ESR detection of free radicals produced in irradiated fresh fruits and dried foods

International Nuclear Information System (INIS)

Bustos G, E.; Gomes, V.; Garcia, F.; Azorin, J.

2007-01-01

Full text: Electron spin resonance (ESR) technique was used to measure the stability of free radicals produced by the irradiation treatment in mangoes and in four spices: black pepper, oregano, 'guajillo' chili and 'morron' chili. The ESR spectra for mangoes were scanned in three different parts from the seeds and were recorded in fresh and dried tissues. The ESR spectra in fresh tissue of no irradiated mangoes, were a sextet line signal produced by Mn 2+ ion and a singlet centered at g = 2.00 produced by the endogenous radical. New resonances were observed in the irradiated samples at 1.5 mT and 3 mT respects to the center line for right and left side. These new resonance signals were-observed for eight days in mangoes treated at 1.00 kGy, and for three days at 0.15 kGy. The resonance due to the irradiation was observed in Iyophilized mangoes only one day after the treatment, in the vacuum dried samples, no new resonances were observed. The triplet signal, as well as the central single line appeared after irradiation in black pepper, morron chili and guajillo chili. These signals were also observed in the irradiated spices at any radiation dose higher than 1.0 kGy. The signals decrease promptly, in ten days after the 'irradiation. It was not possible to observe the triplet signal in oregano, even when the samples were analyzed immediately after irradiation treatment. The only signal observed in irradiated spice was the endogenous radical. This signal increased as the radiation dose increased and decreased during storage time at room temperature. Results showed that free radicals produced in irradiated fresh fruits or dried foods have a quick recombination. It was observed that in the spices the signal remains for several weeks meanwhile only eight days in mangoes. (Author)

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-06-15

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

Radical species involved in hotwire (catalytic) deposition of hydrogenated amorphous silicon

International Nuclear Information System (INIS)

Zheng Wengang; Gallagher, Alan

2008-01-01

Threshold ionization mass spectroscopy is used to measure the radicals that cause deposition of hydrogenated amorphous silicon by 'hotwire' (HW), or 'catalytic,' chemical vapor deposition. We provide the probability of silane (SiH 4 ) decomposition on the HW, and of Si and H release from the HW. The depositing radicals, and H atoms, are measured versus conditions to obtain their radical-silane reaction rates and contributions to film growth. A 0.01-3 Pa range of silane pressures and 1400-2400 K range of HW temperatures were studied, encompassing optimum device production conditions. Si 2 H 2 is the primary depositing radical under optimum conditions, accompanied by a few percent of Si atoms and a lot of H-atom reactions. Negligible SiH n radical production is observed and only a small flux of disilane is produced, but at the higher pressures some Si 3 H n is observed. A Si-SiH 4 reaction rate coefficient of 1.65 * 10 -11 cm 3 /s and a H + SiH 4 reaction rate coefficient of 5 * 10 -14 cm 3 /s are measured

Characterization of Neutral Radicals from a Dissociative Electron Attachment Process

Science.gov (United States)

Li, Zhou; Milosavljević, Aleksandar R.; Carmichael, Ian; Ptasinska, Sylwia

2017-08-01

Despite decades of gas-phase studies on dissociative electron attachment (DEA) to various molecules, as yet there has been no direct detection and characterization of the neutral radical species produced by this process. In this study, we performed stepwise electron spectroscopy to directly measure and characterize the neutrals produced upon zero-electron-energy DEA to the model molecule, carbon tetrachloride (CCl4 ). We observed the direct yield of the trichloromethyl radical (CCl3. ) formed by DEA to CCl4 and measured the appearance energies of all the other neutral species. By combining these experimental findings with high-level quantum chemical calculations, we performed a complete analysis of both the DEA to CCl4 and the subsequent electron-impact ionization of CCl3. . This work paves the way toward a complete experimental characterization of DEA processes, which will lead to a better understanding of the low-energy electron-induced formation of radical species.

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

Energy Technology Data Exchange (ETDEWEB)

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

2012-08-15

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

ESR investigation of L-α-alanine and sucrose radicals produced by heavy-ion irradiation

International Nuclear Information System (INIS)

Nakagawa, K.; Sato, Y.

2005-01-01

We investigated sucrose and L-α-alanine radicals produced by heavy (particle) ion irradiation with various LETs (linear energy transfer). The impact of the heavy ions on the samples produced stable free radicals, which were analyzed by ESR (electron spin resonance). Identical spectra were measured after one year. The obtained spectral patterns were the same as those for helium (He), carbon (C), and neon (Ne) ions irradiation. The absorbed dose dependences for the irradiated sucrose and alanine samples were examined. The ESR response has a linear relation with the absorbed dose. The ESR response at 60 Gy was slightly lower than a linear line for sucrose; however, the response showed good linearity for the alanine. In addition, the total spin concentration obtained by heavy-ion irradiation correlated logarithmically with the LET. Qualitative ESR analyse showed that the production of sucrose and alanine radicals depended on both different particle irradiation and the LET under the same dose. Thus, the present ESR results imply that sucrose together with L-α-alanine can be used to monitor LET as well as the number of ionizing particle for the production of stable free radicals. (author)

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)

Free terminal amines in DNA-binding peptides alter the product distribution from guanine radicals produced by single electron oxidation.

Science.gov (United States)

Konigsfeld, Katie M; Lee, Melissa; Urata, Sarah M; Aguilera, Joe A; Milligan, Jamie R

2012-03-01

Electron deficient guanine radical species are major intermediates produced in DNA by the direct effect of ionizing irradiation. There is evidence that they react with amine groups in closely bound ligands to form covalent crosslinks. Crosslink formation is very poorly characterized in terms of quantitative rate and yield data. We sought to address this issue by using oligo-arginine ligands to model the close association of DNA and its binding proteins in chromatin. Guanine radicals were prepared in plasmid DNA by single electron oxidation. The product distribution derived from them was assayed by strand break formation after four different post-irradiation incubations. We compared the yields of DNA damage produced in the presence of four ligands in which neither, one, or both of the amino and carboxylate termini were blocked with amides. Free carboxylate groups were unreactive. Significantly higher yields of heat labile sites were observed when the amino terminus was unblocked. The rate of the reaction was characterized by diluting the unblocked amino group with its amide blocked derivative. These observations provide a means to develop quantitative estimates for the yields in which these labile sites are formed in chromatin by exposure to ionizing irradiation.

Spectroscopy of reactive species produced by low-energy atmospheric-pressure plasma on conductive target material surface

International Nuclear Information System (INIS)

Yamada, Hiromasa; Sakakita, Hajime; Kato, Susumu; Kim, Jaeho; Kiyama, Satoru; Fujiwara, Masanori; Itagaki, Hirotomo; Ikehara, Yuzuru; Okazaki, Toshiya; Ikehara, Sanae; Nakanishi, Hayao; Shimizu, Nobuyuki

2016-01-01

A method for blood coagulation using low-energy atmospheric-pressure plasma (LEAPP) is confirmed as an alternative procedure to reduce tissue damage caused by heat. Blood coagulation using LEAPP behaves differently depending on working gas species; helium is more effective than argon in promoting fast coagulation. To analyse the difference in reactive species produced by helium and argon plasma, spectroscopic measurements were conducted without and with a target material. To compare emissions, blood coagulation experiments using LEAPP for both plasmas were performed under almost identical conditions. Although many kinds of reactive species such as hydroxyl radicals and excited nitrogen molecules were observed with similar intensity in both plasmas, intensities of nitrogen ion molecules and nitric oxide molecules were extremely strong in the helium plasma. It is considered that nitrogen ion molecules were mainly produced by penning ionization by helium metastable. Near the target, a significant increase in the emissions of reactive species is observed. There is a possibility that electron acceleration was induced in a local electric field formed on the surface. However, in argon plasma, emissions from nitrogen ion were not measured even near the target surface. These differences between the two plasmas may be producing the difference in blood coagulation behaviour. To control the surrounding gas of the plasma, a gas-component-controllable chamber was assembled. Filling the chamber with O 2 /He or N 2 /He gas mixtures selectively produces either reactive oxygen species or reactive nitrogen species. Through selective treatments, this chamber would be useful in studying the effects of specific reactive species on blood coagulation. (paper)

Spectroscopy of reactive species produced by low-energy atmospheric-pressure plasma on conductive target material surface

Science.gov (United States)

Yamada, Hiromasa; Sakakita, Hajime; Kato, Susumu; Kim, Jaeho; Kiyama, Satoru; Fujiwara, Masanori; Itagaki, Hirotomo; Okazaki, Toshiya; Ikehara, Sanae; Nakanishi, Hayao; Shimizu, Nobuyuki; Ikehara, Yuzuru

2016-10-01

A method for blood coagulation using low-energy atmospheric-pressure plasma (LEAPP) is confirmed as an alternative procedure to reduce tissue damage caused by heat. Blood coagulation using LEAPP behaves differently depending on working gas species; helium is more effective than argon in promoting fast coagulation. To analyse the difference in reactive species produced by helium and argon plasma, spectroscopic measurements were conducted without and with a target material. To compare emissions, blood coagulation experiments using LEAPP for both plasmas were performed under almost identical conditions. Although many kinds of reactive species such as hydroxyl radicals and excited nitrogen molecules were observed with similar intensity in both plasmas, intensities of nitrogen ion molecules and nitric oxide molecules were extremely strong in the helium plasma. It is considered that nitrogen ion molecules were mainly produced by penning ionization by helium metastable. Near the target, a significant increase in the emissions of reactive species is observed. There is a possibility that electron acceleration was induced in a local electric field formed on the surface. However, in argon plasma, emissions from nitrogen ion were not measured even near the target surface. These differences between the two plasmas may be producing the difference in blood coagulation behaviour. To control the surrounding gas of the plasma, a gas-component-controllable chamber was assembled. Filling the chamber with O2/He or N2/He gas mixtures selectively produces either reactive oxygen species or reactive nitrogen species. Through selective treatments, this chamber would be useful in studying the effects of specific reactive species on blood coagulation.

A shock tube study of the reactions of the hydroxyl radical with combustion species

Energy Technology Data Exchange (ETDEWEB)

Cohen, N.; Koffend, J.B. [The Aerospace Corporation, Los Angeles, CA (United States)

1993-12-01

To extend the semi-empirical techniques of Benson and coworkers, and to extend the database of reliable high temperature measurements of OH radicals with hydrocarbons and other fuels and their decomposition products, the authors undertook a research program with both experimental and computational tasks. The experimental goal was to design a procedure for measuring, at combustion temperatures, the reaction rate coefficients of OH radicals with fuels and other species of importance in combustion or propulsion systems. The computational effort was intended to refine the semi-empirical transition-state-theory procedures for extrapolating rate coefficients of reactions of OH with combustion species of interest, for predicting rate coefficients for species not studied in the laboratory, and to examine the ability of the theory to predict rate coefficients for different pathways in the case the reagent possessed more than one nonequivalent H atoms.

Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

International Nuclear Information System (INIS)

Arnold, D.W.

1994-08-01

Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O 3 - . A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO 2 , has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO 2 molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO 2 reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C 2 - - C 11 - ), and van der Waals clusters (X - (CO 2 ) n , X = I, Br, Cl; n ≤ 13 and I - (N 2 O) n=1--11 ). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X - (CO 2 )n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products

Long-lived radicals produced by γ-irradiation or vital activity in plants, animals, cells, and protein solution: their observation and inhomogeneous decay dynamics

International Nuclear Information System (INIS)

Miyazaki, Tetsuo; Morikawa, Akiyuki; Kumagai, Jun; Ikehata, Masateru; Koana, Takao; Kikuchi, Shoshi

2002-01-01

Long-lived radicals produced by γ-irradiation or vital activity in plants, animals, cells, and protein (albumin) solution were studied by electron spin resonance spectroscopy. Long-lived radicals produced by vital activity exist in biological systems, such as plants, animals, and cells, in the range of 0.1-20 nmol g -1 . Since vital organs keep the radicals at a constant concentration, the radicals are probably related to life conservation. Long-lived radicals are also produced by γ-irradiation of cells or protein solution. The radicals decay after death of living things or after γ-irradiation. We found that the decay dynamics in all biological systems can be expressed by the same kinetic equation of an inhomogeneous reaction

Locations of radical species in black pepper seeds investigated by CW EPR and 9GHz EPR imaging.

Science.gov (United States)

Nakagawa, Kouichi; Epel, Boris

2014-10-15

In this study, noninvasive 9GHz electron paramagnetic resonance (EPR)-imaging and continuous wave (CW) EPR were used to investigate the locations of paramagnetic species in black pepper seeds without further irradiation. First, lithium phthalocyanine (LiPC) phantom was used to examine 9GHz EPR imaging capabilities. The 9GHz EPR-imager easily resolved the LiPC samples at a distance of ∼2mm. Then, commercially available black pepper seeds were measured. We observed signatures from three different radical species, which were assigned to stable organic radicals, Fe(3+), and Mn(2+) complexes. In addition, no EPR spectral change in the seed was observed after it was submerged in distilled H2O for 1h. The EPR and spectral-spatial EPR imaging results suggested that the three paramagnetic species were mostly located at the seed surface. Fewer radicals were found inside the seed. We demonstrated that the CW EPR and 9GHz EPR imaging were useful for the determination of the spatial distribution of paramagnetic species in various seeds. Copyright © 2014 Elsevier B.V. All rights reserved.

E. s. r. of free radicals in irradiated uracil-. beta. -D-arabinofuranoside

Energy Technology Data Exchange (ETDEWEB)

Bergene, R [Oslo Univ. (Norway). Fysisk Institutt; Vaughan, R A

1976-02-01

Electron-spin-resonance measurements have been made on single crystals of uracil-..beta..-D-arabinofuranoside, which were irradiated by 4.0 MeV electrons at 77 K. At low temperatures, two radicals have been identified, one attributed to a hydrogen abstraction of 05' in the sugar moiety and the other to a radical anion located on the pyrimidine ring. The former was very unstable and seemed to act as a precursor to other unidentified radical species stable at 77 K. At room temperature, the main resonance was due to hydrogen addition to C5 and was probably produced by protonation of the anion. This same radical was also produced by irradiation at room temperature.

Radical chemistry of epigallocatechin gallate and its relevance to protein damage

DEFF Research Database (Denmark)

Hagerman, Ann E; Dean, Roger T; Davies, Michael Jonathan

2003-01-01

The radical chemistry of the plant polyphenolics epigallocatechin gallate (EGCG) and epigallocatechin (EGC) were investigated using electron paramagnetic resonance spectroscopy. Radical species formed spontaneously in aqueous solutions at low pH without external oxidant and were spin stabilized...... redox potentials of EGCG and EGC varied from 1000 mV at pH 3 to 400 mV at pH 8. The polyphenolics did not produce hydroxyl radicals unless reduced metal ions such as iron(II) were added to the system. Zinc(II)-stabilized EGCG radicals were more effective protein-precipitating agents than unoxidized EGCG...

Photoactivation of isoflavonoid phytoalexins: involvement of free radicals

International Nuclear Information System (INIS)

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

1983-01-01

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

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

International Nuclear Information System (INIS)

Adam, F.C.

1976-01-01

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

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

Science.gov (United States)

Utsumi, Hideo; Hyodo, Fuminori

2015-01-01

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

Early events following radiolytic and photogeneration of radical cations in hydrocarbons

International Nuclear Information System (INIS)

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

1992-01-01

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

Quantitative investigation of free radicals in bio-oil and their potential role in condensed-phase polymerization.

Science.gov (United States)

Kim, Kwang Ho; Bai, Xianglan; Cady, Sarah; Gable, Preston; Brown, Robert C

2015-03-01

We report on the quantitative analysis of free radicals in bio-oils produced from pyrolysis of cellulose, organosolv lignin, and corn stover by EPR spectroscopy. Also, we investigated their potential role in condensed-phase polymerization. Bio-oils produced from lignin and cellulose show clear evidence of homolytic cleavage reactions during pyrolysis that produce free radicals. The concentration of free radicals in lignin bio-oil was 7.5×10(20)  spin g(-1), which was 375 and 138 times higher than free-radical concentrations in bio-oil from cellulose and corn stover. Pyrolytic lignin had the highest concentration in free radicals, which could be a combination of carbon-centered (benzyl radicals) and oxygen-centered (phenoxy radicals) organic species because they are delocalized in a π system. Free-radical concentrations did not change during accelerated aging tests despite increases in molecular weight of bio-oils, suggesting that free radicals in condensed bio-oils are stable. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of radicals, clusters and transition state species by anion photoelectron spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Arnold, Don Wesley [Univ. of California, Berkeley, CA (United States)

1994-08-01

Free radicals, elemental and van der Waals clusters and transition state species for bimolecular chemical reactions are investigated using anion photoelectron spectroscopy. Several low-lying electronic states of ozone have been identified via photoelectron spectroscopy of O₃^-. A characterization of these states is important to models for atmospheric ozone reaction kinetics. The fluoroformyloxyl radical, FCO₂, has been investigated, providing vibrational frequencies and energies for two electronic states. The technique has also been employed to make the first direct observation and characterization of the NNO₂ molecule. Several electronic states are observed for this species which is believed to play a role as a reactive intermediate in the N + NO₂ reaction. The experimental results for all three of these radicals are supplemented by ab initio investigations of their molecular properties. The clusters investigations include studies of elemental carbon clusters (C₂^- - C₁₁^-), and van der Waals clusters (X^-(CO₂)_n, X = I, Br, Cl; n {le} 13 and I^- (N₂O)_n=1--11). Primarily linear clusters are observed for the smaller carbon clusters, while the spectra of the larger clusters contain contribution from cyclic anion photodetachment. Very interesting ion-solvent interactions are observed in the X^-(CO₂)n clusters. The transition state regions for several bimolecular chemical reactions have also been investigated by photodetachment of a negative ion precursor possessing a geometry similar to that of the transition state species. These spectra show features which are assigned to motions of the unstable neutral complex existing between reactants and products.

Transformations of dissolved organic matter induced by UV photolysis, Hydroxyl radicals, chlorine radicals, and sulfate radicals in aqueous-phase UV-Based advanced oxidation processes.

Science.gov (United States)

Varanasi, Lathika; Coscarelli, Erica; Khaksari, Maryam; Mazzoleni, Lynn R; Minakata, Daisuke

2018-05-15

Considering the increasing identification of trace organic contaminants in natural aquatic environments, the removal of trace organic contaminants from water or wastewater discharge is an urgent task. Ultraviolet (UV) and UV-based advanced oxidation processes (AOPs), such as UV/hydrogen peroxide (UV/H 2 O 2 ), UV/free chlorine and UV/persulfate, are attractive and promising approaches for the removal of these contaminants due to the high reactivity of active radical species produced in these UV-AOPs with a wide variety of organic contaminants. However, the removal efficiency of trace contaminants is greatly affected by the presence of background dissolved organic matter (DOM). In this study, we use ultrahigh resolution mass spectrometry to evaluate the transformation of a standard Suwanee River fulvic acid DOM isolate in UV photolysis and UV-AOPs. The use of probe compounds allows for the determination of the steady-state concentrations of active radical species in each UV-AOP. The changes in the H/C and O/C elemental ratios, double bond equivalents, and the low-molecular-weight transformation product concentrations of organic acids reveal that different DOM transformation patterns are induced by each UV-AOP. By comparison with the known reactivities of each radical species with specific organic compounds, we mechanistically and systematically elucidate the molecular-level DOM transformation pathways induced by hydroxyl, chlorine, and sulfate radicals in UV-AOPs. We find that there is a distinct transformation in the aliphatic components of DOM due to HO• in UV/H 2 O 2 and UV/free chlorine. Cl• induced transformation of olefinic species is also observed in the UV/free chlorine system. Transformation of aromatic and olefinic moieties by SO 4 •- are the predominant pathways in the UV/persulfate system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hybrid TiO2 -Ruthenium Nano-photosensitizer Synergistically Produces Reactive Oxygen Species in both Hypoxic and Normoxic Conditions.

Science.gov (United States)

Gilson, Rebecca C; Black, Kvar C L; Lane, Daniel D; Achilefu, Samuel

2017-08-28

Photodynamic therapy (PDT) is widely used to treat diverse diseases, but its dependence on oxygen to produce cytotoxic reactive oxygen species (ROS) diminishes the therapeutic effect in a hypoxic environment, such as solid tumors. Herein, we developed a ROS-producing hybrid nanoparticle-based photosensitizer capable of maintaining high levels of ROS under both normoxic and hypoxic conditions. Conjugation of a ruthenium complex (N3) to a TiO 2 nanoparticle afforded TiO 2 -N3. Upon exposure of TiO 2 -N3 to light, the N3 injected electrons into TiO 2 to produce three- and four-fold more hydroxyl radicals and hydrogen peroxide, respectively, than TiO 2 at 160 mmHg. TiO 2 -N3 maintained three-fold higher hydroxyl radicals than TiO 2 under hypoxic conditions via N3-facilitated electron-hole reduction of adsorbed water molecules. The incorporation of N3 transformed TiO 2 from a dual type I and II PDT agent to a predominantly type I photosensitizer, irrespective of the oxygen content. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation of caffeine by phosphate radical anion in aqueous ...

Indian Academy of Sciences (India)

Unknown

reactions in our body generate reactive oxygen species mainly comprising free radicals .... caffeine might be acting as a sensitizer to transfer energy to PDP to produce phosphate ... The lifetime of the excited singlet 21 state of caffeine is of the.

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

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)

Kinetics of the radicals induced in gamma irradiated sulfafurazole: an EPR study

International Nuclear Information System (INIS)

Colak, S.; Korkmaz, M.

2004-01-01

The spectroscopic and kinetic features of the radiolytic intermediates produced in gamma irradiated sulfafurazole (SFZ) were investigated at different temperatures in the dose range 5-50 kGy using EPR and IR techniques. The imodiation produced two species (A, B) in SFZ. The heights of the peaks were used to monitor the temperature, time dependent and kinetic features of the radical species contributing to the EPR spectrum. The applicability of EPR technique for monitoring radiosterilization of SFZ is discussed. The radiation yield of solid SFZ was found to be very low (G=0.16), and basing on this it was concluded that SFZ and SFZ containing drugs can be safely sterilized by radiation. The EPR data were used to characterize the contributing radicals produced in gamma irradiated SFZ. No definite difference was observed between unirradiated and irradiated IR spectra of SFZ. (orig.)

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

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

Science.gov (United States)

Zhuang, Yongliang; Li, Bafang; Zhao, Xue

2009-06-01

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

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)

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.

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.

Correlation between near infrared emission and bismuth radical species of Bi2O3-containing aluminoborate glass

International Nuclear Information System (INIS)

Masai, Hirokazu; Takahashi, Yoshihiro; Fujiwara, Takumi; Suzuki, Takenobu; Ohishi, Yasutake

2009-01-01

A strong correlation between bismuth radical species and emission in the near infrared (NIR) region of SnO-doped bismuth-containing aluminoborate glass, (CaO-B 2 O 3 -Bi 2 O 3 -Al 2 O 3 -TiO 2 ) (CaBBAT), was observed. Since the activation energy of the NIR emission was similar to that of electron spin resonance signal, it is expected that bismuth radical species in the CaBBAT glass is an origin of the NIR emission. Compared to the observed emission spectra with energy diagram of previous data, we have confirmed that bismuth ion possessing low valence is the origin of broad emission in the NIR region.

Density evaluation of remotely-supplied hydrogen radicals produced via tungsten filament method for SiCl4 reduction

Science.gov (United States)

Zohra Dahmani, Fatima; Okamoto, Yuji; Tsutsumi, Daiki; Ishigaki, Takamasa; Koinuma, Hideomi; Hamzaoui, Saad; Flazi, Samir; Sumiya, Masatomo

2018-05-01

Effect of the hydrogen radical on the reduction of a silicon tetrachloride (SiCl4) source was studied. The hydrogen radicals were generated using a tungsten (W) filament in a generation chamber, and were remotely supplied to another reaction chamber. The density of the hydrogen radical was estimated from the optical transmittance of 600-nm-wavelength light through phosphate glass doped with tungsten oxide (WO3). Lifetime of the hydrogen radical seemed sufficiently long, and its density as supplied to the reaction chamber was estimated to be on the order of 1012 cm‑3. Signal intensity of the peak corresponding to SiCl4 (m/z = 170) detected by quadrupole-mass measurement was confirmed to decrease owing to the reaction with the remotely-supplied hydrogen radical. This indicates the possibility that chemically-stable SiCl4, as one of the by-products of the Siemens process, can be reduced to produce silicon.

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.

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)

Potential repair of free radical adducts of dGMP and dG by a series of reductants. A pulse radiolytic study

International Nuclear Information System (INIS)

O'Neill, P.; Chapman, P.W.

1985-01-01

Using the technique of pulse radiolysis, it has been demonstrated that the interaction of hydroxyl-radical adducts of dG and dGMP with a series of reductants with different oxidation potentials at pH 7.0-7.4 proceeds via an electron transfer process (k approx. 1.4-34 x 10 8 dm 3 mol -1 s -1 ). The one-electron oxidation of dGMP (dG) by Br2-anion radicals was shown to result in the formation of a species, the properties of which are similar to those of the OH-radical adduct of dGMP with oxidizing properties based upon both spectral and kinetic information. The nature of the dGMP species produced on interaction with Br2-anion radicals to produce specific base damage. The implications of these findings are presented in terms of potential free radical repair of hydroxyl radical damage and of synergistic effects whereby one reductant may be regenerated at the expense of another reductant. (author)

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

Science.gov (United States)

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

2018-03-01

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

Temperature Effects on Free Radicals in Gamma-sterilized Beef

Science.gov (United States)

Pramanik, S. I.; Jahan, M. S.

1999-11-01

Gamma irradiation has become the method of choice for sterilizing frozen meat and their products to reduce levels of food-borne pathogens and to extend shelf life. In this report we have employed ESR technique for detection of free radicals in sterilized and non-sterilized dry beef without bone. We have also determined the heating effects on free radicals at temperatures 176^°C and 250^°C. Meat samples were dried in a food dehydrator at 60^°C and were packaged in dry N_2. They were then sterilized by γ-irradiation (2.5 MRad), ground into powder, and placed in ESR sample tubes. Non-sterilized powder samples were used as control. While all powder samples, sterilized or not, produced a broad single line in the ESR spectra with (Δ H_pp ~ 9 G) and g = 2.013, the radical concentration in the sterilized samples increased by a factor of five. Heat treatment at 176^°C produced similar radicals. But, when samples were heated 250^°C different radical species were formed which are characterized by narrow width (Δ H_pp ~ 6 G) and lower g-value (g =2.010). In contrast with previous work, where free radicals in chicken bones were reduced by heating [1], we observed an increase in concentration. Results of structural analyses of the radicals will be presented. Ref.[1]: Radiat. Phys. Chem., 49, 477-481, 1997. Work supported by Grants from the University of Memphis

OH radicals distribution in an Ar-H2O atmospheric plasma jet

Science.gov (United States)

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

2013-09-01

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

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.

Electron spin resonance studies of γ-irradiated phosphite and phosphate esters. Identification of phosphinyl, phosphonyl, phosphoranyl, and phosphine dimer cation radicals

International Nuclear Information System (INIS)

Kerr, C.M.L.; Webster, K.; Williams, F.

1975-01-01

The powder ESR spectra of several γ-irradiated phosphorus esters at 77 0 K were analyzed into their distinguishable radical components, each spectrum being generally a composite of anisotropic features from a number of alkyl and phosphorus-centered radicals. Resolution of overlapping spectra was achieved in some instances by radiation-chemical experiments designed to suppress or enhance the products of electron capture relative to the radicals formed by other mechanisms. The radiation chemistry of dialkyl phosphites, (RO) 2 P(O)H, is influenced by the ease with which the P--H bond in these compounds is broken, the principal radicals being the phosphonyl species (RO) 2 PO and ROP(O)O - . Both of these species are thought to be the secondary products of hydrogen atom abstraction by the alkyl radical R which is produced by dissociative electron capture. A similar primary step was found to apply for the trialkyl phosphates, (RO) 3 PO, but in this case only carbon-centered radicals are formed by secondary H-atom abstraction processes. Results for the pyrophosphite differ from those for the trialkyl phosphites in showing the absence of alkyl radicals or their phosphoranyl adducts and the formation of the phosphonyl species (EtO) 2 PO, the latter being produced presumably by cleavage of the P--O--P bridge. The ESR parameters for each of the four main groups of phosphorus-centered radicals are summarized and the electronic structures of these radicals are discussed briefly

Reactions of nitroxide radicals in aqueous solutions exposed to non-thermal plasma: limitations of spin trapping of the plasma induced species

Science.gov (United States)

Gorbanev, Yury; Stehling, Nicola; O'Connell, Deborah; Chechik, Victor

2016-10-01

Low temperature (‘cold’) atmospheric pressure plasmas have gained much attention in recent years due to their biomedical effects achieved through the interactions of plasma-induced species with the biological substrate. Monitoring of the radical species in an aqueous biological milieu is usually performed via electron paramagnetic resonance (EPR) spectroscopy using various nitrone spin traps, which form persistent radical adducts with the short-lived radicals. However, the stability of these nitroxide radical adducts in the plasma-specific environment is not well known. In this work, chemical transformations of nitroxide radicals in aqueous solutions using a model nitroxide 4-oxo-TEMPO were studied using EPR and LC-MS. The kinetics of the nitroxide decay when the solution was exposed to plasma were assessed, and the reactive pathways proposed. The use of different scavengers enabled identification of the types of reactive species which cause the decay, indicating the predominant nitroxide group reduction in oxygen-free plasmas. The 2H adduct of the PBN spin trap (PBN-D) was shown to decay similarly to the model molecule 4-oxo-TEMPO. The decay of the spin adducts in plasma-treated solutions must be considered to avoid rendering the spin trapping results unreliable. In particular, the selectivity of the decay indicated the limitations of the PTIO/PTI nitroxide system in the detection of nitric oxide.

Stability of cellulose radicals produced by radiation in spices as studied by the EPR spectroscopy

International Nuclear Information System (INIS)

Lehner, K.; Stachowicz, W.

2003-01-01

The results are presented of EPR measurements on the stability of cellulose radicals produced in 26 popular spices irradiated with a dose of 7 kGy of gamma rays. EPR measurements were done with the use of an EPR spectrometer EPR-10 MINI at X band (microwave radiation of frequency 9.5 GHz), produced by St. Petersburg Instruments Ltd. The aim of the work was to prove the applicability of the EPR method for the control of irradiation in the investigated spices. (author)

Matrix isolation spectroscopic studies of the radical ions of 2,5-diphenyloxazole (Preprint No. RC-15)

International Nuclear Information System (INIS)

Wani, A.M.

1988-02-01

The radical ions of 2,5-diphenyloxazole (PPO) produced upon γ-irradiation were studied at 77 K in organic glasses by optical absorption spectroscopy. The dependence of absorption spectra on the nature of the matrix, electron and hole scavengers is interpretted and the absorption bands are assigned to the anionic and cationic radical species of PPO. (author). 6 refs

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.

Free radicals produced by the oxidation of gallic acid: An electron paramagnetic resonance study

Directory of Open Access Journals (Sweden)

Wagner Brett A

2010-08-01

Full Text Available Abstract Background Gallic acid (3,4,5-trihydroxybenzoic acid is found in a wide variety of plants; it is extensively used in tanning, ink dyes, as well as in the manufacturing of paper. The gallate moiety is a key component of many functional phytochemicals. In this work electron paramagnetic spectroscopy (EPR was used to detect the free radicals generated by the air-oxidation of gallic acid. Results We found that gallic acid produces two different radicals as a function of pH. In the pH range between 7-10, the spectrum of the gallate free radical is a doublet of triplets (aH = 1.00 G, aH = 0.23 G, aH = 0.28 G. This is consistent with three hydrogens providing hyperfine splitting. However, in a more alkaline environment, pH >10, the hyperfine splitting pattern transforms into a 1:2:1 pattern (aH (2 = 1.07 G. Using D2O as a solvent, we demonstrate that the third hydrogen (i.e. aH = 0.28 G at lower pH is a slowly exchanging hydron, participating in hydrogen bonding with two oxygens in ortho position on the gallate ring. The pKa of this proton has been determined to be 10. Conclusions This simple and novel approach permitted the understanding of the prototropic equilibrium of the semiquinone radicals generated by gallic acid, a ubiquitous compound, allowing new insights into its oxidation and subsequent reactions.

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

International Nuclear Information System (INIS)

Tonegawa, Akira; Takatori, Masahiko; Kawamura, Kazutaka

1995-01-01

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

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

Science.gov (United States)

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

2014-10-01

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

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

EPR and optical spectroscopic studies of neutral free radicals in an adamantane matrix

International Nuclear Information System (INIS)

Jordan, J.E.

1975-03-01

Recent work in our laboratory has demonstrated that neutral free radicals produced by x-irradiation and trapped in adamantane exhibit exceedingly long lifetimes because of the lack of rapid diffusion in the solid matrix. This observation and the fact that samples can be pressed into pellets with high optical transparency in the visible and near uv regions of the spectrum suggested to us that this unique matrix might be used for studying the optical properties of free radicals. The results of a wide variety of experiments of this type are described in this thesis. These include experiments in which secondary free radicals are produced by photoinduced decomposition of primary free radicals by selective irradiation with visible light, the observation of strong optical absorption spectra of free radicals at room temperature using a Cary 14 spectrophotometer, the finding that certain free radicals exhibit strong, visible fluorescence when irradiated with uv light, and the discovery that the absorption intensity of multiplicity-forbidden transition in singlet and doublet state species is enhanced relative to spin-allowed transitions by at least three orders of magnitude. An analysis of these results in terms of molecular orbital theory is given, and experiments designed to obtain the epr spectra of electronically-excited states of free radicals are described

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

International Nuclear Information System (INIS)

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

1991-01-01

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

Effect of radical species density and ion bombardment during ashing of extreme ultralow-κ interlevel dielectric materials

International Nuclear Information System (INIS)

Worsley, M. A.; Bent, S. F.; Fuller, N. C. M.; Tai, T. L.; Doyle, J.; Rothwell, M.; Dalton, T.

2007-01-01

The significance of ion impact and radical species density on ash-induced modification of an extreme ultralow-κ interlevel dielectric (ILD) material (κ 2 and Ar/N 2 dual frequency capacitive discharges is determined by combining plasma diagnostics, modeling of the ion angular distribution function, and material characterization such as angle resolved x-ray photoelectron spectroscopy. Radical species density was determined by optical emission actinometry under the same conditions and in the same reactor in a previous study by the present authors. ILD modification is observed and correlated with changes in the plasma for a range of pressures (5-60 mTorr), bias powers (0-350 W), and percent Ar in the source gas (0%, 85%). For the Ar/O 2 discharge, extensive modification of the ILD sidewall was observed for significant ion scattering conditions, whereas minimal modification of the ILD sidewall was observed under conditions of minimal or no ion scattering. Further, for an identical increase in the O-radical density (∼ an order of magnitude), a different degree of modification was induced at the ILD trench bottom surface depending on whether pressure or percent Ar was used to increase the radical density. The different degrees of modification seemingly correlated with the relative changes in the ion current for increasing pressure or percent Ar. For the Ar/N 2 discharge, reduced damage of the ILD sidewall and trench bottom surfaces was observed for increasing pressure (increasing N-radical density) and decreasing ion current to both surfaces. It is, thus, proposed that the mechanism for modification of the porous ILD is dominated by the creation of reactive sites by ion impact under the present conditions. A detailed discussion of the results which support this proposal is presented

Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR

Science.gov (United States)

Fuchs, Hendrik; Albrecht, Sascha; Acir, Ismail-Hakki; Bohn, Birger; Breitenlechner, Martin; Dorn, Hans-Peter; Gkatzelis, Georgios I.; Hofzumahaus, Andreas; Holland, Frank; Kaminski, Martin; Keutsch, Frank N.; Novelli, Anna; Reimer, David; Rohrer, Franz; Tillmann, Ralf; Vereecken, Luc; Wegener, Robert; Zaytsev, Alexander; Kiendler-Scharr, Astrid; Wahner, Andreas

2018-06-01

The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO2) mainly reacted with NO (high NO case) and for conditions at which other reaction channels could compete (low NO case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model-measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO2 plus HO2 reaction channels as proposed in literature for the major RO2 species formed from the reaction of MVK with OH. However, this study shows that also HO2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO2 radical reactions, but indirectly via increased HO2. Quantum chemical calculations show that HO2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO2 species (reaction rate constant 0

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-09-15

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

Titanium dioxide induced cell damage: A proposed role of the carboxyl radical

Energy Technology Data Exchange (ETDEWEB)

Dodd, Nicholas J.F. [Ecotoxicology and Stress Biology Research Centre, School of Biological Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom); Jha, Awadhesh N. [Ecotoxicology and Stress Biology Research Centre, School of Biological Sciences, University of Plymouth, Drake Circus, Plymouth PL4 8AA (United Kingdom)], E-mail: a.jha@plymouth.ac.uk

2009-01-15

Titanium dioxide (TiO{sub 2}) nanoparticles have been shown to be genotoxic to cells exposed to ultraviolet A (UVA) radiation. Using the technique of electron spin resonance (ESR) spin trapping, we have confirmed that the primary damaging species produced on irradiation of TiO{sub 2} nanoparticles is the hydroxyl (OH) radical. We have applied this technique to TiO{sub 2}-treated fish and mammalian cells under in vitro conditions and observed the additional formation of carboxyl radical anions (CO{sub 2}{sup -}) and superoxide radical anions (O{sub 2}{sup -}). This novel finding suggests a hitherto unreported pathway for damage, involving primary generation of OH radicals in the cytoplasm, which react to give CO{sub 2}{sup -} radicals. The latter may then react with cellular oxygen to form O{sub 2}{sup -} and genotoxic hydrogen peroxide (H{sub 2}O{sub 2})

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.

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)

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)

Extracellular proteolytic enzymes produced by human pathogenic Vibrio species

Directory of Open Access Journals (Sweden)

Shin-Ichi eMiyoshi

2013-11-01

Full Text Available Bacteria in the genus Vibrio produce extracellular proteolytic enzymes to obtain nutrients via digestion of various protein substrates. However, the enzymes secreted by human pathogenic species have been documented to modulate the bacterial virulence. Several species including Vibrio cholerae and V. vulnificus are known to produce thermolysin-like metalloproteases termed vibriolysin. The vibriolysin from V. vulnificus, a causative agent of serious systemic infection, is a major toxic factor eliciting the secondary skin damage characterized by formation of the hemorrhagic brae. The vibriolysin from intestinal pathogens may play indirect roles in pathogenicity because it can activate protein toxins and hemagglutinin by the limited proteolysis and can affect the bacterial attachment to or detachment from the intestinal surface by degradation of the mucus layer. Two species causing wound infections, V. alginolyticus and V. parahaemolyticus, produce another metalloproteases so-called collagenases. Although the detailed pathological roles have not been studied, the collagenase is potent to accelerate the bacterial dissemination through digestion of the protein components of the extracellular matrix. Some species produce cymotrypsin-like serine proteases, which may also affect the bacterial virulence potential. The intestinal pathogens produce sufficient amounts of the metalloprotease at the small intestinal temperature; however, the metalloprotease production by extra-intestinal pathogens is much higher around the body surface temperature. On the other hand, the serine protease is expressed only in the absence of the metalloprotease.

Specific Cα-C Bond Cleavage of β-Carbon-Centered Radical Peptides Produced by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry

Science.gov (United States)

Nagoshi, Keishiro; Yamakoshi, Mariko; Sakamoto, Kenya; Takayama, Mitsuo

2018-04-01

Radical-driven dissociation (RDD) of hydrogen-deficient peptide ions [M - H + H]·+ has been examined using matrix-assisted laser dissociation/ionization in-source decay mass spectrometry (MALDI-ISD MS) with the hydrogen-abstracting matrices 4-nitro-1-naphthol (4,1-NNL) and 5-nitrosalicylic acid (5-NSA). The preferential fragment ions observed in the ISD spectra include N-terminal [a] + ions and C-terminal [x]+, [y + 2]+, and [w]+ ions which imply that β-carbon (Cβ)-centered radical peptide ions [M - Hβ + H]·+ are predominantly produced in MALDI conditions. RDD reactions from the peptide ions [M - Hβ + H]·+ successfully explains the fact that both [a]+ and [x]+ ions arising from cleavage at the Cα-C bond of the backbone of Gly-Xxx residues are missing from the ISD spectra. Furthermore, the formation of [a]+ ions originating from the cleavage of Cα-C bond of deuterated Ala(d3)-Xxx residues indicates that the [a]+ ions are produced from the peptide ions [M - Hβ + H]·+ generated by deuteron-abstraction from Ala(d3) residues. It is suggested that from the standpoint of hydrogen abstraction via direct interactions between the nitro group of matrix and hydrogen of peptides, the generation of the peptide radical ions [M - Hβ + H]·+ is more favorable than that of the α-carbon (Cα)-centered radical ions [M - Hα + H]·+ and the amide nitrogen-centered radical ions [M - HN + H]·+, while ab initio calculations indicate that the formation of [M - Hα + H]·+ is energetically most favorable. [Figure not available: see fulltext.

Presence of hydrogen peroxide, a source of hydroxyl radicals, in acid electrolyzed water.

Directory of Open Access Journals (Sweden)

Takayuki Mokudai

Full Text Available BACKGROUND: Acid electrolyzed water (AEW, which is produced through the electrolysis of dilute sodium chloride (NaCl or potassium chloride solution, is used as a disinfectant in various fields because of its potent antimicrobial activity. The hydroxyl radical, an oxygen radical species, is often suggested as a putative active ingredient for AEW antimicrobial activity. METHODOLOGY/PRINCIPAL FINDINGS: The aim of the present study is to detect hydroxyl radicals in AEW. The hydroxyl radicals in AEW prepared under different conditions were determined using an electron spin resonance (ESR technique. A signal from 5,5-dimethyl-1-pyrroline N-oxide (DMPO-OH, an adduct of DMPO and the hydroxyl radical, was detected in AEW prepared by double or triple electrolyses of 1% NaCl but not of 0.1% NaCl solution. Then the presence of hydrogen peroxide as a proposed source of hydroxyl radicals was examined using a combination of ESR and a Fenton reaction. The DMPO-OH signal was clearly detected, even in AEW prepared by single electrolysis of 0.1% NaCl solution, when ferrous sulfate was added to induce a Fenton reaction, indicating the presence of hydrogen peroxide in the AEW. Since sodium formate, a hydroxyl radical scavenger, did not affect the bactericidal activity of AEW, it is concluded that the radical is unlikely to contribute to the antimicrobial activity of AEW, although a small amount of the radical is produced from hydrogen peroxide. Dimethyl sulfoxide, the other hydroxyl radical scavenger used in the present study, canceled the bactericidal activity of AEW, accompanied by complete depletion of free available chlorine, suggesting that hypochlorous acid is probably a major contributor to the antimicrobial activity. CONCLUSIONS: It is strongly suggested that although hydrogen peroxide is present in AEW as a source of hydroxyl radicals, the antimicrobial activity of AEW does not depend on these radicals.

Talaromyces atroroseus, a new species efficiently producing industrially relevant red pigments.

Directory of Open Access Journals (Sweden)

Jens C Frisvad

Full Text Available Some species of Talaromyces secrete large amounts of red pigments. Literature has linked this character to species such as Talaromyces purpurogenus, T. albobiverticillius, T. marneffei, and T. minioluteus often under earlier Penicillium names. Isolates identified as T. purpurogenus have been reported to be interesting industrially and they can produce extracellular enzymes and red pigments, but they can also produce mycotoxins such as rubratoxin A and B and luteoskyrin. Production of mycotoxins limits the use of isolates of a particular species in biotechnology. Talaromyces atroroseus sp. nov., described in this study, produces the azaphilone biosynthetic families mitorubrins and Monascus pigments without any production of mycotoxins. Within the red pigment producing clade, T. atroroseus resolved in a distinct clade separate from all the other species in multigene phylogenies (ITS, β-tubulin and RPB1, which confirm its unique nature. Talaromyces atroroseus resembles T. purpurogenus and T. albobiverticillius in producing red diffusible pigments, but differs from the latter two species by the production of glauconic acid, purpuride and ZG-1494α and by the dull to dark green, thick walled ellipsoidal conidia produced. The type strain of Talaromyces atroroseus is CBS 133442.

Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals. Final Performance Report, August 1, 1985--July 31, 1994

Science.gov (United States)

Curl, R. F.; Glass, G. P.

1995-06-01

This research was directed at the detection, monitoring, and study (by infrared absorption spectroscopy) of the chemical kinetic behavior of small free radical species thought to be important intermediates in combustion. The work typically progressed from the detection and analysis of the infrared spectrum of combustion radical to the utilization of the infrared spectrum thus obtained in the investigation of chemical kinetics of the radical species. The methodology employed was infrared kinetic spectroscopy. In this technique the radical is produced by UV flash photolysis using an excimer laser and then its transient infrared absorption is observed using a single frequency cw laser as the source of the infrared probe light. When the probe laser frequency is near the center of an absorption line of the radical produced by the flash, the transient infrared absorption rises rapidly and then decays as the radical reacts with the precursor or with substances introduced for the purpose of studying the reaction kinetics or with itself. The decay times observed in these studies varied from less than one microsecond to more than one millisecond. By choosing appropriate time windows after the flash and the average infrared detector signal in a window as data channels, the infrared spectrum of the radical may be obtained. By locking the infrared probe laser to the center of the absorption line and measuring the rate of decay of the transient infrared absorption signal as the chemical composition of the gas mixture is varied, the chemical kinetics of the radical may be investigated. In what follows the systems investigated and the results obtained are outlined.

Talaromyces atroroseus, a new species efficiently producing industrially relevant red pigments

DEFF Research Database (Denmark)

Frisvad, Jens Christian; Yilmaz, Neriman; Thrane, Ulf

2013-01-01

., described in this study, produces the azaphilone biosynthetic families mitorubrins and Monascus pigments without any production of mycotoxins. Within the red pigment producing clade, T. atroroseus resolved in a distinct clade separate from all the other species in multigene phylogenies (ITS, β......Some species of Talaromyces secrete large amounts of red pigments. Literature has linked this character to species such as Talaromyces purpurogenus, T. albobiverticillius, T. marneffei, and T. minioluteus often under earlier Penicillium names. Isolates identified as T. purpurogenus have been...... reported to be interesting industrially and they can produce extracellular enzymes and red pigments, but they can also produce mycotoxins such as rubratoxin A and B and luteoskyrin. Production of mycotoxins limits the use of isolates of a particular species in biotechnology. Talaromyces atroroseus sp. nov...

Structure reactivity relationship in the reaction of DNA guanyl radicals with hydroxybenzoates

Energy Technology Data Exchange (ETDEWEB)

Do, Trinh T.; Tang, Vicky J.; Aguilera, Joseph A. [Department of Radiology University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States); Milligan, Jamie R., E-mail: jmilligan@ucsd.ed [Department of Radiology University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States)

2010-11-15

In DNA, guanine bases are the sites from which electrons are most easily removed. As a result of hole migration to this stable location on guanine, guanyl radicals are major intermediates in DNA damage produced by the direct effect of ionizing radiation (ionization of the DNA itself and not through the intermediacy of water radicals). We have modeled this process by employing gamma irradiation in the presence of thiocyanate ions, a method which also produces single electron oxidized guanyl radicals in plasmid DNA in aqueous solution. The stable products formed in DNA from these radicals are detected as strand breaks after incubation with the FPG protein. When a phenolic compound is present in the solution during gamma irradiation, the formation of guanyl radical species is decreased by electron donation from the phenol to the guanyl radical. We have quantified the rate of this reaction for four different phenolic compounds bearing carboxylate substituents as proton acceptors. A comparison of the rates of these reactions with the redox strengths of the phenolic compounds reveals that salicylate reacts ca. 10-fold faster than its structural analogs. This observation is consistent with a reaction mechanism involving a proton coupled electron transfer, because intra-molecular transfer of a proton from the phenolic hydroxyl group to the carboxylate group is possible only in salicylate, and is favored by the strong 6-membered ring intra-molecular hydrogen bond in this compound.

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

Solvent optimization extraction of antioxidants from foxtail millet species' insoluble fibers and their free radical scavenging properties.

Science.gov (United States)

Bangoura, Mohamed Lamine; Nsor-Atindana, John; Ming, Zhou Hui

2013-11-15

In this study, water and 80% of four organic solvents were employed to optimize the extraction of antioxidants from two species of foxtail millet's insoluble fibers under the same temperature, time, and solid/solvent ratio. The results showed that the acetone was able to extract the maximum amount of antioxidants (2.32 mg/g fiber for white specie and 3.86 mg/g fiber for yellow specie) followed by methanol and propanol from both samples. The neutral and the ethanol on the other hand extracted small amount of the antioxidants from the two fiber materials. While considerable level of Total Polyphenols Content (TPC) was recorded in both the water and the organic solvents' extracts, only traces of Total Flavonoid content (TFC) were observed in water, methanol and ethanol extracts. Propanol and acetone extracts was negative to the TFC test. The potency of both white and yellow foxtail millets' insoluble fibers antioxidant extracts was investigated using five different in vitro tests. It was realized that there was a variation in their capacities to quench DPPH and ABTS(+) radicals for the time running of 0-60 min. The samples from the yellow cereal exhibited high inhibition capacity against ABTS(+). No correlation was observed between TPC and radical scavenging capacities for DPPH and ABTS(+). In general, the yellow species contained more antioxidants in comparison with the white one and this accounted for its high antioxidant activity. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mycotoxins, drugs and other extrolites produced by species in Penicillium subgenus Penicillium

DEFF Research Database (Denmark)

Frisvad, Jens Christian; Smedsgaard, Jørn; Larsen, Thomas Ostenfeld

2004-01-01

extrolite families are reported from the subgenus with an average of 5 extrolite families per species. This is an underestimate as several pigments, volatiles and uncharacterized extrolites are not included in this average. Several reported producers are reidentified and new producers of known extrolites...... species in Penicillium subgenus Penicillium. In most cases these extrolites are produced consistently by all isolates examined in a species. The important antibiotic penicillin is produced by all members of series Chrysogena and P. griseofulvum. The cholesterol-lowering agent compactin is produced by P...

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

Science.gov (United States)

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

Infrared absorption spectroscopy and chemical kinetics of free radicals

International Nuclear Information System (INIS)

Curl, R.F.; Glass, G.P.

1991-01-01

A new channel producing ketenyl radical (HCCO) was discovered in the flash photolysis of ketene at 193 nm. H 2 CCO + hν(193 nm) → H + HCCO by observation near 2020 cm -1 of the infrared fundamental of ketenyl corresponding to the antisymmetric motion of the heavy atoms. This band has been partially rotationally analyzed and the rate constant for the reaction of ketenyl with NO has been determined. The OH stretching fundamental of hydroxymethyl radical (CH 2 OH) has been observed near 3600 cm -1 producing the radical either by the excimer flash photolysis of acetol (CH 3 COCH 2 OH) or by Cl atom abstraction of a methyl hydrogen from methanol. The assignment of the spectrum to CH 2 OH was confirmed by the agreement of the rate constant for the reaction of the species with O 2 with the literature value. The mechanism of the reaction of C 2 H with O 2 has been explored. There appear to be two channels producing CO product: a fast, direct one producing highly vibrationally excited CO up to v = 6 at the same rate C 2 H disappears and a slow, indirect one producing primarily ground state CO on a much longer timescale than the disappearance of C 2 H. The rate constants for the reactions of C 2 H with CH 4 , C 2 H 6 , C 2 H 4 , D 2 , and CO were determined by following the time decay of a C 2 H infrared transient absorption line originating from the ground vibronic state using diode laser spectroscopy creating the C 2 H by excimer laser flash photolysis (ArF, 193 nm) of CF 3 CCH. The branching ratio into OH of the reaction between NH 2 , and NO, which is the channel thought to propagate the radical chain of the Thermal deNOx process, has been measured up to 925 degree C. The OH yield thus obtained appears to be too small to maintain the process. 5 refs., 3 figs

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

International Nuclear Information System (INIS)

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

1991-01-01

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

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....

Synchrotron-based valence shell photoionization of CH radical

Energy Technology Data Exchange (ETDEWEB)

Gans, B., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr; Falvo, C. [Institut des Sciences Moléculaires d’Orsay (ISMO), CNRS, Univ. Paris-Sud, Université Paris-Saclay, F-91405 Orsay (France); Holzmeier, F.; Röder, A. [Institut of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, D-97074 Würzburg (Germany); Krüger, J.; Garcia, G. A. [Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin BP 48, F-91192 Gif sur Yvette Cedex (France); Lopes, A.; Alcaraz, C., E-mail: berenger.gans@u-psud.fr, E-mail: christian.alcaraz@u-psud.fr [Laboratoire de Chimie Physique, UMR 8000 CNRS—Univ. Paris-Sud, Univ. Paris-Saclay, Bât. 350, Centre Universitaire Paris-Sud, F-91405 Orsay Cedex (France); Fittschen, C. [Université Lille, CNRS, UMR 8522–PC2A–Physicochimie des Processus de Combustion et de l’Atmosphère, F-59000 Lille (France); Loison, J.-C. [Institut des Sciences Moléculaires, UMR 5255 CNRS—Université de Bordeaux, Bât. A12, 351 cours de la Libération, F-33405 Talence Cedex (France)

2016-05-28

We report the first experimental observations of X{sup +} {sup 1}Σ{sup +}←X {sup 2}Π and a{sup +} {sup 3}Π←X {sup 2}Π single-photon ionization transitions of the CH radical performed on the DESIRS beamline at the SOLEIL synchrotron facility. The radical was produced by successive hydrogen-atom abstractions on methane by fluorine atoms in a continuous microwave discharge flow tube. Mass-selected ion yields and photoelectron spectra were recorded as a function of photon energy using a double imaging photoelectron/photoion coincidence spectrometer. The ion yield appears to be strongly affected by vibrational and electronic autoionizations, which allow the observation of high Rydberg states of the neutral species. The photoelectron spectra enable the first direct determinations of the adiabatic ionization potential and the energy of the first triplet state of the cation with respect to its singlet ground state. This work also brings valuable information on the complex electronic structure of the CH radical and its cation and adds new observations to complement our understanding of Rydberg states and autoionization processes.

Risk assessment for invasive species produces net bioeconomic benefits.

Science.gov (United States)

Keller, Reuben P; Lodge, David M; Finnoff, David C

2007-01-02

International commerce in live organisms presents a policy challenge for trade globalization; sales of live organisms create wealth, but some nonindigenous species cause harm. To reduce damage, some countries have implemented species screening to limit the introduction of damaging species. Adoption of new risk assessment (RA) technologies has been slowed, however, by concerns that RA accuracy remains insufficient to produce positive net economic benefits. This concern arises because only a small proportion of all introduced species escape, spread, and cause harm (i.e., become invasive), so a RA will exclude many noninvasive species (which provide a net economic benefit) for every invasive species correctly identified. Here, we develop a simple cost:benefit bioeconomic framework to quantify the net benefits from applying species prescreening. Because invasive species are rarely eradicated, and their damages must therefore be borne for long periods, we have projected the value of RA over a suitable range of policy time horizons (10-500 years). We apply the model to the Australian plant quarantine program and show that this RA program produces positive net economic benefits over the range of reasonable assumptions. Because we use low estimates of the financial damage caused by invasive species and high estimates of the value of species in the ornamental trade, our results underestimate the net benefit of the Australian plant quarantine program. In addition, because plants have relatively low rates of invasion, applying screening protocols to animals would likely demonstrate even greater benefits.

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.

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

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

International Nuclear Information System (INIS)

Abbas, Basril; Sudiro, Sutjipto; Hilmy, Nazly

2000-01-01

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

[Comparison of antioxidant activity between two species of chamomiles produced in Xinjiang by TLC-bioautography].

Science.gov (United States)

Han, Song-Lin; Li, Xin-Xia; Mian, Qiang-Hui; Lan, Wei; Liu, Yan

2013-01-01

To compare the antioxidant active components from two species of chamomile-matricaria and Roman chamomile produced in Xinjiang. The TLC-bioautography was used, with 1,1-Diphenyl-2-picrylhydrazyl (DPPH) radical as the experimental model. The peak areas of various antioxidant components were obtained by TLC-scanning for analyzing antioxidant active components contained in volatile oil extracts and flavone extracts from the two species of chamomiles. The total peak area was taken as the indicator for comparing the antioxidant capacities of the two types of extracts, and comparing them with the total antioxidant activity of flavone extracts of the two species of chamomiles. According to the result of TLC-bioautography in volatile oil extracts from the two species of chamomiles, volatile oil extracts from chamomile showed four white antioxidant spots, including en-yne-dicycloether, and volatile oil extracts from Roman chamomile showed only one white antioxidant spot. The TLC-scanning result showed that the peak area of antioxidant spots of volatile oil extracts from chamomile was significantly larger than that of volatile oil extracts from Roman chamomile. According to the test on the antioxidant activity of the two species of chamomiles with ultraviolet-visible spectrophotometry, the concentration of chamomile after scavenging 50% of DPPH radicals was 0.66 g x L(-1), whereas the figure for Roman chamomile was 0.33 g x L(-1). According to the result of TLC-bioautography in flavone extracts from the two species of chamomiles, flavone extracts from chamomile showed seven yellowish antioxidant spots, including apigenin and apigenin-7-glucoside, and flavone extracts of Roman chamomile showed eight yellowish antioxidant spots, including apigenin and apigenin-7-glucoside. The TLC-scanning results showed that the peak area of antioxidant spots of flavone extracts from Roman chamomile was significantly larger than that of flavone extracts from chamomile. Volatile oil extracts

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.

Shock tube study of the reactions of the hydroxyl radical with combustion species and pollutants. Final report

Energy Technology Data Exchange (ETDEWEB)

Cohen, N.; Koffend, J.B.

1998-02-01

Shock heating t-butyl hydroperoxide behind a reflected shock wave has proved to be as a convenient source of hydroxyl radicals at temperatures near 1000 K. We applied this technique to the measurement of reaction rate coefficients of OH with several species of interest in combustion chemistry, and developed a thermochemical kinetics/transition state theory (TK-TST) model for predicting the temperature dependence of OH rate coefficients.

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

Influence of arbuscular mycorrhizal fungus Glomus intra-radices on accumulation of radiocaesium by plant species

International Nuclear Information System (INIS)

Dudchak, S.V.

2012-01-01

The role of arbuscular mycorrhizal fungus Glomus intra-radices in 134 Cs isotope uptake by different plant species is studied. The impact of radiocaesium on mycorrhizal development and functioning of plant photosynthetic apparatus is considered. The possibility of mycorrhizal symbiosis application in phytoremediation of radioactively contaminated areas is analyzed.It is found that colonization of plants with arbuscular mycorrhizal fungus resulted in significant decrease of radiocaesium concentration in their aboveground parts, while it did not have considerable impact on the radionuclide uptake by plant root system

Oxidation of aromatic amines and diamines by OH radicals. Formation and ionization constants of amine cation radicals in water

International Nuclear Information System (INIS)

Hayon, E.; Rao, P.S.

1975-01-01

The one-electron oxidation by hydroxyl radicals of aromatic amines and diamines in water was studied using the fast-reaction technique of pulse radiolysis and kinetic absorption spectrophotometry. The following compounds were examined: N,N,N 1 ,N 1 - tetramethyl-p-phenylenediamine (TMPD), p-phenylenediamine (PD), N,N-dimethyl-p-phenylenediamene (DMPD), N,N,N 1 ,N 1 -tetramethylbenzidine (TMB), and diphenylamine (DPA). The main initial reaction of the OH radicals is suggested to be an addition to these compounds to give absorption spectra which absorb strongly in the visible and uv regions. These OH radical adducts decay by first-order kinetics and have lifetimes of approximately 5-50 μsec, dependent on the pH, buffer concentration, and the nature of the aromatic amines and diamines. They decay to give species with somewhat similar absorption spectra and extinction coefficients, which are very long lived in the absence of oxygen. The latter species are assigned to the cation radicals TMPD. + , PD. + , DMPD. + , TMB. + , and DPA. + . The OH radical adducts and the cation radicals have acid-base properties. The pK/sub a/ values of the cation radicals TMPDH. 2+ , PDH. 2+ , DMPDH. 2+ , TMBH. 2+ , and DPAH. 2+ were found to be 5.3, 5.9, 6.1, 5.1, and 4.2, respectively. The results indicate that these aromatic amines and diamines can be oxidized by free radicals to yield the corresponding cation radicals. (U.S.)

Pulsed EPR studies of small reactive radicals produced by ionizing radiation

International Nuclear Information System (INIS)

Lawler, R.G.

1985-01-01

For several years we have participated in a collaborative research effort to apply the pulsed EPR-pulse radiolysis technique to several problems associated with the dynamics of small reactive radicals formed during radiolysis of aqueous solutions using 3 MeV electrons from a Van de Graaff accelerator. We will discuss experimental techniques and applications arising from this work, with particular emphasis on problems requiring high initial radical concentrations and EPR time resolution of one microsecond or better. 2 figs., 2 tabs

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)

Two new aflatoxin producing species, and an overview of Aspergillus section Flavi

DEFF Research Database (Denmark)

Varga, J.; Frisvad, Jens Christian; Samson, R. A.

2011-01-01

this section. The data indicate that Aspergillus section Flavi involves 22 species, which can be grouped into seven clades. Two new species, A. pseudocaelatus sp. nov. and A. pseudonomius sp. nov. have been discovered, and can be distinguished from other species in this section based on sequence data...... and extrolite profiles. Aspergillus pseudocaelatus is represented by a single isolate collected from Arachis burkartii leaf in Argentina, is closely related to the non-aflatoxin producing A. caelatus, and produces aflatoxins B & G, cyclopiazonic acid and kojic acid, while A. pseudonomius was isolated from...... insects and soil in the USA. This species is related to A. nomius, and produces aflatoxin B-1 (but not G-type aflatoxins), chrysogine and kojic acid. In order to prove the aflatoxin producing abilities of the isolates, phylogenetic analysis of three genes taking part in aflatoxin biosynthesis, including...

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.

The free radical species in polyacrylonitrile fibers induced by γ-radiation and their decay behaviors

International Nuclear Information System (INIS)

Liu Weihua; Wang Mouhua; Xing Zhe; Wu Guozhong

2012-01-01

Free radicals in vacuum, air and oxygen atmospheres were studied using electron spin resonance (ESR). Mainly two types of radicals, namely alkyl radicals and polyimine radicals, are formed in polyacrylonitrile (PAN) fibers after γ-ray irradiation. The G value of the radical formation was calculated to be 2.1 (number of radicals per 100 eV absorbed) in air at room temperature based on the ESR measurements. The radical stability and decay behaviors at room temperature and elevated temperatures were also investigated under different atmospheres. The alkyl radicals were found to be rather stable when stored in vacuum at room temperature, but they decayed via reaction with oxygen when stored in air. The alkyl radicals disappeared completely after a thermal treatment at 110 °C in vacuum, but only 15% of the polyimine radicals decayed; this indicates that polyimine radicals are more stable compared to the alkyl radicals due to their lower mobility. - Highlights: ► Radicals formed by radiation were assigned to polyimine and alkyl radicals. ► G-value of radicals was measured to be 2.1 per 100 eV. ► The radicals were found to be extremely stable in vacuum at room temperature. ► Effect of oxygen on radical decay under various conditions was studied.

Effects of scavengers of reactive oxygen and radical species on cell survival following photodynamic treatment in vitro: comparison to ionizing radiation

International Nuclear Information System (INIS)

Henderson, B.W.; Miller, A.C.

1986-01-01

The effects of various scavengers of reactive oxygen and/or radical species on cell survival in vitro of EMT6 and CHO cells following photodynamic therapy (PDT) or gamma irradiation were compared. None of the agents used exhibited major direct cytotoxicity. Likewise, none interfered with cellular porphyrin uptake, and none except tryptophan altered singlet oxygen production during porphyrin illumination. The radioprotector cysteamine (MEA) was equally effective in reducing cell damage in both modalities. In part, this protection seems to have been induced by oxygen consumption in the system due to MEA autoxidation under formation of H 2 O 2 . The addition of catalase, which prevents H 2 O 2 buildup, reduced the effect of MEA to the same extent in both treatments. Whether the remaining protection was due to MEA's radical-reducing action or some remaining oxygen limitation is unclear. The protective action of MEA was not mediated by a doubling of cellular glutathione levels, since addition of buthionine sulfoximine, which prevented glutathione increase, did not diminish the observed MEA protection. The hydroxyl radical scavenger mannitol also afforded protection in both, but it was approximately twice as effective in gamma irradiation as in PDT. This is consistent with the predominant role of OH radicals in ionizing radiation damage and their presumed minor involvement in PDT damage. Superoxide dismutase, a scavenger of O 2 , acted as a radiation protector but was not significantly effective in PDT. Catalase, which scavenges H 2 O 2 , was ineffective in both modalities. Tryptophan, an efficient singlet oxygen scavenger, reduced cell death through PDT by several orders of magnitude while being totally ineffective in gamma irradiation. These data reaffirm the predominant role of 1O2 in the photodynamic cell killing but also indicate some involvement of free radical species

Aberrant Free Radical Biology Is a Unifying Theme in the Etiology and Pathogenesis of Major Human Diseases

Directory of Open Access Journals (Sweden)

Frederick E. Domann

2013-04-01

Full Text Available The seemingly disparate areas of oxygen toxicity, radiation exposure, and aging are now recognized to share a common feature—the aberrant production and/or removal of biologically derived free radicals and other reactive oxygen and nitrogen species (ROS/RNS. Advances in our understanding of the effects of free radicals in biology and medicine have been, and continue to be, actively translated into clinically tractable diagnostic and therapeutic applications. This issue is dedicated to recent advances, both basic discoveries and clinical applications, in the field of free radicals in biology and medicine. As more is understood about the proximal biological targets of aberrantly produced or removed reactive species, their sensors, and effectors of compensatory response, a great deal more will be learned about the commonalities in mechanisms underlying seemingly disparate disease states. Together with this deeper understanding, opportunities will arise to devise rational therapeutic interventions to decrease the incidence and severity of these diseases and positively impact the human healthspan.

Two new aflatoxin producing species, and an overview of Aspergillus section Flavi

Science.gov (United States)

Varga, J.; Frisvad, J.C.; Samson, R.A.

2011-01-01

Aspergillus subgenus Circumdati section Flavi includes species with usually biseriate conidial heads, in shades of yellow-green to brown, and dark sclerotia. Several species assigned to this section are either important mycotoxin producers including aflatoxins, cyclopiazonic acid, ochratoxins and kojic acid, or are used in oriental food fermentation processes and as hosts for heterologous gene expression. A polyphasic approach was applied using morphological characters, extrolite data and partial calmodulin, β-tubulin and ITS sequences to examine the evolutionary relationships within this section. The data indicate that Aspergillus section Flavi involves 22 species, which can be grouped into seven clades. Two new species, A. pseudocaelatus sp. nov. and A. pseudonomius sp. nov. have been discovered, and can be distinguished from other species in this section based on sequence data and extrolite profiles. Aspergillus pseudocaelatus is represented by a single isolate collected from Arachis burkartii leaf in Argentina, is closely related to the non-aflatoxin producing A. caelatus, and produces aflatoxins B & G, cyclopiazonic acid and kojic acid, while A. pseudonomius was isolated from insects and soil in the USA. This species is related to A. nomius, and produces aflatoxin B1 (but not G-type aflatoxins), chrysogine and kojic acid. In order to prove the aflatoxin producing abilities of the isolates, phylogenetic analysis of three genes taking part in aflatoxin biosynthesis, including the transcriptional regulator aflR, norsolonic acid reductase and O-methyltransferase were also carried out. A detailed overview of the species accepted in Aspergillus section Flavi is presented. PMID:21892243

Bacteroides species produce Vibrio harveyi autoinducer 2-related molecules.

Science.gov (United States)

Antunes, Luis Caetano Martha; Ferreira, Lívia Queiroz; Ferreira, Eliane Oliveira; Miranda, Karla Rodrigues; Avelar, Kátia Eliane Santos; Domingues, Regina Maria Cavalcanti Pilotto; Ferreira, Maria Candida de Souza

2005-10-01

Quorum sensing is a density-dependent gene regulation mechanism that has been described in many bacterial species in the last decades. Bacteria that use quorum sensing as part of their gene regulation circuits produce molecules called autoinducers that accumulate in the environment and activate target genes in a quorum-dependent way. Some specific clues led us to hypothesize that Bacteroides species can produce autoinducers and possess a quorum sensing system. First, Bacteroides are anaerobic bacteria that are frequently involved in polymicrobial infections. These infections often involve Pseudomonas aeruginosa and Staphylococcus aureus, two of the best understood examples of bacteria that employ quorum sensing systems as part of their pathogenesis. Also, studies have detected the presence of a quorum sensing gene involved in the production of autoinducers in Porphyromonas gingivalis, a species closely related to the Bacteroides genus. These and other evidences prompted us to investigate if Bacteroides strains could produce autoinducer molecules that could be detected by a Vibrio harveyi reporter system. In this paper, we show that supernatants of B. fragilis, B. vulgatus and B. distasonis strains are able to stimulate the V. harveyi quorum sensing system 2. Also, we were able to demonstrate that the stimulation detected is due to the production of autoinducer molecules and not the growth of reporter strains after addition of supernatant. Moreover, the phenomenon observed does not seem to represent the degradation of repressors possibly present in the culture medium used. We could also amplify bands from some of the strains tested using primers designed to the luxS gene of Escherichia coli. Altogether, our results show that B. fragilis, B. vulgatus and B. distasonis (but possibly some other species) can produce V. harveyi autoinducer 2-related molecules. However, the role of such molecules in the biology of these organisms remains unknown.

New ochratoxin A producing species of Aspergillus section Circumdati

DEFF Research Database (Denmark)

Frisvad, Jens Christian; Frank, J.M.; Houbraken, J.A.M.P.

2004-01-01

Aspergillus section Circumdati contains species with yellow to ochre conidia and non-black sclerotia that produce at least one of the following extrolites: ochratoxins, penicillic acids, xanthomegnins or melleins. The exception to this is A. robustus, which produces black sclerotia, phototropic...... ochratoxin A production in coffee, rice, beverages and other foodstuffs are A. ochraceus, A. westerdijkiae and A. steynii....

Free radicals generated by radiolysis of aqueous solutions

International Nuclear Information System (INIS)

Schwarz, H.A.

1981-01-01

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

DNA damage produced by exposure of supercoiled plasmid DNA to high- and low-LET ionizing radiation: Effects of hydroxyl radical quenchers. DNA breakage, neutrons, OH radicals

International Nuclear Information System (INIS)

Peak, J.G.; Ito, T.; Peak, M.J.; Robb, F.T.

1994-01-01

A supercoiled plasmid of 7300 base pairs was isolated and exposed in an aqueous environment to 60 Co γ rays and JANUS 0.85 MeV fission-spectrum neutrons. Dose responses for the production of single-strand breaks (SSBs), double-strand breaks (DSBs) and alkali-labile sites (ALSs) were compared with computations made from the conversion of the supercoil to its relaxed and linear forms. The relative biological effectiveness (RBE) for production of SSBs and DSBs was similar to that previously measured in the cellular environment. The RBE for destruction of genetic transforming activity of M13 viral DNA followed that for DNA damage. This is in contrast to the situation for biological effects such as lethality, mutagenesis, and cellular transformation measured in mammalian cells, where the RBE values are reversed. The role of hydroxyl (OH) radical in DNA damage induction by neutrons was investigated by exposure of plasmid in the presence of known quenchers of this species. Of four quenchers tested, all were able to reduce the yields of both SSBs and DSBs. These findings are consistent with a model for SSB and DSB induction by high linear energy transfer that involves OH radical mediation

Electron spin resonance and E.N.D.O.R. double resonance study of free radicals produced by gamma irradiation of imidazole single crystals

International Nuclear Information System (INIS)

Lamotte, B.

1970-01-01

Gamma irradiation of imidazole single crystals at 300 deg. K gives two radicals. Identification and detailed studies of their electronic and geometric structure have been made by ESR and ENDOR techniques. A study of the hydrogen bonded protons hyperfine tensor is made and let us conclude to the inexistence of movement and tunneling of these protons. The principal low temperature radical, produced by gamma irradiation at 77 deg. K has been also studied by ESR and a model has been proposed. (author) [fr

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

Determination of DPPH Radical Oxidation Caused by Methanolic Extracts of Some Microalgal Species by Linear Regression Analysis of Spectrophotometric Measurements

Directory of Open Access Journals (Sweden)

Ulf-Peter Hansen

2007-10-01

Full Text Available The demonstrated modified spectrophotometric method makes use of the 2,2-diphenyl-1-picrylhydrazyl (DPPH radical and its specific absorbance properties. Theabsorbance decreases when the radical is reduced by antioxidants. In contrast to otherinvestigations, the absorbance was measured at a wavelength of 550 nm. This wavelengthenabled the measurements of the stable free DPPH radical without interference frommicroalgal pigments. This approach was applied to methanolic microalgae extracts for twodifferent DPPH concentrations. The changes in absorbance measured vs. the concentrationof the methanolic extract resulted in curves with a linear decrease ending in a saturationregion. Linear regression analysis of the linear part of DPPH reduction versus extractconcentration enabled the determination of the microalgae’s methanolic extractsantioxidative potentials which was independent to the employed DPPH concentrations. Theresulting slopes showed significant differences (6 - 34 μmol DPPH g-1 extractconcentration between the single different species of microalgae (Anabaena sp.,Isochrysis galbana, Phaeodactylum tricornutum, Porphyridium purpureum, Synechocystissp. PCC6803 in their ability to reduce the DPPH radical. The independency of the signal on the DPPH concentration is a valuable advantage over the determination of the EC50 value.

Electron beam treatment with radical scavengers/enhancers

International Nuclear Information System (INIS)

Gehringer, P.

1994-08-01

E-beam treatment of low level contaminated groundwater is best apt to demonstrate the role of scavengers and enhancers, respectively because groundwater already contains some scavengers as natural solutes. The action of ionizing radiation to water is known to result in the formation of ions, molecular and free radical species. For low level contaminations of groundwater (pollutant concentration aqu - and H are of interest for pollutant decomposition. The pollutants have to compete for the free radical species with the natural solutes. 10 figures are discussed. (author)

Aspergillus species as mycotoxin producers in agricultural products in central Europe

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Kočube Šandor

2013-01-01

Full Text Available Aspergillus species are able to produce a range of mycotoxins, includ­ing e.g. aflatoxins, ochratoxins, fumonisins and patulin. Aflatoxins are mainly produced by members of Aspergillus section Flavi, and they contaminate various agricultural products in several parts of the world. Several recent reports have indicated that aflatoxin-producing fungi and consequently aflatoxin contamination occur in agricultural commodities in a number of European countries which have not been faced with this problem before. Indeed, recent surveys have clarified that concentrations of aflatoxins in maize products and milk has been exceeding the EU limit in several regions of Central Europe including Serbia, Slovenia, Croatia, Northern Italy and Romania. However, aflatoxin contamination and aflatoxin-producing Aspergillus species have not been identified yet in maize in Hungary. We examined the presence of potential aflatoxin-producing Aspergilli in maize samples collected in southern parts of Hungary. Several A. flavus isolates were identified, and pre­liminary results indicated that some of the isolates were able to produce aflatoxins. Con­tamination of other agricultural products with aflatoxins can also pose problems in Central Europe due to global warming. Ochratoxin contamination of grapes and grape-derived products is usually caused by black Aspergilli, especially by A. carbonarius and A. niger, although these species have been rare in Central European vineyards due to climatic fac­tors. Ochratoxin contamination of other agricultural products including spices and cereals was also observed in the region. Besides, ochratoxin producing Aspergilli are frequently isolated from imported products including coffee beans, dried fruits and spices, and ochra­toxin contamination of these samples was also observed. Fumonisins are produced mainly by Fusarium species, and by the recently identified producers Aspergillus niger and A. awamori. We examined fumonisin

The radical cations of sulphur (S8sup(.+)) and tetrasulphur tetranitride (S4N4sup(.+)): a radiation-electron spin resonance study

International Nuclear Information System (INIS)

Chandra, Harish; Ramakrishna Rao, D.N.; Symons, M.C.R.

1987-01-01

Exposure of dilute solutions of S 8 and S 4 N 4 in trichlorofluoromethane to 60 Co γ-rays at 77 K gave the corresponding radical cations. Enrichment (99%) with 33 S gave greatly broadened electron spin resonance x and y features, with A( 33 S) approx. = + - 4 G, where A is the first formed species from sulfur. The z features showed a clear central line flanked by others with Asub(z) approx. = 28 G. The results suggest the presence of two equally coupled sulphur atoms. On annealing, species (A) changes irreversibly into species (B),possibly, S 8 radical + in a relaxed form in which two opposite atoms have formed a weak three-electron bond. A clear spectrum was produced from S 4 N 4 which showed little g-value variation and no evidence for 14 N splitting. It is concluded that the S 4 N 4 radical + cation has a relatively isolated semi-occupied molecular orbital, with low spin density on nitrogen. (author)

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

Science.gov (United States)

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

2001-11-16

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

Discerning Silk Produced by Bombyx mori from Those Produced by Wild Species Using an Enzyme-Linked Immunosorbent Assay Combined with Conventional Methods.

Science.gov (United States)

You, Qiushi; Li, Qingqing; Zheng, Hailing; Hu, Zhiwen; Zhou, Yang; Wang, Bing

2017-09-06

Recently, much interest has been paid to the separation of silk produced by Bombyx mori from silk produced by other species and tracing the beginnings of silk cultivation from wild silk exploitation. In this paper, significant differences between silks from Bombyx mori and other species were found by microscopy and spectroscopy, such as morphology, secondary structure, and amino acid composition. For further accurate identification, a diagnostic antibody was designed by comparing the peptide sequences of silks produced by Bombyx mori and other species. The results of the noncompetitive indirect enzyme-linked immunosorbent assay (ELISA) indicated that the antibody that showed good sensitivity and high specificity can definitely discern silk produced by Bombyx mori from silk produced by wild species. Thus, the antibody-based immunoassay has the potential to be a powerful tool for tracing the beginnings of silk cultivation. In addition, combining the sensitive, specific, and convenient ELISA technology with other conventional methods can provide more in-depth and accurate information for species identification.

Visible absorption spectrum of the CH3CO radical.

Science.gov (United States)

Rajakumar, B; Flad, Jonathan E; Gierczak, Tomasz; Ravishankara, A R; Burkholder, James B

2007-09-20

The visible absorption spectrum of the acetyl radical, CH(3)CO, was measured between 490 and 660 nm at 298 K using cavity ring-down spectroscopy. Gas-phase CH(3)CO radicals were produced using several methods including: (1) 248 nm pulsed laser photolysis of acetone (CH(3)C(O)CH(3)), methyl ethyl ketone (MEK, CH(3)C(O)CH(2)CH(3)), and biacetyl (CH(3)C(O)C(O)CH(3)), (2) Cl + CH(3)C(O)H --> CH(3)C(O) + HCl with Cl atoms produced via pulsed laser photolysis or in a discharge flow tube, and (3) OH + CH(3)C(O)H --> CH(3)CO + H(2)O with two different pulsed laser photolysis sources of OH radicals. The CH(3)CO absorption spectrum was assigned on the basis of the consistency of the spectra obtained from the different CH(3)CO sources and agreement of the measured rate coefficients for the reaction of the absorbing species with O(2) and O(3) with literature values for the CH(3)CO + O(2) + M and CH(3)CO + O(3) reactions. The CH(3)CO absorption spectrum between 490 and 660 nm has a broad peak centered near 535 nm and shows no discernible structure. The absorption cross section of CH(3)CO at 532 nm was measured to be (1.1 +/- 0.2) x 10(-19) cm(2) molecule(-1) (base e).

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.

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

Investigating Pigment Radicals in Black Rice Using HPLC and Multi-EPR.

Science.gov (United States)

Nakagawa, Kouichi; Maeda, Hayato

2017-01-01

We investigated the location and distribution of paramagnetic species in black and white rice using electron paramagnetic resonance (EPR), X-band (9 GHz) EPR imaging (EPRI), and HPLC. EPR primarily detected two paramagnetic species in black rice, which were identified as a stable radical and Mn 2+ species, based on the g values and hyperfine components of the EPR signals. The signal from the stable radical appeared at g ≈ 2.00 and was relatively strong and stable. Subsequent noninvasive two-dimensional (2D) EPRI revealed that this stable radical was primarily located in the pigmented region of black rice, while very few radicals were observed in the rice interior. Pigments extracted from black rice were analyzed using HPLC; the major compound was found to be cyanidin-3-glucoside. EPR and HPLC results indicate that the stable radical was only found within the pigmented region of the rice, and that it could either be cyanidin-3-glucoside, or one of its oxidative decomposition products.

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

Science.gov (United States)

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

2017-01-01

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

Electron spin resonance study on γ-ray-induced radical species in ethylene hydrate

International Nuclear Information System (INIS)

Takeya, Kei; Sugahara, Takeshi; Ohgaki, Kazunari; Tani, Atsushi

2007-01-01

Electron spin resonance (ESR) study on γ-irradiated synthetic ethylene hydrate was performed to investigate induced radicals and their thermal stability. ESR spectra of induced 3-butenyl radical (.CH 2 C 2 H 3 =CH 2 ,g=2.0039±0.0005,A α =2.2±0.1mTandA β =3.0±0.1mT) and induced ethyl radical (.C 2 H 5 , g=2.0044±0.0005, A α =2.2±0.1mT and A β =2.7±0.1mT) were observed in irradiated ethylene hydrate. The decay of the 3-butenyl radicals was observed above 200 K with the activation energy of 51.9±4.4kJ/mol. The obvious decay of ethyl radicals starts above 240 K that is close to the dissociation temperature of ethylene hydrate at atmospheric pressure. The activation energy of the ethyl radical decay is estimated as 63.4±8.2kJ/mol and nearly equal to the enthalpy change of ethylene hydrate into liquid water and gaseous ethylene. It is suggested that the decay of ethyl radicals would be caused by the hydrate dissociation and that ethylene hydrate dissociates into water (supercooled) and ethylene at 240-265 K.

DFT studies of the substituent effects of dimethylamino on non-heme active oxidizing species: iron(V)-oxo species or iron(IV)-oxo acetate aminopyridine cation radical species?

Science.gov (United States)

Wang, Fang; Sun, Wei; Xia, Chungu; Wang, Yong

2017-10-01

Through the introduction of dimethylamino (Me 2 N) substituent at the pyridine ring of 2-((R)-2-[(R)-1-(pyridine-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-ylmethyl)pyridine (PDP) ligand, the non-heme Fe II ( Me2N PDP)/H 2 O 2 /AcOH catalyst system was found to exhibit significant higher catalytic activity and enantioselectivity than the non-substituent one in the asymmetric epoxidation experiments. The mechanistic origin of the remarkable substituent effects in these oxidation reactions has not been well established. To ascertain the potent oxidant and the related reaction mechanism, a detailed DFT calculation was performed. Interestingly, a novel Fe(IV)-oxo Me2N PDP cation radical species, [( Me2N PDP) + · Fe IV (O)(OAc)] 2+ ( Me2N 5), with about one spin spreading over the non-heme Me2N PDP ligand was formed via a carboxylic-acid-assisted O-O bond heterolysis, which is reminiscent of Compound I (an Fe(IV)(O)(porphyrin cation radical) species) in cytochrome P450 chemistry. Me2N 5 is energetically comparable with the cyclic ferric peracetate species Me2N 6, while in the pristine Fe(PDP) catalyst system, H 6 is more stable than H 5. Comparison of the activation energy for the ethylene epoxidation promoted by Me2N 5 and Me2N 6, Me2N 5 is supposed as the true oxidant triggering the epoxidation of olefins. In addition, a systematic research on the substituent effects varied from the electron-donating substituent (dMM, the substituents at sites 3, 4, and 5 of the pyridine ring: methyl, methoxyl, and methyl) to the electron-withdrawing one (CF 3 , 2,6-bis(trifluoromethyl)phenyl) on the electronic structure of the reaction intermediates has also been investigated. An alternative cyclic ferric peracetate complex is obtained, indicating that the substituents at the pyridine ring of PDP ligands have significant impacts on the electronic structure of the oxidants.

Lightning-produced Carbon Species in the Atmosphere of Saturn

Science.gov (United States)

Delitsky, Mona; Baines, K. H.

2010-10-01

Recent studies by Baines et al (2009) indicate that thunderstorm-associated clouds on Saturn are spectrally dark from 0.7 to 4 um, darker than regular clouds. This darkening is found to be consistent with the presence of particles of elemental carbon, such as in the form of soot particles mixed in with spectrally bright condensates. This carbon is thought to be generated by lightning-induced dissociation of methane. Lightning on Saturn will input large amounts of energy to a narrow column of atmosphere and generate products at high energies such as radicals and ions. After the column cools down, the new chemical species recombine and are frozen into a new chemical equilibrium. Experimental studies in the literature of reactions of methane and other gases in plasma discharges (which simulate lightning) indicate that, even with high ratios of hydrogen/methane, the elemental carbon obtained will form solid dark particles that persist and have a very high C/H ratio. Basically, they are mostly pure carbon, in the form of soot, amorphous carbon, graphite, graphene, polycyclic aromatic hydrocarbons, carbon black, carbon onions, etc. Hydrogen will act as a sealant onto the particles and attach to dangling bonds on their growing surfaces. Even in experiments to form the most crystalline allotrope of carbon, that is, diamond, the presence of hydrogen does not inhibit diamond formation, even at the low pressures in the atmospheres of the Jovian planets or in the interstellar medium (Allamandola et al 1991). Therefore, some form of elemental carbon is likely produced in Saturnian storm clouds and may occur as dark particles of either amorphous carbon, PAHs or crystalline carbon in a form such as graphite. ..Refs: Baines et al., PSS 57, 1650-1658 (2009) ; Allamandola et al., Meteoritics 26, 313 (1991).

Gamma-irradiation produces active chlorine species (ACS) in physiological solutions: Secoisolariciresinol diglucoside (SDG) scavenges ACS - A novel mechanism of DNA radioprotection.

Science.gov (United States)

Mishra, Om P; Popov, Anatoliy V; Pietrofesa, Ralph A; Christofidou-Solomidou, Melpo

2016-09-01

Secoisolariciresinol diglucoside (SDG), the main lignan in whole grain flaxseed, is a potent antioxidant and free radical scavenger with known radioprotective properties. However, the exact mechanism of SDG radioprotection is not well understood. The current study identified a novel mechanism of DNA radioprotection by SDG in physiological solutions by scavenging active chlorine species (ACS) and reducing chlorinated nucleobases. The ACS scavenging activity of SDG was determined using two highly specific fluoroprobes: hypochlorite-specific 3'-(p-aminophenyl) fluorescein (APF) and hydroxyl radical-sensitive 3'-(p-hydroxyphenyl) fluorescein (HPF). Dopamine, an SDG structural analog, was used for proton (1)H NMR studies to trap primary ACS radicals. Taurine N-chlorination was determined to demonstrate radiation-induced generation of hypochlorite, a secondary ACS. DNA protection was assessed by determining the extent of DNA fragmentation and plasmid DNA relaxation following exposure to ClO(-) and radiation. Purine base chlorination by ClO(-) and γ-radiation was determined by using 2-aminopurine (2-AP), a fluorescent analog of 6-aminopurine. Chloride anions (Cl(-)) consumed >90% of hydroxyl radicals in physiological solutions produced by γ-radiation resulting in ACS formation, which was detected by (1)H NMR. Importantly, SDG scavenged hypochlorite- and γ-radiation-induced ACS. In addition, SDG blunted ACS-induced fragmentation of calf thymus DNA and plasmid DNA relaxation. SDG treatment before or after ACS exposure decreased the ClO(-) or γ-radiation-induced chlorination of 2-AP. Exposure to γ-radiation resulted in increased taurine chlorination, indicative of ClO(-) generation. NMR studies revealed formation of primary ACS radicals (chlorine atoms (Cl) and dichloro radical anions (Cl2¯)), which were trapped by SDG and its structural analog dopamine. We demonstrate that γ-radiation induces the generation of ACS in physiological solutions. SDG treatment scavenged

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

In vivo imaging of free radicals produced by multivitamin-mineral supplements

Science.gov (United States)

Buettner, Garry R.; Fink, Bruno

2015-01-01

Background Redox active minerals in dietary supplements can catalyze unwanted and potentially harmful oxidations. Methods To determine if this occurs in vivo we employed electron paramagnetic (EPR) imaging. We used 1-hydroxy-3-carboxy-2,2,5,5-tetramethylpyrrolidine (CPH) as a reporter for one-electron oxidations, e.g. free radical-mediated oxidations; the one-electron oxidation product of CPH, 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (CP•), is a nitroxide free radical that is relatively persistent in vivo and detectable by EPR. As model systems, we used research formulations of vitamin mineral supplements (RVM) that are typical of commercial products. Results In in vitro experiments, upon suspension of RVM in aqueous solution, we observed: (1) the uptake of oxygen in the solution, consistent with oxidation of the components in the RVM; (2) the ascorbate free radical, a real-time indicator of ongoing oxidations; and (3) when amino acid/oligosaccharide (AAOS; glycinate or aspartate with non-digestible oligofructose) served as the matrix in the RVM, the rate of oxidation was significantly slowed. In a murine model, EPR imaging showed that the ingestion of RVM along with CPH results in the one-electron oxidation of CPH by RVM in the digestive system. The resulting CP• distributes throughout the body. Inclusion of AAOS in the RVM formulation diminished the oxidation of CPH to CP• in vivo. Conclusions These data demonstrate that typical formulations of multivitamin/multimineral dietary supplements can initiate the oxidation of bystander substances and that AAOS-complexes of essential redox active metals, e.g. copper and iron, have reduced ability to catalyze free radical formation and associated detrimental oxidations when a part of a multivitamin/multimineral formulation. PMID:26705481

Marine Vibrio Species Produce the Volatile Organic Compound Acetone

OpenAIRE

Nemecek-Marshall, M.; Wojciechowski, C.; Kuzma, J.; Silver, G. M.; Fall, R.

1995-01-01

While screening aerobic, heterotrophic marine bacteria for production of volatile organic compounds, we found that a group of isolates produced substantial amounts of acetone. Acetone production was confirmed by gas chromatography, gas chromatography-mass spectrometry, and high-performance liquid chromatography. The major acetone producers were identified as nonclinical Vibrio species. Acetone production was maximal in the stationary phase of growth and was stimulated by addition of l-leucine...

Using an integral-field unit spectrograph to study radical species in cometary coma

Science.gov (United States)

Lewis, Benjamin; Pierce, Donna M.; Vaughan, Charles M.; Cochran, Anita

2015-01-01

We have observed several comets using an integral-field unit spectrograph (the George and Cynthia Mitchell Spectrograph) on the 2.7m Harlan J. Smith telescope at McDonald Observatory. Full-coma spectroscopic images were obtained for various radical species (C2, C3, CN, NH2). Various coma enhancements were used to identify and characterize coma morphological features. The azimuthal average profiles and the Haser model were used to determine production rates and possible parent molecules. Here, we present the work completed to date, and we compare our results to other comet taxonomic surveys. This work was funded by the National Science Foundation Graduate K-12 (GK-12) STEM Fellows program (Award No. DGE-0947419), NASA's Planetary Atmospheres program (Award No. NNX14AH18G), and the Fund for Astrophysical Research, Inc.

μSR spectroscopy on free radicals: a complement to ESR spectroscopy

International Nuclear Information System (INIS)

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

1986-12-01

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

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.

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

Directory of Open Access Journals (Sweden)

Atsushi Narumi

2018-06-01

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

Pulsed radiation studies of carotenoid radicals and excited states

International Nuclear Information System (INIS)

Burke, M.

2001-04-01

The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of β-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar (∼1 x 10 7 M -1 s -1 ) for β-carotene and zeaxanthin and somewhat lower (∼0.5 x 10 7 M -1 s -1 ) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for β-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number of conjugated double bonds, the longer chain systems having

CN radical in diffuse interstellar clouds

International Nuclear Information System (INIS)

Federman, S.R.; Danks, A.C.; Lambert, D.L.

1984-01-01

A survey of 15 lines of sight for the CN B 2 Σ + --X 2 Σ + interstellar absorption lines shows that the CN column density in diffuse interstellar clouds follows the relation log N(CN)proportionalm log N(H 2 ), where mroughly-equal3. This result is reproduced by a reaction network in which CN is produced primarily from C 2 by the neutral-neutral reaction C 2 +N → CN+C, and photodissociation is the main destruction pathway for the neutral molecules CH, C 2 , and CN. The CN radical is the first molecular species observed in diffuse clouds that requires a neutral-neutral reaction for its formation in the gas phase. The network also reproduces the observed ratio N(CN)/N(H 2 )

Oxygen activation at the plasma membrane: relation between superoxide and hydroxyl radical production by isolated membranes.

Science.gov (United States)

Heyno, Eiri; Mary, Véronique; Schopfer, Peter; Krieger-Liszkay, Anja

2011-07-01

Production of reactive oxygen species (hydroxyl radicals, superoxide radicals and hydrogen peroxide) was studied using EPR spin-trapping techniques and specific dyes in isolated plasma membranes from the growing and the non-growing zones of hypocotyls and roots of etiolated soybean seedlings as well as coleoptiles and roots of etiolated maize seedlings. NAD(P)H mediated the production of superoxide in all plasma membrane samples. Hydroxyl radicals were only produced by the membranes of the hypocotyl growing zone when a Fenton catalyst (FeEDTA) was present. By contrast, in membranes from other parts of the seedlings a low rate of spontaneous hydroxyl radical formation was observed due to the presence of small amounts of tightly bound peroxidase. It is concluded that apoplastic hydroxyl radical generation depends fully, or for the most part, on peroxidase localized in the cell wall. In soybean plasma membranes from the growing zone of the hypocotyl pharmacological tests showed that the superoxide production could potentially be attributed to the action of at least two enzymes, an NADPH oxidase and, in the presence of menadione, a quinone reductase.

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

Studies of the yields of 57Fe(II)-species produced after the EC-decay and of 60Co(II)-species produced in the (n, γ) reaction in cobalt(III) coordination compounds

International Nuclear Information System (INIS)

Sano, Hirotoshi; Harada, Masayuki; Endo, Kazutoyo

1978-01-01

The yields of 57 Fe(II)-species produced after EC-decay were compared with those of 60 Co(II)-species produced in the 59 Co(n, γ) 60 Co reaction for twelve cobalt(III) coordination compounds. The results indicate that the radiochemical yield of 60 Co(II)-species correlates with the yield of 57 Fe(II)-species except in the case of [Co(NH 3 ) 6 ] 2 (CrO 4 ) 3 . The anomalously low yield of 57 Fe(II)-species in [Co(NH 3 ) 6 ] 2 (CrO 4 ) 3 is ascribed to the reaction of chromate anions with ammine ligands initiated by the nuclear transformation in a solid. (author)

Use of a cocktail of spin traps for fingerprinting large range of free radicals in biological systems.

Science.gov (United States)

Marchand, Valérie; Charlier, Nicolas; Verrax, Julien; Buc-Calderon, Pedro; Levêque, Philippe; Gallez, Bernard

2017-01-01

It is well established that the formation of radical species centered on various atoms is involved in the mechanism leading to the development of several diseases or to the appearance of deleterious effects of toxic molecules. The detection of free radical is possible using Electron Paramagnetic Resonance (EPR) spectroscopy and the spin trapping technique. The classical EPR spin-trapping technique can be considered as a "hypothesis-driven" approach because it requires an a priori assumption regarding the nature of the free radical in order to select the most appropriate spin-trap. We here describe a "data-driven" approach using EPR and a cocktail of spin-traps. The rationale for using this cocktail was that it would cover a wide range of biologically relevant free radicals and have a large range of hydrophilicity and lipophilicity in order to trap free radicals produced in different cellular compartments. As a proof-of-concept, we validated the ability of the system to measure a large variety of free radicals (O-, N-, C-, or S- centered) in well characterized conditions, and we illustrated the ability of the technique to unambiguously detect free radical production in cells exposed to chemicals known to be radical-mediated toxic agents.

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

Science.gov (United States)

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

2015-01-01

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

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

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.

Spectroscopic studies of the molecular parentage of radical species in cometary comae

Science.gov (United States)

Lewis, Benjamin; Pierce, Donna; Cochran, Anita

2015-11-01

We have observed several comets using an integral-field unit spectrograph (the George and Cynthia Mitchell Spectrograph) on the 2.7m Harlan J. Smith telescope at McDonald Observatory. Full-coma spectroscopic images were obtained for various radical species (C2, C3, CH, CN, NH2). By constructing azimuthal average profiles from the full-coma spectroscopic images we can test Haser model parameters with our observations. The Haser model was used to determine production rates and possible parent lifetimes that would be consistent with the model. By iterating through a large range of possible parents lifetimes, we can see what range of values in which the Haser model is consistent with observations. Also, this type of analysis gives us perspective on how sensitive the model's fit quality is to changes in parent lifetimes. Here, we present the work completed to date, and we compare our results to other comet taxonomic surveys.

EPR imaging and HPLC characterization of the pigment-based organic free radical in black soybean seeds.

Science.gov (United States)

Nakagawa, Kouichi; Maeda, Hayato

2017-02-01

We investigated the location and distribution of paramagnetic species in dry black, brown, and yellow (normal) soybean seeds using electron paramagnetic resonance (EPR), X-band (9 GHz) EPR imaging (EPRI), and HPLC. EPR primarily detected two paramagnetic species in black soybean. These two different radical species were assigned as stable organic radical and Mn 2+  species based on the g values and hyperfine structures. The signal from the stable radical was noted at g ≈ 2.00 and was relatively strong and stable. Subsequent noninvasive two-dimensional (2D) EPRI of the radical present in black soybean revealed that the stable radical was primarily located in the pigmented region of the soybean coat, with very few radicals observed in the soybean cotyledon (interior). Pigments extracted from black soybean were analyzed using HPLC. The major compound was found to be cyanidin-3-glucoside. Multi-EPR and HPLC results indicate that the stable radical was only found within the pigmented region of the soybean coat, and it could be cyanidin-3-glucoside or an oxidative decomposition product.

Guild of Frugivores on three fruit-producing tree species Polyscias ...

African Journals Online (AJOL)

Guild of Frugivores on three fruit-producing tree species Polyscias fulva, Syzyguim Guineensis SUBSP. Bamensdae and Pouteria Altissima ) in Ngel Nyaki Forest Reserve, a Montane Forest Ecosystem in Nigeria.

Electron spin ressonance of radicals produced by ultra-violet photolysis of KCL dopped with potassium cyanide and potassium cyanate

International Nuclear Information System (INIS)

Duran, J.E.R.

1975-01-01

The production of radicals by ultra-violet photolysis of KCL dopped with potassium cyanide and potassium cyanate is studied by electron spin resonance. Several new paramagnetic species are detected which are identified as HCNO - , NCN - /NCNO - , CNN - /CNON - and CNOsup(=) all giving isotropic spectra at 77 0 K. The temperature dependence of the CNOsup(=) spectrum is investigated down to 1.6 0 K. It is found that two different recrientation motions ocurr which freeze at different temperatures. The effect of this motion on the line width is analized using Anderson's theory of exchange narrowing. The electronic structure of the CNOsup(=) radical is discussed using the measured the carbon and nitrogen hfs constants. It is found that a bonding scheme similar to that accepted for the isoelectronic molecule NO 2 is applicable, and a one electron molecular orbital scheme is given. Within this scheme a negative contribution to the nitrogen isotropic hfs constant is found which is assumed to originate from the polarization of the fully occupied ls orbitals [pt

Free radicals in cellulose containing food detected by ESR

International Nuclear Information System (INIS)

Abe, Aika; Yogo, Satsuki; Ichii, Akane; Ukai, Mitsuko

2003-01-01

Using electron spin resonance (ESR) spectroscopy, we revealed three radical species in cellulose containing foods, pepper and green tea. These are commercially available in Japan. The representative ESR spectrum is composed of a sextet centered at g=2.0, a singlet at the same g-value, and a singlet at g=4.0. The first one is attributable to a signal with hyperfine (hf) interactions of Mn 2+ ion (hf constant: 7.4 mT). The second one is due to an organic free radical, the third one may be originated from Fe 3+ ion. The progressive saturation behavior (PSB) of the ESR at various microwave power levels were indicated different relaxation behaviors of in those radicals. Namely, the peak intensity of the organic free radical component decreases in a monotonic fashion, whereas the Mn 2+ and Fe 3+ ESR signals substantially keep constant. This reflects the evidence of three independent radical species. The ESR spectrum of the cellulose containing foods shows the same spectral feature irrespective of the tea or pepper. Upon gamma irradiation, a new pair of signals appeared. The PSB of the pair peaks after the irradiation showed a quite different as compared with the free radical centered at g=2. (author)

Investigations of structure, bonding, and reactions of radiation-induced free radicals in the solid state using electron spin resonance spectroscopy

International Nuclear Information System (INIS)

Hudson, R.L.

1978-01-01

Electron spin resonance spectroscopy (ESR) has been used to study the structure, bonding, and reactions of several types of free radicals produced by γ irradiation of solids at 77K. Well-defined spectral patterns and the use of photolysis and annealing treatments assisted the analyses and interpretations. The radical anion BF 3 - was generated and identified unequivocally in a matrix of tetramethylsilane at 77K. Both the ESR data and theoretical calculations support a pyramidal structure with a bond angle of about 110 0 . The present experiments showed that BF 3 - has ESR parameters consistent with those of the isoelectronic radicals CF 3 , NF 3 + , and F 2 NO. γ irradiation of polycrystalline trimethyl borate at 77K gave an ESR spectrum which was assigned to the dimer radical anion [(MeO) 3 B.B(OMe) 3 ] - . Radical anions of dialkyl carbonates were observed for the first time and found to undergo a β-scission reaction to produce alkyl radicals. This free radical reaction is unusual in that it proceeds both thermally and photochemically. For the dimethyl carbonate radical anion, 13 C parameters were obtained from a 13 C enriched sample. The photolysis of trapped radicals in γ irradiated carboxylic esters, RC(O)OR', was studied by ESR spectroscopy and two different reactions were characterized. Two hypervalent silicon radical anions were prepared and examined in SI(OCH 3 ) 4 . The results of the present work thus represent the first complete sets of data on the silicon 3s and 3p spin densities for such species. The first PL 3 - radical anion was prepared by the γ irradiation of crystalline trimethylphosphite, and identified through its photolysis reactions and from the results of radiation chemical experiments

Radical pair formation in γ-irradiated 2-methyltetrahydrofuran rigid solutions of polynitrobenzenes

International Nuclear Information System (INIS)

Konishi, S.; Hoshino, M.; Imamura, M.

1981-01-01

The γ-irradiated MTHF (2-methyltetrahydrofuran) rigid solutions of mDNB (m-dinitrobenzene) and sTNB (s-trinitrobenzene) showed at 77 K ESR spectra characteristic of triplet species in addition to the spectra of doublet species, whereas no triplet ESR spectra were observed for the mononitrobenzene and o- and p-di-nitrobenzene solutions. The distances of the unpaired spins evaluated from the observed fine structure constants by using a point-dipole approximation are 4.3 and 4.6 A for the mDNB solution and 3.9 and 4.7 A for the sTNB solution. The detection of only the solute anion radicals by the optical absorption spectra of the irradiated solutions and the difference of the rate of formation for the triplet species and the solute anion strongly suggest that the triplet species are ascribed to the solute anion-solvent radical pairs. Such radical pairs are most likely to be formed through the migration of a MTHF cation radical, i.e., so-called hole migration, to a specific site between the two nitro groups on the meta positions of a solute anion followed by the production of a stable solvent radical, which is paired with the solute anion

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

Studies on free radical scavenging activity in Chinese seaweeds part I. Screening results

Science.gov (United States)

Yan, Xiao-Jun; Fang, Guo-Ming; Lou, Qing-Xiang

1999-09-01

Antioxidants have attracted the attention of researchers due to their beneficial effects as free radical scavengers. Application of a stable free radical named 1, 1-diphenyl-2-picrylhydrazyl(DPPH) to screen the free radical scavenging activity in 27 species of Chinese seaweed showed that 15 of them had significant activity in at least one of the organic solvent extracts. The most interesting seaweed species were Gelidium amansii, Gloiosiphonia capillaris, Polysiphonia urceolata, Sargassum kjellmanianum, Desmarestia viridis, and Rhodomela teres.

Pulsed radiation studies of carotenoid radicals and excited states

Energy Technology Data Exchange (ETDEWEB)

Burke, M

2001-04-01

The one-electron reduction potentials of the radical cations of five dietary carotenoids, in aqueous micellar environments, have been obtained from a pulse radiolysis study of electron transfer between the carotenoids and tryptophan radical cations as a function of pH, and lie in the range 980 to 1060 mV. The decays of the carotenoid radical cations suggest a distribution of exponential lifetimes. The radicals persist for up to about one second, depending on the medium and may re-orientate within a biological environment to react with other biomolecules, such as tyrosine, cysteine or ascorbic acid, which was indeed confirmed. Spectral information of carotenoid pigmented liposomes has been collected, subsequently pulse radiolysis was used to generate the radical cations of {beta}-carotene, zeaxanthin and lutein, in unilamellar vesicles of dipalmitoyl phosphatidyl choline. The rate constants for the 'repair' of these carotenoid radical cations by water-soluble vitamin C were found to be similar ({approx}1 x 10{sup 7} M{sup -1}s{sup -1}) for {beta}-carotene and zeaxanthin and somewhat lower ({approx}0.5 x 10{sup 7} M{sup -1}s{sup -1}) for lutein. The results are discussed in terms of the microenvironment of the carotenoids and suggest that for {beta}-carotene, a hydrocarbon carotenoid, the radical cation is able to interact with a water-soluble species even though the parent hydrocarbon carotenoid is probably entirely in the non-polar region of the liposome. Studies investigating the ability of ingested lycopene to protect human lymphoid cells against singlet oxygen and nitrogen dioxide radical mediated cell damage have shown that a high lycopene diet is beneficial in protecting human cells against reactive oxygen species. Triplet states of carotenoids were produced in benzene solvent and their triplet lifetimes were found to depend on the concentration of the parent molecule. The rate constants obtained for ground state quenching correlate with the number

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.

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.

Role of distonic dimer radical cations in the radiation-induced polymerisation of vinyl ethers

International Nuclear Information System (INIS)

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

2005-01-01

The experimental low-temperature EPR results and the quantum chemical calculations suggest that dimer radical cations of cyclic and aliphatic vinyl ethers (VE) plays a key role in starting of radiation-induced polymerisation. The main species observed at high 2,3-dihydrofuran (DHF), 2,3-dihydropyran (DHP) and VE concentration is the dimer radical cation. In the case of cyclic VE the dimer radical cation transforms through H-abstraction from neutral molecule into a carbocation and radical, which could start both cationic and free-radical polymerisation. However, in the case of aliphatic VE no further reactive species, which could start polymerisation, were observed. This is caused (in agreement with experiment and quantum chemical calculations) by the very high stability of dimer radical cation and calculated endothermity of H-abstraction reaction by dimer radical cation from monomer

The role of water radicals in thermorestoration of bacterial spores

International Nuclear Information System (INIS)

Friedman, Y.S.; Grecz, N.

1974-01-01

Fully hydrated bacterial spores exposed to 0.45 Mrad showed a characteristic pattern of survival associated with thermorestoration. When temperature during radiation was controlled at -15 0 to +120 0 C, the lowest viable cell counts were at 0 0 C. Above 0 0 C radiosurvival gradually increased by 2 to 3 log cycles reaching peak at 75 0 C (Bacillus cereus T heat sensitive spores) and at 95 0 C (B.stearothermophilus, heat resistant spores). Simultaneously high survival was observed in the solidly frozen state at -15 0 C to -5 0 C since harmful radicals produced by radiation were trapped in ice. Radiation modifying effects, i.e., protection by 2M ethanol (a scavenger of OH radicals) and sensitization by 1M sodium nitrate (a scavenger of H radicals and hydrated electrons), were studied. The results with ethanol and nitrate confirm the idea that in aqueous sytems below 50 0 C the lethal action is due to oxidizing OH radicals known to attack cell DNA. However, the reversal of scavenger actions above 50 0 C indicates that at those high temperatures lethal effects may also involve the reducing H and esub(aq), which at lower temperatures appear not to affect spore survival though they are known to attack proteins. In this case, it is proposed that radiation inactivation of spores at temperatures below 50 0 C is due to DNA damage inflicted by OH radicals whereas spore death above 50 0 C seems to involve protein /enzyme/ inactivation due to a combined action of heat plus reducing (H, esub(aq)) as well as oxidizing (OH) radical species. From the practical point of view it is important that normally radioprotective effects of such substances as ethanol or ground beef are progressively lost when radiation is carried out at temperatures above 50 0 C. (F.J.)

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

New penicillin-producing Penicillium species and an overview of section Chrysogena

DEFF Research Database (Denmark)

Houbraken, J.; Frisvad, Jens Christian; Seifert, K. A.

2012-01-01

Species classified in Penicillium sect. Chrysogena are primary soil-borne and the most well-known members are P. chrysogenum and P. nalgiovense. Penicillium chrysogenum has received much attention because of its role in the production on penicillin and as a contaminant of indoor environments....... Each species produces a unique extrolite profile. The species share phenotypic characters, such as good growth on CYA supplemented with 5 % NaCl, ter- or quarterverticillate branched conidiophores and short, ampulliform phialides (colours, production of ascomata and ascospores, shape...

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.

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...

ESR and spin-trapping study of room-temperature radicals in γ-irradiated polycrystalline pyrimidine nucleotides

International Nuclear Information System (INIS)

Zhang, Z.; Kuwabara, M.; Yoshii, G.

1983-01-01

Free radicals produced in γ-irradiated polycrystalline 5'-dCMP (free acid and 2Na), 3'-CMP (free acid and Li), and 5'-UMP (2Na) were studied by ESR and spin-trapping. The results were compared with those of previous single-crystal studies. Furthermore, attempts to identify free radicals in γ-irradiated 5'-dUMP (2Na), 5'-CMP (free acid and 2Na), and 3'-UMP (Na), which have not been the subject of single-crystal studies to date, were made. After γ-irradiation at room temperature to a dose of 100 kGy, the polycrystalline samples were dissolved in aqueous solutions of t-nitrosobutane in the presence or absence of oxygen. The presence or absence of oxygen was helpful in analyzing the presence of more than one radical species. Thus two types of radicals could be established for all samples. Radical -C 5 H-C 6 H 2 -, formed by H addition to the double bond of the base, was observed in the presence of oxygen, and radical -C/sub 5'/H 2 , formed by the transformation of the radical due to loss of an H atom at the C/sub 5'/ position of the sugar moiety, was observed in the absence of oxygen. In some cases, radicals located at the C/sub 1'/, C/sub 4'/, and C/sub 5'/ of the sugar moiety were tentatively identified. For the ESR spectrum associated with radical at C/sub 1'/ the possibility of another explanation was also discussed in relation to the spectrum due to radical at C 5 of the base. Radical -C 5 H 2 -C 6 H-, formed by H addition to the double bond of the base, was not identified

Allelopathic effect of scarlet pimpernel (anagallis arvensis) on seed germination and radical elongation of mung bean and pearl millet

International Nuclear Information System (INIS)

Salam, I.U.; Ahmed, M.; Ali, S.T.

2011-01-01

The green house based experiments were conducted in the Department of Botany FUUAST, Karachi to study the allelopathic effects of root and shoot leachates of Anagallis arvensis on the two test species viz., bajra and mungbean. The percentage of seed germination, speed of germination and radical elongation of the test species were recorded after 10 days. Both leachates have no effect on seed germination and speed of germination of the test species. Radical elongation of two test species showed different response. Mung radical growth was significantly reduced while bajra radical growth was significantly enhanced by the root leachate of weed. (author)

Visible light-induced OH radicals in Ga2O3: an EPR study.

Science.gov (United States)

Tzitrinovich, Zeev; Lipovsky, Anat; Gedanken, Aharon; Lubart, Rachel

2013-08-21

Reactive oxygen species (ROS) were found to exist in water suspensions of several metal oxide nanoparticles (NPs), such as CuO, TiO2 and ZnO. Visible light irradiation enhanced the capability of TiO2 and ZnO NPs to generate ROS, thus increasing their antibacterial effects. Because of the possible toxic effects on the host tissue it is desired to find nano-metal oxides which do not produce ROS under room light, but only upon a strong external stimulus. Using the technique of electron-spin resonance (ESR) coupled with spin trapping, we examined the ability of Ga2O3 submicron-particle suspensions in water to produce reactive oxygen species with and without visible light irradiation. We found that in contrast to ZnO and TiO2 NPs, no ROS are produced by Ga2O3 under room light. Nevertheless blue light induced hydroxyl radical formation in Ga2O3. This finding might suggest that NPs of Ga2O3 could be used safely for infected skin sterilization.

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.

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

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

Reactions of Hydroxyalkyl Radicals with Cysteinyl Peptides in a NanoESI Plume

Science.gov (United States)

Stinson, Craig A.; Xia, Yu

2014-07-01

In biological systems, carbon-centered small molecule radicals are primarily formed via external radiation or internal radical reactions. These radical species can react with a variety of biomolecules, most notably nucleic acids, the consequence of which has possible links to gene mutation and cancer. Sulfur-containing peptides and proteins are reactive toward a variety of radical species and many of them behave as radical scavengers. In this study, the reactions between alkyl alcohol carbon-centered radicals (e.g., •CH2OH for methanol) and cysteinyl peptides within a nanoelectrospray ionization (nanoESI) plume were explored. The reaction system involved ultraviolet (UV) irradiation of a nanoESI plume using a low pressure mercury lamp consisting of 185 and 254 nm emission bands. The alkyl alcohol was added as solvent into the nanoESI solution and served as the precursor of hydroxyalkyl radicals upon UV irradiation. The hydroxyalkyl radicals subsequently reacted with cysteinyl peptides either containing a disulfide linkage or free thiol, which led to the formation of peptide- S-hydroxyalkyl product. This radical reaction coupled with subsequent MS/MS was shown to have analytical potential by cleaving intrachain disulfide linked peptides prior to CID to enhance sequence information. Tandem mass spectrometry via collision-induced dissociation (CID), stable isotope labeling, and accurate mass measurement were employed to verify the identities of the reaction products.

Role of free radicals in radiation chemical aging

Energy Technology Data Exchange (ETDEWEB)

Greenstock, C L

1986-01-01

Ionizing radiation initiates chemical changes in DNA, phospholipid membranes and other critical cell targets, that, if allowed to accumulate unrepaired, may lead to aging and other chronic effects. The chemical effects are free radical mediated, the principal damaging species being radical OH and to a lesser extent O2-anion radical and the molecular product H/sub 2/O/sub 2/. Many compounds can act in combination with ionizing radiation, to amplify the potential oxidative stress. Chemicals, ultra-violet light, lipid peroxides and their breakdown products may increase the extent of acute and chronic radiobiological effects.

Atomic collisions research with excited atomic species

International Nuclear Information System (INIS)

Hoogerland, M.D.; Gulley, R.J.; Colla, M.; Lu, W.; Milic, D.; Baldwin, K.G.H.; Buckman, S.J.

1999-01-01

Measurements and calculations of fundamental atomic collision and spectroscopic properties such as collision cross sections, reaction rates, transition probabilities etc. underpin the understanding and operation of many plasma and gas-discharge-based devices and phenomena, for example plasma processing and deposition. In almost all cases the complex series of reactions which sustains the discharge or plasma, or produces the reactive species of interest, has a precursor electron impact excitation, attachment, dissociation or ionisation event. These processes have been extensively studied in a wide range of atomic and molecular species and an impressive data base of collision cross sections and reaction rates now exists. However, most of these measurements are for collisions with stable atomic or molecular species which are initially in their ground electronic state. Relatively little information is available for scattering from excited states or for scattering from unstable molecular radicals. Examples of such species would be metastable excited rare gases, which are often used as buffer gases, or CF 2 radicals formed by electron impact dissociation in a CF 4 plasma processing discharge. We are interested in developing experimental techniques which will enable the quantitative study of such exotic atomic and molecular species. In this talk I would like to outline one such facility which is being used for studies of collisions with metastable He(2 3 S) atoms

Emericella venezuelensis, a new species with stellate ascospores producing sterigmatocystin and aflatoxin B-1

DEFF Research Database (Denmark)

Frisvad, Jens Christian; Samson, R.A.

2004-01-01

Emericella venezuelensis is a new species, differing from two other species with stellate ascospores, E. variecolor and E. pluriseminata, by triangular flaps on the convex sides of the ascospores, and further from E. variecolor by producing an Aspergillus anamorph only on unconventional growth......, variecoxanthone A, B, C, isoemericellin, kojic acid, varitriol, varioxiran, dihydroterrein, 7-hydroxyemodin, avariquinone and stromemycin. E. pluriseminata produces several unknown specific extrolites. E. venezuelensis is the first organism of marine origin reported to produce aflatoxin. Aflatoxin production by E....... venezuelensis makes this species an attractive model organism for the study of the regulation of this important type of carcinogenic mycotoxins in combination with the knowledge on sterigmatocystin production by E. nidulans, soon to be whole genome sequenced. The isolates were also analyzed cladistically using...

Infrared Spectra of the n-PROPYL and i-PROPYL Radicals in Solid Para-Hydrogen

Science.gov (United States)

Pullen, Gregory T.; Franke, Peter R.; Douberly, Gary E.; Lee, Yuan-Pern

2017-06-01

We report the infrared spectra of the n-propyl and i-propyl radicals measured in solid para-hydrogen (p-H_2) matrices at 3.2 K. n-Propyl and i-propyl radicals were produced via the 248 nm irradiation of matrices formed by co-depositing p-H_2 and either 1-Iodopropane (n-propyl) or 2-Iodopropane (i-propyl). Secondary photolysis was used to group spectral lines all due to the same species. Lines in the C-H stretching region were compared to previous work using the Helium Nanodroplet Isolation (HENDI) technique, and are in excellent agreement. In addition to a few lines previously measured in Ar matrices, we observe many previously unreported bands below 2000 \\wn, which we attribute to the n-propyl and i-propyl radicals. The assignment of features below 2000 \\wn are made via comparisons to anharmonic VPT2+K frequency computations. Peter R. Franke, Daniel P. Tabor, Christopher P. Moradi, Gary E. Douberly, Jay Agarwal, Henry F. Schaefer III, and Edwin L. Sibert III, Journal of Chemical Physics 145, 224304 (2016).

Fast Resonance Raman Spectroscopy of Short-Lived Radicals

DEFF Research Database (Denmark)

Pagsberg, Palle Bjørn; Wilbrandt, Robert Walter; Hansen, Karina Benthin

1976-01-01

We report the first application of pulsed resonance Raman spectroscopy to the study of short-lived free radicals produced by pulse radiolysis. A single pulse from a flash-lamp pumped tunable dye laser is used to excite the resonance Raman spectrum of the p-terphenyl anion radical with an initial...

Knock investigation by flame and radical species detection in spark ignition engine for different fuels

International Nuclear Information System (INIS)

Merola, Simona S.; Vaglieco, Bianca M.

2007-01-01

The present paper aims to evaluate the phenomena of normal combustion and knocking in a single cylinder, ported fuel injection, four-stroke spark-ignition engine with a four-valve production head. All the measurements were realized in an optically accessible engine equipped with a wide quartz window in the bottom of the chamber. The study was carried out using optical techniques based on flame natural emission imaging and spectroscopy from UV to visible. Radical species such as OH and HCO were detected and correlated to the onset and the duration of knock and presence of hot-spots in end-gas. Measurements were carried out at 1000 rpm with wide-open throttle and stoichiometric mixture. Pure iso-octane, suitable mixtures of iso-octane and n-heptane and commercial gasoline were used

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

Science.gov (United States)

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

2012-10-01

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

Particle size-dependent radical generation from wildland fire smoke

International Nuclear Information System (INIS)

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

2007-01-01

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

Controlling Fluences of Reactive Species Produced by Multipulse DBDs onto Wet Tissue: Frequency and Liquid Thickness

Science.gov (United States)

Tian, Wei; Kushner, Mark J.

2015-09-01

Tissue covered by a thin liquid layer treated by atmospheric pressure plasmas for biomedical applications ultimately requires a reproducible protocol for human healthcare. The outcomes of wet tissue treatment by dielectric barrier discharges (DBDs) depend on the plasma dose which determines the integral fluences of radicals and ions onto the tissue. These fluences are controlled in part by frequency and liquid thickness. In this paper, we report on results from a computational investigation of multipulse DBDs interacting with wet tissue. The DBDs were simulated for 100 stationary or random streamers at different repetition rates and liquid thicknesses followed by 10 s to 2 min of afterglow. At 100 Hz, NOaq and OHaq are mixed by randomly striking streamers, although they have different rates of solvation. NOaq is nearly completely consumed by reactions with OHaq at the liquid surface. Only H2O2aq, produced through OHaq mutual reactions, survives to reach the tissue. After 100 pulses, the liquid becomes ozone-rich, in which the nitrous ion, NO2-aq, is converted to the nitric ion, NO3-aq. Reducing the pulse frequency to 10 Hz results in significant fluence of NOaq to the tissue as NOaq can escape during the interpulse period from the liquid surface where OHaq is formed. For the same reason, NO2-aq can also reach deeper into the liquid at lower frequency. Frequency and thickness of the liquid are methods to control the plasma produced aqueous species to the underlying tissue. Work supported by DOE (DE-SC0001319) and NSF (CHE-1124724).

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.

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.

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.

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)

Hydroxyl radical production in plasma electrolysis with KOH electrolyte solution

Energy Technology Data Exchange (ETDEWEB)

Saksono, Nelson; Febiyanti, Irine Ayu, E-mail: irine.ayu41@ui.ac.id; Utami, Nissa; Ibrahim [Department of Chemical Engineering, Universitas Indonesia, Depok 16424, Indonesia Phone: +62217863516, Fax: +62217863515 (Indonesia)

2015-12-29

Plasma electrolysis is an effective technology for producing hydroxyl radical (•OH). This method can be used for waste degradation process. This study was conducted to obtain the influence of applied voltage, electrolyte concentration, and anode depth in the plasma electrolysis system for producing hydroxyl radical. The materials of anode and cathode, respectively, were made from tungsten and stainless steel. KOH solution was used as the solution. Determination of hydroxyl radical production was done by measuring H{sub 2}O{sub 2} amount formed in plasma system using an iodometric titration method, while the electrical energy consumed was obtained by measuring the electrical current throughout the process. The highest hydroxyl radical production was 3.51 mmol reached with 237 kJ energy consumption in the power supply voltage 600 V, 0.02 M KOH, and 0.5 cm depth of anode.

The role of water radicals in thermorestoration of bacterial spores

Energy Technology Data Exchange (ETDEWEB)

Friedman, Y S; Grecz, N [Illinois Inst. of Tech., Chicago (USA). Dept. of Biology

1974-01-01

Fully hydrated bacterial spores exposed to 0.45 Mrad showed a characteristic pattern of survival associated with thermorestoration. When temperature during radiation was controlled at -15/sup 0/ to +120/sup 0/C, the lowest viable cell counts were at 0/sup 0/C. Above 0/sup 0/C radiosurvival gradually increased by 2 to 3 log cycles reaching peak at 75/sup 0/C (Bacillus cereus T heat sensitive spores) and at 95/sup 0/C (B.stearothermophilus, heat resistant spores). Simultaneously high survival was observed in the solidly frozen state at -15/sup 0/C to -5/sup 0/C since harmful radicals produced by radiation were trapped in ice. Radiation modifying effects, i.e., protection by 2M ethanol (a scavenger of OH radicals) and sensitization by 1M sodium nitrate (a scavenger of H radicals and hydrated electrons), were studied. The results with ethanol and nitrate confirm the idea that in aqueous sytems below 50/sup 0/C the lethal action is due to oxidizing OH radicals known to attack cell DNA. However, the reversal of scavenger actions above 50/sup 0/C indicates that at those high temperatures lethal effects may also involve the reducing H and esub(aq), which at lower temperatures appear not to affect spore survival though they are known to attack proteins. In this case, it is proposed that radiation inactivation of spores at temperatures below 50/sup 0/C is due to DNA damage inflicted by OH radicals whereas spore death above 50/sup 0/C seems to involve protein /enzyme/ inactivation due to a combined action of heat plus reducing (H, esub(aq)) as well as oxidizing (OH) radical species. From the practical point of view it is important that normally radioprotective effects of such substances as ethanol or ground beef are progressively lost when radiation is carried out at temperatures above 50/sup 0/C.

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

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

Science.gov (United States)

Fabbri, Claudia; Bietti, Massimo; Lanzalunga, Osvaldo

2005-04-01

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

Radical Addition to Iminium Ions and Cationic Heterocycles

Directory of Open Access Journals (Sweden)

Johannes Tauber

2014-10-01

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

Test for antioxidant ability by scavenging long-lived mutagenic radicals in mammalian cells and by blood test with intentional radicals: an application of gallic acid

International Nuclear Information System (INIS)

Kumagai, Jun; Kawaura, Tomoko; Miyazaki, Tetsuo; Prost, Michel; Prost, Emmanuelle; Watanabe, Masami; Quetin-Leclercq, J.Joeelle

2003-01-01

Antioxidant ability of gallic acid (GA) are determined both by electron spin resonance measurement of long-lived radicals produced in γ-ray irradiated Syrian golden hamster embryo cells with GA and by hemolysis measurement with GA when blood cells are submitted to radicals. Scavenging properties of GA are determined by the reaction rate constant with long-lived mutagenic radicals in the cells while the blood test allows to analyze the global effects of this compound: radical scavenger+metal ion chelator+regeneration of intra- and extra-cellular antioxidant

Study progress on free radicals and graves disease

International Nuclear Information System (INIS)

Zhang Ruiguo; Jin Jianhua

2009-01-01

Free radical-mediated oxidative injury has been closely implicated in the occurrence and development of many diseases. Graves disease was also accompanied by changes of the free radicals, especially for reactive oxygen species and reactive nitrogen, et al, and the oxidative stress can cause a certain degree of injury on the thyroid and other human important organs. Antithyroid drug and 131 I treatment of Graves disease, the oxidative and antioxidative parameters can also be changed. (authors)

Primordial germ cell-mediated chimera technology produces viable pure-line Houbara bustard offspring: potential for repopulating an endangered species.

Directory of Open Access Journals (Sweden)

Ulrich Wernery

2010-12-01

Full Text Available The Houbara bustard (Chlamydotis undulata is a wild seasonal breeding bird populating arid sandy semi-desert habitats in North Africa and the Middle East. Its population has declined drastically during the last two decades and it is classified as vulnerable. Captive breeding programmes have, hitherto, been unsuccessful in reviving population numbers and thus radical technological solutions are essential for the long term survival of this species. The purpose of this study was to investigate the use of primordial germ cell-mediated chimera technology to produce viable Houbara bustard offspring.Embryonic gonadal tissue was dissected from Houbara bustard embryos at eight days post-incubation. Subsequently, Houbara tissue containing gonadal primordial germ cells (gPGCs was injected into White Leghorn chicken (Gallus gallus domesticus embryos, producing 83/138 surviving male chimeric embryos, of which 35 chimeric roosters reached sexual maturity after 5 months. The incorporation and differentiation of Houbara gPGCs in chimeric chicken testis were assessed by PCR with Houbara-specific primers and 31.3% (5/16 gonads collected from the injected chicken embryos showed the presence of donor Houbara cells. A total of 302 semen samples from 34 chimeric roosters were analyzed and eight were confirmed as germline chimeras. Semen samples from these eight roosters were used to artificially inseminate three female Houbara bustards. Subsequently, 45 Houbara eggs were obtained and incubated, two of which were fertile. One egg hatched as a male live born Houbara; the other was female but died before hatching. Genotyping confirmed that the male chick was a pure-line Houbara derived from a chimeric rooster.This study demonstrates for the first time that Houbara gPGCs can migrate, differentiate and eventually give rise to functional sperm in the chimeric chicken testis. This approach may provide a promising tool for propagation and conservation of endangered avian

Dissociation of metastable CH3CO radicals studied by time-resolved photofragment imaging

Science.gov (United States)

Suzuki, Toshinori; Shibata, Takeshi; Li, Haiyang

1998-05-01

A novel experimental technique to measure the energy- dependent unimolecular dissociation rate k(E) of radical species is presented. Internally excited CH3CO radicals were formed by ultraviolet photodissociation of CH3COCl, and the subsequent decay of these radicals was detected by subpicosecond time-clocked photofragment imaging. The CH3CO radicals with different internal energies were dispersed in space by their recoil velocities, and their decay rates were measured for each internal energy.

Muon level crossing resonance spectroscopy applied to free-radical formation

International Nuclear Information System (INIS)

Venkateswaran, K.; Barnabas, M.V.; Walker, D.C.

1989-01-01

Muon Level Crossing Resonance Spectroscopy has been used to explore two aspects of muonium chemistry: unique free radicals and muonated radical yields. (1) A variety of new free-radicals have been seen by LCR. For instance, in thioacetamide the only radical produced from muonium is the S sm-bullet radical formed when Mu adds to the C of the C=S bond. In allylbenzene a whole range of radicals form with substantial yields (two side-chain and three ring additions); whereas in styrene, 85% of the radicals have Mu bonded to the end C of the side-chain and there is no meta-adduct at all. (2) Absolute yields of the radicals formed by interaction of muonium atoms in water with acrylamide as a solute (and with benzene in n-hexane) have shown that all muons not directly incorporated into diamagnetic molecules (such as MuH) appear as muonated free radicals. i.e. the missing fraction is found

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

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

Geminate free radical processes and magnetic field effects

International Nuclear Information System (INIS)

Eveson, Robert W.

2000-01-01

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

Thermal evolution of the morphology of Ni/Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface

Energy Technology Data Exchange (ETDEWEB)

Tomaszewska, Agnieszka; Huang, Xiao-Lan; Chang, Kuo-Wei; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

2012-08-31

The temperature-driven changes in morphology of the interface formed by room temperature (RT) deposition of Ni atoms onto an Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface were investigated by scanning tunneling microscopy. Roughly 70% of Ni deposition diffused into bulk substrate within the temperature range between RT and 573 K. The images as obtained after annealing up to 670 K correspond to the formation of nano-sized islands of nickel silicides. Two types of islands, large triangular islands typical of the whole range of applied coverage, and smaller islands of different shapes, coexist at Ni coverage higher than 1 monolayer. Annealing above 870 K led to the formation of a 7 Multiplication-Sign 7 phase in coexistence with small 5 Multiplication-Sign 5 domains at the expense of a complete disappearance of the {radical}3 Multiplication-Sign {radical}3 phase. Also, formation of Ni,Si alloy was observed at the temperature, along with segregation of bulk-dissolved Ni species onto the surface. - Highlights: Black-Right-Pointing-Pointer We examine changes in morphology of Ni/Ag/Si(111)-{radical}3 Multiplication-Sign {radical}3 surface upon annealing. Black-Right-Pointing-Pointer 70% of deposited Ni atoms diffuse into the bulk after annealing at 570 K. Black-Right-Pointing-Pointer A variety of nano-sized Ni, Si islands develops after annealing at 670 K. Black-Right-Pointing-Pointer 5 Multiplication-Sign 5 reconstruction as an evidence for mass transport during the island growth.

Formation of 5,6-dihydroxydihydrothymine-type products in DNA by hydroxyl radicals

International Nuclear Information System (INIS)

Remsen, J.F.; Roti, J.L.R.

1977-01-01

The purpose of the study is to determine whether 5,6-dihydroxydihydrothymine type products in purified DNA and in intact cells results from direct or indirect action and, if indirect, which radical species is primarily responsible. It is concluded that hydroxyl radical is primarily responsible. (U.K.)

Free radical scavenging properties of some wine probes

International Nuclear Information System (INIS)

Stasko, A.; Liptakova, M.; Malik, F.

1999-01-01

There are preliminary results of investigation of scavenging properties of 8 probes of Slovak wines (consisting of one reference, 3 probes of white wine and 4 probes of red wine). According to the literature so far, wine probes contain paramagnetic species (Mn 2+ , characterised with sextet spectrum, and a singlet line around g=2,00). In our probes we observed Mn 2+ signals, but no significant evidence for a single line of free radical was found. We can conclude that Mn 2+ content in the red wines is generally higher than in the white ones. Further, we investigated the scavenging activities of the probes adding solution of dinitropicryl hydrazyl (DPPH-stable radical) to them. Their ability to terminate free radicals resulted in the decrease of the final DPPH concentrations in the probes. The red wines have significantly higher capability to scavenge free radicals than the probes of white wines. (authors)

Modifications induced by swift heavy ions on poly(hydroxybutyrate-hydroxyvalerate) (PHB/HV) and poly(ε-caprolactone) (PCL). Part 2. Radicals characterization

International Nuclear Information System (INIS)

Rouxhet, L.; Mestdagh, M.; Legras, R.

2000-01-01

Modifications induced by different energetic heavy ions ( 40 Ar 9+ , 80 Kr 15+ , 129 Xe 24+ , 208 Pb 53+ and 208 Pb 56+ ) on poly(ε-caprolactone) (PCL) and poly(hydroxybutyrate-hydroxyvalerate) (PHB/HV) have been investigated by electron spin resonance (ESR). Indeed, film irradiation by heavy ions leads to, among other phenomena, the formation of radicals in the ion tracks. Thanks to ESR, it is possible to detect these radicals and to identify them or at least to characterize them by following the evolution of the radical signal as a function of parameters, like temperature, or the kinetic of disappearance of the radical species at ambient temperature in vacuum or ambient atmosphere. This study confirmed the generation of radicals by the irradiation of PHB/HV samples with energetic heavy ions reported in the literature. The study on PCL was not pursued after a few preliminary studies, revealing the presence of an ESR signal in the non-irradiated sample. Electronic stopping power has a major influence on radical decrease at ambient temperature. The ion used for the irradiation did not modify very much the radical signal and the evolution of the radicalar signal intensity with temperature. Different reasoning and experiments revealed that the glass transition temperature is a key temperature above which irreversible recombinations of the most stable radicals take place. A simulation study indicated that the most stable radical produced was probably a tertiary radical formed by the stabilization of the secondary radical resulting from the abstraction of a highly mobile hydrogen adjacent to the carbonyl

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

Science.gov (United States)

Wink, David A.; Desrosiers, Marc F.

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

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

Science.gov (United States)

Valavanidis, Athanasios; Vlachogianni, Thomais; Fiotakis, Konstantinos

2009-01-01

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

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

Directory of Open Access Journals (Sweden)

Konstantinos Fiotakis

2009-02-01

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

EPR detection of free radicals in UV-irradiated skin: mouse versus human

International Nuclear Information System (INIS)

Jurkiewicz, B.A.; Buettner, G.R.

1996-01-01

Ultraviolet radiation produces free radicals in Skh-1 mouse skin, contributing to photoaging and carcinogenesis. If a mouse model is a general indicator of free radical processes in human skin photobiology, then radical production observed in mouse and human skin should be directly comparative. In this work we show that UV radiation (λ > 300 nm, 14 μW/cm 2 UVB; 3.5 mW/cm 2 UVA) increases the ascorbate free radical (Asc) electron paramagnetic resonance (EPR) signal in both Skh-1 mouse skin (45%) and human facial skin biopsies (340%). Visible light (λ > 400 nm; 0.23 mW/cm 2 UVA) also increased the Ascsignal in human skin samples (45%) but did not increase baseline mouse Asc, indicating that human skin is more susceptible to free radical formation and that a chromophore for visible light may be present. Using EPR spin-trapping techniques, UV radiation produced spin adducts consistent with trapping lipid alkyl radicals in mouse skin (α-[4-pyridyl 1-oxide]-N-tert-butyl nitrone/alkyl radical adduct; a N = 15.56 G and a H 2.70 G) and lipid alkoxyl radicals in human skin (5,5-dimethylpyrroline -1-oxide/alkoxyl radical adduct; a N = 14.54 G and a H = 16.0 G). Topical application of the iron chelator Desferal to human skin significantly decreases these radicals (∼50%), indicating a role for iron in lipid peroxidation. (Author)

Trichloroethylene Radicals: An EPR/SPIN Trapping Study

National Research Council Canada - National Science Library

Steel-Goodwin, Linda

1995-01-01

.... As part of the process to develop environmental and health effects criteria for base clean-up the initial radicals produced by TCE were studied by electron paramagnetic resonance spectroscopy (EPR...

Time-resolved FTIR emission studies of laser photofragmentation and radical reactions

Energy Technology Data Exchange (ETDEWEB)

Leone, S.R. [Univ. of Colorado, Boulder (United States)

1993-12-01

Recent studies have focused specifically on collision processes, such as single collision energy transfer, reaction dynamics, and radical reactions. The authors employ novel FTIR techniques in the study of single collision energy transfer processes using translationally fast H atom, as well as radical-radical reactions, e.g. CH{sub 3} + O, CF{sub 3} + H(D), and Cl + C{sub 2}H{sub 5}. The fast atoms permit unique high energy regions of certain transition states of combustion species to be probed for the first time.

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

Science.gov (United States)

Van Hoomissen, Daniel J; Vyas, Shubham

2017-11-16

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

Photo-electron spectroscopy using synchrotron radiation of molecular radicals and fragments produced by laser photo-dissociation

International Nuclear Information System (INIS)

Nahon, Laurent

1991-01-01

This research thesis reports the combined use of a laser and of a synchrotron radiation in order to respectively photo-dissociate a molecule and to photo-ionize fragments which are analysed by photo-electron spectroscopy. This association allows, on the one hand, radical photo-ionization to be studied, and, on the other hand, polyatomic molecule photo-dissociation to be studied. The author studied the photo-excitation and/or photo-ionization in layer 4d (resp. 3d) of atomic iodine (resp. bromine) produced almost complete laser photo-dissociation of I_2 (resp. Br_2). He discuses the processes of relaxation of transitions from valence 4d to 5p (resp. 3d to 4p) which occur either by direct self-ionization or by resonant Auger effect, and reports the study of photo-dissociation of s-tetrazine (C_2N_4H_2) [fr

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)

Role of Free Radicals, Oxidative Stress and Xenobiotics in Carcinogenesis by Environmental Pollutants

Directory of Open Access Journals (Sweden)

Dibyajyoti Saha

2014-09-01

Full Text Available Carcinogenesis by many small molecular weight chemicals involves either a direct action of the chemical on cellular DNA or metabolism of the parent chemical to an active or ultimate form, which can than react with cellular DNA to produce a permanent chemical change in a DNA structure. A free radical is an atom or molecule that has one or more unpaired electron(s. These are highly reactive species capable of wide spread, indiscriminate oxidation and per oxidation of proteins, lipids and DNA which can lead to significant cellular damage and even tissue and/or organ failure. . Oxidative stress is a leading cause to damage cells by oxidation. The rate at which oxidative damage is induced (input and the rate at which it is efficiently repaired and removed (output. Xenobiotics are a compound that is foreign to the body. Xenobiotics can produce a variety of biological effects, including pharmacologic responses, toxicity, genes, immunologic reactions and cancer. Oxidative stress is a leading cause to damage cells by oxidation. The rate at which oxidative damage is induced (input and the rate at which it is efficiently repaired and removed (output. This communication highlights the role of carcinogens as environmental pollutants with the possible mechanism of free radicals, oxidative stress and xenobiotics.

Mass spectrometric characterization of a pyrolytic radical source using femtosecond ionization

Energy Technology Data Exchange (ETDEWEB)

Frey, H M; Beaud, P; Mischler, B; Radi, P P; Tzannis, A P; Gerber, T [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1997-06-01

Radicals play, as reactive species, an important role in the chemistry of combustion. In contrast to atmospheric flames where spectra are congested due to high vibrational and rotational excitation, experiments in the cold environment of a molecular beam (MB) yield clean spectra that can be easily attributed to one species by Resonantly Enhanced Multi Photon Ionization (REMP). A pyrolytic radical source has been set up. To characterize the efficiency of the source `soft` ionization with femto second pulses is applied which results in less fragmentation, simplifying the interpretation of the mass spectrum. (author) figs., tabs., refs.

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...

ESR-ENDOR study of x-irradiated single crystals of α.D.glucopyranose and α-methyl.D.glucopyranoside; environmental effects upon radiation and free radical chemistry in carbohydrate model systems

International Nuclear Information System (INIS)

Madden, K.P.

1980-01-01

Single crystals of x-irradiated α-D-glucopyranose (αGlu) and α-methyl-D-glucopyranoside (αMeGlu) were studied using electron spin resonance and electron nuclear double resonance spectroscopy, to determine products and reaction mechanisms in carbohydrate radiation and free-radical chemistry. Four free-radical products were identified in αMeGlu single crystals irradiated and studied at 77K. Irradiation and observation at 12K produced yet another species. Four free radicals were identified in αGlu single crystals irradiated and observed at 12K and 77K. Free radical reaction in αGlu and αMeGlu were induced by slowly warming crystals irradiated at 77K until conversion occurred. Environmental influences upon these free-radical reaction mechanisms are discussed. The results from previous work on irradiated aqueous glasses of αGlu is briefly reviewed, and compared to those obtained from the single crystal system

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

Energy Technology Data Exchange (ETDEWEB)

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

1991-01-01

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

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

International Nuclear Information System (INIS)

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

1991-01-01

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

Neuroprotection by Radical Avoidance: Search for Suitable Agents

Directory of Open Access Journals (Sweden)

Rüdiger Hardeland

2009-12-01

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

Purification and properties of extracellular polysaccharide (EPS) antigens produced by different mould species.

Science.gov (United States)

Notermans, S; Wieten, G; Engel, H W; Rombouts, F M; Hoogerhout, P; van Boom, J H

1987-02-01

Extracellular polysaccharide (EPS) antigens produced by different mould species were purified and partially characterized. Purification included (NH4)2SO4 treatment, Sepharose CL-4B column chromatography and Con A-sepharose chromatography. The EPS of Penicillium digitatum, Mucor racemosus and Cladosporium cladosporioides showed high antigenic capacities. Immunologically the EPS were partially genus-specific, but cross-reactivity was observed. The EPS antigens produced by species of Penicillium, Aspergillus repens and Geotrichum candidum lost their immunological activity upon heating (100 degrees C) at pH 1.8, while the EPS antigen of M. racemosus, Rhizopus oligosporus and C. cladosporioides were stable under the same conditions. The dominant monosaccharides present in the EPS antigen were mannose, galactose and glucose. The EPS obtained from cultures of M. racemosus and R. oligosporus also contained rhamnose. In the EPS produced by Penicillium spp. and A. repens the galactose residues were determined to be immunodominant.

Photoactivation by visible light of CdTe quantum dots for inline generation of reactive oxygen species in an automated multipumping flow system

Energy Technology Data Exchange (ETDEWEB)

Ribeiro, David S.M.; Frigerio, Christian; Santos, Joao L.M. [Requimte, Department of Chemical Sciences, Laboratory of Applied Chemistry, Faculty of Pharmacy, University of Porto, Rua de Jorge Viterbo Ferreira no. 228, 4050-313 Porto (Portugal); Prior, Joao A.V., E-mail: joaoavp@ff.up.pt [Requimte, Department of Chemical Sciences, Laboratory of Applied Chemistry, Faculty of Pharmacy, University of Porto, Rua de Jorge Viterbo Ferreira no. 228, 4050-313 Porto (Portugal)

2012-07-20

Highlights: Black-Right-Pointing-Pointer CdTe quantum dots generate free radical species upon exposure to visible radiation. Black-Right-Pointing-Pointer A high power visible LED lamp was used as photoirradiation element. Black-Right-Pointing-Pointer The laboratory-made LED photocatalytic unit was implemented inline in a MPFS. Black-Right-Pointing-Pointer Free radical species oxidize luminol producing a strong chemiluminescence emission. Black-Right-Pointing-Pointer Epinephrine scavenges free radical species quenching chemiluminescence emission. - Abstract: Quantum dots (QD) are semiconductor nanocrystals able to generate free radical species upon exposure to an electromagnetic radiation, usually in the ultraviolet wavelength range. In this work, CdTe QD were used as highly reactive oxygen species (ROS) generators for the control of pharmaceutical formulations containing epinephrine. The developed approach was based on the chemiluminometric monitoring of the quenching effect of epinephrine on the oxidation of luminol by the produced ROS. Due to the relatively low energy band-gap of this chalcogenide a high power visible light emitting diode (LED) lamp was used as photoirradiation element and assembled in a laboratory-made photocatalytic unit. Owing to the very short lifetime of ROS and to ensure both reproducible generation and time-controlled reaction implementation and development, all reactional processes were implemented inline by using an automated multipumping micro-flow system. A linear working range for epinephrine concentration of up to 2.28 Multiplication-Sign 10{sup -6} mol L{sup -1} (r = 0.9953; n = 5) was verified. The determination rate was about 79 determinations per hour and the detection limit was about 8.69 Multiplication-Sign 10{sup -8} mol L{sup -1}. The results obtained in the analysis of epinephrine pharmaceutical formulations by using the proposed methodology were in good agreement with those furnished by the reference procedure, with

High-field/ high-frequency EPR study on stable free radicals formed in sucrose by gamma-irradiation.

Science.gov (United States)

Georgieva, Elka R; Pardi, Luca; Jeschke, Gunnar; Gatteschi, Dante; Sorace, Lorenzo; Yordanov, Nicola D

2006-06-01

The EPR spectrum of sucrose irradiated by high-energy radiation is complex due to the presence of more than one radical species. In order to decompose the spectrum and elucidate the radical magnetic parameters a high-field (HF(-)EPR) study on stable free radicals in gamma-irradiated polycrystalline sucrose (table sugar) was performed at three different high frequencies--94, 190 and 285 GHz as well as at the conventional X-band. We suggest a presence of three stable radicals R1, R2 and R3 as the main radical species. Due to the increase of g-factor resolution at high fields the g-tensors of these radicals could be extracted by accurate simulations. The moderate g-anisotropy suggests that all three radicals are carbon-centred. Results from an earlier ENDOR study on X-irradiated sucrose single crystals (Vanhaelewyn et al., Appl Radiat Isot, 52, 1221 (2000)) were used for analyzing of the spectra in more details. It was confirmed that the strongest hyperfine interaction has a relatively small anisotropy, which indicates either the absence of alpha-protons or a strongly distorted geometry of the radicals.

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

International Nuclear Information System (INIS)

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

2000-01-01

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

Radicals of DNA and DNA nucleotides generated by ionising radiation

International Nuclear Information System (INIS)

Przybytniak, G.

2004-01-01

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

The scavenger activities of tea polyphenol and quercetin against oxygen radicals

International Nuclear Information System (INIS)

Fang Ruoying; Cheng Jiwu; Hu Tianxi; Tu Tiecheng; Dong Jirong; Wang Wenfeng; Lin nianyun

1992-01-01

Studies of free radical biology and medicine have shown that carcinogenesis, vascular diseases of heart and brain, radiation injuries, ageing etc are strictly correlated with free radical injury of tissues. Thus, pharmacologists and biologists are focusing attention on searching for scavengers, especially naturally occurring antioxidant of oxidizing free radicals. Previous studies have indicated that phenolic antioxidants have efficient scavenger activities. Utilizing following methods including chemical luminescence, ESR spectroscopy and pulse radiolysis techniques the scavenger activities of tea polyphenols and quercetin against active species of oxygen have been studied

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.

Study of the promissory species producers of coloring in the Amazonic trapeze

International Nuclear Information System (INIS)

Braham, William Klinger

1998-01-01

During 1995 and 1996 the Universidad Distrltal Francisco Jose de Caldas, with the economic support of the national program for the transfer of agricultural technology and the active participation of the indigenous communities seated in the Amazonic trapeze, advanced the present study guided to the search of alternative of use of products different from the wood, with the purpose of giving a bigger integrally to the use of the forest, inside a mark of sustainable development. The investigation had as objectives, to identify the species producers of coloring in the Amazonic trapeze, to determine the part of the plant used in the obtaining of these colorings, the color type taken place by each species and the yields reached in its production, to identify the autochthonous technologies used in its prosecution and the uses local to the colorings, to select species potentially important and to determine them the use possibilities in the textile and cosmetic, nutritious, handmade industries and of paintings, as well as to discover basic aspects on its propagation. They were in the area of study 29 species producers of colorings that they make part of very varied families, being the most representative in their order, rubiaceae, palmae and mimoisaceae. The parts of the plants used for the obtaining of the colorings are the leaves (48.28%) the bark (27.57%), the fruits (10.34%), the perspired (6.90%) and the seeds and roots with (3.95%) each one. The range of colors is very wide, yellow, coffee, green, red and purple they are those that stand out. Most of identified species are not used as coloring by the local communities and to the few that are given this use; they are used mainly for three (3) activities, the make-up of the body, the preparation of foods and the elaboration of crafts. The work allowed to conclude that the high number of species producers of coloring existent in the Amazonic trapeze it makes think of the possibilities of an integral use of the forest that

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

Study of new compounds for their application on free radicals EPR dosimetry

International Nuclear Information System (INIS)

Condes N, C.S.

1996-01-01

L- α alanine is an amino acid which has been used for electron and γ ray dosimetric purposes, when crystallites of L-α alanine are irradiated with ionizing radiation free radicals are produced. The yield of free radicals produced by irradiation of alanine crystals can be evaluated by EPR spectrometry, however when L- α alanine crystals are irradiated with thermal neutrons the yield of the free radicals produced is very low and in consequence it's EPR-signal response is poor. In this work we mixed L-α alanine together with some lithium compounds such as LiF, LiBO 2 , LiOH and Li 2 CO 3 . In this way when we irradiate the respective mixture of alanine-lithium with thermal neutrons, the nuclear reactions 6 Li (n,α)T and 10 B (n, α) 7 Li can be produced with a high probability. As a consequence α particles and recoil atoms emerging from the nuclear reactions can impinge on alanine molecules, producing extra free radicals. From the alanine-lithium mixtures obtained, we made dosemeters (30 mm long., 3.9 mm diameter) which were irradiated in the thermal column of the TRIGA Mark III Nuclear Reactor with a flux of thermal neutrons of 5 x 10 7 n/ cm 2 s. Irradiations were made at different periods. Experimental evaluations indicate that the mixtures can be used for dosimetric purposes. (Author)

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...

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

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

Science.gov (United States)

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

2017-11-01

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

N-tert-butylmethanimine N-oxide is an efficient spin-trapping probe for EPR analysis of glutathione thiyl radical

Science.gov (United States)

Scott, Melanie J.; Billiar, Timothy R.; Stoyanovsky, Detcho A.

2016-01-01

The electron spin resonance (EPR) spin-trapping technique allows detection of radical species with nanosecond half-lives. This technique is based on the high rates of addition of radicals to nitrones or nitroso compounds (spin traps; STs). The paramagnetic nitroxides (spin-adducts) formed as a result of reactions between STs and radical species are relatively stable compounds whose EPR spectra represent “structural fingerprints” of the parent radical species. Herein we report a novel protocol for the synthesis of N-tert-butylmethanimine N-oxide (EBN), which is the simplest nitrone containing an α-H and a tertiary α′-C atom. We present EPR spin-trapping proof that: (i) EBN is an efficient probe for the analysis of glutathione thiyl radical (GS•); (ii) β-cyclodextrins increase the kinetic stability of the spin-adduct EBN/•SG; and (iii) in aqueous solutions, EBN does not react with superoxide anion radical (O2−•) to form EBN/•OOH to any significant extent. The data presented complement previous studies within the context of synthetic accessibility to EBN and efficient spin-trapping analysis of GS•. PMID:27941944

Stereocontrol during the radical polymerization of methyl methacrylates with combined Lewis acids:Aluminium trichloride（AlCl3） and iron dichloride tetrahydrate

Institute of Scientific and Technical Information of China (English)

无

2010-01-01

The radical polymerization of methyl methacrylate(MMA) was carried out in the presence of combined Lewis acids of the AlCl3-FeCl2 system.Compared with the polymerization produced in the presence of single Lewis acids,AlCl3 or FeCl2,the MMA polymerization in the presence of AlCl3-FeCl2 composite in CHCl3 or 1-butanol produced a polymer with a higher isotacticity and in toluene produced a polymer with a much higher isotacticity(mm=50%) .The molecular weight and polydispersity of PMMA in the presence of Lewis acids were similar with those in the absence of Lewis acids,although Lewis acids decelerate the polymerization of MMA.The effects of the Lewis acids were greater in a solvent with a lower polarity.A possible stereocontrol mechanism of the polymerization was proposed.The Lewis acid composite of AlCl3-FeCl2 readily formed a complex with growing species.These complexes possessed apparent bulkiness that changes the direction of monomer addition to the growing radical center.

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.

One-electron oxidation of the hydroquinonic form of vitamin K by OH· and N3· free radicals. A steady-state gamma radiolysis study

International Nuclear Information System (INIS)

Nguyen Van Binh, E.; Gardes-Albert, M.; Ferradini, C.; Acher, F.; Azerad, R.

1991-01-01

The oxidation of a water-soluble model of vitamin K hydroquinone, symbolised by KH 2 p, has been studied by γ radiolysis using OH· or N 3 · free radicals as oxidants. Irradiation doses were up to 300 Gy. The analysis of final products by spectrophotometric absorption and HPLC allowed to characterize the formation of the quinone K and to estimate the initial yield of KH 2 p-disappearance and K-formation. N 3 · radicals led selectively to the formation of the quinone K with a G-value of (3.0 ± 0.3) x 10 -7 mol/J, thus involving a simple one-electron oxidation mechanism. On the contrary, when OH· radicals oxidized KH 2 p, in addition to the quinone, other non identified species were simultaneously produced during the radiolysis, thus requiring a more complex oxidation mechanism [fr

Electron paramagnetic relaxation studies of free radicals in. gamma. -irradiated DNA

Energy Technology Data Exchange (ETDEWEB)

Kuwabara, M; Yoshi, G [Hokkaido Univ., Sapporo (Japan)

1980-01-01

Using the continuous microwave power saturation method the T/sub 1/ spin-lattice relaxation time and T/sub 2/ spin-spin relaxation time for DNA radicals (measured at 297/sup 0/K) are reported. Identical experiments carried out on thymidine-5'-monophosphate sodium salt (TMP) and deoxycytidine-5'-monophosphate sodium salt (dCMP) are also reported. Irradiated DNA produces TMP radicals on the base moiety and dCMP radicals on the sugar moiety. Comparing the relaxation times of DNA with those of TMP and dCMP provided a reliable analysis of the nature of DNA radicals.

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

Science.gov (United States)

Irikura, Karl K

2013-03-14

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

Oxidation of Cu(II) aminopolycarboxylates by carbonate radical. A flash photolysis study

International Nuclear Information System (INIS)

Mandal, P.C.; Bardhan, D.K.

1999-01-01

Reactions of carbonate radical (CO 3 -. ) generated by photolysis or by radiolysis of a carbonate solution, with Cu(II) complexes of aminopolycarboxylic acids viz., Cu(II)ethylenediamine tetraacetate [Cu II EDTA] 2- and Cu(II)-iminodiacetate [Cu II IDA] were studied at pH 10.5 and ionic strength 0.2 mol x dm -3 . Time-resolved spectroscopy and kinetics for the transients were studied using flash photolysis and stable products arising from the ligand degradation of the complex were ascertained by steady-state radiolysis experiments. From the kinetic data it is observed that CO 3 -. radical reacts initially with Cu II -complex to form a transient intermediate having maximum absorption at 335 nm and 430 nm. From the subsequent reactions of this intermediate it was assigned to be Cu III .species. This Cu(III) species undergoes intermolecular electron transfer with the Cu II -complex to give a radical intermediate which again slowly reacts with Cu II -complex to give a long lived species containing Cu-C bond. This long lived species, however, slowly decomposed to give glyoxalic reaction between Cu III -complex and a suitable donor, the one electron reduction potential for [Cu III EDTA] 1- /[Cu II EDTA] 2- and [Cu III IDA] +1 /Cu II IDA was determined. (author)

Quenching of photoluminescence of colloidal ZnO nanocrystals by nitronyl nitroxide radicals

Energy Technology Data Exchange (ETDEWEB)

Stroyuk, Oleksandr L., E-mail: stroyuk@inphyschem-nas.kiev.ua [L.V. Pysarzhevsky Institute of Physical Chemistry of National Academy of Sciences of Ukraine, 31 Nauky avenue, 03028 Kyiv (Ukraine); Yakovenko, Anastasiya V.; Raevskaya, Oleksandra E. [L.V. Pysarzhevsky Institute of Physical Chemistry of National Academy of Sciences of Ukraine, 31 Nauky avenue, 03028 Kyiv (Ukraine); Plyusnin, Victor F. [Institute of Chemical Kinetics and Combustion of Siberian Branch of Russian Academy of Sciences, Novosibirsk (Russian Federation)

2014-11-15

Quenching of the photoluminescence of colloidal zinc oxide nanocrystals by a series of stable nitronyl nitroxide radicals was studied by means of stationary and time-resolved luminescence spectroscopy. Among the studied radicals the most efficient quenchers of the ZnO luminescence are the carboxyl-substituted species. The meta-substituted radical was found to be a more active quencher, than para-substituted one due to a closer proximity of the radical center to the nanocrystals surface. The PL quenching has a complex dynamic/static character. The dynamic quenching arises from photocatalytic radical reduction by ZnO conduction band electrons, while the static quenching is caused by adsorption of the photoreduction products on the nanocrystal surface. The non-substituted and OH-substituted radicals are inferior to the products of their photoreduction in capability of adsorption of the ZnO surface, and the quenching is dominated by interactions between the nanocrystals and photoreduced hydroxylamines. In case of COOH-substituted radicals, however, the radicals compete with the photoreduction products for the surface sites of ZnO nanocrystals resulting in a dynamic character of photoluminescence quenching.

Direct detection of radicals in intact soybean nodules

DEFF Research Database (Denmark)

Mathieu, C; Moreau, S; Frendo, P

1998-01-01

Electron paramagnetic resonance spectroscopy has been employed to examine the nature of the metal ions and radicals present in intact root nodules of soybean plants grown in the absence of nitrate. The spectra obtained from nodules of different ages using this non-invasive technique show dramatic...... differences, suggesting that there are both qualitative and quantitative changes in the metal ion and radical species present. A major component of the spectra obtained from young nodules is assigned to a complex (Lb-NO) of nitric oxide (NO.) with the heme protein leghemoglobin (Lb). This Lb-NO species, which...... has not been previously detected in intact root nodules of plants grown in the absence of nitrate, is thought to be formed by reaction of nitric oxide with iron(II) leghemoglobin. The nitric oxide may be generated from arginine via a nitric oxide synthase-like activity present in the nodules...

Hydroxyl radical reactivity at the air-ice interface

Directory of Open Access Journals (Sweden)

T. F. Kahan

2010-01-01

Full Text Available Hydroxyl radicals are important oxidants in the atmosphere and in natural waters. They are also expected to be important in snow and ice, but their reactivity has not been widely studied in frozen aqueous solution. We have developed a spectroscopic probe to monitor the formation and reactions of hydroxyl radicals in situ. Hydroxyl radicals are produced in aqueous solution via the photolysis of nitrite, nitrate, and hydrogen peroxide, and react rapidly with benzene to form phenol. Similar phenol formation rates were observed in aqueous solution and bulk ice. However, no reaction was observed at air-ice interfaces, or when bulk ice samples were crushed prior to photolysis to increase their surface area. We also monitored the heterogeneous reaction between benzene present at air-water and air-ice interfaces with gas-phase OH produced from HONO photolysis. Rapid phenol formation was observed on water surfaces, but no reaction was observed at the surface of ice. Under the same conditions, we observed rapid loss of the polycyclic aromatic hydrocarbon (PAH anthracene at air-water interfaces, but no loss was observed at air-ice interfaces. Our results suggest that the reactivity of hydroxyl radicals toward aromatic organics is similar in bulk ice samples and in aqueous solution, but is significantly suppressed in the quasi-liquid layer (QLL that exists at air-ice interfaces.

Primordial Germ Cell-Mediated Chimera Technology Produces Viable Pure-Line Houbara Bustard Offspring: Potential for Repopulating an Endangered Species

Science.gov (United States)

Wernery, Ulrich; Liu, Chunhai; Baskar, Vijay; Guerineche, Zhor; Khazanehdari, Kamal A.; Saleem, Shazia; Kinne, Jörg; Wernery, Renate

2010-01-01

Background The Houbara bustard (Chlamydotis undulata) is a wild seasonal breeding bird populating arid sandy semi-desert habitats in North Africa and the Middle East. Its population has declined drastically during the last two decades and it is classified as vulnerable. Captive breeding programmes have, hitherto, been unsuccessful in reviving population numbers and thus radical technological solutions are essential for the long term survival of this species. The purpose of this study was to investigate the use of primordial germ cell-mediated chimera technology to produce viable Houbara bustard offspring. Methodology/Principal Findings Embryonic gonadal tissue was dissected from Houbara bustard embryos at eight days post-incubation. Subsequently, Houbara tissue containing gonadal primordial germ cells (gPGCs) was injected into White Leghorn chicken (Gallus gallus domesticus) embryos, producing 83/138 surviving male chimeric embryos, of which 35 chimeric roosters reached sexual maturity after 5 months. The incorporation and differentiation of Houbara gPGCs in chimeric chicken testis were assessed by PCR with Houbara-specific primers and 31.3% (5/16) gonads collected from the injected chicken embryos showed the presence of donor Houbara cells. A total of 302 semen samples from 34 chimeric roosters were analyzed and eight were confirmed as germline chimeras. Semen samples from these eight roosters were used to artificially inseminate three female Houbara bustards. Subsequently, 45 Houbara eggs were obtained and incubated, two of which were fertile. One egg hatched as a male live born Houbara; the other was female but died before hatching. Genotyping confirmed that the male chick was a pure-line Houbara derived from a chimeric rooster. Conclusion This study demonstrates for the first time that Houbara gPGCs can migrate, differentiate and eventually give rise to functional sperm in the chimeric chicken testis. This approach may provide a promising tool for propagation

Analysis of potential fumonisin-producing Fusarium species in corn products from three main maize-producing areas in eastern China.

Science.gov (United States)

Zhang, Liping; Wang, Jiansheng; Zhang, Chulong; Wang, Qiaomei

2013-02-01

Fusarium species are common fungal contaminants of maize and a number of them can produce mycotoxin fumonisins. China is one of the largest maize producers in the world. This study investigated the contamination of maize samples from three areas in eastern China by Fusarium and fumonisin-producing fungi as well as their fumonisin-producing potential. A total of 22 Fusarium strains were isolated, 19 of which were able to produce fumonisin. Among the 19 strains, 16 belonged to F. verticillioides, two to F. subglutinans and one to F. proliferatum. The majority (17/19) of the fumonisin-forming strains were high FB(1) producers, which is a potential health risk for the population in these areas. Fusarium contamination in samples from the mideastern area was the most serious (11 Fusarium strains, with nine producing fumonisin, isolated from 24 samples), followed by the northeastern area (nine Fusarium strains, with all nine producing fumonisin, isolated from 21 samples) and the southeastern area (two Fusarium strains, with one producing fumonisin, isolated from 19 samples). Although the overall levels of FBs and contamination by fumonisin-producing fungi in corn samples were not serious, the contaminating Fusarium strains possessed fairly strong toxicogenic ability and potential risk for food safety. Copyright © 2012 Society of Chemical Industry.

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.

Initial decay process of radicals induced in irradiated food

International Nuclear Information System (INIS)

Kaimori, Yoshihiko; Sakamoto, Yuki; Nakamura, Hideo; Ukai, Mitsuko; Kikuchi, Masahiro; Shimoyama, Yuhei; Kobayashi, Yasuhiko; Kameya, Hiromi

2011-01-01

In order to determine radial decay behaviors of γ-irradiated food, we analyzed radicals in the food using ESR. We detected the ESR signal of specimens just several minutes after irradiation. The singlet signal intensity at g=2.0, originated from organic free radicals was increased as followed by the increasing radiation dose. Singlet signal intensity that increased by γ-irradiation was decreased with time. The phenomena of decay of the ESR singlet signal showed two phase that are rapid decay and slow decay. It was suggested that those two phase decay is due to at least the two radical species. Also we concluded that after three hours of radiation treatment long life radical as ESR signal intensity was detected in irradiated specimen; black pepper, green coffee bean and ginseng, showed the same decay phenomena. But the signal intensity of irradiated black pepper was three times larger than that of irradiated green coffee bean and irradiated ginseng. (author)

In vitro free radical scavenging activity of platinum nanoparticles

Energy Technology Data Exchange (ETDEWEB)

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

2009-11-11

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

Quantum Chemical Benchmarking, Validation, and Prediction of Acidity Constants for Substituted Pyridinium Ions and Pyridinyl Radicals.

Science.gov (United States)

Keith, John A; Carter, Emily A

2012-09-11

Sensibly modeling (photo)electrocatalytic reactions involving proton and electron transfer with computational quantum chemistry requires accurate descriptions of protonated, deprotonated, and radical species in solution. Procedures to do this are generally nontrivial, especially in cases that involve radical anions that are unstable in the gas phase. Recently, pyridinium and the corresponding reduced neutral radical have been postulated as key catalysts in the reduction of CO2 to methanol. To assess practical methodologies to describe the acid/base chemistry of these species, we employed density functional theory (DFT) in tandem with implicit solvation models to calculate acidity constants for 22 substituted pyridinium cations and their corresponding pyridinyl radicals in water solvent. We first benchmarked our calculations against experimental pyridinium deprotonation energies in both gas and aqueous phases. DFT with hybrid exchange-correlation functionals provide chemical accuracy for gas-phase data and allow absolute prediction of experimental pKas with unsigned errors under 1 pKa unit. The accuracy of this economical pKa calculation approach was further verified by benchmarking against highly accurate (but very expensive) CCSD(T)-F12 calculations. We compare the relative importance and sensitivity of these energies to selection of solvation model, solvation energy definitions, implicit solvation cavity definition, basis sets, electron densities, model geometries, and mixed implicit/explicit models. After determining the most accurate model to reproduce experimentally-known pKas from first principles, we apply the same approach to predict pKas for radical pyridinyl species that have been proposed relevant under electrochemical conditions. This work provides considerable insight into the pitfalls using continuum solvation models, particularly when used for radical species.

Characteristics of ultraviolet light and radicals formed by pulsed discharge in water

Science.gov (United States)

Sun, Bing; Kunitomo, Shinta; Igarashi, Chiaki

2006-09-01

In this investigation, the ultraviolet light characteristics and OH radical properties produced by a pulsed discharge in water were studied. For the plate-rod reactor, it was found that the ultraviolet light energy has a 3.2% total energy injected into the reactor. The ultraviolet light changed with the peak voltage and electrode distance. UV characteristics in tap water and the distilled water are given. The intensity of the OH radicals was the highest for the 40 mm electrode distance reactor. In addition, the properties of hydrogen peroxide and ozone were also studied under arc discharge conditions. It was found that the OH radicals were in the ground state and the excited state when a pulsed arc discharge was used. The ozone was produced by the arc discharge even if the oxygen gas is not bubbled into the reactor. The ozone concentration produces a maximum value with treatment time.

Characteristics of ultraviolet light and radicals formed by pulsed discharge in water

Energy Technology Data Exchange (ETDEWEB)

Sun Bing [Dalian Maritime University, College of Environment, 1st Linghai Road, Dalian (China); Kunitomo, Shinta [Ebara Corporation, 1-6-27, Konan, Minato-ku 108-8480 (Japan); Igarashi, Chiaki [Ebara Research Co. Ltd, 2-1, Honfujisawa 4-chome, Fujisawa 251-8502 (Japan)

2006-09-07

In this investigation, the ultraviolet light characteristics and OH radical properties produced by a pulsed discharge in water were studied. For the plate-rod reactor, it was found that the ultraviolet light energy has a 3.2% total energy injected into the reactor. The ultraviolet light changed with the peak voltage and electrode distance. UV characteristics in tap water and the distilled water are given. The intensity of the OH radicals was the highest for the 40 mm electrode distance reactor. In addition, the properties of hydrogen peroxide and ozone were also studied under arc discharge conditions. It was found that the OH radicals were in the ground state and the excited state when a pulsed arc discharge was used. The ozone was produced by the arc discharge even if the oxygen gas is not bubbled into the reactor. The ozone concentration produces a maximum value with treatment time.

Changes in free-radical scavenging ability of kombucha tea during fermentation.

Science.gov (United States)

Jayabalan, R; Subathradevi, P; Marimuthu, S; Sathishkumar, M; Swaminathan, K

2008-07-01

Kombucha tea is a fermented tea beverage produced by fermenting sugared black tea with tea fungus (kombucha). Free-radical scavenging abilities of kombucha tea prepared from green tea (GTK), black tea (BTK) and tea waste material (TWK) along with pH, phenolic compounds and reducing power were investigated during fermentation period. Phenolic compounds, scavenging activity on DPPH radical, superoxide radical (xanthine-xanthine oxidase system) and inhibitory activity against hydroxyl radical mediated linoleic acid oxidation (ammonium thiocyanate assay) were increased during fermentation period, whereas pH, reducing power, hydroxyl radical scavenging ability (ascorbic acid-iron EDTA) and anti-lipid peroxidation ability (thiobarbituric assay) were decreased. From the present study, it is obvious that there might be some chances of structural modification of components in tea due to enzymes liberated by bacteria and yeast during kombucha fermentation which results in better scavenging performance on nitrogen and superoxide radicals, and poor scavenging performance on hydroxyl radicals. Copyright © 2007 Elsevier Ltd. All rights reserved.

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

DEFF Research Database (Denmark)

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

2017-01-01

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

Dialogue between E. coli free radical pathways and the mitochondria of C. elegans.

Science.gov (United States)

Govindan, J Amaranath; Jayamani, Elamparithi; Zhang, Xinrui; Mylonakis, Eleftherios; Ruvkun, Gary

2015-10-06

The microbial world presents a complex palette of opportunities and dangers to animals, which have developed surveillance and response strategies to hints of microbial intent. We show here that the mitochondrial homeostatic response pathway of the nematode Caenorhabditis elegans responds to Escherichia coli mutations that activate free radical detoxification pathways. Activation of C. elegans mitochondrial responses could be suppressed by additional mutations in E. coli, suggesting that C. elegans responds to products of E. coli to anticipate challenges to its mitochondrion. Out of 50 C. elegans gene inactivations known to mediate mitochondrial defense, we found that 7 genes were required for C. elegans response to a free radical producing E. coli mutant, including the bZip transcription factor atfs-1 (activating transcription factor associated with stress). An atfs-1 loss-of-function mutant was partially resistant to the effects of free radical-producing E. coli mutant, but a constitutively active atfs-1 mutant growing on wild-type E. coli inappropriately activated the pattern of mitochondrial responses normally induced by an E. coli free radical pathway mutant. Carbonylated proteins from free radical-producing E. coli mutant may directly activate the ATFS-1/bZIP transcription factor to induce mitochondrial stress response: feeding C. elegans with H2O2-treated E. coli induces the mitochondrial unfolded protein response, and inhibition of a gut peptide transporter partially suppressed C. elegans response to free radical damaged E. coli.

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

Reactivity of hydropersulfides toward the hydroxyl radical unraveled: disulfide bond cleavage, hydrogen atom transfer, and proton-coupled electron transfer.

Science.gov (United States)

Anglada, Josep M; Crehuet, Ramon; Adhikari, Sarju; Francisco, Joseph S; Xia, Yu

2018-02-14

Hydropersulfides (RSSH) are highly reactive as nucleophiles and hydrogen atom transfer reagents. These chemical properties are believed to be key for them to act as antioxidants in cells. The reaction involving the radical species and the disulfide bond (S-S) in RSSH, a known redox-active group, however, has been scarcely studied, resulting in an incomplete understanding of the chemical nature of RSSH. We have performed a high-level theoretical investigation on the reactions of the hydroxyl radical (˙OH) toward a set of RSSH (R = -H, -CH 3 , -NH 2 , -C(O)OH, -CN, and -NO 2 ). The results show that S-S cleavage and H-atom abstraction are the two competing channels. The electron inductive effect of R induces selective ˙OH substitution at one sulfur atom upon S-S cleavage, forming RSOH and ˙SH for the electron donating groups (EDGs), whereas producing HSOH and ˙SR for the electron withdrawing groups (EWGs). The H-Atom abstraction by ˙OH follows a classical hydrogen atom transfer (hat) mechanism, producing RSS˙ and H 2 O. Surprisingly, a proton-coupled electron transfer (pcet) process also occurs for R being an EDG. Although for RSSH having EWGs hat is the leading channel, S-S cleavage can be competitive or even dominant for the EDGs. The overall reactivity of RSSH toward ˙OH attack is greatly enhanced with the presence of an EDG, with CH 3 SSH being the most reactive species found in this study (overall rate constant: 4.55 × 10 12 M -1 s -1 ). Our results highlight the complexity in RSSH reaction chemistry, the extent of which is closely modulated by the inductive effect of the substituents in the case of the oxidation by hydroxyl radicals.

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.

The induction of mycotoxins by trichothecene producing Fusarium species.

Science.gov (United States)

Lowe, Rohan; Jubault, Mélanie; Canning, Gail; Urban, Martin; Hammond-Kosack, Kim E

2012-01-01

In recent years, many Fusarium species have emerged which now threaten the productivity and safety of small grain cereal crops worldwide. During floral infection and post-harvest on stored grains the Fusarium hyphae produce various types of harmful mycotoxins which subsequently contaminate food and feed products. This article focuses specifically on the induction and production of the type B sesquiterpenoid trichothecene mycotoxins. Methods are described which permit in liquid culture the small or large scale production and detection of deoxynivalenol (DON) and its various acetylated derivatives. A wheat (Triticum aestivum L.) ear inoculation assay is also explained which allows the direct comparison of mycotoxin production by species, chemotypes and strains with different growth rates and/or disease-causing abilities. Each of these methods is robust and can be used for either detailed time-course studies or end-point analyses. Various analytical methods are available to quantify the levels of DON, 3A-DON and 15A-DON. Some criteria to be considered when making selections between the different analytical methods available are briefly discussed.

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

International Nuclear Information System (INIS)

Uhm, Han S.

2015-01-01

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

Free radical production by high energy shock waves--comparison with ionizing irradiation.

Science.gov (United States)

Morgan, T R; Laudone, V P; Heston, W D; Zeitz, L; Fair, W R

1988-01-01

Fricke chemical dosimetry is used as an indirect measure of the free radical production of ionizing irradiation. We adapted the Fricke ferrous sulfate radiation dosimeter to examine the chemical effects of high energy shock waves. Significant free radical production was documented. The reaction was dose dependent, predictably increased by acoustic impedance, but curvilinear. A thousand shocks at 18 kilovolts induced the same free radical oxidation as 1100 rad cobalt-60 gamma ionizing irradiation, increasing to 2900 rad in the presence of an air-fluid zone of acoustic impedance. The biological effect of these free radicals was compared to that of cobalt-60 ionizing irradiation by measuring the affect on Chinese hamster cells by clonogenic assay. While cobalt-60 irradiation produced a marked decrease in clonogenic survivors, little effect was noted with high energy shock waves. This suggested that the chemical effects produced by shock waves were either absent or attenuated in the cells, or were inherently less toxic than those of ionizing irradiation.

Apoptotic and free radical scavenging properties of the methanolic extract of Gentianella alborosea.

Science.gov (United States)

Acero, Nuria; Llinares, Francisco; Galán de Mera, Antonio; Oltra, Beatriz; Muñoz-Mingarro, Dolores

2006-09-01

Gentianella alborosea ("Hercampure") is a Peruvian species used in folk medicine for the treatment of a variety of health disorders. We tested the free radical scavenging (DPPH) and induction of apoptosis on a human uterus tumor cell line (HeLa) by its methanolic extract. The results showed a noticeable radical scavenging activity and a dose-dependent apoptotic effect.

Reactions of the nitrate radical with a series og reduced organic sulfur-compounds in air

DEFF Research Database (Denmark)

JENSEN, NR; HJORTH, J; LOHSE, C

1992-01-01

A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO3, and the reduced organic sulphur compounds CH3CH2SH, (CH3CH2)2S, (CH3CH2)2S2, and CH3CH2SCH3 in air. The pro......A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO3, and the reduced organic sulphur compounds CH3CH2SH, (CH3CH2)2S, (CH3CH2)2S2, and CH3CH2SCH3 in air......, and CH3SSCH3 lead to the conclusion that all these species, in the reaction with the NO3 radical, follow a similar degradation mechanism producing SO2, H2SO4, R-SO3H, R-CHO, and R-CH2ONO2, as the main reaction products. The inital step of the reaction of NO3 with R-S-R and R-S- H type (R = CH3, CH2CH3...

Effect of curcumin against oxidation of biomolecules by hydroxyl radicals.

Science.gov (United States)

Borra, Sai Krishna; Mahendra, Jaideep; Gurumurthy, Prema; Jayamathi; Iqbal, Shabeer S; Mahendra, Little

2014-10-01

Among various reactive oxygen species, hydroxyl radicals have the strongest chemical activity, which can damage a wide range of essential biomolecules such as lipids, proteins, and DNA. The objective of this study was to investigate the beneficial effects of curcumin on prevention of oxidative damage of biomolecules by hydroxyl radicals generated in in vitro by a Fenton like reaction. We have incubated the serum, plasma and whole blood with H2O2/Cu2+/ Ascorbic acid system for 4 hours at 37 0C and observed the oxidation of biomolecules like albumin, lipids, proteins and DNA. Curcumin at the concentrations of 50,100 and 200 μmoles, prevented the formation of ischemia modified albumin, MDA, protein carbonyls, oxidized DNA and increased the total antioxidant levels and GSH significantly. These observations suggest the hydroxyl radical scavenging potentials of curcumin and protective actions to prevent the oxidation of biomolecules by hydroxyl radicals.

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

International Nuclear Information System (INIS)

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

1976-01-01

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

Transverse flow reactor studies of the dynamics of radical reactions

Energy Technology Data Exchange (ETDEWEB)

Macdonald, R.G. [Argonne National Laboratory, IL (United States)

1993-12-01

Radical reactions are in important in combustion chemistry; however, little state-specific information is available for these reactions. A new apparatus has been constructed to measure the dynamics of radical reactions. The unique feature of this apparatus is a transverse flow reactor in which an atom or radical of known concentration will be produced by pulsed laser photolysis of an appropriate precursor molecule. The time dependence of individual quantum states or products and/or reactants will be followed by rapid infrared laser absorption spectroscopy. The reaction H + O{sub 2} {yields} OH + O will be studied.

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

Science.gov (United States)

Chaturvedi, Prachee

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

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.

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?

Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

International Nuclear Information System (INIS)

Grodkowski, J.; Bobrowski, K.; Mehnert, R.; Brede, O.

1989-01-01

The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl 4 and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN +radical ) and the former to the known carbonium ion of malachite green dye (MG + ). Observation of the consecutive charge transfer via the schemes: DCE +radical → BPh +radical → MGCN +radical and DCE +radical → MGCN +radical → TMPD +radical , allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV MGCN +radical radical cation is located in the ''aniline'' part of the molecule. (author)

Electron Paramagnetic Resonance Measurements of Reactive Oxygen Species by Cyclic Hydroxylamine Spin Probes.

Science.gov (United States)

Dikalov, Sergey I; Polienko, Yuliya F; Kirilyuk, Igor

2018-05-20

Oxidative stress contributes to numerous pathophysiological conditions such as development of cancer, neurodegenerative, and cardiovascular diseases. A variety of measurements of oxidative stress markers in biological systems have been developed; however, many of these methods are not specific, can produce artifacts, and do not directly detect the free radicals and reactive oxygen species (ROS) that cause oxidative stress. Electron paramagnetic resonance (EPR) is a unique tool that allows direct measurements of free radical species. Cyclic hydroxylamines are useful and convenient molecular probes that readily react with ROS to produce stable nitroxide radicals, which can be quantitatively measured by EPR. In this work, we critically review recent applications of various cyclic hydroxylamine spin probes in biology to study oxidative stress, their advantages, and the shortcomings. Recent Advances: In the past decade, a number of new cyclic hydroxylamine spin probes have been developed and their successful application for ROS measurement using EPR has been published. These new state-of-the-art methods provide improved selectivity and sensitivity for in vitro and in vivo studies. Although cyclic hydroxylamine spin probes EPR application has been previously described, there has been lack of translation of these new methods into biomedical research, limiting their widespread use. This work summarizes "best practice" in applications of cyclic hydroxylamine spin probes to assist with EPR studies of oxidative stress. Additional studies to advance hydroxylamine spin probes from the "basic science" to biomedical applications are needed and could lead to better understanding of pathological conditions associated with oxidative stress. Antioxid. Redox Signal. 28, 1433-1443.

Comparative in vitro study on free radical scavenging potential of selected bivalve species

Digital Repository Service at National Institute of Oceanography (India)

Shenai-Tirodkar, P.S.; Pawar, R.T.; Jagtap, T.G.

Bivalves such as, Crassostrea spp., Meretrix casta, Placuna placenta and Polymesoda erosa are largely consumed as edible seafood. It forms natural source of nutrition in coastal and worldwide population. Free radical scavenging activities...

Nuclear coupling of 33S and the nature of free radicals in irradiated crystals of N-acetyl-L-cysteine

International Nuclear Information System (INIS)

Hadley, J.H. Jr.; Gordy, W.

1977-01-01

Hyperfine structure due to 33 S in its natural abundance of 0.76% has been measured in the electron spin resonance of free radicals produced by x-irradiation of single crystals of N-acetyl-L-cysteine at 77 K. These measurements proved that the radicals produced at 77 K with principal g values of 1.990, 2.006, and 2.214 are monosulfide radicals with the 3p unpaired electron density of 0.70 on the S. They are believed to be negatively charged molecules RCH 2 S - H or neutral RCH 2 SH 2 radicals in which 90% of the spin density of the captured electron is concentrated in a d-p hybrid orbital on the S. As the temperature is raised to 300 0 K, these, as well as the carbon-centered radicals produced at the lower temperature, are mostly converted to neutral disulfide radicals RCH 2 SS like those observed in irradiated cysteine

Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

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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.

Radical scavenging potentials of single and combinatorial herbal formulations in vitro

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Okey A. Ojiako

2016-04-01

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

Oxidants, Antioxidants, and the Beneficial Roles of Exercise-Induced Production of Reactive Species

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Elisa Couto Gomes

2012-01-01

Full Text Available This review offers an overview of the influence of reactive species produced during exercise and their effect on exercise adaptation. Reactive species and free radicals are unstable molecules that oxidize other molecules in order to become stable. Although they play important roles in our body, they can also lead to oxidative stress impairing diverse cellular functions. During exercise, reactive species can be produced mainly, but not exclusively, by the following mechanisms: electron leak at the mitochondrial electron transport chain, ischemia/reperfusion and activation of endothelial xanthine oxidase, inflammatory response, and autooxidation of catecholamines. Chronic exercise also leads to the upregulation of the body's antioxidant defence mechanism, which helps minimize the oxidative stress that may occur after an acute bout of exercise. Recent studies show a beneficial role of the reactive species, produced during a bout of exercise, that lead to important training adaptations: angiogenesis, mitochondria biogenesis, and muscle hypertrophy. The adaptations occur depending on the mechanic, and consequently biochemical, stimulus within the muscle. This is a new area of study that promises important findings in the sphere of molecular and cellular mechanisms involved in the relationship between oxidative stress and exercise.

Oxidants, Antioxidants, and the Beneficial Roles of Exercise-Induced Production of Reactive Species

Science.gov (United States)

Gomes, Elisa Couto; Silva, Albená Nunes; de Oliveira, Marta Rubino

2012-01-01

This review offers an overview of the influence of reactive species produced during exercise and their effect on exercise adaptation. Reactive species and free radicals are unstable molecules that oxidize other molecules in order to become stable. Although they play important roles in our body, they can also lead to oxidative stress impairing diverse cellular functions. During exercise, reactive species can be produced mainly, but not exclusively, by the following mechanisms: electron leak at the mitochondrial electron transport chain, ischemia/reperfusion and activation of endothelial xanthine oxidase, inflammatory response, and autooxidation of catecholamines. Chronic exercise also leads to the upregulation of the body's antioxidant defence mechanism, which helps minimize the oxidative stress that may occur after an acute bout of exercise. Recent studies show a beneficial role of the reactive species, produced during a bout of exercise, that lead to important training adaptations: angiogenesis, mitochondria biogenesis, and muscle hypertrophy. The adaptations occur depending on the mechanic, and consequently biochemical, stimulus within the muscle. This is a new area of study that promises important findings in the sphere of molecular and cellular mechanisms involved in the relationship between oxidative stress and exercise. PMID:22701757

Investigation of radical locations in various sesame seeds by CW EPR and 9-GHz EPR imaging.

Science.gov (United States)

Nakagawa, K; Hara, H

2015-01-01

We investigated the location of radical in various sesame seeds using continuous-wave (CW) electron paramagnetic resonance (EPR) and 9-GHz EPR imaging. CW EPR detected persistent radicals (single line) for various sesame seeds. The EPR linewidth of black sesame seeds was narrower than that of the irradiated white sesame seeds. A very small signal was detected for the white sesame seeds. Two-dimensional (2D) imaging using a 9-GHz EPR imager showed that radical locations vary for various sesame seeds. The paramagnetic species in black sesame seeds were located on the seed coat (skin) and in the hilum region. The signal with the highest intensity was obtained from the hilum part. A very low-intensity image was observed for the white sesame seeds. In addition, the 2D imaging of the irradiated white sesame seeds showed that free radicals were located throughout the entire seed. For the first time, CW EPR and 9-GHz EPR imaging showed the exact location of radical species in various sesame seeds.

Evaluation of Polyphenol Anthocyanin-Enriched Extracts of Blackberry, Black Raspberry, Blueberry, Cranberry, Red Raspberry, and Strawberry for Free Radical Scavenging, Reactive Carbonyl Species Trapping, Anti-Glycation, Anti-β-Amyloid Aggregation, and Microglial Neuroprotective Effects

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Hang Ma

2018-02-01

Full Text Available Glycation is associated with several neurodegenerative disorders, including Alzheimer’s disease (AD, where it potentiates the aggregation and toxicity of proteins such as β-amyloid (Aβ. Published studies support the anti-glycation and neuroprotective effects of several polyphenol-rich fruits, including berries, which are rich in anthocyanins. Herein, blackberry, black raspberry, blueberry, cranberry, red raspberry, and strawberry extracts were evaluated for: (1 total phenolic and anthocyanins contents, (2 free radical (DPPH scavenging and reactive carbonyl species (methylglyoxal; MGO trapping, (3 anti-glycation (using BSA-fructose and BSA-MGO models, (4 anti-Aβ aggregation (using thermal- and MGO-induced fibrillation models, and, (5 murine microglia (BV-2 neuroprotective properties. Berry crude extracts (CE were fractionated to yield anthocyanins-free (ACF and anthocyanins-enriched (ACE extracts. The berry ACEs (at 100 μg/mL showed superior free radical scavenging, reactive carbonyl species trapping, and anti-glycation effects compared to their respective ACFs. The berry ACEs (at 100 μg/mL inhibited both thermal- and MGO-induced Aβ fibrillation. In addition, the berry ACEs (at 20 μg/mL reduced H2O2-induced reactive oxygen species production, and lipopolysaccharide-induced nitric oxide species in BV-2 microglia as well as decreased H2O2-induced cytotoxicity and caspase-3/7 activity in BV-2 microglia. The free radical scavenging, reactive carbonyl trapping, anti-glycation, anti-Aβ fibrillation, and microglial neuroprotective effects of these berry extracts warrant further in vivo studies to evaluate their potential neuroprotective effects against AD.

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

International Nuclear Information System (INIS)

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

1998-01-01

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

Suppression of Raman electron spin relaxation of radicals in crystals. Comparison of Cu2+ and free radical relaxation in triglycine sulfate and Tutton salt single crystals.

Science.gov (United States)

Hoffmann, S K; Goslar, J; Lijewski, S

2011-08-31

Electron spin-lattice relaxation was measured by the electron spin echo method in a broad temperature range above 4.2 K for Cu(2+) ions and free radicals produced by ionizing radiation in triglycine sulfate (TGS) and Tutton salt (NH4)(2)Zn(SO4)2 ⋅ 6H2O crystals. Localization of the paramagnetic centres in the crystal unit cells was determined from continuous wave electron paramagnetic resonance spectra. Various spin relaxation processes and mechanisms are outlined. Cu(2+) ions relax fast via two-phonon Raman processes in both crystals involving the whole phonon spectrum of the host lattice. This relaxation is slightly slower for TGS where Cu(2+) ions are in the interstitial position. The ordinary Raman processes do not contribute to the radical relaxation which relaxes via the local phonon mode. The local mode lies within the acoustic phonon band for radicals in TGS but within the optical phonon range in (NH4)(2)Zn(SO4)2 ⋅ 6H2O. In the latter the cross-relaxation was considered. A lack of phonons around the radical molecules suggested a local crystal amorphisation produced by x- or γ-rays.

Airborne measurement of peroxy radicals in the lower troposphere

Science.gov (United States)

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

2013-04-01

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

Infrared absorption spectroscopy and chemical kinetics of free radicals

Energy Technology Data Exchange (ETDEWEB)

Curl, R.F.; Glass, G.P. [Rice Univ., Houston, TX (United States)

1993-12-01

This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

Developments in laser-induced fluorescence spectroscopy for quantitative in situ measurements of free radicals in the troposphere

Science.gov (United States)

Heard, Dwayne

2015-04-01

Photo-oxidation in the troposphere is highly complex, being initiated by short lived free radical species, in the daytime dominated by the hydroxyl radical, OH. Chemical oxidation cycles, which also involve peroxy radicals (HO2 and RO2), remove natural or anthropogenic emissions (for example methane) and generate a range of secondary products, for example ozone, nitrogen dioxide, acidic and multifunctional organic species, and secondary organic aerosol, which impact on human health and climate. Owing to their short lifetime in the atmosphere, the abundance of radicals is determined solely by their rate of chemical production and loss, and not by transport. Field measurements of the concentrations of radicals and comparison with calculations using a numerical model therefore constitutes one of the very best ways to test whether the chemistry in each of these locations is understood and accurately represented in the model. Validation of the chemistry is important, as the predictions of climate and air quality models containing this chemistry are used to drive the formulation of policy and legislation. However, in situ measurements of radical species, owing to their very low abundance (often sub part per trillion) and short lifetimes (pulse repetition rate tunable laser systems, will be discussed, together with calibration methods to make signals absolute, and identification of potential interferences. LIF instruments have been operated on ground, ship and aircraft platforms at a number of locations worldwide, and examples from recent fieldwork involving the Leeds instruments will be presented.

Bergenin Content and Free Radical Scavenging Activity of Bergenia Extracts. .

Science.gov (United States)

Hendrychová, Helena; Martin, Jan; Tůmová, Lenka; Kočevar-Glavač, Nina

2015-07-01

Our research was focused on the evaluation of bergenin content and free radical scavenging activity of extracts prepared from three different species of Bergenia - B. crassifolia (L.) Fritsch., B. ciliata (Haw.) Sternb. and B. x ornata Stein. collected during different seasons. Using an HPLC method, the highest total amount of bergenin was revealed in the leaves of B. x ornata and B. crassifolia (4.9 - 5.1 mg x g(-1)). Free radical scavenging power was determined by two methods--FRAP and NADH. The best free radical scavengers were B. crassifolia (FRAP: 6.7 - 15.9 mg GAE. 100g(-1); NADH: 20.3 - 50.9%) and B. ornata (FRAP: 13.7 - 15.2 mg GAE. 100g(-1); NADH: 29.3 - 31.1%). The lowest content of bergenin and the weakest radical scavenger was B. ciliata (bergenin: 3.1 mg x g(-1); FRAP: 5.5 - 11.0 mg GAE.100g(-1); NADH: 23.2 - 25.6%). The presence of a large percentage of bergenin is responsible for the radical scavenging activity, as shown by the results from the FRAP and NADH assays. Significant, positive correlation was found between bergenin content and radical scavenging activity in both methods.

A pulse radiolysis study of the reaction of the sulphate radical ion in aqueous solutions of styrene

International Nuclear Information System (INIS)

McAskill, N.A.; Sangster, D.F.

1979-01-01

The ultraviolet absorption spectra of the transient species formed during the pulse radiolysis of styrene and peroxydisulfate solutions showed that a benzyl-type radical was formed from styrene and the SO 4 - radical. The effect of adding Cl - was also studied. These results are in conflict with the claim that a phenylethyl radical was formed from SO 4 - via the styrene cation radical. That study was made on acetonitrile solutions of styrene, S 2 O 8 2- CUCl 2 and LiCl and the present results suggest that up to 70% of the SO 4 - radicals may have been converted into Cl 2 - radical which then reacted with styrene

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

Energy Technology Data Exchange (ETDEWEB)

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

1982-06-15

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

Quantification of Radicals Generated in a Sonicator

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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.

Phytochemical investigation of crude methanol extracts of different species of Swertia from Nepal.

Science.gov (United States)

Khanal, Supreet; Shakya, Niroj; Thapa, Krishna; Pant, Deepak Raj

2015-12-26

The genus Swertia is reported to contain potent bitter compounds like iridoids, xanthones and c-glucoflavones that are known to heal many human disorders. In contrast to high ethnomedicinally valued Swertia chirayita, its other species have not been studied extensively, in spite of their common use in traditional medicinal system in Nepalese communities. So, the present study attempts to investigate the content of total polyphenols, flavonoids, antioxidant activity and estimate the rough content of amarogentin, swertiamarin and mangiferin from different species of Swertia from Nepalese Himalayas. Whole plant parts of S. chirayita (SCH), S. angustifolia (SAN), S. paniculata (SPA), S. racemosa (SRA), S. nervosa (SNE), S. ciliata (SCI) and S. dilatata (SDI) were collected; total phenolic and flavonoid contents were quantified spectrophotometrically and in vitro DPPH free radical scavenging assay was measured. Thin layer chromatography was performed on TLC aluminium plates pre-coated with silica gel for identification of swertiamarin, amarogentin and mangiferin from those species and semi quantitative estimation was done using GelQuant.NET software using their standard compounds. The phenolic content was highest in the methanol extract of SCH (67.49 ± 0.5 mg GAE/g) followed by SDI, SRA, SNE, SCI, SPA and SAN. The contents of flavonoids were found in the order of SCH, SPA, SRA, SNE, SDI, SCI and SAN. Promising concentration of phenolics and flavonoids produced promising DPPH free radical scavenging values. The IC50 values for the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging test was lowest in SCH (23.35 ± 0.6 μg/ml), even lower than the standard ascorbic acid among the seven studied species. A significant correlation of 0.977 was observed between the polyphenol content and antioxidant values. The TLC profile showed the presence of all three major phytochemicals; amarogentin, swertiamarin and mangiferin in all of the plant samples. Among the seven studied

Formation of gas-phase π-allyl radicals from propylene over bismuth oxide and γ-bismuth molybdate catalysts

International Nuclear Information System (INIS)

Martir, W.; Lunsford, J.H.

1981-01-01

Gas-phase π-allyl radicals were produced when propylene reacted over Bi 2 O 3 and γ-bismuth molybdate catalysts at 723 K. The pressure in the catalyst zone was varied between 5 x 10 -3 and 1 torr. The radicals were detected by EPR spectroscopy together with a matrix isolation technique in which argon was used as the diluent. The matrix was formed on a sapphire rod at 12 K which was located 33-cm downstream from the catalyst. Bismuth oxide was more effective in the production of gas-phase allyl radicals than γ-bismuth molybdate. By contrast α-bismuth molybdate was ineffective in forming allyl radicals and MoO 3 acted as a sink for radicals which were produced elsewhere in the system. Comparison of the π-allyl radical and the stable product concentrations over Bi 2 O 3 revealed that gas-phase radical recombination reactions served as a major pathway for the formation of 1,5-hexadiene. Addition of small amounts of gas-phase oxygen increased the concentration of allyl radicals, and at greater oxygen levels allyl peroxy radicals were detected. Because of the effect of temperature on the equilibrium between allyl and allyl peroxy radicals, the latter product must be formed in the cooler part of the system

Aquatic species and habitats

Science.gov (United States)

Danny C. Lee; James R. Sedell; Bruce E. Rieman; Russell F. Thurow; Jack E. Williams

1998-01-01

Continuing human activities threaten the highly prized aquatic resources of the interior Columbia basin. Precipitous declines in native species, particularly Pacific salmon, and a large influx of introduced species have radically altered the composition and distribution of native fishes. Fortunately, areas of relatively high aquatic integrity remain, much of it on...

Free radical formation in single crystals of 9-methyladenine X-irradiated at 10 K. An electron paramagnetic resonance and electron nuclear double resonance study

International Nuclear Information System (INIS)

Hole, E.O.; Sagstuen, E.; Nelson, W.H.

1995-01-01

Single crystals of 9-methyladenine were X-irradiated at 10 K and at 65 K and were studied using K-band EPR, ENDOR and field-swept ENDOR (FSE) techniques in the temperature range 10 K to 290 K. Three major radicals are stabilized in 9-methyladenine at 10 K. These are: MA1, the adenine anion, probably protonated at N3; MA2, the species formed by net hydrogen abstraction from the 9-methyl group; and MA3, the radical formed by net hydrogen addition to C8 of the adenine moiety. Radical MA1 decayed at about 80 K, possibly into the C2 H adduct (MA4). The other two species (MA2, MA3) were stable at room temperature. A fifth radical species was clearly present in the EPR spectra at 10 K but was not detectable by ENDOR. This species, which decayed above 200 K (possibly into MA3), remains unidentified. The radical population at room temperature is as described by previous authors. The mechanisms for radical formation in 9-methyladenine are discussed in light of the hydrogen bonding scheme and molecular stacking interactions. 32 refs., 4 figs., 2 tabs

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.

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.

Two new Penicillium species Penicillium buchwaldii and Penicillium spathulatum, producing the anticancer compound asperphenamate

DEFF Research Database (Denmark)

Frisvad, Jens Christian; Houbraken, Jos; Popma, Suuske

2013-01-01

Penicillium buchwaldii sp. nov. (type strain CBS 117181(T) = IBT 6005(T) = IMI 30428(T) ) and Penicillium spathulatum sp. nov. (CBS 117192(T) = IBT 22220(T) ) are described as new species based on a polyphasic taxonomic approach. Isolates of P. buchwaldii typically have terverticillate...... conidiophores with echinulate thick-walled conidia and produce the extrolites asperphenamate, citreoisocoumarin, communesin A and B, asperentin and 5'-hydroxy-asperentin. Penicillium spathulatum is unique in having restricted colonies on Czapek yeast agar (CYA) with an olive grey reverse, good growth on CYA...... supplemented with 5% NaCl, terverticillate bi- and ter-ramulate conidiophores and consistently produces the extrolites benzomalvin A and D and asperphenamate. The two new species belong to Penicillium section Brevicompacta and are phylogenetically closely related to Penicillium tularense. With exception...

Chemical determination of free radical-induced damage to DNA.

Science.gov (United States)

Dizdaroglu, M

1991-01-01

Free radical-induced damage to DNA in vivo can result in deleterious biological consequences such as the initiation and promotion of cancer. Chemical characterization and quantitation of such DNA damage is essential for an understanding of its biological consequences and cellular repair. Methodologies incorporating the technique of gas chromatography/mass spectrometry (GC/MS) have been developed in recent years for measurement of free radical-induced DNA damage. The use of GC/MS with selected-ion monitoring (SIM) facilitates unequivocal identification and quantitation of a large number of products of all four DNA bases produced in DNA by reactions with hydroxyl radical, hydrated electron, and H atom. Hydroxyl radical-induced DNA-protein cross-links in mammalian chromatin, and products of the sugar moiety in DNA are also unequivocally identified and quantitated. The sensitivity and selectivity of the GC/MS-SIM technique enables the measurement of DNA base products even in isolated mammalian chromatin without the necessity of first isolating DNA, and despite the presence of histones. Recent results reviewed in this article demonstrate the usefulness of the GC/MS technique for chemical determination of free radical-induced DNA damage in DNA as well as in mammalian chromatin under a vast variety of conditions of free radical production.

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)

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...

Atmospheric implications of simultaneous nighttime measurements of NO3 radicals and hono

International Nuclear Information System (INIS)

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

1984-01-01

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

EPR investigation of zinc/iodine exchange between propargyl iodides and diethylzinc: detection of propargyl radical by spin trapping.

Science.gov (United States)

Maury, Julien; Jammi, Suribabu; Vibert, François; Marque, Sylvain R A; Siri, Didier; Feray, Laurence; Bertrand, Michèle

2012-10-19

The production of propargyl radicals in the reaction of dialkylzincs with propargyl iodides in nondegassed medium was investigated by EPR using tri-tert-butylnitrosobenzene (TTBNB) as a spin trap. The radical mechanism and the nature of the observed species were confirmed by the trapping of propargyl radicals generated by an alternative pathway: i.e., upon irradiation of propargyl iodides in the presence of hexa-n-butyldistannane. In dialkylzinc-mediated experiments a high concentration of adduct was instantaneously observed, whereas no spontaneous production of spin adduct was detected in a blank experiment performed with the propargylic iodide and TTBNB in the absence of diethylzinc. Under irradiation in the presence of distannane, two different species were observed at the very beginning of the irradiation; the nitroxide resulting from the trapping of propargyl radical at the propargyl carbon remained the only species detected after irradiating for several minutes. The absence of adducts resulting from the trapping of allenyl canonical forms was supported by DFT calculations and by the preparation of an authentic sample.

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.

Impact of plasma jet vacuum ultraviolet radiation on reactive oxygen species generation in bio-relevant liquids

Energy Technology Data Exchange (ETDEWEB)

Jablonowski, H.; Hammer, M. U.; Reuter, S. [Center for Innovation Competence plasmatis, Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany); Leibniz Institute for Plasma Science and Technology, INP Greifswald e.V. Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany); Bussiahn, R.; Weltmann, K.-D.; Woedtke, Th. von [Leibniz Institute for Plasma Science and Technology, INP Greifswald e.V. Felix-Hausdorff-Str. 2, 17489 Greifswald (Germany)

2015-12-15

Plasma medicine utilizes the combined interaction of plasma produced reactive components. These are reactive atoms, molecules, ions, metastable species, and radiation. Here, ultraviolet (UV, 100–400 nm) and, in particular, vacuum ultraviolet (VUV, 10–200 nm) radiation generated by an atmospheric pressure argon plasma jet were investigated regarding plasma emission, absorption in a humidified atmosphere and in solutions relevant for plasma medicine. The energy absorption was obtained for simple solutions like distilled water (dH{sub 2}O) or ultrapure water and sodium chloride (NaCl) solution as well as for more complex ones, for example, Rosewell Park Memorial Institute (RPMI 1640) cell culture media. As moderate stable reactive oxygen species, hydrogen peroxide (H{sub 2}O{sub 2}) was studied. Highly reactive oxygen radicals, namely, superoxide anion (O{sub 2}{sup •−}) and hydroxyl radicals ({sup •}OH), were investigated by the use of electron paramagnetic resonance spectroscopy. All species amounts were detected for three different treatment cases: Plasma jet generated VUV and UV radiation, plasma jet generated UV radiation without VUV part, and complete plasma jet including all reactive components additionally to VUV and UV radiation. It was found that a considerable amount of radicals are generated by the plasma generated photoemission. From the experiments, estimation on the low hazard potential of plasma generated VUV radiation is discussed.

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

Science.gov (United States)

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

2006-01-03

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

Antioxidant and free radical scavenging activities of plant extracts ...

African Journals Online (AJOL)

Twenty-two species of medicinal plants collected in the Mexican state of Morelos were selected to evaluate their free radical scavenging and antioxidant activities. The extracts from the aerial parts of the plants were obtained using hexane, acetone and methanol (66 extracts). The initial qualitative screening of antioxidants ...

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

Science.gov (United States)

Kamogawa, Erisa; Sueishi, Yoshimi

2014-03-01

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

Anti-inflammatory and cytotoxic activities of five Veronica species.

Science.gov (United States)

Harput, U Sebnem; Saracoglu, Iclal; Inoue, Makoto; Ogihara, Yukio

2002-04-01

Biological activities of five Veronica species (Scrophulariaceae), V. cymbalaria, V. hederifolia, V. pectinata var. glandulosa, V. persica and V. polita were studied for their anti-inflammatory and cytotoxic activities. Their methanol extracts showed both the inhibitory activity of nitric oxide (NO) production in lipopolysaccharide (LPS)-stimulated macrophages and cytotoxic activity against KB epidermoid carcinoma and B16 melanoma. When the methanol extracts were fractionated between water and chloroform, water fractions significantly inhibited NO production without any cytotoxicity, while chloroform fractions showed cytotoxicity dose-dependently. When the radical scavenging activity was determined using 2,2-diphenyl-1-picryl-hydrazyl (DPPH), water fractions of the five Veronica species scavenged free radicals effectively, suggesting that the inhibitory effect of this species on NO production was due to their radical scavenging activity. On the other hand, chloroform fractions of Veronica species except for V. cymbalaria showed similar cytotoxic activity against KB and B16 melanoma cells.

Quantification of superoxide radical production in thylakoid membrane using cyclic hydroxylamines.

Science.gov (United States)

Kozuleva, Marina; Klenina, Irina; Mysin, Ivan; Kirilyuk, Igor; Opanasenko, Vera; Proskuryakov, Ivan; Ivanov, Boris

2015-12-01

Applicability of two lipophilic cyclic hydroxylamines (CHAs), CM-H and TMT-H, and two hydrophilic CHAs, CAT1-H and DCP-H, for detection of superoxide anion radical (O2(∙-)) produced by the thylakoid photosynthetic electron transfer chain (PETC) of higher plants under illumination has been studied. ESR spectrometry was applied for detection of the nitroxide radical originating due to CHAs oxidation by O2(∙-). CHAs and corresponding nitroxide radicals were shown to be involved in side reactions with PETC which could cause miscalculation of O2(∙-) production rate. Lipophilic CM-H was oxidized by PETC components, reducing the oxidized donor of Photosystem I, P700(+), while at the same concentration another lipophilic CHA, TMT-H, did not reduce P700(+). The nitroxide radical was able to accept electrons from components of the photosynthetic chain. Electrostatic interaction of stable cation CAT1-H with the membrane surface was suggested. Water-soluble superoxide dismutase (SOD) was added in order to suppress the reaction of CHA with O2(∙-) outside the membrane. SOD almost completely inhibited light-induced accumulation of DCP(∙), nitroxide radical derivative of hydrophilic DCP-H, in contrast to TMT(∙) accumulation. Based on the results showing that change in the thylakoid lumen pH and volume had minor effect on TMT(∙) accumulation, the reaction of TMT-H with O2(∙-) in the lumen was excluded. Addition of TMT-H to thylakoid suspension in the presence of SOD resulted in the increase in light-induced O2 uptake rate, that argued in favor of TMT-H ability to detect O2(∙-) produced within the membrane core. Thus, hydrophilic DCP-H and lipophilic TMT-H were shown to be usable for detection of O2(∙-) produced outside and within thylakoid membranes. Copyright © 2015 Elsevier Inc. All rights reserved.

EPR study of the production of OH radicals in aqueous solutions of uranium irradiated by ultraviolet light

Directory of Open Access Journals (Sweden)

MARKO DAKOVIĆ

2009-06-01

Full Text Available The aim of the study was to establish whether hydroxyl radicals (•OH were produced in UV-irradiated aqueous solutions of uranyl salts. The production of •OH was studied in uranyl acetate and nitrate solutions by an EPR spin trap method over a wide pH range, with variation of the uranium concentrations. The production of •OH in uranyl solutions irradiated with UV was unequivocally demonstrated for the first time using the EPR spin-trapping method. The production of •OH can be connected to speciation of uranium species in aqueous solutions, showing a complex dependence on the solution pH. When compared with the results of radiative de-excitation of excited uranyl (*UO22+ by the quenching of its fluorescence, the present results indicate that the generation of hydroxyl radicals plays a major role in the fluorescence decay of *UO22+. The role of the presence of carbonates and counter ions pertinent to environmental conditions in biological systems on the production of hydroxyl radicals was also assessed in an attempt to reveal the mechanism of *UO22+ de-excitation. Various mechanisms, including •OH production, are inferred but the main point is that the generation of •OH in uranium containing solutions must be considered when assessing uranium toxicity.

Resonance Raman Spectrum of the Transient (SCN)2 Free Radical Anion

DEFF Research Database (Denmark)

Wilbrandt, Robert Walter; Jensen, N. H.; Pagsberg, Palle Bjørn

1979-01-01

The resonance Raman spectrum of the transient species (λmax = 475 nm, τ½ = 1.6 μs) formed by pulse radiolysis of aqueous solutions of thiocyanate, SCN2−, is reported. The spectrum is discussed in terms of the previous assignment of this transient to the radical anion, (SCN)−2. The observed...... vibrational frequencies of the radical anion are consistent with substantial weakening of the S---S and the Ctriple bond; length as m-dashN bonds are compared with neutral thiocyanogen....

Reactive Oxygen Species Production by Forward and Reverse Electron Fluxes in the Mitochondrial Respiratory Chain

Science.gov (United States)

Selivanov, Vitaly A.; Votyakova, Tatyana V.; Pivtoraiko, Violetta N.; Zeak, Jennifer; Sukhomlin, Tatiana; Trucco, Massimo; Roca, Josep; Cascante, Marta

2011-01-01

Reactive oxygen species (ROS) produced in the mitochondrial respiratory chain (RC) are primary signals that modulate cellular adaptation to environment, and are also destructive factors that damage cells under the conditions of hypoxia/reoxygenation relevant for various systemic diseases or transplantation. The important role of ROS in cell survival requires detailed investigation of mechanism and determinants of ROS production. To perform such an investigation we extended our rule-based model of complex III in order to account for electron transport in the whole RC coupled to proton translocation, transmembrane electrochemical potential generation, TCA cycle reactions, and substrate transport to mitochondria. It fits respiratory electron fluxes measured in rat brain mitochondria fueled by succinate or pyruvate and malate, and the dynamics of NAD+ reduction by reverse electron transport from succinate through complex I. The fitting of measured characteristics gave an insight into the mechanism of underlying processes governing the formation of free radicals that can transfer an unpaired electron to oxygen-producing superoxide and thus can initiate the generation of ROS. Our analysis revealed an association of ROS production with levels of specific radicals of individual electron transporters and their combinations in species of complexes I and III. It was found that the phenomenon of bistability, revealed previously as a property of complex III, remains valid for the whole RC. The conditions for switching to a state with a high content of free radicals in complex III were predicted based on theoretical analysis and were confirmed experimentally. These findings provide a new insight into the mechanisms of ROS production in RC. PMID:21483483

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

International Nuclear Information System (INIS)

Nakagawa, Seiko; Ohta, Nobuaki; Murakami, Takeshi

2010-01-01

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

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)

Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

Energy Technology Data Exchange (ETDEWEB)

Grodkowski, J; Bobrowski, K; Mehnert, R; Brede, O

1989-01-01

The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl/sub 4/ and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN/sup +radical/) and the former to the known carbonium ion of malachite green dye (MG/sup +/). Observation of the consecutive charge transfer via the schemes: DCE/sup +radical/ -> BPh/sup +radical/ -> MGCN/sup +radical/ and DCE/sup +radical/ -> MGCN/sup +radical/ -> TMPD/sup +radical/, allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV < Ip/sub MGCN/ < 8.27 eV. Presented results and literature data suggest that positive charge in MGCN/sup +radical/ radical cation is located in the ''aniline'' part of the molecule. (author).

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

International Nuclear Information System (INIS)

Horton, Jureta W.

2003-01-01

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

Atom transfer radical copolymerization of styrene and butyl acrylate

NARCIS (Netherlands)

Chambard, G.; Klumperman, B.; Matyjaszewski, K.

2000-01-01

Atom transfer radical polymerization of styrene and butyl acrylate has been investigated from a kinetic point of view. Attention is focused on the activation of the dormant species as well as on the termination that plays a role in these reactions. It has been shown that the activation of a styrene

Photodissociation dynamics and spectroscopy of free radical combustion intermediates

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-01

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

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.

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

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.

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

Directory of Open Access Journals (Sweden)

Balakrishna Shrilatha

2009-04-01

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

Free radical-mediated stimulation of tyrosine-specific protein kinase in rat liver plasma membrane

International Nuclear Information System (INIS)

Chan, T.M.; Tatoyan, A.; Cheng, E.; Shargill, N.S.; Pleta, M.

1986-01-01

Incorporation of 32 P from (γ- 32 P)-ATP into endogenous proteins of plasma membranes isolated from rat liver was significantly increased by several naphthoquinones including menadione. This apparent stimulation of membrane-associated protein kinase activity by these compounds was most striking (up to 6-7 fold) when the synthetic copolymers containing glutamate and tyrosine residues (4:1) was used as substrate. Since tyrosine residues are the only possible phosphate acceptor in the copolymers, the quinone-stimulated liver membrane protein kinase is most likely tyrosine specific. Although not required for protein kinase activity, dithiothreitol (DTT) was necessary for its stimulation by these quinonoid compounds. Hydrolysis of ATP was not significantly affected by quinones under the experimental conditions. Both menadione and vitamin k 5 increased phosphorylation of plasma membrane proteins of molecular weight 45 and 60 kd. The stimulatory effect of menadione on protein phosphorylation was prevented by the addition of superoxide dismutase. Dihydroxyfumerate, which spontaneously produces various radical species, and H 2 O 2 , also stimulated tyrosine-specific protein phosphorylation. DTT was also required for their full effect. It, therefore, appears that quinonone stimulation of tyrosine-specific protein phosphorylation is mediated by oxygen radicals

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

International Nuclear Information System (INIS)

Rosilio, C.

1969-01-01

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

Relaxation behavior of radicals produced in irradiated black pepper under various moisture conditions by ESR

International Nuclear Information System (INIS)

Kameya, Hiromi; Kawauchi, Risa; Shimoyama, Yuhei; Kaeda, Yoko; Ogawa, Satoko; Nakamura, Hideo; Ukai, Mitsuko

2008-01-01

Black pepper is easy to be contaminated by microorganism and often processed to γ-irradiation. ESR has been used for the detection of radicals induced in irradiated spices. Using ESR, we revealed the effects of moisture condition during storage of irradiated black pepper on the saturation behavior of ESR signal. The ESR spectrum of black pepper consists of a broad sextet centered at g=2.0, a singlet as same g-value and a singlet at g=4.0. The irradiation causes two new signals, one is the strong and sharp singlet signal at g=2.0 and the other is the side signal. We found that the signal intensity originated by the radicals of black pepper with and without radiation decayed in the high humidity condition during storage. The ESR signal intensity of irradiated black pepper decayed during storage and showed almost the same intensity level as that of non-irradiated black pepper during storage. (author)

Formation of Hydroxylamine from Ammonia and Hydroxyl Radicals

Science.gov (United States)

Krim, Lahouari; Zins, Emilie-Laure

2014-06-01

In the interstellar medium, as well as in icy comets, ammonia may be a crucial species in the first step toward the formation of amino-acids and other prebiotic molecules such as hydroxylamine (NH2OH). It is worth to notice that the NH3/H2 ratio in the ISM is 3 10-5 compared the H2O/H2 one which is only 7 10-5. Using either electron-UV irradiations of water-ammonia ices or successive hydrogenation of solid nitric oxide, laboratory experiments have already shown the feasibility of reactions that may take place on the surface of ice grains in molecular clouds, and may lead to the formation of this precursor. Herein is proposed a new reaction pathway involving ammonia and hydroxyl radicals generated in a microwave discharge. Experimental studies, at 3 and 10 K, in solid phase as well as in neon matrix have shown that this reaction proceed via a hydrogen abstraction, leading to the formation of NH2 radical, that further recombine with hydroxyl radical to form hydroxylamine, under non-energetic conditions.

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

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

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

International Nuclear Information System (INIS)

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

1982-01-01

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

Investigation Into In-Vitro Radical Scavenging And In-Vivo Anti ...

African Journals Online (AJOL)

This, then necessitated the use of DPPH (2,2-diphenyl-1-picrylhydrazyl hydrate) and ... and the lowest 50 % inhibitory concentration of free radical oxidative species ... (HEX) and the chloroform (CHL) fractions displayed a below 25 % inhibition. ... fraction: the ethylacetate fraction (ETA) revealed a dose dependent trend.

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

International Nuclear Information System (INIS)

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

1995-01-01

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

Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery.

Science.gov (United States)

Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric; Lawrence, Chad; Vijayakumar, M; Henderson, Wesley A; Liu, Tianbiao; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent; Wang, Wei

2015-07-20

Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all-organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical-based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface modification of polystyrene with atomic oxygen radical anions-dissolved solution

International Nuclear Information System (INIS)

Wang Lian; Yan Lifeng; Zhao Peitao; Torimoto, Yoshifumi; Sadakata, Masayoshi; Li Quanxin

2008-01-01

A novel approach to surface modification of polystyrene (PS) polymer with atomic oxygen radical anions-dissolved solution (named as O - water) has been investigated. The O - water, generated by bubbling of the O - (atomic oxygen radical anion) flux into the deionized water, was characterized by UV-absorption spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. The O - water treatments caused an obvious increase of the surface hydrophilicity, surface energy, surface roughness and also caused an alteration of the surface chemical composition for PS surfaces, which were indicated by the variety of contact angle and material characterization by atomic force microscope (AFM) imaging, field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and attenuated total-reflection Fourier transform infrared (ATR-FTIR) measurements. Particularly, it was found that some hydrophilic groups such as hydroxyl (OH) and carbonyl (C=O) groups were introduced onto the polystyrene surfaces via the O - water treatment, leading to the increases of surface hydrophilicity and surface energy. The active oxygen species would react with the aromatic ring molecules on the PS surfaces and decompose the aromatic compounds to produce hydrophilic hydroxyl and carbonyl compounds. In addition, the O - water is also considered as a 'clean solution' without adding any toxic chemicals and it is easy to be handled at room temperature. Present method may suit to the surface modification of polymers and other heat-sensitive materials potentially

High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction

Science.gov (United States)

Weidman, Jared D.; Allen, Ryan T.; Moore, Kevin B.; Schaefer, Henry F.

2018-05-01

Numerous processes in atmospheric and combustion chemistry produce the vinoxy radical (•CH2CHO). To understand the fate of this radical and to provide reliable energies needed for kinetic modeling of such processes, we have examined its reaction with O2 using highly reliable theoretical methods. Utilizing the focal point approach, the energetics of this reaction and subsequent reactions were obtained using coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set limit. These extrapolated energies were appended with several corrections including a treatment of full triples and connected quadruple excitations, i.e., CCSDT(Q). In addition, this study models the initial vinoxy radical + O2 reaction for the first time with multireference methods. We predict a barrier for this reaction of approximately 0.4 kcal mol-1. This result agrees with experimental findings but is in disagreement with previous theoretical studies. The vinoxy radical + O2 reaction produces a 2-oxoethylperoxy radical which can undergo a number of unimolecular reactions. Abstraction of a β-hydrogen (a 1,4-hydrogen shift) and dissociation back to reactants are predicted to be competitive to each other due to their similar barriers of 21.2 and 22.3 kcal mol-1, respectively. The minimum-energy β-hydrogen abstraction pathway produces a hydroperoxy radical (QOOH) that eventually decomposes to formaldehyde, CO, and •OH. Two other unimolecular reactions of the peroxy radical are α-hydrogen abstraction (38.7 kcal mol-1 barrier) and HO2• elimination (43.5 kcal mol-1 barrier). These pathways lead to glyoxal + •OH and ketene + HO2• formation, respectively, but they are expected to be uncompetitive due to their high barriers.

Cyclic Versus Linear Isomers Produced by Reaction of the Methylidyne Radical (CH) with Small Unsaturated Hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Goulay, Fabien; Trevitt, Adam J.; Meloni, Giovanni; Selby, Talitha M.; Osborn, David L.; Taatjes, Craig A.; Vereecken, Luc; Leone, Stephen R.

2008-12-05

The reactions of the methylidyne radical (CH) with ethylene, acetylene, allene, and methylacetylene are studied at room temperature using tunable vacuum ultraviolet (VUV) photoionization and time-resolved mass spectrometry. The CH radicals are prepared by 248 nm multiphoton photolysis of CHBr3 at 298 K and react with the selected hydrocarbon in a helium gas flow. Analysis of photoionization efficiency versus VUV photon wavelength permits isomer-specific detection of the reaction products and allows estimation of the reaction product branching ratios. The reactions proceed by either CH insertion or addition followed by H atom elimination from the intermediate adduct. In the CH + C2H4 reaction the C3H5 intermediate decays by H atom loss to yield 70(+-8)percent allene, 30(+-8)percent methylacetylene and less than 10percent cyclopropene, in agreement with previous RRKM results. In the CH + acetylene reaction, detection of mainly the cyclic C3H2 isomer is contrary to a previous RRKM calculation that predicted linear triplet propargylene to be 90percent of the total H-atom co-products. High-level CBS-APNO quantum calculations and RRKM calculation for the CH + C2H2 reaction presented in this manuscript predict a higher contribution of the cyclic C3H2 (27.0percent) versus triplet propargylene (63.5percent) than these earlier predictions. Extensive calculations on the C3H3 and C3H2D system combined with experimental isotope ratios for the CD + C2H2 reaction indicate that H-atom assisted isomerization in the present experiments is responsible for the discrepancy between the RRKM calculations and the experimental results. Cyclic isomers are also found to represent 30(+-6)percent of the detected products in the case of CH + methylacetylene, together with 33(+-6)percent 1,2,3-butatriene and 37(+-6)percent vinylacetylene. The CH + allene reaction gives 23(+-5)percent 1,2,3-butatriene and 77(+-5)percent vinylacetylene, whereas cyclic isomers are produced below the detection limit

Liquid-State ¹³C Polarization of 30% through Photoinduced Nonpersistent Radicals

DEFF Research Database (Denmark)

Capozzi, Andrea; Karlsson, Magnus; Petersen, Jan Raagaard

2018-01-01

of the nuclear spin polarizationtogether with the constraint of having to polarize the spins nearthe MRI magnet. As recently demonstrated, the employment of UV-inducednonpersistent radicals represents an elegant solution to tacklingthese drawbacks. Nevertheless, since its introduction, the spreadof the technique......-radical technique. Under optimal conditions,it was possible to produce up to 60 mM radical in less than 5 minand reach maximum DNP enhancement with a buildup time constant ofapproximately 25 min at 6.7 T and 1 K, resulting in 30% 13C liquid-state polarization....

A reappraisal of Aspergillus section Nidulantes with descriptions of two new sterigmatocystin-producing species

DEFF Research Database (Denmark)

Hubka, Vit; Nováková, Alena; Peterson, Stephen W.

2016-01-01

Aspergillus section Nidulantes is a speciose group of microscopic fungi whose species are important in indoor air quality, food spoilage, mycotoxin production and human pathogenicity. We assembled as many species from the section as possible with either type specimens or protologues for analysis...... that both species are able to produce the mycotoxin sterigmatocystin and some additional compounds....

Sea Cucumber Glycosides: Chemical Structures, Producing Species and Important Biological Properties.

Science.gov (United States)

Mondol, Muhammad Abdul Mojid; Shin, Hee Jae; Rahman, M Aminur; Islam, Mohamad Tofazzal

2017-10-17

Sea cucumbers belonging to echinoderm are traditionally used as tonic food in China and other Asian countries. They produce abundant biologically active triterpene glycosides. More than 300 triterpene glycosides have been isolated and characterized from various species of sea cucumbers, which are classified as holostane and nonholostane depending on the presence or absence of a specific structural unit γ(18,20)-lactone in the aglycone. Triterpene glycosides contain a carbohydrate chain up to six monosaccharide units mainly consisting of d-xylose, 3-O-methy-d-xylose, d-glucose, 3-O-methyl-d-glucose, and d-quinovose. Cytotoxicity is the common biological property of triterpene glycosides isolated from sea cucumbers. Besides cytotoxicity, triterpene glycosides also exhibit antifungal, antiviral and hemolytic activities. This review updates and summarizes our understanding on diverse chemical structures of triterpene glycosides from various species of sea cucumbers and their important biological activities. Mechanisms of action and structural-activity relationships (SARs) of sea cucumber glycosides are also discussed briefly.

beta-Scission of C-3 (beta-carbon) alkoxyl radicals on peptides and proteins

DEFF Research Database (Denmark)

Headlam, H A; Mortimer, A; Easton, C J

2000-01-01

Exposure of proteins to radicals in the presence of O(2) brings about multiple changes in the target molecules. These alterations include oxidation of side chains, fragmentation, cross-linking, changes in hydrophobicity and conformation, altered susceptibility to proteolytic enzymes, and formation...... of methanal (formaldehyde). This product has been quantified with a number of oxidized peptides and proteins, and can account for up to 64% of the initial attacking radicals with some Ala peptides. When quantified together with the hydroperoxide precursors, these species account for up to 80% of the initial...... radicals, confirming that this is a major process. Methanal causes cell toxicity and DNA damage and is an animal carcinogen and a genotoxic agent in human cells. Thus, the formation and subsequent reaction of alkoxyl radicals formed at the C-3 position on aliphatic amino acid side chains on peptides...

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

Science.gov (United States)

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

2014-10-01

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

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...

Aspergillus korhogoensis, a Novel Aflatoxin Producing Species from the Côte d’Ivoire

Directory of Open Access Journals (Sweden)

Amaranta Carvajal-Campos

2017-10-01

Full Text Available Several strains of a new aflatoxigenic species of Aspergillus, A. korhogoensis, were isolated in the course of a screening study involving species from section Flavi found contaminating peanuts (Arachis hypogaea and peanut paste in the Côte d’Ivoire. Based on examination of four isolates, this new species is described using a polyphasic approach. A concatenated alignment comprised of nine genes (ITS, benA, cmdA, mcm7, amdS, rpb1, preB, ppgA, and preA was subjected to phylogenetic analysis, and resulted in all four strains being inferred as a distinct clade. Characterization of mating type for each strain revealed A. korhogoensis as a heterothallic species, since three isolates exhibited a singular MAT1-1 locus and one isolate exhibited a singular MAT1-2 locus. Morphological and physiological characterizations were also performed based on their growth on various types of media. Their respective extrolite profiles were characterized using LC/HRMS, and showed that this new species is capable of producing B- and G-aflatoxins, aspergillic acid, cyclopiazonic acid, aflavarins, and asparasones, as well as other metabolites. Altogether, our results confirm the monophyly of A. korhogoensis, and strengthen its position in the A. flavus clade, as the sister taxon of A. parvisclerotigenus.

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

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

International Nuclear Information System (INIS)

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

1990-01-01

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

Spectroscopy, Kinetics, and Dynamics of Combustion Radicals

Energy Technology Data Exchange (ETDEWEB)

Nesbitt, David J. [Research/Professor

2013-08-06

Spectroscopy, kinetics and dynamics of jet cooled hydrocarbon transients relevant to the DOE combustion mission have been explored, exploiting i) high resolution IR lasers, ii) slit discharge sources for formation of jet cooled radicals, and iii) high sensitivity detection with direct laser absorption methods and near the quantum shot noise limit. What makes this combination powerful is that such transients can be made under high concentrations and pressures characteristic of actual combustion conditions, and yet with the resulting species rapidly cooled (T ≈10-15K) in the slit supersonic expansion. Combined with the power of IR laser absorption methods, this provides novel access to spectral detection and study of many critical combustion species.

The games radicals play : special issue on free radicals and radical ions

OpenAIRE

Walton, J.C.; Williams, F.

2015-01-01

Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and a...

Time resolved resonance Raman spectra of anilino radical and aniline radical cation

International Nuclear Information System (INIS)

Tripathi, G.N.R.; Schuler, R.H.

1987-01-01

We report, in this paper, submicrosecond time resolved resonance Raman spectra of anilino radical and its radical cation as observed in pulse radiolytic studies of the oxidation of aniline in aqueous solution. By excitation in resonance with the broad and weak electronic transition of anilino radical at 400 nm (ε--1250 M -1 cm -1 ) we have observed, for the first time, the vibrational features of this radical. The Wilson ν 8 /sub a/ ring stretching mode at 1560 cm -1 is most strongly resonance enhanced. The ν 7 /sub a/ CN stretching band at 1505 cm -1 , which is shifted to higher frequency by 231 cm -1 with respect to aniline, is also prominent. The frequency of this latter mode indicates that the CN bond in the radical has considerable double bond character. The Raman spectrum of aniline radical cation, excited in resonance with the --425 nm electronic absorption (ε--4000 M -1 cm -1 ), shows features which are similar to phenoxyl radical. Most of the observed frequencies of this radical in solution are in good agreement with vibrational energies determined by recent laser photoelectron spectroscopic studies in the vapor phase. The bands most strongly enhanced in the resonance Raman spectrum are, however, weak in the photoelectron spectrum. While the vibrational frequencies observed for anilino radical and its isoelectronic cation are quite similar, the resonance enhancement patterns are very different. In particular the ν 14 b 2 mode of anilino radical observed at 1324 cm -1 is highly resonance enhanced because of strong vibronic coupling between the 400 nm 2 A 2 -- 2 B 1 and the higher 2 B 1 -- 2 B 1 electronic transitions

Involvement of hydroxyl radicals in the release by ionizing radiation of a cell surface nuclease from Micorcoccus radiodurans

International Nuclear Information System (INIS)

Mitchel, R.E.J.

1975-01-01

The ionizing radiation-induced release of a surface exonuclease from Micrococcus radiodurans is to a large extent inhibited by the removal of water. Irradiation of a cell suspension saturated with O 2 (an effective aqueous electron and hydrogen atom scavenger) allows the same release as irradiation in the presence of N 2 . Ethanol (a good hydroxyl radical scavenger) protects the enzyme from release. These data suggest that hydroxyl radicals produced by the radiolysis of water are important releasing agents. Hydroxyl radicals produced by the ultraviolet decomposition of H 2 O 2 were effective in releasing the enzyme

Millimeterwave spectroscopy of transient molecules produced in a ...

Indian Academy of Sciences (India)

produced inside the cell in a low pressure DC discharge of precursor gases. ... SO radical was also produced outside the cell by reactions of discharged oxygen .... have been reported by Dodd and Little [15] who have also calculated force.

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

Science.gov (United States)

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

2006-10-01

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

The microwave and millimeter spectrum of ZnCCH (X̃2Σ+): a new zinc-containing free radical.

Science.gov (United States)

Min, J; Halfen, D T; Sun, M; Harris, B; Ziurys, L M

2012-06-28

The pure rotational spectrum of the ZnCCH (X̃(2)Σ(+)) radical has been measured using Fourier transform microwave (FTMW) and millimeter direct-absorption methods in the frequency range of 7-260 GHz. This work is the first study of ZnCCH by any type of spectroscopic technique. In the FTMW system, the radical was synthesized in a mixture of zinc vapor and 0.05% acetylene in argon, using a discharge assisted laser ablation source. In the millimeter-wave spectrometer, the molecule was created from the reaction of zinc vapor, produced in a Broida-type oven, with pure acetylene in a dc discharge. Thirteen rotational transitions were recorded for the main species, (64)ZnCCH, and between 4 and 10 for the (66)ZnCCH, (68)ZnCCH, (64)ZnCCD, and (64)Zn(13)C(13)CH isotopologues. The fine structure doublets were observed in all the data, and in the FTMW spectra, hydrogen, deuterium, and carbon-13 hyperfine splittings were resolved. The data have been analyzed with a (2)Σ Hamiltonian, and rotational, spin-rotation, and H, D, and (13)C hyperfine parameters have been established for this radical. From the rotational constants, an r(m) ((1)) structure was determined with r(Zn-C) = 1.9083 Å, r(C-C) = 1.2313 Å, and r(C-H) = 1.0508 Å. The geometry suggests that ZnCCH is primarily a covalent species with the zinc atom singly bonded to the C≡C-H moiety. This result is consistent with the hyperfine parameters, which suggest that the unpaired electron is localized on the zinc nucleus. The spin-rotation constant indicates that an excited (2)Π state may exist ∼19,000 cm(-1) in energy above the ground state.

Atmospherically Relevant Radicals Derived from the Oxidation of Dimethyl Sulfide.

Science.gov (United States)

Mardyukov, Artur; Schreiner, Peter R

2018-02-20

atmosphere. The application of matrix-isolation techniques in combination with quantum-mechanical calculations on the generation and structural elucidation of CH 3 SO x (x = 0-3) radicals is reviewed in the present Account. Experimental matrix IR and UV/vis data for all known species of this substance class are summarized together with data obtained using other spectroscopic techniques, including time-resolved spectroscopy, electron paramagnetic resonance spectroscopy, and others. We also discuss the reactivity and experimental characterization of these species to illustrate their practical relevance and highlight spectroscopic techniques available for the elucidation of their geometric and electronic structures. The present Account summarizes recent results regarding the preparation, characterization, and reactivity of various radical species with the formula CH 3 SO x (x = 0-3).

Catalase expression is modulated by vancomycin and ciprofloxacin and influences the formation of free radicals in Staphylococcus aureus cultures

DEFF Research Database (Denmark)

Wang, Ying; Hougaard, Anni Bygvrå; Paulander, Wilhelm Erik Axel

2015-01-01

Detection of free radicals in biological systems is challenging due to their short half-lives. We have applied electron spin resonance (ESR) spectroscopy combined with spin traps using the probes PBN (N-tert-butyl-α-phenylnitrone) and DMPO (5,5-dimethyl-1-pyrroline N-oxide) to assess free radical...... that in S. aureus, bactericidal antibiotics modulate catalase expression, which in turn influences the formation of free radicals in the surrounding broth medium. If similar regulation is found in other bacterial species, it might explain why bactericidal antibiotics are perceived as inducing formation...... of free radicals....

Evaluation of antimalarial, free-radical-scavenging and insecticidal activities of Artemisia scoparia and A. Spicigera, Asteraceae

Directory of Open Access Journals (Sweden)

Fariba H. Afshar

2011-12-01

Full Text Available Artemisia species (Asteraceae, widespread throughout the world, are a group of important medicinal plants. The extracts of two medicinal plants of this genus, Artemisia scoparia Waldst. & Kit. and A. spicigera C. Koch, were evaluated for potential antimalarial, free-radical-scavenging and insecticidal properties, using the heme biocrystallisation and inhibition assay, the DPPH assay and the contact toxicity bioassay using the pest Tribolium castaneum, respectively. The methanol extracts of both species showed strong free-radical-scavenging activity and the RC50 values were 0.0317 and 0.0458 mg/mL, respectively, for A. scoparia and A. spicigera. The dichloromethane extracts of both species displayed a moderate level of potential antimalarial activity providing IC50 at 0.778 and 0.999 mg/mL for A. scoparia and A. spicigera, respectively. Both species of Artemisia showed insecticidal properties. However, A. spicigera was more effective than A. scoparia.

Selective degradation of lignin and elimination of HO radicals in pulps by O3 and UV laser flash irradiation

Institute of Scientific and Technical Information of China (English)

林鹿; 周贤涛; 邱玉桂

2002-01-01

HO radical is an aggressive reagent to abstract hydrogen from diverse substitutes and lead them to degradation, however, in reaction of active oxygen species with lignins, complex phenolic polymers, in dispersed lignocellulose such as pulp for environment-benign delignification, HO radicals should be eliminated as more as possible to prevent cellulose from unfavorably concomitant degradation. A reaction system of O3 is constructed under UV laser flash irradiation, and HO radicals are controlled efficiently by it. A new mechanism is proposed, for the first time, that O radicals generated from reaction of O3 with UV laser flash irradiation might be the contributor to scavenge HO radicals.

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)

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

Science.gov (United States)

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

2002-07-01

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

Esterified dendritic TAM radicals with very high stability and enhanced oxygen sensitivity.

Science.gov (United States)

Song, Yuguang; Liu, Yangping; Hemann, Craig; Villamena, Frederick A; Zweier, Jay L

2013-02-15

In this work, we have developed a new class of dendritic TAM radicals (TG, TdG, and dTdG) through a convergent method based on the TAM core CT-03 or its deuterated analogue dCT-03 and trifurcated Newkome-type monomer. Among these radicals, dTdG exhibits the best EPR properties with sharpest EPR singlet and highest O(2) sensitivity due to deuteration of both the ester linker groups and the TAM core CT-03. Like the previous dendritic TAM radicals, these new compounds also show extremely high stability toward various reactive species owing to the dendritic encapsulation. The highly charged nature of these molecules resulting from nine carboxylate groups prevents concentration-dependent EPR line broadening at physiological pH. Furthermore, we demonstrate that these TAM radicals can be easily derivatized (e.g., PEGylation) at the nine carboxylate groups and the resulting PEGylated analogue dTdG-PEG completely inhibits the albumin binding, thereby enhancing suitability for in vivo applications. These new dendritic TAM radicals show great potential for in vivo EPR oximetric applications and provide insights on approaches to develop improved and targeted EPR oximetric probes for biomedical applications.

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

Radical distributions in ammonium tartrate single crystals exposed to photon and neutron beams

International Nuclear Information System (INIS)

Marrale, M.; Longo, A.; Brai, M.; Barbon, A.; Brustolon, M.

2014-01-01

The radiation therapy carried out by means of heavy charged particles (such as carbon ions) and neutrons is rapidly becoming widespread worldwide. The success of these radiation therapies relies on the high density of energy released by these particles or by secondary particles produced after primary interaction with matter. The biological damages produced by ionising radiations in tissues and cells depend more properly on the energy released per unit pathlength, which is the linear energy transfer and which determines the radiation quality. To improve the therapy effectiveness, it is necessary to grasp the mechanisms of free radical production and distribution after irradiation with these particles when compared with the photon beams. In this work some preliminary results on the analysis of the spatial distributions of the free radicals produced after exposure of ammonium tartrate crystals to various radiation beams ( 60 Co gamma photons and thermal neutrons) were reported. Electron spin resonance analyses were performed by the electron spin echo technique, which allows the determination of local spin concentrations and by double electron-electron resonance technique, which is able to measure the spatial distance distribution (range 1.5-8 nm) among pairs of radicals in solids. The results of these analyses are discussed on the basis of the different distributions of free radicals produced by the two different radiation beams used. This paper extends to the single crystal case, a similar work done on AT powder irradiated with different beams, with assessment of microscopic radical concentration by determining the amount of ID contribution and obtaining the inter-radical distance distributions by double microwave irradiation. In this paper single crystals of AT have been exposed to 60 Co photons and neutrons. The results confirm that advanced pulse EPR techniques allow the direct measurement of the local free radical concentration and provide information about the

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)

Molecular identification of Aspergillus and Eurotium species isolated from rice and their toxin-producing ability.

Science.gov (United States)

Yazdani, D; Zainal Abidin, M A; Tan, Y H; Kamaruzaman, S

2011-01-01

Thirty milled rice samples were collected from retailers in 4 provinces of Malaysia. These samples were evaluated for Aspergillus spp. infection by direct plating on malt extract salt agar (MESA). All Aspergillus holomorphs were isolated and identified using nucleotide sequences of ITS 1 and ITS 2 of rDNA. Five anamorphs (Aspergillus flavus, A. oryzae, A. tamarii, A. fumigatus and A. niger) and 5 teleomorphs (Eurotium rubrum, E. amstelodami, E. chevalieri, E. cristatum and E. tonophilum) were identified. The PCR-sequencing based technique for sequences of ITS 1 and ITS 2 is a fast technique for identification of Aspergillus and Eurotium species, although it doesn't work flawlessly for differentiation of Eurotium species. All Aspergillus and Eurotium isolates were screened for their ability to produce aflatoxin and ochratoxin A (OTA) by HPLC and TLC techniques. Only A. flavus isolate UPM 89 was able to produce aflatoxins B1 and B2.

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

Science.gov (United States)

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

2010-10-07

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

Measurements of Free Radical in Vitamin E-Doped Ultra-High Molecular Weight Polyethylene: Dependence on Materials Processing and Irradiation Environments

International Nuclear Information System (INIS)

Ridley, M. D.

2006-01-01

In an effort to combat oxidation of the load-bearing, polyethylene (PE) components of total hip- and knee-joint replacement devices, antioxidant such as vitamin E (α-Tocopherol (α-T)) has been introduced into polymer matrix. In this study we investigated effect of α-T on free radicals in medical grade ultra-high molecular weight polyethylene (UHMWPE), GUR 1020 resin. Since oxidation resistance depends on radical reaction, we used electron spin resonance (ESR) technique for direct detection of free radicals before and after irradiation. High concentration (20% by vol.) of α-T was used so its ESR signal (due to α-T-O degree radical) could be distinguished among the overwhelming signals due to PE radicals. Two groups of samples were investigated. In one group, samples were prepared from blends of α-T and UHMWPE powder (α-T-P), and in the second group, from compression molded blocks (α-T-B). In each group, samples were γ-irradiated in sealed packages filled with N 2 , or in open air, and free radicals were measured in open air environment as a function of time. Also included in this study were α-T, and powder resin and compression molded blocks without any α-T. Following irradiation in air, α-T-P and α-T produced identical ESR spectra showing characteristic feature of α-T-O degree radical. Absence of PE radicals in the ESR signals suggests quenching/repairing of PE radicals by α-T in presence of oxygen. However, when irradiation was performed in N 2 , ESR signals of α-T-P exhibited superimposed resonance lines due to PE and α-T-O degree radicals. Furthermore, presence of a-T or α-T-O degree radicals did not prevent subsequent oxidation of PE radicals in producing stable, oxygen-induced radicals (OIR). Post-irradiation oxidation index measured by FTIR, however, did not show any difference between these samples. Compression molded samples, with or without α-T, produced ESR spectra showing features characteristics of PE radicals only, and there was no

Rate Constants for Reactions of Radiation-Produced Transients in Aqueous Solutions of Actinides

International Nuclear Information System (INIS)

Gordon, S.; Sullivan, J.C.; Ross, A.B.

1986-01-01

Rate constants have been critically compiled for reactions of ions of the actinides Am, Cf, Cm, Np, Pu, Th, and U, as well as the element Tc, in different oxidation states with various chemical species in aqueous solution. The reactants include products of the radiolysis of water (hydrated electrons, hydrogen atoms, hydroxyl radicals, hydrogen peroxide) and transient species derived from other solutes (e.g., carbonate radical). The data are useful in the estimation of migration properties of actinides, which are relevant to waste management studies

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.

Evaluation of Antioxidant and Free Radical Scavenging Abilities of ...

African Journals Online (AJOL)

Objective: This study was aimed at determining the antioxidants and free radical scavenging abilities of some packaged fruit juices (PFJ) widely used as source of fluids in Nigeria. Materials and methods: Packaged fruit juice samples produced by The Coca cola Company and Chi company namely: Apple(AP), blackcurrant, ...

Anion photoelectron spectroscopy of radicals and clusters

Energy Technology Data Exchange (ETDEWEB)

Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

1999-12-01

Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying ²Σ and ²π states of C_2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C₂H and C₄H. Other radicals studied include NCN and I₃. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I₃ revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

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.

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.

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.

Thermionic Properties of Carbon Based Nanomaterials Produced by Microhollow Cathode PECVD

Science.gov (United States)

Haase, John R.; Wolinksy, Jason J.; Bailey, Paul S.; George, Jeffrey A.; Go, David B.

2015-01-01

Thermionic emission is the process in which materials at sufficiently high temperature spontaneously emit electrons. This process occurs when electrons in a material gain sufficient thermal energy from heating to overcome the material's potential barrier, referred to as the work function. For most bulk materials very high temperatures (greater than 1500 K) are needed to produce appreciable emission. Carbon-based nanomaterials have shown significant promise as emission materials because of their low work functions, nanoscale geometry, and negative electron affinity. One method of producing these materials is through the process known as microhollow cathode PECVD. In a microhollow cathode plasma, high energy electrons oscillate at very high energies through the Pendel effect. These high energy electrons create numerous radical species and the technique has been shown to be an effective method of growing carbon based nanomaterials. In this work, we explore the thermionic emission properties of carbon based nanomaterials produced by microhollow cathode PECVD under a variety of synthesis conditions. Initial studies demonstrate measureable current at low temperatures (approximately 800 K) and work functions (approximately 3.3 eV) for these materials.

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.

A mesophilic Clostridium species that produces butanol from monosaccharides and hydrogen from polysaccharides.

Science.gov (United States)

Bramono, Sandhi Eko; Lam, Yuen Sean; Ong, Say Leong; He, Jianzhong

2011-10-01

A unique mesophilic Clostridium species strain BOH3 is obtained in this study, which is capable of fermenting monosaccharides to produce butanol and hydrolyzing polysaccharides to produce hydrogen (H(2)) and volatile fatty acids (VFAs). From 30 g/L of glucose and xylose each, batch culture BOH3 was able to produce 4.67 and 4.63 g/L of butanol. Enhancement treatments by increasing the inoculated cells improved butanol production to 7.05 and 7.41 g/L, respectively. Hydrogen production (2.47 and 1.93 mmol) was observed when cellulose and xylan (10 g/L each) were used, suggesting that strain BOH3 possesses xylanolytic and cellulolytic capabilities. These unique features reveal the strain's novelty as most wild-type solventogenic strains have not been reported to have such properties. Therefore, culture BOH3 is promising in generating butanol and hydrogen from renewable feedstock. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Radiolytic oxidation of tamoxifen using the free radicals .OH and (or) HO2

International Nuclear Information System (INIS)

Leguene, C.; Clavere, P.; Jore, D.; Gardes-Albert, M.

2001-01-01

Tamoxifen is the most widely used antiestrogen in the treatment of breast cancer. In this work, we have studied its antioxidant properties. We have investigated the ability of tamoxifen to scavenge, in vitro, . OH and (or) HO 2 . free radicals that are produced by water radiolysis. Aqueous solutions of tamoxifen of concentrations ranging between 10 -5 and 2.5 x 10 -5 M have been irradiated (γ 137 Cs) in aerated acidic medium (H 3 PO 4 10 -3 M or HCOOH 10 -1 M). The results show that tamoxifen reacts quantitatively with . OH free radicals but does not react with HO 2 . free radicals under our experimental conditions. (author)

Free radical scavenging potential, reducing power, phenolic and biochemical constituents of Porphyra species from India

Digital Repository Service at National Institute of Oceanography (India)

Pise, N.M.; Jena, K.B.; Maharana, D.; Gaikwad, D.; Jagtap, T.G.

. Antioxidant potentials of algae were assessed through phenolic content, 2, 2-diphenyl-1- picrylhydrazyl (DPPH) activity, hydrogen peroxide (H sub(2)O sub(2)), scavenging power and reducing potential. A dose-dependent free radical scavenging action against DPPH...

Identification of Shewanella baltica as the most important H2S-producing species during iced storage of danish marine fish

DEFF Research Database (Denmark)

Vogel, Birte Fonnesbech; Venkateswaran, K.; Satomi, M.

2005-01-01

are important in fish spoilage. More than 500 H2S-producing strains were isolated from iced stored marine fish (cod, plaice, and flounder) caught in the Baltic Sea during winter or summer time. All strains were identified as Shewanella species by phenotypic tests. Different Shewanella species were present...... unchanged (i.e., trimethylamine-N-oxide reduction and H2S production); however, the main H2S-producing organism was identified as S. baltica....

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.

Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

Science.gov (United States)

Faxon, Cameron; Hammes, Julia; Le Breton, Michael; Kant Pathak, Ravi; Hallquist, Mattias

2018-04-01

The gas-phase nitrate radical (NO3⚫) initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA) formation and organic nitrates may serve as a NOx reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO3⚫ with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO). Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM) limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C10H15NO6, C10H17NO6, C8H11NO6, C10H17NO7, and C9H13NO7) that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO3⚫ produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.

Characterization of organic nitrate constituents of secondary organic aerosol (SOA from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

Directory of Open Access Journals (Sweden)

C. Faxon

2018-04-01

Full Text Available The gas-phase nitrate radical (NO3⚫ initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA formation and organic nitrates may serve as a NOx reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO3⚫ with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS combined with a Filter Inlet for Gases and AEROsols (FIGAERO. Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C10H15NO6, C10H17NO6, C8H11NO6, C10H17NO7, and C9H13NO7 that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO3⚫ produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.

Proceedings of the fourteenth annual meeting of the Society for Free Radical Research-India and international conference on translational research in ionizing radiation, free radicals, antioxidants and functional food

International Nuclear Information System (INIS)

2016-01-01

The major aim and objective of this conference is to foster improved understanding of radical species and related oxidants and reductants with particular reference to the processes of industrial and medical importance for the benefit of human being. Papers relevant to INIS are indexed separately

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

Notes on free radicals in the field of human and environmental protection against ionizing radiations

International Nuclear Information System (INIS)

Bittel, R.

It is well known that ionizing radiations, in vitro and in vivo produce, free radicals which may be considered as mediators between physical agents and biological targets. Some aspects of this vast problem are accentuated. Ionizing radiations act either directly on the organic molecules of tissues or indirectly by creating, in the surroundings and in tissular water, inorganic free radicals which act on biochemical molecules to gives new radicals. Analysis of the free radical initiation phenomenon in vivo shows that many initiating agents exist, ionizing radiations representing only one group. The role of oxydants, especially oxydising polluants, and the part played by various enzyme systems (super-oxide dismutase, oxydases etc...) are emphasized. After propagation the chain reactions end in combinations between radicals are stopped by certain organic molecules (radical scavengers). Examples are given (free radical formation from compounds of great biological importance: puric and pyrimidic bases, nucleic acids in particular). These aspects are discussed from the viewpoint of their effects on human and environmental protection against both ionizing radiations and certain chemical pollution [fr

A numerical simulation study on active species production in dense methane-air plasma discharge

Science.gov (United States)

Gui, LI; Muyang, QIAN; Sanqiu, LIU; Huaying, CHEN; Chunsheng, REN; Dezhen, WANG

2018-01-01

Recently, low-temperature atmospheric pressure plasmas have been proposed as a potential type of ‘reaction carrier’ for the conversion of methane into value-added chemicals. In this paper, the multi-physics field coupling software of COMSOL is used to simulate the detailed discharge characteristics of atmospheric pressure methane-air plasma. A two-dimensional axisymmetric fluid model is constructed, in which 77 plasma chemical reactions and 32 different species are taken into account. The spatial density distributions of dominant charged ions and reactive radical species, such as {{{CH}}}4+, {{{CH}}}3+, {{{N}}}2+, {{{O}}}2+, H, O, CH3, and CH2, are presented, which is due to plasma chemical reactions of methane/air dissociation (or ionization) and reforming of small fragment radical species. The physicochemical mechanisms of methane dissociation and radical species recombination are also discussed and analyzed.

Role of oxygen free radicals in the induction of sister chromatid exchanges by cigarette smoke

International Nuclear Information System (INIS)

Lee, C.K.; Brown, B.G.; Rice, W.Y. Jr.; Doolittle, D.J.

1989-01-01

Cigarette smoke has been reported to contain free radicals and free radical generators in both the gas and particulate phases. Studies in our laboratory have shown that both cigarette smoke condensate (CSC) and smoke bubbled through phosphate buffered saline solution (smoke-PBS) increased sister chromatid exchanges (SCE) in Chinese hamster ovary cells in a dose-dependent manner. Since oxygen free radicals have been shown to cause SCEs and other chromosomal damage, we investigated the role of these radicals in the induction of SCEs by CSC and smoke-PBS. Addition of the antioxidant enzymes catalase and superoxide dismutase or the oxygen-radical scavenger ascorbic acid failed to reduce the SCE frequency in the presence of either CSC or smoke-PBS. Additional studies indicated that the quantity of hydrogen peroxide produced in CSC or smoke-PBS is too small to account for the observed SCE induction. It appears, therefore, that SCE induction by CSC or smoke-PBS does not involve the participation of oxygen free radicals

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

Atmospheric hydroxyl radical production from electronically excited NO2 and H2O.

Science.gov (United States)

Li, Shuping; Matthews, Jamie; Sinha, Amitabha

2008-03-21

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

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

Dietary Protection Against Free Radicals: A Case for Multiple Testing to Establish Structure-activity Relationships for Antioxidant Potential of Anthocyanic Plant Species

Directory of Open Access Journals (Sweden)

Chiara Cheng Lim

2009-03-01

Full Text Available DNA damage by reactive species is associated with susceptibility to chronic human degenerative disorders. Anthocyanins are naturally occurring antioxidants, that may prevent or reverse such damage. There is considerable interest in anthocyanic food plants as good dietary sources, with the potential for reducing susceptibility to chronic disease. While structure-activity relationships have provided guidelines on molecular structure in relation to free hydroxyl- radical scavenging, this may not cover the situation in food plants where the anthocyanins are part of a complex mixture, and may be part of complex structures, including anthocyanic vacuolar inclusions (AVIs. Additionally, new analytical methods have revealed new structures in previously-studied materials. We have compared the antioxidant activities of extracts from six anthocyanin-rich edible plants (red cabbage, red lettuce, blueberries, pansies, purple sweetpotato skin, purple sweetpotato flesh and Maori potato flesh using three chemical assays (DPPH, TRAP and ORAC, and the in vitro Comet assay. Extracts from the flowering plant, lisianthus, were used for comparison. The extracts showed differential effects in the chemical assays, suggesting that closely related structures have different affinities to scavenge different reactive species. Integration of anthocyanins to an AVI led to more sustained radical scavenging activity as compared with the free anthocyanin. All but the red lettuce extract could reduce endogenous DNA damage in HT-29 colon cancer cells. However, while extracts from purple sweetpotato skin and flesh, Maori potato and pansies, protected cells against subsequent challenge by hydrogen peroxide at 0oC, red cabbage extracts were pro-oxidant, while other extracts had no effect. When the peroxide challenge was at 37oC, all of the extracts appeared pro-oxidant. Maori potato extract, consistently the weakest antioxidant in all the chemical assays, was more effective in the

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

Science.gov (United States)

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

2016-12-01

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

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

Science.gov (United States)

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

2017-12-19

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

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...

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

Science.gov (United States)

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

2017-06-01

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

Contribution to the study of recoil species produced by potassium ferrocyanide neutron irradiation

International Nuclear Information System (INIS)

Meriadec Vernier de Byans, B.

1969-04-01

The chemical species produced by potassium ferrocyanide neutron irradiation were separated and identified. The study of their behaviour upon thermal annealing has allowed to establish a scheme of reaction as well as a kinetic treatment of the data. Activation energies are determined in different conditions and the effects of radiation dose, oxygen and water of crystallisation upon the activation energies were studied. Preliminary E.S.R. data and its relevance to the decomposition process is also discussed. (authors) [fr

Simultaneous electrochemical-electron spin resonance studies of carotenoid cation radicals and dications

International Nuclear Information System (INIS)

Khaled, M.; Hadjipetrou, A.; Xinhai Chen; Kispert, L.

1989-01-01

Carotenoids are present in the chloroplasts of photosynthetic green plants and serve as photoprotect devices and antenna pigments, and active role in the photosynthetic electron-transport chain with the carotenoid cation radical as an integral part of the electron-transfer process. The research reported herein has confirmed that carotenoid cation radicals have a lifetime that is sensitive to solvent, being longest in CH 2 Cl 2 and are best prepared electrochemically. Semiempirical AM1 and INDO calculations of the trans and cis isomers of β-carotene, canthaxanthin and β-apo-8'-carotenal cation radicals predicted the unresolved EPR line whose linewidth varies to a measurable degree with carotenoid, which subsequent experimental observations affirmed. Simultaneous electrochemical - electron spin resonance studies of carotenoid cation radicals and dications have shown the radicals detected by EPR are formed by the one electron oxidation of the carotenoid, that dimers are not formed upon decay of the radical cations and an estimate of the rate of comproportionation as a function of carotenoid can be given. The formal rate constant K' for heterogenous electron transfer rate at the electrode surface has been deduced from rotating disc experiments. Upon deuteration, and in the presence of excess β-carotene, the half-life for decay of the carotenoid radical cation increased an order of magnitude due to the reaction between diffusion carotenoid dications and carotenoids to form additional radical cations. The carotenoid diffusion coefficients deduced by chronocoulometry substantiates this measurement. The produces formed upon electrochemical studies are being studied by HPLC and the isomers formed thermally are being separated. Additional radical reactions are currently being studied by EPR and electrochemical methods

Integrated in situ characterization of molten salt catalyst surface: Evidence of sodium peroxide and OH radical formation

KAUST Repository

Takanabe, Kazuhiro; Khan, Abdulaziz M.; Tang, Yu; Nguyen, Luan; Ziani, Ahmed; Jacobs, Benjamin W; Elbaz, Ayman M.; Sarathy, S Mani; Tao, Franklin Feng

2017-01-01

Na-based catalysts (i.e., Na2WO4) were proposed to selectively catalyze OH radical formation from H2O and O2 at high temperatures. This reaction may proceed on molten salt state surfaces due to the lower melting point of the used Na salts compared to the reaction temperature. This study provides direct evidence of the molten salt state of Na2WO4, which can form OH radicals, using in situ techniques including X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), laser induced fluorescence (LIF) spectrometer, and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). As a result, Na2O2 species, which were hypothesized to be responsible for the formation of OH radicals, has been identified on the outer surfaces at temperatures ≥800°C, and these species are useful for various gas-phase hydrocarbon reactions including the selective transformation of methane to ethane.

Integrated in situ characterization of molten salt catalyst surface: Evidence of sodium peroxide and OH radical formation

KAUST Repository

Takanabe, Kazuhiro

2017-06-26

Na-based catalysts (i.e., Na2WO4) were proposed to selectively catalyze OH radical formation from H2O and O2 at high temperatures. This reaction may proceed on molten salt state surfaces due to the lower melting point of the used Na salts compared to the reaction temperature. This study provides direct evidence of the molten salt state of Na2WO4, which can form OH radicals, using in situ techniques including X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), laser induced fluorescence (LIF) spectrometer, and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). As a result, Na2O2 species, which were hypothesized to be responsible for the formation of OH radicals, has been identified on the outer surfaces at temperatures ≥800°C, and these species are useful for various gas-phase hydrocarbon reactions including the selective transformation of methane to ethane.

Formation and reactivity of free radicals in 5-hydroxymethyl-2-furaldehyde--the effect on isoprenaline photostability.

Science.gov (United States)

Brustugun, Jørgen; Tønnesen, Hanne H; Edge, Ruth; Navaratnam, Suppiah

2005-05-13

Solutions of glucose are used as diluents for drugs in various drug infusions. When sterilized by heat small amounts of the substance 5-hydroxymethyl-2-furaldehyde (5-HMF) is produced from glucose. At a hospital ward such infusions may be exposed to irradiation; including UV-light. The photoreactivity of the furaldehyde is investigated. It is shown to photodestabilize the catecholamine isoprenaline. It is shown to be a producer, but also a consumer, of singlet oxygen. The excited triplet, cation and anion radical have been produced by pulse radiolysis and flash photolysis and their absorbance characteristics have been determined. The triplet absorption spectrum showed absorption bands at 320 and 430 nm with molar absorption coefficients of 4700 and 2600 M-1 cm-1, respectively. The anion radical showed absorption bands at 330 and 420 nm with molar absorption coefficients of 2000 and 300 M-1 cm-1, respectively. The cation radical had an absorption band at 320 nm with a molar absorption coefficient of 5000 M-1 cm-1. The quantum yield for the production of singlet oxygen, sensitized by the 5-HMF triplet, was determined to be 0.6, whilst the quantum yield for the triplet formation was 1.0. Aqueous solutions of 5-HMF were found to photoionize to yield the hydrated electron and the cation radical of 5-HMF in a biphotonic process. The influences of pH, buffer and glucose on the formation of transients were evaluated. The reactions between 5-HMF and the solvated electron, the hydroxyl radical and the superoxide were also studied.

Charged particle multiplicities at {radical}(s)=0.9, 2.36 and 7.0 TeV with the CMS detector at LHC

Energy Technology Data Exchange (ETDEWEB)

Rougny, Romain [Universiteit Antwerpen, Gratiekapelstraat 10, BE-2000 Antwerpen (Belgium); De Wolf, E.A.; Janssen, X.; Mucibello, L.; Van Remortel, N.; Lee, Y.J.; Busza, Wit

2010-07-01

The charged particle multiplicity, n, is an essential observable in hadron collisions. It is the result of the counting of all charged particles produced by the primary proton-proton interaction. In particular, the events collected by minimum bias triggers contain soft interactions and produce mostly particles with low transverse momenta. The shape of the charged particle multiplicity spectrum is sensitive to the particle production mechanism of these soft interactions which are described by non-perturbative models, inspired by QCD. The correlations between produced hadrons are reflected in the shape of the multiplicity spectrum, while the mean multiplicity increases with the center of mass energy of the collision. We present the measurement of the charged particle multiplicity distributions, 1/s d{sigma}/dn, in increasing sub-domains of pseudorapidity and transverse momentum acceptance, for non single diffractive interactions. The data are further corrected for the trigger and event selection efficiency and the effects of tracking inefficiency and secondary tracks originating from the decay of long lived particles and products of interaction with the beam pipe and the detector material. This measurement is based on minimum bias data collected by the CMS detector at {radical}(s) = 0.9, 2.36 and 7 TeV. The data were collected during the LHC commissioning run in 2009 and at the beginning of 2010. (authors)

Detection of free radicals in γ-irradiated seasnail hard tissues by electron paramagnetic resonance

International Nuclear Information System (INIS)

Koeseoglu, Rahmi; Koeksal, Fevzi

2003-01-01

Gamma-irradiated seasnail (from family of Helix lukortium) hard tissues (CaCO 3 ) were investigated by electron paramagnetic resonance (EPR) at room temperature. The radicals produced by γ-irradiation in seasnail were attributed to orthorhombic C · O 2 - , freely rotating C · O 2 - , orthorhombic C · O 3 - , axial C · O 3 - , and axial C · O 3 3- free radicals. Unirradiated seasnail hard tissues also feature Mn 2+ ions in their EPR spectra. The hyperfine values were determined for the 13 C nucleus in the orthorhombic C · O 2 - and axial C · O 3 3- free radicals and for the manganese impurity ions. The g values of all the free radicals have been measured. The results were compared with the literature data for similar defects

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.

Radicalizing electoral system effects on support for nationalist hardliners in Serbia

DEFF Research Database (Denmark)

Bochsler, Daniel

2013-01-01

This paper investigates electoral outcomes produced by the two-round majority system in ethnically divided societies. Earlier studies, focused mainly on the Southern American states, have revealed that in ethnically mixed environments, com- petitors with radical positions on ethnic issues perform...

Computerized screening for novel producers of Monascus-like food pigments in Penicillium species

DEFF Research Database (Denmark)

Mapari, Sameer Shamsuddin; Hansen, Michael Adsetts Edberg; Meyer, Anne S.

2008-01-01

, rubropunctamine, and citrinin. The cross hits were then manually identified on the basis of their UV-vis and mass spectra. X-hitting was found to be a good tool in the rapid screening of crude pigment extracts. Monascus pigments were discovered in the extracts of two closely related species of Penicillium...... Penicillium extracts showed the presence of citrinin. Thus, the present study brought out two novel promising sources of yellow, orange, and purple-red Monascus-like food pigments in the species of Penicillia that do not produce citrinin and opened the door to look for several more new promising sources...... that were only distantly related to the genus Monascus. Monascorubrin, xanthomonasin A, and threonine derivatives of rubropunctatin were identified in the extract of Penicillium aculeatum IBT 14263, and monascorubrin was identified in the extract of Penicillium pinophilum IBT 13104. None of the tested...

Diddensiella caesifluorescens gen. nov., sp. nov., a riboflavin-producing yeast species of the family Trichomonascaceae

Science.gov (United States)

Four strains of a novel heterothallic yeast species were isolated from rotten wood collected in or near the Pilis Mountains in Hungary. The strains produced riboflavin in liquid culture. Analysis of gene sequences for the D1/D2 domains of the large subunit nuclear ribosomal RNA (rRNA), as well as an...

Effects of gas-flow structures on radical and etch-product density distributions on wafers in magnetomicrowave plasma etching reactors

International Nuclear Information System (INIS)

Ikegawa, Masato; Kobayashi, Jun'ichi; Fukuyama, Ryoji

2001-01-01

To achieve high etch rate, uniformity, good selectivity, and etch profile control across large diameter wafers, the distributions of ions, radicals, and etch products in magnetomicrowave high-etch-rate plasma etching reactors must be accurately controlled. In this work the effects of chamber heights, a focus ring around the wafer, and gas supply structures (or gas flow structures) on the radicals and etch products flux distribution onto the wafer were examined using the direct simulation Monte Carlo method and used to determine the optimal reactor geometry. The pressure uniformity on the wafer was less than ±1% when the chamber height was taller than 60 mm. The focus ring around the wafer produced uniform radical and etch-product fluxes but increased the etch-product flux on the wafer. A downward-flow gas-supply structure (type II) produced a more uniform radical distribution than that produced by a radial gas-supply structure (type I). The impact flow of the type II structure removed etch products from the wafer effectively and produced a uniform etch-product distribution even without the focus ring. Thus the downward-flow gas-supply structure (type II) was adopted in the design for the second-generation of a magnetomicrowave plasma etching reactor with a higher etching rate

Reduction of time for producing and acclimatizing two bamboo species in a greenhouse

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Giovanni Aquino Gasparetto

2013-03-01

Full Text Available China has been investing in bamboo cultivation in Brazilian lands. However, there’s a significant deficit of seedling production for civil construction and the charcoal and cellulose sectors, something which compromises a part of the forestry sector. In order to contribute so that the bamboo production chain solves this problem, this study aimed to check whether the application of indole acetic acid (IAA could promote plant growth in a shorter cultivation time. In the study, Bambusa vulgaris and B. vulgaris var. vitatta stakes underwent two treatments (0.25% and 5.0% of IAA and they were grown on washed sand in a greenhouse. Number of leaves, stem growth, rooting, and chlorophyll content were investigated. There was no difference with regard to stem growth, root length, and number of leaves for both species in the two treatments (0.25% and 5% IAA. The chlorophyll content variation between the two species may constitute a quality parameter of forest seedling when compared to other bamboo species. After 43 days, the seedlings are ready for planting in areas of full sun. For the species studied here, the average time to the seedling sale is from 4 to 6 months, with no addition of auxin. Using this simple and low cost technique, several nurserymen will produce bamboo seedlings with reduced time, costs, and manpower.

Radical Evil

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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.

Multiplex polymerase chain reaction assay for the differential detection of trichothecene- and fumonisin-producing species of Fusarium in cornmeal.

Science.gov (United States)

Bluhm, B H; Flaherty, J E; Cousin, M A; Woloshuk, C P

2002-12-01

The genus Fusarium comprises a diverse group of fungi including several species that produce mycotoxins in food commodities. In this study, a multiplex polymerase chain reaction (PCR) assay was developed for the group-specific detection of fumonisin-producing and trichothecene-producing species of Fusarium. Primers for genus-level recognition of Fusarium spp. were designed from the internal transcribed spacer regions (ITS1 and ITS2) of rDNA. Primers for group-specific detection were designed from the TRI6 gene involved in trichothecene biosynthesis and the FUM5 gene involved in fumonisin biosynthesis. Primer specificity was determined by testing for cross-reactivity against purified genomic DNA from 43 fungal species representing 14 genera, including 9 Aspergillus spp., 9 Fusarium spp., and 10 Penicillium spp. With purified genomic DNA as a template, genus-specific recognition was observed at 10 pg per reaction; group-specific recognition occurred at 100 pg of template per reaction for the trichothecene producer Fusarium graminearum and at 1 ng of template per reaction for the fumonisin producer Fusarium verticillioides. For the application of the PCR assay, a protocol was developed to isolate fungal DNA from cornmeal. The detection of F. graminearum and its differentiation from F. verticillioides were accomplished prior to visible fungal growth at cornmeal. This level of detection is comparable to those of other methods such as enzyme-linked immunosorbent assay, and the assay described here can be used in the food industry's effort to monitor quality and safety.