different proposed electricity price models for pricing derivatives and in the numerical methods used to price and hedge the most prominent derivatives in electricity markets, namely power plants and swings. The mathematical content of the book has intentionally been made light in order to concentrate on the main subject matter, avoiding fastidious computations. Wherever possible, the models are illustrated by diagrams. The book should allow prospective researchers in the field of electricity derivatives to focus on the actual difficulties associated with the subject. It should also offer a brief but exhaustive overview of the latest techniques used by financial engineers in energy utilities and energy trading desks.

  9. E. P. R. spectroscopic study of nitroxide mono- and bi-radicals

    International Nuclear Information System (INIS)

    Lemaire, H.

    1966-09-01

    A nitroxide is a molecule containing the group N-O where the oxygen atom made only one bond instead of the usual two. The main advantage of these radicals is their exceptional stability; this allows the study of well defined chemical structures while varying at will the experimental conditions. Studies by electron paramagnetic resonance of nitroxide mono-radicals have given the principal directions and the principal values of the electron-nitrogen nucleus hyperfine tensor and of the anisotropic g-factor tensor. The results were then related to the electronic structure of radicals. An understanding was obtained of the influence of the solvent on the principal values of the tensors, and the marked differences observed in the broadening of hyperfine lines when the medium become viscous. In the nitroxide biradicals, the hyperfine spectra depends not only on the magnetic interactions relative to each monomer, but also on the magnitude of the exchange interaction between the singlet and the triplet states of the dimer; the biradicals studied here are the first organic compounds which show clearly the influence of this exchange on the hyperfine structure. The two unpaired electrons also interact by a magnetic dipolar interaction: in the intermediate case, this can be used to derive the sign of the exchange interaction if the bi-radical is studied in a liquid crystal. Just as for mono-radicals, the hyperfine spectra of bi-radicals show selective broadening in viscous media, which is caused by an overall motional modulation of the anisotropic tensors. This gives another way to determine the sign of the exchange interaction. (author) [fr

  10. Radical radiotherapy for T3 laryngeal cancers

    International Nuclear Information System (INIS)

    Uno, T.; Itami, J.; Kotaka, K.; Toriyama, M.

    1996-01-01

    From 1974 through 1992, 37 previously untreated patients with T3 laryngeal cancer (supraglottic 15, glottic 22) were treated with initial radical radiotherapy and surgery for salvage. Two-year local control rate with radiotherapy alone, ultimate voice preservation rate, and ultimate local control rate for T3 supraglottic cancer were 33%, 33%, and 60%, respectively. Corresponding figures for T3 glottic cancer were 32%, 23%, and 77%, respecitvely. Five-year cause-specific survival rate for T3 supraglottic cancer and glottic cancer were 47% and 77%, respectively. In T3 supraglottic cancer, none of the 4 patients with subglottic tumor extension attained local control by radiotherapy alone, and local-regional recurrence-free time were significantly shorter in patients with subglottic tumor extension or tracheostomy before radiotherapy. There were no serious late complications such as chondronecrosis, rupture of carotid artery attributed to radical radiotherapy, while 3 patients had severe laryngeal edema requiring total laryngectomy. (orig.) [de

  11. Editorial: RADICALISM AND POLITICS OF RELIGION

    Directory of Open Access Journals (Sweden)

    Editorial Al-Jami'ah: Journal of Islamic Studies

    2008-02-01

    Full Text Available Radical Islamism has become the “sexiest” issue in the international scholarship of religion since the September 11 tragedy in 2001. It has been associated with a number of terrorist attacks not only in the West but also in Muslim countries. Every single of radical Islamism has caught the interest of not only scholars and policy makers but also general public. Interestingly, the general assumption that religion is the source of peace has been seriously challenged, not by non-religious communities, but by the violent practices of particular religious groups, however small they are. Indeed, there are certain groups striving for Islam but by using acts which could give awful image on Islam itself and against humanity.

  12. Freedom Now! Radical Jazz and Social Movements

    Directory of Open Access Journals (Sweden)

    Przemysław Pluciński

    2014-01-01

    Full Text Available Music is obviously not only an aesthetic phenomenon. It is embeddedin a dense network of social relations. However, its social involvementis rather ambiguous, particularly since the second half of the twentiethcentury. On the one hand, music is one of the main elements of culturalcapitalism and a part of the system of domination. On the other hand,music provokes, (coproduces or possibly strengthens and coexists witha number of counterdiscourses and social projects of counterhegemoniccharacter.The main objective of the paper is to examine relationships between both, revolutionary jazz and revolutionary social movements, namely the civil rights movement, but above all radical movements, especially black power movement. The crucial questions I am interested in are problems of selforganization, performative social practices, as well as alternatives elaborated by radical-oriented jazz circles in various social dimensions, for instance economic or symbolic.

  13. Electronic spectrum of 9-methylanthracenium radical cation

    Energy Technology Data Exchange (ETDEWEB)

    O’Connor, Gerard D.; Schmidt, Timothy W., E-mail: timothy.schmidt@unsw.edu.au [School of Chemistry, UNSW Sydney, New South Wales 2052 (Australia); Sanelli, Julian A.; Dryza, Vik; Bieske, Evan J. [School of Chemistry, The University of Melbourne, Victoria 3010 (Australia)

    2016-04-21

    The predissociation spectrum of the cold, argon-tagged, 9-methylanthracenium radical cation is reported from 8000 cm{sup −1} to 44 500 cm{sup −1}. The reported spectrum contains bands corresponding to at least eight electronic transitions ranging from the near infrared to the ultraviolet. These electronic transitions are assigned through comparison with ab initio energies and intensities. The infrared D{sub 1}←D{sub 0} transitions exhibit significant vibronic activity, which is assigned through comparison with TD-B3LYP excited state frequencies and intensities, as well as modelled vibronic interactions. Dissociation of 9-methylanthracenium is also observed at high visible-photon energies, resulting in the loss of either CH{sub 2} or CH{sub 3}. The relevance of these spectra, and the spectra of other polycyclic aromatic hydrocarbon radical cations, to the largely unassigned diffuse interstellar bands, is discussed.

  14. Peace journalism and radical media ethics

    Directory of Open Access Journals (Sweden)

    Marta Natalia Lukacovic

    2016-10-01

    Full Text Available The radical characteristics of peace journalism position it as a model that expands the current understandings of normative media theory. Peace journalism echoes the most innovative calls of media ethicists, such as the proposition of radical media ethics. This idea asserts the necessity to expand media ethics to better fit the globalized and democratized media landscape, which is enabled by contemporary new media technologies. Essentially a global shift, among professionals as well as regular citizen-communicators, should advance towards conflict sensitivity in order to transcend the culturally violent elements of covering conflicts. Similar efforts will bring numerous challenges, however, these efforts are tremendously worthwhile with their potential to assist the creation of more peace-prone global societies.

  15. Radical pancreatectomy: postoperative evaluation by CT

    Energy Technology Data Exchange (ETDEWEB)

    Heiken, J.P.; Balfe, D.M.; Picus, D.; Scharp, D.W.

    1984-10-01

    Twenty-four patients who had undergone radical pancreatic resection were evaluated by CT one week to 11 years after surgery. Eighteen patients had had the Whipple procedure; six had had total pancreatectomy. The region between the aorta and superior mesenteric artery, previously occupied by the uncinate process of the pancreas, is an important area to evaluate for tumor recurrence because periampullary tumors tend to metastasize to the lymph nodes in this region. Tumor recurrence here is readily detectable by CT since radical pancreatectomy leaves this area area free of soft tissue attenuation material. CT demonstrated postoperative complications or tumor recurrence in 16 of the 24 patients and was 100% accurate in patients who had follow-up.

  16. International Radical Cystectomy Consortium: A way forward

    Directory of Open Access Journals (Sweden)

    Syed Johar Raza

    2014-01-01

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

  17. Coming to Grips with Radical Social Constructivisms

    Science.gov (United States)

    Phillips, D. C.

    This essay distinguishes two broad groups - psychological constructivists and social constructivists - but focusses upon the second of these, although it is stressed that there is great within group variation. More than half of the paper is devoted to general clearing of the ground, during which the reasons for the growing acrimony in the debates between social constructivists and their opponents are assessed, an important consequence of these debates for education is discussed, and an examination is carried out of the radical social constructivist tendency to make strong and exciting but untenable claims which are then backed away from (a tendency which is documented by a close reading of the early pages in Bloors classic book). The last portion of the essay focuses upon social constructivist accounts of the causes of belief in science - the more radical of which denegrate the role of warranting reasons, and which give an exalted place to quasi-anthropological or sociological studies of scientific communities.

  18. Radical pancreatectomy: postoperative evaluation by CT

    International Nuclear Information System (INIS)

    Heiken, J.P.; Balfe, D.M.; Picus, D.; Scharp, D.W.

    1984-01-01

    Twenty-four patients who had undergone radical pancreatic resection were evaluated by CT one week to 11 years after surgery. Eighteen patients had had the Whipple procedure; six had had total pancreatectomy. The region between the aorta and superior mesenteric artery, previously occupied by the uncinate process of the pancreas, is an important area to evaluate for tumor recurrence because periampullary tumors tend to metastasize to the lymph nodes in this region. Tumor recurrence here is readily detectable by CT since radical pancreatectomy leaves this area area free of soft tissue attenuation material. CT demonstrated postoperative complications or tumor recurrence in 16 of the 24 patients and was 100% accurate in patients who had follow-up

  19. EPR study of free radicals in bread

    Science.gov (United States)

    Yordanov, Nicola D.; Mladenova, Ralitsa

    2004-05-01

    The features of the recorded EPR spectra of paramagnetic species formed in bread and rusk are reported. The appearance of free radicals in them is only connected with their thermal treatment since the starting materials (flour and grains) exhibit very weak EPR signal. The obtained EPR spectra are complex and indicate that: (i) the relative number of paramagnetic species depends on the temperature and treating time of the raw product; (ii) the g-values are strongly temperature dependent with a tendency to coincide at t≥220 °C. Because of the relatively low (150-220 °C) temperature of thermal treatment, the studied free radicals can be assumed to appear in the course of the browning (Maillard) reaction and not to the carbonization of the material.

  20. EARLY POSTOPERATIVE COMPLICATIONS AFTER RADICAL CYSTECTOMY

    Directory of Open Access Journals (Sweden)

    V. O. Mager

    2014-08-01

    Full Text Available Radical cystectomy (RCE is associated with a considerable number of early postoperative complications as before. Based on 10 years’ experience, this paper demonstrates the frequency (33.9 % and types of early complications following RCE, as well as postoperative mortality (5.5 % and its resulting causes. Although postoperative mortality is relatively low today, the frequency of early postoperative complications remains high as before.

  1. Hydroxyl free radical production during torsional phacoemulsification.

    Science.gov (United States)

    Aust, Steven D; Hebdon, Thomas; Humbert, Jordan; Dimalanta, Ramon

    2010-12-01

    To quantitate free radical generation during phacoemulsification using an ultrasonic phacoemulsification device that includes a torsional mode and evaluate tip designs specific to the torsional mode. Chemistry and Biochemistry Department, Utah State University, Logan, Utah, USA. Experimental study. Experiments were performed using the Infiniti Vision System and OZil handpiece. Hydroxyl radical concentrations in the aspirated irrigation solution during torsional phacoemulsification were quantitated as nanomolar malondialdehyde (nM MDA) and determined spectrophotometrically using the deoxyribose assay. The mean free radical production during phacoemulsification with torsional modality at 100% amplitude was 30.1 nM MDA ± 5.1 (SD) using a 0.9 mm 45-degree Kelman tapered ABS tip. With other tip designs intended for use with the torsional modality, free radical production was further reduced when fitted with the 0.9 mm 45-degree Kelman mini-flared ABS tip (13.2 ± 5.6 nM MDA) or the 0.9 mm 45-degree OZil-12 mini-flared ABS tip (14.3 ± 6.7 nM MDA). Although the measurements resulting from the use of the latter 2 tips were not statistically significantly different (P ≈ .25), they were different from those of the tapered tip (P<.0001). The MDA concentration in the aspirated irrigation solution using the torsional modality was approximately one half that reported for the handpiece's longitudinal modality in a previous study using the same bent-tip design (Kelman tapered, P<.0001). The level of MDA was further reduced approximately one half with torsional-specific tips. Copyright © 2010 ASCRS and ESCRS. Published by Elsevier Inc. All rights reserved.

  2. How Hume's Philosophy Informed Radical Behaviorism.

    Science.gov (United States)

    Nuzzolilli, Andrew E; Diller, James W

    2015-05-01

    The present paper analyzes consistencies between the philosophical systems of David Hume and B. F. Skinner, focusing on their conceptualization of causality and attitudes about scientific behavior. The ideas that Hume initially advanced were further developed in Skinner's writings and shaped the behavior-analytic approach to scientific behavior. Tracing Skinner's logical antecedents allows for additional historical and philosophical clarity when examining the development of radical behaviorism.

  3. Western Radicalization: Rethinking the Psychology of Terrorism

    Science.gov (United States)

    2017-03-01

    to do so, they assert, locks both the researcher and the research subject into a “spiral of ignorance and suspicion.” Moreover, “social identity ...percentage of firefighters who commit this type of arson do so to establish an identity and sense of belonging. Similarly, disconnected Westerners...percentage of firefighters who commit this type of arson do so to establish an identity and sense of belonging. Similarly, disconnected Westerners radicalize

  4. Computed tomography after radical pancreaticoduodenectomy (Whipple's procedure)

    International Nuclear Information System (INIS)

    Smith, S.L.; Hampson, F.; Duxbury, M.; Rae, D.M.; Sinclair, M.T.

    2008-01-01

    Whipple's procedure (radical pancreaticoduodenectomy) is currently the only curative option for patients with periampullary malignancy. The surgery is highly complex and involves multiple anastomoses. Complications are common and can lead to significant postoperative morbidity. Early detection and treatment of complications is vital, and high-quality multidetector computed tomography (MDCT) is currently the best method of investigation. This review outlines the surgical technique and illustrates the range of normal postoperative appearances together with the common complications

  5. 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

  6. Free radicals induced archive paper by irradiation

    International Nuclear Information System (INIS)

    Cutrubinis, M.; Moise, I.V.; Negut, C.D.; Georgescu, R.; Suvaila, R.; Virgolici, M.; Manea, M.M.

    2011-01-01

    Complete text of publication follows. Irradiation of archive paper (document archives of institutions, companies etc. and library or museum collections of books and documents) can solve the problems related to the bio-deterioration and bio-contamination of paper and sometimes save valuable cultural heritage paper items. For valuable paper items care should be taken to the degradation induced instantly by the ionising radiation to the cellulosic support and also to the long term post-irradiation effects. The free radicals formed due to the irradiation treatment could contribute to instant degradation of paper. Part of them are also trapped for months and years after irradiation and they could be related to the post-irradiation effects in paper items. In this study, different sorts of cellulosic support samples (soft wood and hard wood cellulose, contemporary paper, paper from archives and from collections etc.) have been irradiated with dosis up to 100 kGy and the radiation induced free radicals have been measured by ESR spectrometry. The ESR signals have shown the type and quantity of radiation induced free radicals. Their study can be used for a realistic estimation of the degradative effect of the ionising radiation treatment of archive paper.

  7. Complications of Radical Cystectomy and Orthotopic Reconstruction

    Directory of Open Access Journals (Sweden)

    Wei Shen Tan

    2015-01-01

    Full Text Available Radical cystectomy and orthotopic reconstruction significant morbidity and mortality despite advances in minimal invasive and robotic technology. In this review, we will discuss early and late complications, as well as describe efforts to minimize morbidity and mortality, with a focus on ileal orthotopic bladder substitute (OBS. We summarise efforts to minimize morbidity and mortality including enhanced recovery as well as early and late complications seen after radical cystectomy and OBS. Centralisation of complex cancer services in the UK has led to a fall in mortality and high volume institutions have a significantly lower rate of 30-day mortality compared to low volume institutions. Enhanced recovery pathways have resulted in shorter length of hospital stay and potentially a reduction in morbidity. Early complications of radical cystectomy occur as a direct result of the surgery itself while late complications, which can occur even after 10 years after surgery, are due to urinary diversion. OBS represents the ideal urinary diversion for patients without contraindications. However, all patients with OBS should have regular long term follow-up for oncological surveillance and to identify complications should they arise.

  8. Radical Homemaking in Contemporary American Environmental Fiction

    Directory of Open Access Journals (Sweden)

    Kristin J. Jacobson

    2018-02-01

    Full Text Available Ursula K. Heise in ‘Ecocriticism and the Transnational Turn in American Studies’ critiques ‘the portrayal of multicultural and sometimes transnational nuclear families as the narrative solution to environmental and political problems’ (Heise, 2008: 383. This essay places Heise’s critique of the ‘ecological family romance’ in conversation with three other ecological domestic fictions: T. C. Boyle’s 'A Friend of the Earth' (2000, Jonathan Franzen’s 'Freedom' (2010, and Barbara Kingsolver’s 'Flight Behavior' (2012. Heise’s critique and Shannon Hayes’ 'Radical Homemakers' (2010 frame my close readings of the novels’ interconnected themes of radical homemaking, transnationalism, and environmentalism. My reading of the novels highlights their shared use of marginalized, racially-other characters to develop their entwined romantic and environmental plots (Lalitha in 'Freedom', several minor characters in 'A Friend of the Earth', and Ovid in 'Flight Behavior' and their use of sentimental deaths, especially of key female characters (Lalitha in Freedom, Sierra in A Friend of the Earth, and Dellarobia’s uncertain fate in Flight Behavior. By adopting the sentimental, domestic romance plot for ecological aims, the three novels highlight how environmental aims get stymied when cultural and ecological diversity are relegated to the margins. They also suggest that more is gained than lost through their use of ecological allegory. While the fictions do not offer solutions, they do push their readers to confront the Anthropocene’s ecological realities and their radical domestic-environmental politics.

  9. 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.

  10. Laparoscopic radical prostatectomy in the canine model.

    Science.gov (United States)

    Price, D T; Chari, R S; Neighbors, J D; Eubanks, S; Schuessler, W W; Preminger, G M

    1996-12-01

    The purpose of this study was to determine the feasibility of performing laparoscopic radical prostatectomy in a canine model. Laparoscopic radical prostatectomy was performed on six adult male canines. A new endoscopic needle driver was used to construct a secure vesicourethral anastomosis. Average operative time required to complete the procedure was 304 min (range 270-345 min). Dissection of the prostate gland took an average of 67 min (range 35-90 min), and construction of the vesicourethral anastomosis took 154 min (rage 80-240 min). There were no intraoperative complications and only one postoperative complication (anastomotic leak). Five of the six animals recovered uneventfully from the procedure, and their foley catheters were removed 10-14 days postoperatively after a retrograde cystourethrogram demonstrated an intact vesicourethral anastomosis. Four (80%) of the surviving animals were clinically continent within 10 days after catheter removal. Post mortem examination confirmed that the vesicourethral anastomosis was intact with no evidence of urine extravasation. These data demonstrate the feasibility of laparoscopic radical prostatectomy in a canine model, and suggest that additional work with this technique should be continued to develop its potential clinical application.

  11. Radical inactivation of a biological sulphydryl molecule

    International Nuclear Information System (INIS)

    Lin, W.S.; Lal, M.; Gaucher, G.M.; Armstrong, D.A.

    1977-01-01

    Reactive species produced from the free radical-induced chain oxidation of low molecular weight sulphydryl-containing molecules in aerated solutions deactivate the sulphydryl-containing enzyme papain, forming both reparable mixed disulphides and non-reparable products. This inactivation is highly efficient for penicillamine and glutathione, but almost negligible with cysteine, which is a protector of papain for [cysteine] / [papain] >= 5 under all conditions used. In the case of glutathione, superoxide dismutase caused only a small reduction in the inactivation and peroxide yields were small, implying that the deactivating species are not .O 2 - but RSOO. radicals or products from them. For penicillamine, however, dimutase was highly effective and the peroxide yields were relatively large, demonstrating that .O 2 - or a radical with similar capabilities for forming H 2 O 2 and being deactivated by dismutase was involved. Although in the presence of dismutase penicillamine is a better protector of non-reparable papain inactivation than glutathione, it suffers from a deficiency in that the papain-penicillamine mixed disulphide, which is always formed, cannot be repaired by spontaneous reaction with RSH molecules. (author)

  12. 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…

  13. 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...

  14. 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.

  15. 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

  16. Reactions of melatonin with radicals in deoxygenated aqueous solution

    International Nuclear Information System (INIS)

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

    1998-01-01

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

  17. 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.

  18. 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.

  19. Hypochlorite and superoxide radicals can act synergistically to induce fragmentation of hyaluronan and chondroitin sulphates

    DEFF Research Database (Denmark)

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

    2004-01-01

    at pH 7.4). Exposure of glycosaminoglycans to a MPO-H2O2-Cl- system or reagent HOCl generates long-lived chloramides [R-NCl-C(O)-R'] derived from the glycosamine N-acetyl functions. Decomposition of these species by transition metal ions gives polymer-derived amidyl (nitrogen-centred) radicals [R......-carboxybenzyl)hyponitrite] was demonstrated to be entirely chloramide dependent as no fragmentation occurred with the native polymers or when the chloramides were quenched by prior treatment with methionine. EPR spin-trapping experiments using 5,5-dimethyl1-pyrroline-N-oxide and 2-methyl-2-nitrosopropane have...

  20. Total free radical species and oxidation equivalent in polluted air.

    Science.gov (United States)

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

    2017-12-31

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

  1. Electron spin resonance study of radicals in irradiated polyethylene

    International Nuclear Information System (INIS)

    Fujimura, Takashi

    1979-02-01

    In order to elucidate radiation effect in polyethylene, the nature and behavior of radicals produced in polyethylene and the model compound of polyethylene irradiated at 77 0 K were studied by using electron spin resonance. The structure of radical pairs, which are composed of two radicals produced very closely each other, was investigated in drawn polyethylene and the single crystal of n-eicosane. The radical pairs of intrachain type and interchain type were found in polyethylene and n-eicosane respectively. It was suggested that these two types of radical pairs are the precursors of double bonds and crosslinks respectively. The thermal decay reactions of radicals themselves produced in irradiated polyethylene were investigated. It was made clear that the short range distances between two radicals play an important role in the decay reaction of alkyl radicals at low temperatures. The trapping regions of radicals were studied and it was clarified that allyl radicals, which are produced by the reaction of alkyl radicals with double bonds, are trapped both in the crystalline and non-crystalline regions. (author)

  2. OH radical induced depolymerization of poly(methacrylic acid)

    Science.gov (United States)

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

    1999-05-01

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

  3. Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

    International Nuclear Information System (INIS)

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

    1992-01-01

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

  4. ESR investigation of radicals formed in γ-irradiated vinylidene fluoride based copolymer: P(VDF-co-HFP)

    International Nuclear Information System (INIS)

    Dumas, Ludovic; Albela, Belén; Bonneviot, Laurent; Portinha, Daniel; Fleury, Etienne

    2013-01-01

    Samples of copolymer based on vinylidene fluoride and hexafluoropropene P(VDF-co-HFP) were exposed to γ-radiation performed under an inert atmosphere and the total amount of radicals was quantified by electron spin resonance spectroscopy (ESR). An in-depth study of recorded ESR spectra allowed the identification of several types of radical species formed during radiolysis. Starting from an ESR simulation model established for irradiated PVDF, seven radical species have been identified in the case of P(VDF-co-HFP): five of them are related to the VDF units while the two others are derived from the HFP unit. The model used to simulate the complex superimposed ESR signals is presented. The proportions of each species are discussed and correlated to the amount of HFP units contained in the copolymer, and to the stability of each species depending on their local environment. Furthermore, the evolution of radical density with radiation dose and the decay resulting from annealing at a given temperature are presented. Corresponding spectral evolution shows the progressive predominance of most stable species. - Highlights: ► ESR signal of γ-irradiated P(vinylidene fluoride-co-hexafluoropropene) containing 6 wt% of hexafluoropropene is modeled. ► The formation of seven major radical species is proposed for the first time. ► Despite a low comonomer content, 43% of radicals are localized on hexafluoropropene. ► Effect of dose and annealing highlight radical stability. ► Radical stability is found to depend on both chemical environment and chain location

  5. Influence of the medium on the reaction rate of the t-butoxyl radical with iron(II)

    International Nuclear Information System (INIS)

    Mihaljevic, B.; Razem, D.

    2002-01-01

    Complete text of publication follows. Tert-butoxyl radicals (t-BuO.) were generated by homolytic photodecomposition of di-tert-butylperoxide using ruby laser flashes at 347 nm. The reaction of t-BuO. radicals with Fe 2+ was studied under pseudo-first order conditions. The quantum yield Φ(Fe 3+ ) was determined by measuring the absorbance of Fe 3+ ion as [FeCl] 2+ complex at 360 nm 2 μs after the flash. According to the equation derived from the reaction scheme, the rate constant k 3 was obtained from the relative rate constant k r (k r =k 0 /k 3 ) and the value of k 0 ; the latter refers to the overall rate of the competing disappearance of t-BuO. radicals from the system (reaction 2), including the highest contribution of β-cleavage. The rate constant k 0 was determined using diphenylmethanol instead of Fe 2+ . The known rate constant of the reaction of t-BuO. radical with diphenylmethanol giving ketyl radicals (6.9 x 10 6 dm 3 mol -1 s -1 ) was applied. The quantum yield of ketyl radicals was determined by measuring the maximum of absorbance at 535 nm. At acid concentration of 0.023 mol dm -3 HCl the rate constant k 3 = 3.4 x 10 8 dm 3 mol -1 s -1 was determined. The relative rate constant increased with an increase of the hydrochloric acid concentration which has been ascribed to the lower stability of t-BuO. radical at higher acidity of the medium. The effect of polarity of the medium on the reaction rate was also determined. Decreasing k 3 in media of increasing polarity were explained by increasing of the β-scission rate of t-BuO. radical with increasing polarity of the medium

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

    Directory of Open Access Journals (Sweden)

    Simson Tarigan

    1999-03-01

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

  7. Evaluation of Both Free Radical Scavenging Capacity and Antioxidative Damage Effect of Polydatin.

    Science.gov (United States)

    Jin, Ju; Li, Yan; Zhang, Xiuli; Chen, Tongsheng; Wang, Yifei; Wang, Zhiping

    Cellular damage such as oxidation and lipid peroxidation, and DNA damage induced by free-radicals like reactive oxygen species, has been implicated in several diseases. Radicals generated by 2,2-azobis (2-amidino-propane) dihydrochloride (AAPH) are similar to physiologically active ones. In this study we found that polydatin, a resveratrol natural precursor derived from many sources, has the capacity of free radical scavenging and antioxidative damage. Using free radical scavenging assays, the IC50 values of polydatin were 19.25 and 5.29 μg/ml with the DPPH and the ABTS assay, respectively, and 0.125 mg ferrous sulfate/1 mg polydatin with the FRAP assay. With the AAPH-induced oxidative injury cell model assay, polydatin showed a strong protective effect against the human liver tumor HepG2 cell oxidative stress damage. These results indicate that the antioxidant properties of polydatin have great potential for use as an alternative to more toxic synthetic antioxidants as an additive in food, cosmetics and pharmaceutical preparations for the treatment of oxidative diseases.

  8. 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)

  9. Detecting free radicals in biochars and determining their ability to inhibit the germination and growth of corn, wheat and rice seedlings.

    Science.gov (United States)

    Liao, Shaohua; Pan, Bo; Li, Hao; Zhang, Di; Xing, Baoshan

    2014-01-01

    Biochar can benefit human society as a carbon-negative material and soil amendment. However, negative biochar impacts on plant germination and growth have been observed, and they have not been fully explained. Therefore, protocols to avoid these risks cannot be proposed. We hypothesized that the free radicals generated during charring may inhibit plant germination and growth. Significant electron paramagnetic resonance (EPR) signals were observed in the biochars derived from several types of common biomass (corn stalk, rice, and wheat straws) and the major biopolymer components of biomass (cellulose and lignin), but not in the original materials, suggesting the ubiquitous presence of free radicals in biochars. EPR signal intensity increased with increasing pyrolysis temperature, and it was dominantly contributed by oxygen centered in the mixture of oxygen- and carbon-centered free radicals as the temperature increased. The free radicals in biochars induced strong ·OH radicals in the aqueous phase. Significant germination inhibition, root and shoot growth retardation and plasma membrane damage were observed for biochars with abundant free radicals. Germination inhibition and plasma membrane damage were not obvious for biochars containing low free radicals, but they were apparent at comparable concentrations of conventional contaminants, such as heavy metals and polyaromatic hydrocarbons. The potential risk and harm of relatively persistent free radicals in biochars must be addressed to apply them safely.

  10. Even free radicals should follow some rules: a guide to free radical research terminology and methodology.

    Science.gov (United States)

    Forman, Henry Jay; Augusto, Ohara; Brigelius-Flohe, Regina; Dennery, Phyllis A; Kalyanaraman, Balaraman; Ischiropoulos, Harry; Mann, Giovanni E; Radi, Rafael; Roberts, L Jackson; Vina, Jose; Davies, Kelvin J A

    2015-01-01

    Free radicals and oxidants are now implicated in physiological responses and in several diseases. Given the wide range of expertise of free radical researchers, application of the greater understanding of chemistry has not been uniformly applied to biological studies. We suggest that some widely used methodologies and terminologies hamper progress and need to be addressed. We make the case for abandonment and judicious use of several methods and terms and suggest practical and viable alternatives. These changes are suggested in four areas: use of fluorescent dyes to identify and quantify reactive species, methods for measurement of lipid peroxidation in complex biological systems, claims of antioxidants as radical scavengers, and use of the terms for reactive species. Copyright © 2014 Elsevier Inc. All rights reserved.

  11. 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.

  12. 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.)

  13. Polysulfides and products of H2S/S-nitrosoglutathione in comparison to H2S, glutathione and antioxidant Trolox are potent scavengers of superoxide anion radical and produce hydroxyl radical by decomposition of H2O2.

    Science.gov (United States)

    Misak, Anton; Grman, Marian; Bacova, Zuzana; Rezuchova, Ingeborg; Hudecova, Sona; Ondriasova, Elena; Krizanova, Olga; Brezova, Vlasta; Chovanec, Miroslav; Ondrias, Karol

    2018-06-01

    Exogenous and endogenously produced sulfide derivatives, such as H 2 S/HS - /S 2- , polysulfides and products of the H 2 S/S-nitrosoglutathione interaction (S/GSNO), affect numerous biological processes in which superoxide anion (O 2 - ) and hydroxyl (OH) radicals play an important role. Their cytoprotective-antioxidant and contrasting pro-oxidant-toxic effects have been reported. Therefore, the aim of our work was to contribute to resolving this apparent inconsistency by studying sulfide derivatives/free radical interactions and their consequent biological effects compared to the antioxidants glutathione (GSH) and Trolox. Using the electron paramagnetic resonance (EPR) spin trapping technique and O 2 - , we found that a polysulfide (Na 2 S 4 ) and S/GSNO were potent scavengers of O 2 - and cPTIO radicals compared to H 2 S (Na 2 S), GSH and Trolox, and S/GSNO scavenged the DEPMPO-OH radical. As detected by the EPR spectra of DEPMPO-OH, the formation of OH in physiological solution by S/GSNO was suggested. All the studied sulfide derivatives, but not Trolox or GSH, had a bell-shaped potency to decompose H 2 O 2 and produced OH in the following order: S/GSNO > Na 2 S 4  ≥ Na 2 S > GSH = Trolox = 0, but they scavenged OH at higher concentrations. In studies of the biological consequences of these sulfide derivatives/H 2 O 2 properties, we found the following: (i) S/GSNO alone and all sulfide derivatives in the presence of H 2 O 2 cleaved plasmid DNA; (ii) S/GSNO interfered with viral replication and consequently decreased the infectivity of viruses; (iii) the sulfide derivatives induced apoptosis in A2780 cells but inhibited apoptosis induced by H 2 O 2 ; and (iv) Na 2 S 4 modulated intracellular calcium in A87MG cells, which depended on the order of Na 2 S 4 /H 2 O 2 application. We suggest that the apparent inconsistency of the cytoprotective-antioxidant and contrasting pro-oxidant-toxic biological effects of sulfide derivatives results from their time

  14. Radiation Protection Using Carbon Nanotube Derivatives

    Science.gov (United States)

    Conyers, Jodie L., Jr.; Moore, Valerie C.; Casscells, S. Ward

    2010-01-01

    BHA and BHT are well-known food preservatives that are excellent radical scavengers. These compounds, attached to single-walled carbon nanotubes (SWNTs), could serve as excellent radical traps. The amino-BHT groups can be associated with SWNTs that have carbolyxic acid groups via acid-base association or via covalent association. The material can be used as a means of radiation protection or cellular stress mitigation via a sequence of quenching radical species using nano-engineered scaffolds of SWNTs and their derivatives. It works by reducing the number of free radicals within or nearby a cell, tissue, organ, or living organism. This reduces the risk of damage to DNA and other cellular components that can lead to chronic and/or acute pathologies, including (but not limited to) cancer, cardiovascular disease, immuno-suppression, and disorders of the central nervous system. These derivatives can show an unusually high scavenging ability, which could prove efficacious in protecting living systems from radical-induced decay. This technique could be used to protect healthy cells in a living biological system from the effects of radiation therapy. It could also be used as a prophylactic or antidote for radiation exposure due to accidental, terrorist, or wartime use of radiation- containing weapons; high-altitude or space travel (where radiation exposure is generally higher than desired); or in any scenario where exposure to radiation is expected or anticipated. This invention s ultimate use will be dependent on the utility in an overall biological system where many levels of toxicity have to be evaluated. This can only be assessed at a later stage. In vitro toxicity will first be assessed, followed by in vivo non-mammalian screening in zebra fish for toxicity and therapeutic efficacy.

  15. 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.

  16. Resonance Raman study of benzyl radical

    DEFF Research Database (Denmark)

    Langkilde, F.W.; Bajdor, K.; Wilbrandt, R.

    1992-01-01

    Time-resolved resonance Raman spectra are obtained of benzyl radicals created by laser flash photolysis of benzylchloride and diphenylacetone in solution. The spectra are obtained in resonance with the intense 2 2A2-1 B-2(2) transition of benzyl. The strong Raman bands are assigned to totally...... symmetric a1 modes. The remaining observed bands are tentatively assigned to fundamental modes of b1, a2, and b2 symmetry, and to overtones and combinations. The resonance Raman spectra are found to be quite different from previous fluorescence spectra of benzyl, and the origins of these differences...

  17. Dissociative Photoionization of the Elusive Vinoxy Radical.

    Science.gov (United States)

    Adams, Jonathan D; Scrape, Preston G; Lee, Shih-Huang; Butler, Laurie J

    2017-08-24

    These experiments report the dissociative photoionization of vinoxy radicals to m/z = 15 and 29. In a crossed laser-molecular beam scattering apparatus, we induce C-Cl bond fission in 2-chloroacetaldehyde by photoexcitation at 157 nm. Our velocity measurements, combined with conservation of angular momentum, show that 21% of the C-Cl photofission events form vinoxy radicals that are stable to subsequent dissociation to CH 3 + CO or H + ketene. Photoionization of these stable vinoxy radicals, identified by their velocities, which are momentum-matched with the higher-kinetic-energy Cl atom photofragments, shows that the vinoxy radicals dissociatively photoionize to give signal at m/z = 15 and 29. We calibrated the partial photoionization cross section of vinoxy to CH 3 + relative to the bandwidth-averaged photoionization cross section of the Cl atom at 13.68 eV to put the partial photoionization cross sections on an absolute scale. The resulting bandwidth-averaged partial cross sections are 0.63 and 1.3 Mb at 10.5 and 11.44 eV, respectively. These values are consistent with the upper limit to the cross section estimated from a study by Savee et al. on the O( 3 P) + propene bimolecular reaction. We note that the uncertainty in these values is primarily dependent on the signal attributed to C-Cl primary photofission in the m/z = 35 (Cl + ) time-of-flight data. While the value is a rough estimate, the bandwidth-averaged partial photoionization cross section of vinoxy to HCO + calculated from the signal at m/z = 29 at 11.53 eV is approximately half that of vinoxy to CH 3 + . We also present critical points on the potential energy surface of the vinoxy cation calculated at the G4//B3LYP/6-311++G(3df,2p) level of theory to support the observation of dissociative ionization of vinoxy to both CH 3 + and HCO + .

  18. Processing of free radical damaged DNA bases

    International Nuclear Information System (INIS)

    Wallace, S.

    2003-01-01

    Free radicals produced during the radiolysis of water gives rise to a plethora of DNA damages including single strand breaks, sites of base loss and a wide variety of purine and pyrimidine base lesions. All these damages are processed in cells by base excision repair. The oxidative DNA glycosylases which catalyze the first step in the removal of a base damage during base excision repair evolved primarily to protect the cells from the deleterious mutagenic effects of single free radical-induced DNA lesions arising during oxidative metabolism. This is evidenced by the high spontaneous mutation rate in bacterial mutants lacking the oxidative DNA glycosylases. However, when a low LET photon transverses the DNA molecule, a burst of free radicals is produced during the radiolysis of water that leads to the formation of clustered damages in the DNA molecule, that are recognized by the oxidative DNA glycosylases. When substrates containing two closely opposed sugar damages or base and sugar damages are incubated with the oxidative DNA glycosylases in vitro, one strand is readily incised by the lyase activity of the DNA glycosylase. Whether or not the second strand is incised depends on the distance between the strand break resulting from the incised first strand and the remaining DNA lesion on the other strand. If the lesions are more than two or three base pairs apart, the second strand is readily cleaved by the DNA glycosylase, giving rise to a double strand break. Even if the entire base excision repair system is reconstituted in vitro, whether or not a double strand break ensues depends solely upon the ability of the DNA glycosylase to cleave the second strand. These data predicted that cells deficient in the oxidative DNA glycosylases would be radioresistant while those that overproduce an oxidative DNA glycosylase would be radiosensitive. This prediction was indeed borne in Escherichia coli that is, mutants lacking the oxidative DNA glycosylases are radioresistant

  19. 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.

  20. Antioxidant activity of the giant jellyfish Nemopilema nomurai measured by the oxygen radical absorbance capacity and hydroxyl radical averting capacity methods.

    Science.gov (United States)

    Harada, Kazuki; Maeda, Toshimichi; Hasegawa, Yoshiro; Tokunaga, Takushi; Ogawa, Shinya; Fukuda, Kyoko; Nagatsuka, Norie; Nagao, Keiko; Ueno, Shunshiro

    2011-01-01

    The giant jellyfish Nemopilema nomurai (reaching sizes of up to 2 m diameter and 150 kg), which forms dense blooms, has caused extensive damage to fisheries by overloading trawl nets, while its toxic nematocysts cause dermatological symptoms. Giant jellyfish are currently discarded on the grounds of pest control. However, the giant jellyfish is considered to be edible and is part of Chinese cuisine. Therefore, we investigated whether any benefits for human health may be derived from consumption of the jellyfish in order to formulate medicated diets. Antioxidant activity of Nemopilema nomurai was measured using the oxygen radical absorbance capacity (ORAC) and hydroxyl radical averting capacity (HORAC) methods. Based on the results, the ORAC value of the giant jellyfish freeze-dried sample was 541 µmol trolox equivalent (TE)/100 g and the HORAC value was 3,687 µmol gallic acid equivalent (GAE)/100 g. On the other hand, the IC50 value of hydroxyl radical scavenging activity measured by using the electron spin resonance method was 3.3%. In conclusion, the results suggest that the freeze-dried powder of the giant jellyfish Nemopilema nomurai is a potentially beneficial food for humans.

  1. Exploración del efecto protector frente a radicales libres de derivados de la uva (Vitis vinifera L. Cv. Tannat en Saccharomyces cerevisiae Analysis of a putative protection against free radicals by grape derivatives (Vitis vinifera L. Cv. Tannat in Saccharomyces cerevisiae

    Directory of Open Access Journals (Sweden)

    N. Bracesco

    2007-03-01

    Full Text Available Se exploró un posible efecto protector del genoma por parte de un derivado de la uva (vino Tannat. Se utilizaron poblaciones celulares haploides y diploides de Saccharomyces cerevisiae como modelo eucariota. Muestras celulares se expusieron a H2O2 en medio nutriente. El ADN se analizó por densitometría láser, luego de su aislamiento y separación por electroforesis con campos pulsados. Se aplicó la distribución de Poisson para la determinación de roturas dobles. El número de roturas dobles del ADN y la frecuencia mutagénica aumentaron en función de la dosis de H2O2, disminuyendo la probabilidad de sobrevida. La combinación de H2O2 con vino Tannat aumentó significa-tivamente la probabilidad de sobrevida y disminuyó el número de roturas dobles. No se observó efecto mutagénico por el vino Tannat. Estos efectos pudieron simularse utilizando altas concentraciones de α-tocoferol. Los resultados indican que un derivado de Vitis vinifera puede, en ciertas condiciones, disminuir las dobles roturas de ADN producidas por el H2O2 e incrementar las probabilidades de sobrevida celular. Los blancos involucrados podrían ser, entre otros, componentes intracelulares de las cascadas redox y/o enzimas de reparación del ADN.The aim of this work was to analyse a possible genome protection provided by a grape derivative (Tannat wine in yeast cell populations exposed to H2O2. Haploid and diploid strains of Saccharomyces cerevisiae were used as eukaryotic model. Cell samples were exposed to H2O2 in a nutrient medium. Chromosomal DNA was analysed after isolation and separation by pulsed field electrophoresis. Double strand breaks were determined by laser densitometry and application of Poisson distribution. Both haploid and diploid cells showed H2O2 dose dependent DNA fractionation, as well as an increase of lethal -and mutation- events. Upon combination of the Tannat wine and H2O2 a significant decrease of double strand breaks was observed, in

  2. Interactions of coffee and bread crust melanoidins with hydroxycinnamic and hydroxybenzoic acids in aqueous radical environment.

    Science.gov (United States)

    Çelik, Ecem Evrim; Rubio, Jose Manuel Amigo; Andersen, Mogens Larsen; Gökmen, Vural

    2018-06-01

    The interactions of coffee and bread crust melanoidins with hydroxycinnamic and hydroxybenzoic acids (HCA/HBA) containing different numbers of -OH and -OCH₃ groups localized at different positions on the aromatic ring were investigated. By doing so, mechanism of the interactions was intended to be explained with a structural approach. Experimental studies were carried out in DPPH radical medium. Chemometric methods were used for experimental design and multivariate data analysis. Area under the curve (AUC) values calculated from the plots of time versus inhibition (%) for coffee and bread crust melanoidins and HCA/HBA derivatives were ranged between 6532 ± 97-19,106 ± 85, 3997 ± 102-7565 ± 159 and - 1678 ± 81-22,486 ± 119, respectively. Synergistic interactions were revealed for both coffee and bread crust melanoidins and HCA/HBA derivatives. The significance of the concentrations of coffee and bread crust melanoidins on radical scavenging activity was clearly centered from the scores plots obtained via Principal component analysis (PCA). Phases of radical scavenging reactions were also revealed from the loadings plots. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J. [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico); Gonzalez, Ignacio [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, Area de Electroquimica, Apartado Postal 55-534, 09340, D.F. (Mexico); Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos [Instituto de Quimica e Biotecnologia, Universidade Federal de Alagoas, Tabuleiro do Martins, Maceio, AL, 57072-970 (Brazil); Ribeiro, Rogerio Tavares; Longo, Ricardo L. [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Navarro, Marcelo, E-mail: navarro@ufpe.b [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Frontana, Carlos, E-mail: ultrabuho@yahoo.com.m [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico)

    2010-11-30

    The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A{sup 2-} + A {yields} 2A{center_dot}{sup -}). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

  4. Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

    International Nuclear Information System (INIS)

    Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J.; Gonzalez, Ignacio; Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos; Ribeiro, Rogerio Tavares; Longo, Ricardo L.; Navarro, Marcelo; Frontana, Carlos

    2010-01-01

    The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A 2- + A → 2A· - ). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

  5. NOx removal characteristics of corona radical shower with ammonia and methylamine radical injections

    Energy Technology Data Exchange (ETDEWEB)

    Urashima, K.; Ara, M.; Chang, J.S. [McMaster Univ., Hamilton, ON (Canada). Dept. of Engineering Physics; Uchida, Y. [Aichi Inst. of Technology, (Japan). Dept. of Engineering

    2010-07-01

    Air pollutants such as nitrogen oxides (NOx) and sulfur oxides (SOx) are the major cause of acid rain. There are different types of NOx and SOx conversion techniques such as wet scrubber, selective catalytic reactor, sorbent injection, and low NOx burner. Non-thermal plasma techniques have also been utilized in commercial plants, but the energy efficiency of the non-thermal plasma reactors have not yet been optimized. The direct plasma treatments of flue gases including, the electron beam, barrier discharge and pulsed corona reactors, may lose input energy to activate unwanted components of flue gases such as carbon dioxide (CO{sub 2}) and nitrogen (N{sub 2}). The corona discharge ammonia radical shower system has demonstrated significant NOx removal with higher energy efficiency for large bench scale and pilot plant tests for combustion exhausts. An experiment has also demonstrated that methane can replace ammonia as an injection gas with less NOx removal efficiency. This paper presented an experimental investigation that compared methylamine radical injection with traditional ammonia and methane radical injections. The paper discussed the bench scale test facilities and corona radical shower plasma reactor. It was concluded that the processes to form ammonium nitrate could be observed from trace white solid particles deposited on the reactor wall as observed by scanning electron microscopy pictures. 10 refs., 5 figs., 2 appendices.

  6. Encapsulation of Gibbsite platelets with free radical and controlled radical emulsion polymerization approaches, a small review

    NARCIS (Netherlands)

    Loiko, O.P.; Spoelstra, A.B.; van Herk, A.M.; Meuldijk, J.; Heuts, J.P.A.

    2016-01-01

    Water-borne anisotropic polymer-Gibbsite latex particles were prepared by a conventional and an atom transfer radical polymerisation (ATRP) based starved-feed emulsion polymerisation without any chemical modification of the platelet surface. Anionic co-oligomers, synthesised via ATRP, were used in

  7. 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

  8. Electron spin resonance spectroscopy of organic radicals spectroscopy of organic radicals

    CERN Document Server

    Gerson, Fabian

    2006-01-01

    ""This book should serve as a comprehensive one-volume source for finding what is known about the splitting constants and g factors of virtually all types of organic radicals."" Journal of the American Chemistry Society, 2004, Vol. 126 No. 20

  9. Hydrogen Radicals, Nitrogen Radicals, and the Production of Ozone in the Middle and Upper Troposphere

    Science.gov (United States)

    Bui, T. P.

    1997-01-01

    The concentrations of hydrogen radicals, OH and HO2, in the middle and upper troposphere were measured simultaneously with those of NO, O3,CO, H20, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field.

  10. Radical constructivism and radical constructedness: Luhmann's sociology of semantics, organizations, and self-organization

    NARCIS (Netherlands)

    Leydesdorff, L.

    2012-01-01

    Context: Using radical constructivism, society can be considered from the perspective of asking the question, "Who conceives of society?" In Luhmann’s social systems theory, this question itself is considered as a construct of the communication among reflexive agents. Problem: Structuration of

  11. COST Action CM1201 "Biomimetic Radical Chemistry": free radical chemistry successfully meets many disciplines

    Czech Academy of Sciences Publication Activity Database

    Ferreri, C.; Golding, B. T.; Jahn, Ullrich; Ravanat, J. L.

    2016-01-01

    Roč. 50, Suppl 1 (2016), S112-S128 ISSN 1071-5762 Institutional support: RVO:61388963 Keywords : radical enzyme * membrane stress * phospholipid remodeling * DNA damage and repair * biomimetic models * bio-inspired synthetic methodologies Subject RIV: CC - Organic Chemistry Impact factor: 3.188, year: 2016 http://www.tandfonline.com/doi/full/10.1080/10715762.2016.1248961

  12. The mitochondrial free radical theory of aging.

    Science.gov (United States)

    Barja, Gustavo

    2014-01-01

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

  13. Fast beam studies of free radical photodissociation

    Energy Technology Data Exchange (ETDEWEB)

    Cyr, Douglas Robert [Univ. of California, Berkeley, CA (United States)

    1993-11-01

    The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward.

  14. The Rovibronic Spectra of the Cyclopentadienyl Radical

    Science.gov (United States)

    Sharma, Ketan; Miller, Terry A.; Stanton, John F.; Nesbitt, David

    2017-06-01

    Cyclopentadienyl (Cp) radical has been subject to numerous studies for the greater part of half a century. Experimental work has involved photo-electron spectroscopy, laser induced fluorescence excitation and emission, infrared absorption spectroscopy, and recently rotationally resolved spectra in the CH stretch region taken at JILA. Even more theoretical works appear in the literature, but substantial advances in computation have occurred since their completion. Cp's highly symmetric (D_{5h}) structure and doubly degenerate electronic ground (˜{X}^2E_1^{''}), which is subject to linear Jahn-Teller distortion, have been a great motivation for work on it. We have commenced new computational work to obtain a broad understanding of the electronic, vibrational, and rotational, i.e. rovibronic, structure of the Cp radical as revealed by its spectra, with particular emphasis on the new infrared spectra. The goal is to guide experiments and their analyses and reconcile results from spectroscopy and quantum chemistry calculations. T. Ichino, et al. J. Chem. Phys. 129, 084310 (2008) L. Yu, S. C. Foster, J. M. Williamson, M. C. Heaven and T. A. Miller J. Phys. Chem. 92, 4263 (1988) B. E. Applegate, A. J. Bezant and T. A. Miller J. Chem. Phys 114, 4869 (2001) D. Leicht, M. Kaufmann, G. Schwaab, and M. Havenith J. Chem. Phys. 145, 7 (2016), 074304.

  15. 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...

  16. 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.

  17. 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

  18. Fast beam studies of free radical photodissociation

    International Nuclear Information System (INIS)

    Cyr, D.R.; California Univ., Berkeley, CA

    1993-11-01

    The photodissociation of free radicals is studied in order to characterize the spectroscopy and dissociation dynamics of the dissociative electronic states in these species. To accomplish this, a novel method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with a highly complementary form of photofragment translational spectroscopy. The optical spectroscopy of transitions to dissociative states is determined by monitoring the total photofragment yield as a function of dissociation photon energy. Branching ratios to various product channels, internal energy distributions of the fragments, bond dissociation energies, and the translational energy-dependent photofragment recoil angular distributions are then determined at selected excitation energies. A detailed picture of the dissociation dynamics can then be formulated, allowing insight concerning the interactions of potential energy surfaces involved in the dissociation. After an introduction to the concepts and techniques mentioned above, the experimental apparatus used in these experiments is described in detail. The basis and methods used in the treatment of data, especially in the dissociation dynamics experiments, are then put forward

  19. Ascorbyl radical disproportionation in reverse micellar systems

    Science.gov (United States)

    Gębicki, J. L.; Szymańska-Owczarek, M.; Pacholczyk-Sienicka, B.; Jankowski, S.

    2018-04-01

    Ascorbyl radical was generated by the pulse radiolysis method and observed with the fast kinetic spectrophotometry within reverse micelles stabilized by AOT in n-heptane or by Igepal CO-520 in cyclohexane at different water to surfactant molar ratio, w0. Rate constants for the disproportionation of the ascorbyl radicals were smaller than those for intermicellar exchange for both type of reverse micelles and slower than those in homogeneous aqueous solutions. However, they increased with increasing w0 for AOT/n-heptane system, while they decreased for Igepal CO-520 system. The absorption spectra of ascorbic acid AOT/n-heptane reverse micellar system showed that the "pH" sensed by this molecule is lower than that in respective homogeneous aqueous solutions. The obtained results were rationalized taking into account three main factors (i) preferential location of ascorbic acid molecules in the interfacial region of the both types of reverse micelles; (ii) postulate that the pH of the interface is lower than that of the water pool of reverse micelles and (iii) different structure of the interface of the reverse micelles made by AOT in n-heptane and those formed by Igepal CO-520 I cyclohexane. Some possible consequences of these findings are discussed.

  20. The Prospects of Radical Change Today

    Directory of Open Access Journals (Sweden)

    Slavoj Žižek

    2018-05-01

    Full Text Available In this contribution, Slavoj Žižek takes the occasion of Marx’s bicentenary for reflecting on the prospects of radical change today. First, it is shown that under Stalinism, Lenin’s works were quoted out of context in an arbitrary way in order to legitimise arbitrary political measures. Marxism thereby became an ideology that justified brutal subjective interventions. Second, this contribution poses the question of the revolutionary subject and democracy today. It stresses the role of both contingency and strategy in revolutions. In political assemblages taking place on public squares, the inert mass of ordinary people is transubstantiated into a politically engaged united force. The basic political problem today is how to best reconfigure democracy. Third, this contribution analyses the “interesting times” we live in. These are times that feature multiple crises, right-wing populism à la Donald Trump and Marine Le Pen, the lower classes’ opposition to immigration, and the refugee crisis. Questions about human rights and their violation and about radical change need to be asked in this context.