Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm

Science.gov (United States)

Sullivan, Erin N.; Nichols, Bethan; Neumark, Daniel M.

2018-01-01

The photodissociation dynamics of the simplest alkyl peroxy radicals, methyl peroxy (CH3OO) and ethyl peroxy (C2H5OO), are investigated using fast beam photofragment translational spectroscopy. A fast beam of CH3OO- or C2H5OO- anions is photodetached to generate neutral radicals that are subsequently dissociated using 248 nm photons. The coincident detection of the photofragment positions and arrival times allows for the determination of mass, translational energy, and angular distributions for both two-body and three-body dissociation events. CH3OO exhibits repulsive O loss resulting in the formation of O(1D) + CH3O with high translational energy release. Minor two-body channels leading to OH + CH2O and CH3O + O(3P) formation are also detected. In addition, small amounts of H + O(3P) + CH2O are observed and attributed to O loss followed by CH3O dissociation. C2H5OO exhibits more complex dissociation dynamics, in which O loss and OH loss occur in roughly equivalent amounts with O(1D) formed as the dominant O atom electronic state via dissociation on a repulsive surface. Minor two-body channels leading to the formation of O2 + C2H5 and HO2 + C2H4 are also observed and attributed to a ground state dissociation pathway following internal conversion. Additionally, C2H5OO dissociation yields a three-body product channel, CH3 + O(3P) + CH2O, for which the proposed mechanism is repulsive O loss followed by the dissociation of C2H5O over a barrier. These results are compared to a recent study of tert-butyl peroxy (t-BuOO) in which 248 nm excitation results in three-body dissociation and ground state two-body dissociation but no O(1D) production.

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

DEFF Research Database (Denmark)

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

2015-01-01

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

Comparison of COD removal from pharmaceutical wastewater by electrocoagulation, photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes

International Nuclear Information System (INIS)

Farhadi, Sajjad; Aminzadeh, Behnoush; Torabian, Ali; Khatibikamal, Vahid; Alizadeh Fard, Mohammad

2012-01-01

Highlights: ► Hydrogen peroxide improves the performance of electrocoagulation process. ► UV light can be effective on the performance on peroxi-electrocoagulation and electrocoagulation processes. ► The optimal amount of hydrogen peroxide for peroxi-electrocoagulation process for COD removal from pharmaceutical wastewater is 300 mg/L. ► The optimal values of pH for electrocoagulation and peroxi-electrocoagulation are 7 and 3, respectively. - Abstract: This work makes a comparison between electrocoagulation (EC), photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes to investigate the removal of chemical oxygen demand (COD) from pharmaceutical wastewater. The effects of operational parameters such as initial pH, current density, applied voltage, amount of hydrogen peroxide and electrolysis time on COD removal efficiency were investigated and the optimum operating range for each of these operating variables was experimentally determined. In electrocoagulation process, the optimum values of pH and voltage were determined to be 7 and 40 V, respectively. Desired pH and hydrogen peroxide concentration in the Fenton-based processes were found to be 3 and 300 mg/L, respectively. The amounts of COD, pH, electrical conductivity, temperature and total dissolved solids (TDS) were on-line monitored. Results indicated that under the optimum operating range for each process, the COD removal efficiency was in order of peroxi-electrocoagulation > peroxi-photoelectrocoagulation > photoelectrocoagulation > electrocoagulation. Finally, a kinetic study was carried out using the linear pseudo-second-order model and results showed that the pseudo-second-order equation provided the best correlation for the COD removal rate.

Comparison of COD removal from pharmaceutical wastewater by electrocoagulation, photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes

Energy Technology Data Exchange (ETDEWEB)

Farhadi, Sajjad, E-mail: sajjadfarhadi@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of); Aminzadeh, Behnoush, E-mail: bamin@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of); Torabian, Ali, E-mail: atorabi@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of); Khatibikamal, Vahid, E-mail: vahidkhatibi@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of); Alizadeh Fard, Mohammad, E-mail: malizadeh1987@ut.ac.ir [Department of Civil and Environmental Engineering, Graduate Faculty of Environment, University of Tehran (Iran, Islamic Republic of)

2012-06-15

Highlights: Black-Right-Pointing-Pointer Hydrogen peroxide improves the performance of electrocoagulation process. Black-Right-Pointing-Pointer UV light can be effective on the performance on peroxi-electrocoagulation and electrocoagulation processes. Black-Right-Pointing-Pointer The optimal amount of hydrogen peroxide for peroxi-electrocoagulation process for COD removal from pharmaceutical wastewater is 300 mg/L. Black-Right-Pointing-Pointer The optimal values of pH for electrocoagulation and peroxi-electrocoagulation are 7 and 3, respectively. - Abstract: This work makes a comparison between electrocoagulation (EC), photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes to investigate the removal of chemical oxygen demand (COD) from pharmaceutical wastewater. The effects of operational parameters such as initial pH, current density, applied voltage, amount of hydrogen peroxide and electrolysis time on COD removal efficiency were investigated and the optimum operating range for each of these operating variables was experimentally determined. In electrocoagulation process, the optimum values of pH and voltage were determined to be 7 and 40 V, respectively. Desired pH and hydrogen peroxide concentration in the Fenton-based processes were found to be 3 and 300 mg/L, respectively. The amounts of COD, pH, electrical conductivity, temperature and total dissolved solids (TDS) were on-line monitored. Results indicated that under the optimum operating range for each process, the COD removal efficiency was in order of peroxi-electrocoagulation > peroxi-photoelectrocoagulation > photoelectrocoagulation > electrocoagulation. Finally, a kinetic study was carried out using the linear pseudo-second-order model and results showed that the pseudo-second-order equation provided the best correlation for the COD removal rate.

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

Science.gov (United States)

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

2015-12-01

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

Comparison of COD removal from pharmaceutical wastewater by electrocoagulation, photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes.

Science.gov (United States)

Farhadi, Sajjad; Aminzadeh, Behnoush; Torabian, Ali; Khatibikamal, Vahid; Alizadeh Fard, Mohammad

2012-06-15

This work makes a comparison between electrocoagulation (EC), photoelectrocoagulation, peroxi-electrocoagulation and peroxi-photoelectrocoagulation processes to investigate the removal of chemical oxygen demand (COD) from pharmaceutical wastewater. The effects of operational parameters such as initial pH, current density, applied voltage, amount of hydrogen peroxide and electrolysis time on COD removal efficiency were investigated and the optimum operating range for each of these operating variables was experimentally determined. In electrocoagulation process, the optimum values of pH and voltage were determined to be 7 and 40 V, respectively. Desired pH and hydrogen peroxide concentration in the Fenton-based processes were found to be 3 and 300 mg/L, respectively. The amounts of COD, pH, electrical conductivity, temperature and total dissolved solids (TDS) were on-line monitored. Results indicated that under the optimum operating range for each process, the COD removal efficiency was in order of peroxi-electrocoagulation > peroxi-photoelectrocoagulation > photoelectrocoagulation>electrocoagulation. Finally, a kinetic study was carried out using the linear pseudo-second-order model and results showed that the pseudo-second-order equation provided the best correlation for the COD removal rate. Copyright © 2012 Elsevier B.V. All rights reserved.

Tropospheric chemistry of natural hydrocarbons, aldehydes, and peroxy radicals: Their connections to sulfuric acid production and climate effects

International Nuclear Information System (INIS)

Gaffney, J.S.; Marley, N.A.

1993-05-01

Recent work has shown that natural hydrocarbon emissions can significantly affect the levels of urban and regional tropospheric ozone. We report on the reactivities of these biogenic trace gases, particularly isoprene, focusing on their importance in the production of aldehydes and peroxy radicals, leading to increased levels of hydrogen over regional forests. Hydrogen peroxide can lead to the wet oxidation of sulfur dioxide to acidic sulfate in aerosols, fogs, and clouds. In turn, acidic sulfate can act to as a light scattering aerosol and a source of cloud condensation nuclei (CCN), potentially leading to global cooling. Aerosol sulfate and other dissolved organic and inorganic compounds can also play important roles as a greenhouse species in the lower troposphere

Composite wastewater treatment by aerated electrocoagulation and modified peroxi-coagulation processes.

Science.gov (United States)

Kumar, Abhijeet; Nidheesh, P V; Suresh Kumar, M

2018-08-01

Treatment of composite wastewater generating from the industrial estates is a great challenge. The present study examines the applicability of aerated electrocoagulation and modified peroxi-coagulation processes for removing color and COD from composite wastewater. Iron plates were used as anodes and cathodes in both electrochemical processes and experiments were carried out in a working volume of 2 L. Aeration enhanced the efficiency of electrocoagulation process significantly. More than 50% of COD and 60% of color were removed after 1 h of electrocoagulation process operated at pH 3 and applied voltage of 1 V. Efficiency of the modified peroxi-coagulation process was significantly higher than that of aerated electrocoagulation. COD and color removal efficiencies of the modified peroxi-coagulation process were found as 77.7% and 97%, respectively after 1 h of electrolysis operated at 1 V, solution pH 3 and 50 mM hydrogen peroxide addition. This improved efficiency of modified peroxi-coagulation compared to aerated electrocoagulation is mainly due to the attack of in-situ generated hydroxyl radicals. Copyright © 2018 Elsevier Ltd. All rights reserved.

Peroxy bleaches

Energy Technology Data Exchange (ETDEWEB)

Carson, P.A. [Unilever Research, Port Sunlight Laboratory (United States) and Chemistry Department, University of Manchester, Institute of Science and Technology (United States)]. E-mail: pcarson2005@aol.com; Fairclough, C.S. [Unilever Research, Port Sunlight Laboratory (United States); Mauduit, C. [Chemistry Department, University of Manchester, Institute of Science and Technology (United States); Colsell, M. [Chemistry Department, University of Manchester, Institute of Science and Technology (United States)

2006-08-25

Fabric laundering is now a sophisticated chemical process involving a variety of operations including bleaching. The chemistry of peroxy bleaches is described including the use of novel organic compounds to provide effective bleaching at the lower temperatures of modern wash cycles. The instability of peroxy compounds is illustrated using cameo case histories to relate theory and practice. Techniques available for determining their thermochemistry are summarised. A model is provided for hazard and risk assessment of development projects in general (particularly those involving new molecules, processes or formulations) from ideas phase through exploratory laboratory investigations to pilot plant scale-up and eventual manufacture and commercial exploitation. This paper is a prelude to Part 2, which describes the determination of thermodynamic and kinetic properties of peroxy bleaches and discusses the implication of the results in terms of precautions for their safe storage and incorporation into detergent formulations during processing.

Peroxy bleaches

International Nuclear Information System (INIS)

Carson, P.A.; Fairclough, C.S.; Mauduit, C.; Colsell, M.

2006-01-01

Fabric laundering is now a sophisticated chemical process involving a variety of operations including bleaching. The chemistry of peroxy bleaches is described including the use of novel organic compounds to provide effective bleaching at the lower temperatures of modern wash cycles. The instability of peroxy compounds is illustrated using cameo case histories to relate theory and practice. Techniques available for determining their thermochemistry are summarised. A model is provided for hazard and risk assessment of development projects in general (particularly those involving new molecules, processes or formulations) from ideas phase through exploratory laboratory investigations to pilot plant scale-up and eventual manufacture and commercial exploitation. This paper is a prelude to Part 2, which describes the determination of thermodynamic and kinetic properties of peroxy bleaches and discusses the implication of the results in terms of precautions for their safe storage and incorporation into detergent formulations during processing

Understanding in situ ozone production in the summertime through radical observations and modelling studies during the Clean air for London project (ClearfLo)

Science.gov (United States)

Whalley, Lisa K.; Stone, Daniel; Dunmore, Rachel; Hamilton, Jacqueline; Hopkins, James R.; Lee, James D.; Lewis, Alastair C.; Williams, Paul; Kleffmann, Jörg; Laufs, Sebastian; Woodward-Massey, Robert; Heard, Dwayne E.

2018-02-01

Measurements of OH, HO2, RO2i (alkene and aromatic-related RO2) and total RO2 radicals taken during the ClearfLo campaign in central London in the summer of 2012 are presented. A photostationary steady-state calculation of OH which considered measured OH reactivity as the OH sink term and the measured OH sources (of which HO2+ NO reaction and HONO photolysis dominated) compared well with the observed levels of OH. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2, however, highlighted a substantial discrepancy between radical observations under lower NOx conditions ([NO] model was missing a significant peroxy radical sink; the model overpredicted HO2 by up to a factor of 10 at these times. Known radical termination steps, such as HO2 uptake on aerosols, were not sufficient to reconcile the model-measurement discrepancies alone, suggesting other missing termination processes. This missing sink was most evident when the air reaching the site had previously passed over central London to the east and when elevated temperatures were experienced and, hence, contained higher concentrations of VOCs. Uncertainties in the degradation mechanism at low NOx of complex biogenic and diesel related VOC species, which were particularly elevated and dominated OH reactivity under these easterly flows, may account for some of the model-measurement disagreement. Under higher [NO] (> 3 ppbv) the box model increasingly underpredicted total [RO2]. The modelled and observed HO2 were in agreement, however, under elevated NO concentrations ranging from 7 to 15 ppbv. The model uncertainty under low NO conditions leads to more ozone production predicted using modelled peroxy radical concentrations ( ˜ 3 ppbv h-1) versus ozone production from peroxy radicals measured ( ˜ 1 ppbv h-1). Conversely, ozone production derived from the predicted peroxy radicals is up to an order of magnitude lower than from the observed peroxy radicals as [NO

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-06-04

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

Direct detection of OH formation in the reactions of HO2 with CH3C(OO2 and other substituted peroxy radicals

Directory of Open Access Journals (Sweden)

J. N. Crowley

2008-08-01

Full Text Available This work details the first direct observation of OH as a product from (R1: HO2+CH3C(OO2→(products, which has generally been considered an atmospheric radical termination process. The technique of pulsed laser photolysis radical generation, coupled to calibrated laser induced fluorescence detection was used to measure an OH product yield for (R1 of α1(298 K=(0.5±0.2. This study of (R1 included the measurement of a rate coefficient k1(298 K=(1.4±0.5×10−11cm3 molecule−1 s−1, substantially reducing the uncertainties in modelling this important atmospheric reaction. OH was also detected as a product from the reactions of HO2 with three other carbonyl-containing peroxy radicals, albeit at smaller yield, e.g. (R2: HO2+CH3C(OCH2O2→(products, α2≈0.15. By contrast, OH was not observed (α<0.06 as a major product from reactions where carbonyl functionality was absent, e.g. HO2+HOCH2CH2O2 (R8, and HO2+CH3CH(OHCH2O2 (R9.

Measurements of Peroxy Radicals and Related Species At A Rural Site During The Escompte Campaign

Science.gov (United States)

Pinceloup, S.; Laverdet, G.; Le Bras, G.

The chemical amplifier technique has been used to measure peroxy radicals (RO2) concentrations at a rural site (Dupail), located 35 km North East of Marseille, during the ESCOMPTE campaign in June-July 2001. Daily profiles of RO2 and also ozone and NOx concentrations have been recorded everyday including those of the four in- tensive observation periods (IOP). The NOx levels were most of the time lower than a few ppbv, ie characteristic of a rural site. Typical diurnal profiles of RO2 were ob- served with maxima in the range 40-180 pptv. The RO2 signals were corrected from the influence of relative humidity based on calibration of the chemical amplifier in separate laboratory experiments under controlled water vapor concentrations. Prelim- inary interpretation of the data shows very different ratios of photochemically pro- duced/transported ozone related to meteorological conditions. Further interpretation of the data is underway integrating additional measurements of a large variety of hy- drocarbons as well as some hydroperoxides and aldehydes made at the site by other groups. The results of the comparison of calculated steady state concentrations of RO2 and ozone production rate with the measured values will be presented and discussed in relation with our understanding of the tropospheric ozone production.

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

Energy Technology Data Exchange (ETDEWEB)

Pinceloup, St.

2002-10-01

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

Radical-induced oxidation of RAFT agents : a kinetic study

NARCIS (Netherlands)

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

2011-01-01

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

Small molecule n-(alpha-peroxy) indole compounds and methods of use

KAUST Repository

Wang, Xinbo; Lai, Zhiping; Pan, Yupeng; Huang, Kuo-Wei; Wang, Zhigang

2017-01-01

The invention relates to novel N-(α-peroxy)indole compounds of Formula I and methods for use. (I) The N-(α-peroxy)indole compounds described herein are useful for treating or preventing parasitic infections, bacterial infections, and cancer in subjects. The methods include administering an N-(α-peroxy)indole compound as described herein to a subject. Also described herein are methods for synthesizing N-(α-peroxy )indole compounds.

Small molecule n-(alpha-peroxy) carbazole compounds and methods of use

KAUST Repository

Wang, Xinbo; Lai, Zhiping; Pan, Yupeng; Huang, Kuo-Wei

2017-01-01

The invention relates to novel N-(α-peroxy)carbazole compounds of Formula I and methods for use. (I) The N-(α-peroxy)carbazole compounds described herein are useful for treating or preventing parasitic infections, bacterial infections, and cancer in subjects. The methods include administering an N-(α-peroxy)carbazole compound as described herein to a subject. Also described herein are methods for synthesizing N-(α-peroxy)carbazole compounds.

Small molecule n-(alpha-peroxy) indole compounds and methods of use

KAUST Repository

Wang, Xinbo

2017-11-16

The invention relates to novel N-(α-peroxy)indole compounds of Formula I and methods for use. (I) The N-(α-peroxy)indole compounds described herein are useful for treating or preventing parasitic infections, bacterial infections, and cancer in subjects. The methods include administering an N-(α-peroxy)indole compound as described herein to a subject. Also described herein are methods for synthesizing N-(α-peroxy )indole compounds.

Small molecule n-(alpha-peroxy) carbazole compounds and methods of use

KAUST Repository

Wang, Xinbo

2017-11-16

The invention relates to novel N-(α-peroxy)carbazole compounds of Formula I and methods for use. (I) The N-(α-peroxy)carbazole compounds described herein are useful for treating or preventing parasitic infections, bacterial infections, and cancer in subjects. The methods include administering an N-(α-peroxy)carbazole compound as described herein to a subject. Also described herein are methods for synthesizing N-(α-peroxy)carbazole compounds.

Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

International Nuclear Information System (INIS)

Bors, W.; Saran, M.; Michel, C.

1982-01-01

The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

Science.gov (United States)

Sebbar, N; Bozzelli, J W; Bockhorn, H

2014-01-09

Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

A pulse radiolysis study of the OH radical induced autoxidation of methanesulfinic acid

DEFF Research Database (Denmark)

Sehested, K.; Holcman, J.

1996-01-01

Methanesulfinic acid, CH3SO2H, reacts with OH radicals at pH 7 forming CH3SO2 radicals with a rate constant k = (6.0 +/- 1.0) x 10(9) M(-1) s(-1). The CH3SO2 radical absorbs at 325 nm with an extinction coefficient of 900 +/- 100 M(-1) cm(-1) and disappears in a second order self-reaction with k...... takes place. During the course of the chain oxidation a peroxyacid, presumably methaneperoxymonosulfonic acid, is formed and accumulated. This acid absorbs in the UV and eventually decays by reaction with excess methanesulfinic acid k = 5 x 10(3) M(-1) s(-1). The final product of the chain autoxidation...... = (1.0 +/- 0.2) x 10(9) M(-1) s(-1). This radical reacts with oxygen, k = (1.2 +/- 0.3) x 10(9) M(-1) s(-1), forming a peroxy radical which absorbs in the UV below 300 nm. The peroxy radical reacts in turn with methanesulfinic acid reforming the CH3SO2 radical whereby a chain oxidation of sulfinic acid...

Peroxy bleaches

International Nuclear Information System (INIS)

Carson, P.A.; Fairclough, C.S.; Mauduit, C.; Colsell, M.

2006-01-01

The thermodynamic and kinetic properties of a series of inorganic and organic peroxy bleaches were determined using adiabatic rate calorimetry and isothermal microcalorimetry. Results are compared to calculated oxygen balance values. The decomposition of the majority of the compounds is complex. Data indicate the need for cooling during the storage and transport for some materials evaluated. Although no overall structure/activity relationship could be established because of the diversity of molecular architectures studied, a combination of decomposition and activation energy data provides a means for hazard and risk classification

Plasma thiobarbituric acid reactivity: reaction conditions and the role of iron, antioxidants and lipid peroxy radicals on the quantitation of plasma lipid peroxides

Energy Technology Data Exchange (ETDEWEB)

Wade, C.R.; van Rij, A.M.

1988-01-01

The effects of Fe/sup 3 +/, lipid peroxy radicals and the antioxidant butylated hydroxytoluene on the 2-thiobarbituric (TBA) acid quantitation of plasma lipid peroxides were investigated. Whole plasma and plasma fractions prepared by trichloroacetic acid (TCA) protein precipitation and lipid extraction, demonstrated markedly differing TBA reactivities in the presence or absence of added Fe/sup 3 +/. Examination of the spectral profiles of the TBA reacted whole plasma and TCA precipitated fractions demonstrated the presence of interfering compounds which gave rise to an artifactual increase in lipid peroxide concentrations. In contrast the TBA reacted lipid extracts had low levels of interfering compounds that could be removed by our previously described high pressure liquid chromatographic method. Further characterization of the TBA reactivity of the lipid extract showed that Fe/sup 3 +/ at an optimal concentration of 0.5 mM was necessary for the quantitative decomposition of the lipid peroxides to the TBA reactive product malondialdehyde (MDA). However the presence of Fe/sup 3 +/ resulted in further peroxidation of any unsaturated lipids present.

The research progress of several kinds of free radical scavengers

International Nuclear Information System (INIS)

Qian Liren; Huang Yuecheng; Cai Jianming

2009-01-01

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

Total free radical species and oxidation equivalent in polluted air.

Science.gov (United States)

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

2017-12-31

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

One electron transfer redox potentials of free radicals. I. The oxygen-superoxide system. Progress report, September 1, 1975--July 1, 1976

International Nuclear Information System (INIS)

Ilan, Y.A.; Czapski, G.; Meisel, D.

1976-01-01

The method of determination of Redox potentials of radicals, using the pulse radiolysis technique, is outlined. The method is based on the determination of equilibria constants of electron transfer reactions between the radicals and appropriate acceptors. The limitations of this technique are discussed. The redox potentials of several quinones--semi-quinones are calculated, as well as the standard redox potential of the peroxy radical. E 0 /sub O 2 /O 2 /sup -/ = -0.33 V and the redox oxidation properties of the peroxy radical in various systems and pH are discussed. The value determined for the redox potentials of O 2 /O 2 - is higher by more than 0.2 volts than earlier estimates, which has important implications on the possible role of O 2 - in biological processes of O 2 fixation

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

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

Science.gov (United States)

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

2017-12-01

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

Radicals in the marine boundary layer during NEAQS 2004: a model study of day-time and night-time sources and sinks

Directory of Open Access Journals (Sweden)

R. Sommariva

2009-05-01

Full Text Available This paper describes a modelling study of several HO_x and NO_x species (OH, HO₂, organic peroxy radicals, NO₃ and N₂O₅ in the marine boundary layer. A model based upon the Master Chemical Mechanism (MCM was constrained to observations of chemical and physical parameters made onboard the NOAA ship R/V Brown as part of the New England Air Quality Study (NEAQS in the summer of 2004. The model was used to calculate [OH] and to determine the composition of the peroxy radical pool. Modelled [NO₃] and [N₂O₅] were compared to in-situ measurements by Cavity Ring-Down Spectroscopy. The comparison showed that the model generally overestimated the measurements by 30–50%, on average.

The model results were analyzed with respect to several chemical and physical parameters, including uptake of NO₃ and N₂O₅ on fog droplets and on aerosol, dry deposition of NO₃ and N₂O₅, gas-phase hydrolysis of N₂O₅ and reactions of NO₃ with NMHCs and peroxy radicals. The results suggest that fog, when present, is an important sink for N₂O₅ via rapid heterogeneous uptake. The comparison between the model and the measurements were consistent with values of the heterogeneous uptake coefficient of N₂O₅ (γ_N2O5>1×10⁻², independent of aerosol composition in this marine environment. The analysis of the different loss processes of the nitrate radical showed the important role of the organic peroxy radicals, which accounted for a significant fraction (median: 15% of NO₃ gas-phase removal, particularly in the presence of high concentrations of dimethyl sulphide (DMS.

Degradation and biodegradability improvement of the olive mill wastewater by peroxi-electrocoagulation/electrooxidation-electroflotation process with bipolar aluminum electrodes.

Science.gov (United States)

Esfandyari, Yahya; Mahdavi, Yousef; Seyedsalehi, Mahdi; Hoseini, Mohammad; Safari, Gholam Hossein; Ghozikali, Mohammad Ghanbari; Kamani, Hossein; Jaafari, Jalil

2015-04-01

Olive mill wastewater is considered as one of the most polluting effluents of the food industry and constitutes a source of important environmental problems. In this study, the removal of pollutants (chemical oxygen demand (COD), biochemical oxygen demand (BOD5), polyphenols, turbidity, color, total suspended solids (TSS), and oil and grease) from olive oil mill processing wastewater by peroxi-electrocoagulation/electrooxidation-electroflotation process with bipolar aluminum electrodes was evaluated using a pilot continuous reactor. In the electrochemical unit, aluminum (Al), stainless steel, and RuO2/Ti plates were used. The effects of pH, hydrogen peroxide doses, current density, NaCl concentrations, and reaction times were studied. Under optimal conditions of pH 4, current density of 40 mA/m(2), 1000 mg/L H2O2, 1 g/L NaCl, and 30-min reaction time, the peroxi-electrochemical method yielded very effective removal of organic pollution from the olive mill wastewater diluted four times. The treatment process reduced COD by 96%, BOD5 by 93.6%, total, polyphenols by 94.4%, color by 91.4%, turbidity by 88.7, suspended solids by 97% and oil and grease by 97.1%. The biodegradability index (BOD5/COD) increased from 0.29 to 0.46. Therefore, the peroxi-electrocoagulation/electrooxidation-electroflotation process is considered as an effective and feasible process for pre-treating olive mill wastewater, making possible a post-treatment of the effluent in a biological system.

Impact of biomass burning emission on total peroxy nitrates: fire plume identification during the BORTAS campaign

Directory of Open Access Journals (Sweden)

E. Aruffo

2016-11-01

Full Text Available Total peroxy nitrate ( ∑ PN concentrations have been measured using a thermal dissociation laser-induced fluorescence (TD-LIF instrument during the BORTAS campaign, which focused on the impact of boreal biomass burning (BB emissions on air quality in the Northern Hemisphere. The strong correlation observed between the  ∑ PN concentrations and those of carbon monoxide (CO, a well-known pyrogenic tracer, suggests the possible use of the  ∑ PN concentrations as marker of the BB plumes. Two methods for the identification of BB plumes have been applied: (1  ∑ PN concentrations higher than 6 times the standard deviation above the background and (2  ∑ PN concentrations higher than the 99th percentile of the  ∑ PNs measured during a background flight (B625; then we compared the percentage of BB plume selected using these methods with the percentage evaluated, applying the approaches usually used in literature. Moreover, adding the pressure threshold ( ∼  750 hPa as ancillary parameter to  ∑ PNs, hydrogen cyanide (HCN and CO, the BB plume identification is improved. A recurrent artificial neural network (ANN model was adapted to simulate the concentrations of  ∑ PNs and HCN, including nitrogen oxide (NO, acetonitrile (CH3CN, CO, ozone (O3 and atmospheric pressure as input parameters, to verify the specific role of these input data to better identify BB plumes.

Rare earths: preparation of spectro chemically pure standards, study of their carbonates and synthesis of a new compound series - the peroxy carbonates

International Nuclear Information System (INIS)

Queiroz, Carlos Alberto da Silva

1996-05-01

In this work the following studies are concerned: I) preparation of lanthanum, cerium, praseodymium, neodymium and samarium oxides for use as spectro chemically pure standards; II) behavior of the rare earth (La, Ce, Pr, Nd, Sm) carbonates soluble in ammonium carbonate and mixture of ammonium carbonate/ammonium hydroxide, and III) synthesis and characterization of rare earth peroxy carbonates - a new series of compounds. Data for the synthesis and characterization of the rare earths peroxy carbonates described for the first time in this work are presented and discussed. With the aid of thermal analysis (TG-DTG) the thermal stability and the stoichiometric composition for new compounds were established and a mechanism of thermal decomposition was proposed. The peroxy carbonate was prepared by the addition of hydrogen peroxyde to the complexed soluble rare earths carbonates. These studies included also the determinations of active oxygen, the total rare earth oxide by gravimetry and complexometry and the C, H and N contents by microanalysis. The new compounds were also investigated by infrared spectroscopy. (author)

One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

KAUST Repository

Wang, Xinbo; Pan, Yupeng; Huang, Kuo-Wei; Lai, Zhiping

2015-01-01

A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction

Kinetics of the Reaction of CH3O2 Radicals with OH Studied over the 292-526 K Temperature Range.

Science.gov (United States)

Yan, Chao; Kocevska, Stefani; Krasnoperov, Lev N

2016-08-11

Reaction of methyl peroxy radicals with hydroxyl radicals, CH3O2 + OH → CH3O + HO2 (1a) and CH3O2 + OH → CH2OO + H2O (1b) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 292-526 K temperature range and pressure 1 bar (bath gas He). Hydroxyl radicals were generated in the reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N2O at 193.3 nm, with H2O. Methyl peroxy radicals were generated in the reaction of methyl radicals, CH3, produced in the photolysis of acetone at 193.3 nm, and subsequent reaction of CH3 with O2. Temporal profiles of OH were monitored via transient absorption of light from a DC discharge H2O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The overall rate constant of the reaction is k1a+1b = (8.4 ± 1.7) × 10(-11)(T/298 K)(-0.81) cm(3) molecule(-1) s(-1) (292-526 K). The branching ratio of channel 1b at 298 K is less than 5%.

Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air.

Science.gov (United States)

Zhao, Yue; Wingen, Lisa M; Perraud, Véronique; Greaves, John; Finlayson-Pitts, Barbara J

2015-05-21

Ozonolysis of alkenes is an important source of secondary organic aerosol (SOA) in the atmosphere. However, the mechanisms by which stabilized Criegee intermediates (SCI) react to form and grow the particles, and in particular the contributions from oligomers, are not well understood. In this study, ozonolysis of trans-3-hexene (C6H12), as a proxy for small alkenes, was investigated with an emphasis on the mechanisms of particle formation and growth. Ozonolysis experiments were carried out both in static Teflon chambers (18-20 min reaction times) and in a glass flow reactor (24 s reaction time) in the absence and presence of OH or SCI scavengers, and under different relative humidity (RH) conditions. The chemical composition of polydisperse and size-selected SOA particles was probed using different mass spectrometric techniques and infrared spectroscopy. Oligomers having SCI as the chain unit are found to be the dominant components of such SOA particles. The formation mechanism for these oligomers suggested by our results follows the sequential addition of SCI to organic peroxy (RO2) radicals, in agreement with previous studies by Moortgat and coworkers. Smaller particles are shown to have a relatively greater contribution from longer oligomers. Higher O/C ratios are observed in smaller particles and are similar to those of oligomers resulting from RO2 + nSCI, supporting a significant role for longer oligomers in particle nucleation and early growth. Under atmospherically relevant RH of 30-80%, water vapor suppresses oligomer formation through scavenging SCI, but also enhances particle nucleation. Under humid conditions, or in the presence of formic or hydrochloric acid as SCI scavengers, peroxyhemiacetals are formed by the acid-catalyzed particle phase reaction between oligomers from RO2 + nSCI and a trans-3-hexene derived carbonyl product. In contrast to the ozonolysis of trans-3-hexene, oligomerization involving RO2 + nSCI does not appear to be prevalent in the

Total cross section for chloroflouromethanes and CClx radicals by electron impact

International Nuclear Information System (INIS)

Gupta, Dhanoj; Antony, Bobby

2013-01-01

Highlights: ► A model to find total CS for freons and CCl x by e − impact is employed. ► Complex optical potential formalism is used to find total inelastic and elastic CS. ► Result shows very good agreement with previous data wherever available. ► Maiden attempt to find cross section for the CCl x radicals. -- Abstract: We report here the total cross section for chloroflouromethanes namely CCl 3 F (Freon 11), CCl 2 F 2 (Freon 12), CClF 3 (Freon 13), CCl 4 and CCl x (x = 1–3), radicals by electron impact 50 to 5000 eV. The total inelastic and elastic cross sections are obtained employing a complex optical potential formalism and solving the Schrödinger equation through partial wave analysis. The total cross section is obtained as the sum of total inelastic and elastic cross sections. The results obtained are compared with the existing experimental and theoretical data, wherever available. The present result shows reasonable agreement with previous data. For the CCl x radicals, we have predicted the total cross sections for the first time. The data reported here has immense interest to atmospheric and technological plasma modelling

Observation and Modelling of the OH, HO2 and RO2 Radicals at a Regional Site of Beijing in Winter 2016.

Science.gov (United States)

Tan, Z.; Lu, K.; Ma, X.; Bohn, B.; Hofzumahaus, A.; Broch, S.; Fuchs, H.; Holland, F.; Liu, Y.; Li, X.; Novelli, A.; Rohrer, F.; Wang, H.; Wu, Y.; Shao, M.; Zeng, L.; Kiendler-Scharr, A.; Wahner, A.; Zhang, Y.

2017-12-01

A comprehensive field campaign was carried out in winter 2016 in the campus of UCAS (University of Chinese Academy of Science), located in a small town 60 km northeast of urban Beijing. Concentrations of OH, HO2 and RO2 radicals as well as the total OH reactivity were measured by a laser induced fluorescence instrument. Maximum hourly averaged OH, HO2 and RO2 radical concentrations were (3±2)×106cm-3, (8±6)×107 cm-3 and (7±5)×107 cm-3, respectively. These radical concentrations were smaller than those observed during summer because of the reduced solar radiation. A chemical modulation device to separate atmospheric OH radicals from any interfering species was applied for few days showing negligible interference for both clean and polluted air masses.HONO and HCHO photolysis were found to be the most important primary sources of ROx radicals. CO and NOx were the important OH reactants which contributed more than half of the total OH reactivity. The relative high OH concentrations in polluted episode enabled a fast oxidation of fresh emitted pollutants and the formation of secondary air products. The observed radical concentrations were compared with the results from a chemical box model. The model is capable of reproducing radical concentrations for moderate NOx conditions but larger discrepancies are observed for both low and high NOx regimes for the peroxy radical concentrations. The underestimation of RO2 radical concentrations for high NOx conditions is discussed in the context of recent campaigns.

The Atmospheric Oxidation of Volatile Organic Compounds Through Hydrogen Shift Reactions

DEFF Research Database (Denmark)

Knap, Hasse Christian

a radical is denoted as a H-shift reaction. Quantum chemical calculations were carried out to investigate the potential energy surface of the H-shift reactions and the subsequent decomposition pathways. The transition state theory including the Eckart quantum tunneling correction have been used to calculate...... the reaction rate constants of the H-shift reactions. The autoxidation of volatile organic compounds is an important oxidation mechanism that produces secondary organic aerosols (SOA) and recycles hydroxyl (OH) radicals. The autoxidation cycle produces a second generation peroxy radical (OOQOOH) through...... a series of H-shift reactions and O2 attachments. I have investigated the H-shift reactions in two OOQOOH radicals (hydroperoxy peroxy radicals and hydroperoxy acyl peroxy radicals). The H-shift reaction rate constants have been compared with the bimolecular reaction rate constants of the peroxy radicals...

Peroxi-coagulation degradation of C.I. Basic Yellow 2 based on carbon-PTFE and carbon nanotube-PTFE electrodes as cathode

International Nuclear Information System (INIS)

Zarei, Mahmoud; Salari, Darioush; Niaei, Aligoli; Khataee, Alireza

2009-01-01

The electrochemical treatment of solutions containing C.I. Basic Yellow 2 (BY2) in aqueous solutions with carbon-PTFE (polytetrafluoroethylene) and carbon nanotube (CNT)-PTFE electrodes as cathode has been studied. The fabricated electrodes were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The amount of electrogenerated H 2 O 2 on the surface of these electrodes was investigated, too. The results showed that the amount of H 2 O 2 obtained with the CNT-PTFE electrode was nearly three times higher than that of carbon-PTFE electrode. The decolorization efficiency of BY2 in peroxi-coagulation process reached 62% and 96% in the first 10 min by carbon-PTFE and CNT-PTFE electrodes at 100 mA, respectively. The effect of operational parameters such as applied current, initial pH and initial dye concentration was studied in an attempt to reach higher decolorization efficiency. The degradation and mineralization of BY2 using CNT-PTFE electrode were followed by total organic carbon (TOC) and GC-MS analysis. The results of TOC measurements indicated that peroxi-coagulation with carbon-PTFE allowed 81% mineralization after 6 h of electrolysis; whereas peroxi-coagulation with CNT-PTFE yields 92% mineralization under the same conditions. GC-MS analysis verified the identity of intermediates and a reaction pathway based on them was proposed.

Application of thermal-dissociation laser induced fluorescence (TD-LIF to measurement of HNO3, Σalkyl nitrates, Σperoxy nitrates, and NO2 fluxes using eddy covariance

Directory of Open Access Journals (Sweden)

D. K. Farmer

2006-01-01

Full Text Available Nitrogen exchange between the atmosphere and biosphere directly influences atmospheric composition. While much is known about mechanisms of NO and N2O emissions, instrumentation for the study of mechanisms contributing to exchange of other major nitrogen species is quite limited. Here we describe the application of a new technique, thermal dissociation-laser induced fluorescence (TD-LIF, to eddy covariance measurements of the fluxes of NO2, total peroxy acyl and peroxy nitrates, total alkyl and multifunctional alkyl nitrates, and nitric acid. The technique offers the potential for investigating mechanisms of exchange of these species at the canopy scale over timescales from days to years. Examples of flux measurements at a ponderosa pine plantation in the mid-elevation Sierra Nevada Mountains in California are reported and used to evaluate instrument performance.

In situ characterization of Ti-peroxy gel during formation on titanium surfaces in hydrogen peroxide containing solutions

International Nuclear Information System (INIS)

Muyco, Julie J.; Gray, Jeremy J.; Ratto, Timothy V.; Orme, Christine A.; McKittrick, Joanna; Frangos, John

2006-01-01

Three possible functions of Ti-peroxy gel are: reduction of the inflammatory response through the reduction of hydrogen peroxide and other reactive oxygen species; creation of a favorable surface for calcium phosphate nucleation; and as a transitional layer between the compliant surrounding tissue and the stiff titanium. Traditional surface characterization techniques operate in high vacuum environments that alter the actual sample-solution interface. Our studies used techniques that allowed samples to remain in solution and be observed over time. Atomic force microscopy (AFM) force-distance curves, electrochemical impedance spectroscopy (EIS), and Raman spectroscopy were each used in situ to define kinetic and mechanical properties of Ti-peroxy gel as it formed over time on titanium during exposure to hydrogen peroxide. Our studies enabled us to monitor real-time changes in the native oxide layer on titanium in hydrogen peroxide containing solution, including the formation of a Ti-peroxy gel layer above the native oxide. Peaks attributed to Ti-peroxy gel were seen to emerge over the course of several hours using in situ Raman spectroscopy. Force-distance curves suggest a layer that thickens with time on the titanium sample surface. EIS data showed that changes in the surface layers could be monitored in solution over time

One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

KAUST Repository

Wang, Xinbo

2015-11-06

A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction discovered, a new synthetic proposal for Fumitremorgin A and Verruculogen is introduced. Such a protocol could be easily handled and scaled up in an open atmosphere with a wide substrate scope, enabling the construction of a new molecule library.

Modeling the oxidative capacity of the atmosphere of the south coast air basin of California. 2. HOx radical production.

Science.gov (United States)

Griffin, Robert J

2004-02-01

The production of HOx radicals in the South Coast Air Basin of California is investigated during the smog episode of September 9, 1993 using the California Institute of Technology (CIT) air-quality model. Sources of HOx(hydroxyl, hydroperoxy, and organic peroxy radicals) incorporated into the associated gas-phase chemical mechanism include the combination of excited-state singlet oxygen (formed from ozone (O3) photolysis (hv)) with water, the photolysis of nitrous acid, hydrogen peroxide (H2O2), and carbonyl compounds (formaldehyde (HCHO) or higher aldehydes and ketones), the consumption of aldehydes and alkenes (ALK) by the nitrate radical, and the consumption of alkenes by O3 and the oxygen atom (O). At a given time or location for surface cells and vertical averages, each route of HOx formation may be the greatest contributor to overall formation except HCHO-hv, H2O2-hv, and ALK-O, the latter two of which are insignificant pathways in general. The contribution of the ALK-O3 pathway is dependent on the stoichiometric yield of OH, but this pathway, at least for the studied smog episode, may not be as generally significant as previous research suggests. Future emissions scenarios yield lower total HOx production rates and a shift in the relative importance of individual pathways.

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

International Nuclear Information System (INIS)

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

1983-01-01

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

Safety of total laparoscopic modified radical hysterectomy with or without lymphadenectomy for endometrial cancer

Directory of Open Access Journals (Sweden)

Masakazu Kitagawa

2017-02-01

Conclusion: Total laparoscopic modified radical hysterectomy is safe and feasible for the treatment of early stage endometrial cancer. This procedure can be an alternative to total laparoscopic hysterectomy, especially when the uterus must be removed completely.

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

Science.gov (United States)

Chien, Chao-Jung

2001-07-01

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

Enthalpies of vaporization of some acetylene peroxy derivatives of carboranes-12

International Nuclear Information System (INIS)

Dibrivnyj, V.N.; Pistun, Z.E.; Van-Chin-Syan, Yu.Ya.; Yuvchenko, A.P.; Zvereva, T.D.

1999-01-01

Temperature dependences of saturated vapor pressure and vaporization enthalpies of five acetylene peroxy derivatives of carboranes-12 are determined by the Knudsen effusion method. Enthalpies and melting points of crystals, as well as temperatures of liquid compounds decomposition start are determined by the method of differential scanning calorimetry. Comparison of evaporation enthalpies determined in the study confirms the conclusions on non-additive character of intermolecular interaction in carboranes and their derivatives, which have been made previously [ru

Peroxy defects in Rocks and H2O2 formation on the early Earth

Science.gov (United States)

Gray, A.; Balk, M.; Mason, P.; Freund, F.; Rothschild, L.

2013-12-01

An oxygen-rich atmosphere appears to have been a prerequisite for complex life to evolve on Earth and possibly elsewhere in the Universe. The question is still shrouded in uncertainty how free oxygen became available on the early Earth. Here we study processes of peroxy defects in silicate minerals which, upon weathering, generate mobilized electronic charge carriers resulting in oxygen formation in an initially anoxic subsurface environment. Reactive Oxygen Species (ROS) are precursors to molecular oxygen during this process. Due to their toxicity they may have strongly influenced the evolution of life. ROS are generated during hydrolysis of peroxy defects, which consist of pairs of oxygen anions. A second pathway for formation occurs during (bio) transformations of iron sulphide minerals. ROS are produced and consumed by intracellular and extracellular reactions of Fe, Mn, C, N, and S species. We propose that despite an overall reducing or neutral oxidation state of the macroenvironment and the absence of free O2 in the atmosphere, microorganisms on the early Earth had to cope with ROS in their microenvironments. They were thus under evolutionary pressure to develop enzymatic and other defenses against the potentially dangerous, even lethal effects of ROS and oxygen. We have investigated how oxygen might be released through weathering and test microorganisms in contact with rock surfaces. Our results show how early Life might have adapted to oxygen. Early microorganisms must have "trained" to detoxify ROS prior to the evolution of aerobic metabolism and oxygenic photosynthesis. A possible way out of this dilemma comes from a study of igneous and high-grade metamorphic rocks, whose minerals contain a small but significant fraction of oxygen anions in the valence state 1- , forming peroxy links of the type O3Si-OO-SiO3 [1, 2]. As water hydrolyzes the peroxy links hydrogen peroxide, H2O2, forms. Continued experimental discovery of H2O2 formation at rock

The ability of Abelmoschus manihot L. leaf extract in scavenging of free radical DPPH and total flavonoid determination

Science.gov (United States)

Sudewi, S.; Lolo, W. A.; Warongan, M.; Rifai, Y.; Rante, H.

2017-11-01

Abelmoschus manihot L. has reported to have flavonoids content. This study aims were to determine the ability of A. manihot extract in counteracting free radical DPPH and determine the content of total flavonoids. A. manihot leaf was taken from 2 regions in North Sulawesi, namely Tomohon and Kotamobagu. The maceration was carried out to extract the active compound in a 96% ethanol solvent. Free radical scavenging analysis was carried out by DPPH and determination of its total flavonoid in the extract was measured using spectrophotometri method. The results showed that A. manihot extract from Tomohon and Kotamobagu could counteract free radical of DPPH with value of free radical activity of 88.151 and 88.801 %, respectively. A. manihot leaf from Kotamobagu has higher total flavonoids content 61.763 mg/g compare to Tomohon 46.679 mg/g which presented as quercetin. A. manihot has antioxidant activity.

Global modelling of the total OH reactivity: investigations on the “missing” OH sink and its atmospheric implications

Directory of Open Access Journals (Sweden)

V. Ferracci

2018-05-01

Full Text Available The hydroxyl radical (OH plays a crucial role in the chemistry of the atmosphere as it initiates the removal of most trace gases. A number of field campaigns have observed the presence of a missing OH sink in a variety of regions across the planet. A comparison of direct measurements of the OH loss frequency, also known as total OH reactivity (kOH, with the sum of individual known OH sinks (obtained via the simultaneous detection of species such as volatile organic compounds and nitrogen oxides indicates that, in some cases, up to 80 % of kOH is unaccounted for. In this work, the UM-UKCA chemistry-climate model was used to investigate the wider implications of the missing reactivity on the oxidising capacity of the atmosphere. Simulations of the present-day atmosphere were performed and the model was evaluated against an array of field measurements to verify that the known OH sinks were reproduced well, with a resulting good agreement found for most species. Following this, an additional sink was introduced to simulate the missing OH reactivity as an emission of a hypothetical molecule, X, which undergoes rapid reaction with OH. The magnitude and spatial distribution of this sink were underpinned by observations of the missing reactivity. Model runs showed that the missing reactivity accounted for on average 6 % of the total OH loss flux at the surface and up to 50 % in regions where emissions of the additional sink were high. The lifetime of the hydroxyl radical was reduced by 3 % in the boundary layer, whilst tropospheric methane lifetime increased by 2 % when the additional OH sink was included. As no OH recycling was introduced following the initial oxidation of X, these results can be interpreted as an upper limit of the effects of the missing reactivity on the oxidising capacity of the troposphere. The UM-UKCA simulations also allowed us to establish the atmospheric implications of the newly characterised reactions of peroxy

Development of thermoresponsive non-woven 3D scaffold for smart cell culture

CSIR Research Space (South Africa)

Mahlangu, T

2012-10-01

Full Text Available morphology of the NWF scaffolds. 2-2-Diphenyl-1-picrylhydrazyl (DPPH), a stable free radical, was used to quantify the amount of peroxy free radicals on the oNWF. Scheme 1: A schematic representation showing the possible mechanism for oxyfluorination... 2: Typical ATR-FTIR spectra of pNWF, oNWF, PP-g-PNIPAAm (gNWF) and PNIPAAm homopolymer It is well-known that oxyfluorination produces peroxy free radicals on polymer surfaces. After oxyfluorination, new bands were observed on the oNWF at 3 700...

Rare earths: preparation of spectro chemically pure standards, study of their carbonates and synthesis of a new compound series - the peroxy carbonates; Terras-raras: obtencao de padroes espectroquimicos, estudo dos carbonatos e sintese dos peroxicarbonatos. Uma nova serie de compostos

Energy Technology Data Exchange (ETDEWEB)

Queiroz, Carlos Alberto da Silva

1996-05-01

In this work the following studies are concerned: I) preparation of lanthanum, cerium, praseodymium, neodymium and samarium oxides for use as spectro chemically pure standards; II) behavior of the rare earth (La, Ce, Pr, Nd, Sm) carbonates soluble in ammonium carbonate and mixture of ammonium carbonate/ammonium hydroxide, and III) synthesis and characterization of rare earth peroxy carbonates - a new series of compounds. Data for the synthesis and characterization of the rare earths peroxy carbonates described for the first time in this work are presented and discussed. With the aid of thermal analysis (TG-DTG) the thermal stability and the stoichiometric composition for new compounds were established and a mechanism of thermal decomposition was proposed. The peroxy carbonate was prepared by the addition of hydrogen peroxyde to the complexed soluble rare earths carbonates. These studies included also the determinations of active oxygen, the total rare earth oxide by gravimetry and complexometry and the C, H and N contents by microanalysis. The new compounds were also investigated by infrared spectroscopy. (author)

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

Science.gov (United States)

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

2013-01-01

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

Evaluation of free radical scavenging capacity and antioxidative damage effect of resveratrol-nanostructured lipid carriers

Science.gov (United States)

Jin, Ju; Shi, Fan; Li, Qiu-wen; Li, Pei-shan; Chen, Tong-sheng; Wang, Yi-fei; Wang, Zhi-ping

2016-03-01

Cellular damage induced by free-radicals like reactive oxygen species has been implicated in several diseases. 2, 2-azobis(2-amidino-propane) dihydrochloride(AAPH) generates two potent ROS capable of inducing lipid peroxidation: alkoxy radical(RO-) and peroxy radical(ROO-). These radicals are similar to those that are physiologically active and thus might initiate a cascade of intracellular toxic events leading to oxidation, lipid peroxidation, DNA damage and subsequent cell death. Hence naturally anti-oxidant play a vital role in combating these conditions. In this study, resveratrol loaded nanostructured lipid carriers (Res-NLC) was prepared by hot melting and then high pressure homogenization technique. The effects of Res-NLC on free radical scavenging capacity and antioxidative damage is investigated. The particle size and zeta potential of Res-NLC were 139.3 ± 1.7 nm and -11.21 ± 0.41 mV, respectively. By free radical scavenging assays, the IC50 value of Res-NLC were 19.25, 5.29 μg/mL with DPPH, ABTS assay respectively, and 0.161 mg ferrous sulfate/1 mg Res-NLC with FRAP assay; and by AAPH-induced oxidative injury cell model assay, Res-NLC showed the strong protective effect against the human liver tumor HepG2 cell oxidative stress damage. These results indicated that the antioxidant properties of Res-NLC hold great potential used as an alternative to more toxic synthetic antioxidants as an additive in food, cosmetic and pharmaceutical preparations for the oxidative diseases treatment.

Suppression of new particle formation from monoterpene oxidation by NOx

Science.gov (United States)

Wildt, J.; Mentel, T. F.; Kiendler-Scharr, A.; Hoffmann, T.; Andres, S.; Ehn, M.; Kleist, E.; Müsgen, P.; Rohrer, F.; Rudich, Y.; Springer, M.; Tillmann, R.; Wahner, A.

2014-03-01

The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NOx conditions ([BVOC] / [NOx] 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NOx conditions ([NOx] ~300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching -2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NOx concentrations. If at all, yields were reduced by about an order of magnitude only at very high NOx concentrations.

Products of BVOC oxidation: ozone and organic aerosols

Science.gov (United States)

Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

2015-04-01

Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of dimers that, in case of monoterpenes as reactants, consist of a skeleton with 20 carbon atoms. These dimers seem to

Novel Profluorescent Nitroxides for Monitoring Alkyl Radical Reactions During Radiation Degradation

International Nuclear Information System (INIS)

George, G.

2006-01-01

Hindered amine stabilizers (HAS) are effective at retarding the photo-oxidative and high energy radiation degradation of PP and in certain circumstances, also thermo-oxidative degradation. The effectiveness of HAS as retarders of oxidation relies on the oxidation of the N-C bond by polymer hydroperoxide, ROOH, to form the nitroxyl group -NO which is the scavenger of polymer alkyl radicals, R. This reaction, which produces the alkoxy amine: -NO-R, must be competitive with the reaction of R with oxygen (which gives the chain-carrying peroxy radical, RO 2 ) if this stabilization mechanism is to be important in the inhibition of radiation-induced oxidative degradation of polyolefins by HAS. The rate of this reaction is high and in solution the rate coefficient is from 1 to 9x10 8 l mol - 1 s - 1. The efficient radical trapping by nitroxides has been widely employed in spin-trapping studies by electron spin resonance (esr) spectroscopy]. In addition to the hindered piperidine structure of commercial HAS, more rigid aromatic systems have been studied that are more stable to oxidative degradation and are more efficient at scavenging alkyl radicals. One such family is the iso-indoline nitroxide system, TMDBIO, shown below which, as it contains the phenanthrene fluorophore, is termed phenanthrene nitroxide. This nitroxide only becomes fluorescent when it reacts with alkyl radicals or is reduced and is termed profluorescent. TMDBIO has a vanishingly small fluorescence quantum yield (φ∼10 - 4) due to the enhanced intersystem crossing from the first excited singlet state to the ground state due to electron exchange interactions of the nitroxyl radical. When the nitroxide traps an alkyl radical, R, the resulting alkoxy amine is fluorescent (φ∼10 - 1) and the emission intensity is a measure of the number of reactions that have occurred. This property may be exploited by using quantitative fluorescence spectroscopy to follow the reaction of the nitroxide with alkyl radicals

Investigation of reactions and species dominating low temperature combustion - Final report

Energy Technology Data Exchange (ETDEWEB)

Gerber, T.; Radi, P.; Knopp, G.; Tulej, M.

2007-07-01

This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Paul Scherrer Institute PSI in Switzerland on the quantitative description of ignition. processes and the influence of peroxy radicals that determine ignition and speciation of the intermediates initially present and, thereby, the progress of subsequent reactions. The authors note that for the preparation of peroxy radicals, a dedicated molecular beam apparatus has been built by the PSI's 'Molecular Dynamics' group. A novel radical source is operational. In many cases, specific radicals can be prepared with high selectivity. A description of flame chemistry is being worked on that can reliably predict the speciation of intermediate products during ignition. Laser-based measurement techniques are being applied at PSI to measure the static and dynamic properties of alkyl peroxy radicals in order to accurately describe their reaction behaviour in combustion processes. A dedicated synchrotron beam line is installed at the Swiss Light Source (SLS) that extends the available range of spectroscopic measurements into the VUV (vacuum-ultraviolet) wavelength domain. The results obtained are presented and discussed.

The use of total ossicular replacement prosthesis after radical tympanomastoidectomy

Directory of Open Access Journals (Sweden)

Rančić Dejan

2013-01-01

Full Text Available Background/Aim. This paper presents our operative method for hearing recovery after the previous radical tympanomastoidectomy, radical trepanation of the temporal bone (trepanatio radicalis ossis temporalis - TROT in eight patients submitted to operations for giant cholesteatotoma. Methods. All the patients were admitted to our clinic after TROT. There were no signs of cholesteatoma or infection. The patients refused any stent implantations or any hearing aids due to possible aesthetic problems. The described procedure developed in two steps. The first one was to restore the destroyed cavum tympany and to covert with chondroperichondral new membrane with a pin-like “guide” as collumela. The second step was to insert a TORP (total ossicular replacement prosthesis after guide excision. Results. After the first operation (stage one there were no infections in the operated area nor chondroperichondral graft rejection. Postoperative audiometry (6 to 8 weeks was done to demonstrate the improvement of air conduction. Three months following the first, the second (stage two operation was performed and 2.5 to 3 months after this operation even greater audiometry revealed hearing improvement in air- and bone-conduction. The patients were dismissed from the hospital 2 days after each procedure without any complications. They did not experience any dizziness, vomiting nor a severe pain. Three months after the second operative stage, otoscopic findings were very good. The audiometry findings after a 3-months period (after stage one and 3 months after final TORP insertion was done for each of the patients. After one year, the audiometric curve was the same. Clinical and audiometry follow up demonstrated a hearing recovery and closure of air bone gap (ABG to values of 5 to 15 dB. Conclusion. The use of TORP after radical tympanomastoidectomy is feasible. The first step of the procedure is the fixation of a neomembrane. A stabilized neomembrane is essential

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

International Nuclear Information System (INIS)

Oral, E.

2006-01-01

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

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.

Novel process window for the safe and continuous synthesis of tert.-butyl peroxy pivalate in a micro reactor

NARCIS (Netherlands)

Illg, T.; Hessel, V.; Löb, P.; Schouten, J.C.

2011-01-01

In this paper, the two step synthesis of tert.-butyl peroxy pivalate using two different flow regimes is introduced, in particular the use of "segmented flow" and the concept of "dispersed flow". The use of the segmented flow process, in this case, is challenging due to the very low interfacial

Peroxy-Titanium Complex-based inks for low temperature compliant anatase thin films.

Science.gov (United States)

Shabanov, N S; Asvarov, A Sh; Chiolerio, A; Rabadanov, K Sh; Isaev, A B; Orudzhev, F F; Makhmudov, S Sh

2017-07-15

Stable highly crystalline titanium dioxide colloids are of paramount importance for the establishment of a solution-processable library of materials that could help in bringing the advantages of digital printing to the world of photocatalysis and solar energy conversion. Nano-sized titanium dioxide in the anatase phase was synthesized by means of hydrothermal methods and treated with hydrogen peroxide to form Peroxy-Titanium Complexes (PTCs). The influence of hydrogen peroxide on the structural, optical and rheological properties of titanium dioxide and its colloidal solutions were assessed and a practical demonstration of a low temperature compliant digitally printed anatase thin film given. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

High-Pressure Limit Rate Rules for α-H Isomerization of Hydroperoxyalkylperoxy Radicals

KAUST Repository

Mohamed, Samah Y

2018-03-09

Hydroperoxyalkylperoxy (OOQOOH) radical isomerization is an important low-temperature chain branching reaction within the mechanism of hydrocarbon oxidation. This isomerization may proceed via the migration of the α-hydrogen to the hydroperoxide group. In this work, a combination of high level composite methods - CBS-QB3, G3 and G4 - is used to determine the high-pressure-limit rate parameters for the title reaction. Rate rules for H-migration reactions proceeding through 5-, 6-, 7- and 8-membered ring transitions states are determined. Migrations from primary, secondary and tertiary carbon sites to the peroxy group are considered. Chirality is also investigated by considering two diastereomers for reactants and transition states with two chiral centers. This is important since chirality may influence the energy barrier of the reaction as well as the rotational energy barriers of hindered rotors in chemical species and transition states. The effect of chirality and hydrogen bonding interactions in the investigated energies and rate constants is studied. The results show that while the energy difference between two diastereomers ranges from 0.1 - 3.2 kcal, chirality hardly affects the kinetics, except at low temperatures (atmospheric conditions) or when two chiral centers are present in the reactant. Regarding the effects of the peroxy group position and the H-migration ring size, it is found that in most cases, the 1,5 and 1,6 H-migration reactions have similar rates at low temperatures (below ~830K) since the 1,6 H-migration proceeds via a cyclohexane-like transition state similar to that of the 1,5 H-migration.

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.

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

Science.gov (United States)

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

2013-01-01

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

Reassessing the atmospheric oxidation mechanism of toluene

Science.gov (United States)

Ji, Yuemeng; Zhao, Jun; Terazono, Hajime; Misawa, Kentaro; Levitt, Nicholas P.; Li, Yixin; Lin, Yun; Peng, Jianfei; Wang, Yuan; Duan, Lian; Pan, Bowen; Zhang, Fang; Feng, Xidan; An, Taicheng; Marrero-Ortiz, Wilmarie; Secrest, Jeremiah; Zhang, Annie L.; Shibuya, Kazuhiko; Molina, Mario J.; Zhang, Renyi

2017-08-01

Photochemical oxidation of aromatic hydrocarbons leads to tropospheric ozone and secondary organic aerosol (SOA) formation, with profound implications for air quality, human health, and climate. Toluene is the most abundant aromatic compound under urban environments, but its detailed chemical oxidation mechanism remains uncertain. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Our experimental work indicates a larger-than-expected branching ratio for cresols, but a negligible formation of ring-opening products (e.g., methylglyoxal). Quantum chemical calculations also demonstrate that cresols are much more stable than their corresponding peroxy radicals, and, for the most favorable OH (ortho) addition, the pathway of H extraction by O2 to form the cresol proceeds with a smaller barrier than O2 addition to form the peroxy radical. Our results reveal that phenolic (rather than peroxy radical) formation represents the dominant pathway for toluene oxidation, highlighting the necessity to reassess its role in ozone and SOA formation in the atmosphere.

Total laparoscopic radical hysterectomy with pelvic lymphadenectomy for endometrial cancer.

Science.gov (United States)

Vasilescu, C; Stănciulea, Oana; Popa, Monica; Anghel, Rodica; Herlea, V; Florescu, Arleziana

2008-01-01

The surgical treatment of endometrial cancer is still a matter of debate. Two of the most controversial issues are the beneficial effect of lymphadenectomy and the feasibility of laparoscopy. The aim of the case report was to describe the feasibility of total laparoscopic radical hysterectomy with pelvic lymphadenectomy in a 56-years-old Caucasian woman diagnosed with endometrial cancer. After a CO2 pneumoperitoneum was created the peritoneum was incised cranially to the para-colic fossa just above the external iliac vessels until the psoas muscle is visualized. The external iliac vessels were identified and lymph nodes from the anterior and the medial surface were removed until the iliac bifurcation and placed in an Endo-bag. The procedure continued with the identification of the hypo-gastric and the umbilical artery which were pulled medially in order to open the obturator fossa and remove the lymphatic tissue superior to the obturator nerve. The next step was the opening of the para-vesical and pararectal spaces by using blunt dissection; this maneuver was facilitated by pulling the uterine fundus towards the opposite direction with the uterine manipulator. The parametrium being isolated between the two spaces can be safely divided. At the superior limit of the parametrium the uterine artery is identified and divided at its origin. Thereafter, by placing the uterine fundus in median and posterior position, the vesicouterine peritoneal fold was opened by scissors and a bladder dissection from the low uterine segment down to the vagina was performed. Then the ureter is dissected, freed from its attachments to the parametria and de-crossed from the uterine artery down to its entry into the bladder. Next the rectovaginal space is opened and the utero-sacral ligaments divided; this allows the division of para-vaginal attachments. The vagina is sectioned and the specimen is extracted transvaginally. Then the vaginal stump was sutured by laparoscopy. Total laparoscopic

UV absorption spectra, kinetics and mechanisms of the self-reaction of CHF2O2 radicals in the gas phase at 298-K

DEFF Research Database (Denmark)

Nielsen, O.J.; Ellermann, T.; Bartkiewicz, E.

1992-01-01

The ultraviolet-absorption spectrum and the self-reaction of CHF2O2 radicals have been studied in the gas phase at 298 K using the pulse radiolysis technique and long-pathlength Fourier transform infrared spectroscopy. Absorption cross sections were quantified over the wavelength range 220-280 nm....... The measured cross section near the absorption maximum was sigma(CHF2O2)(240 nm) = (2.66 +/- 0.46) x 10(-18) cm2 molecule-1. The absorption cross section data were used to derive the observed self-reaction rate constant for the reaction CHF2O2 + CHF2O2 --> products, defined as d[R]/dt = 2k(1obs)[CHF2O2]2, k(1......obs) = (5.0 +/- 0.7) x 10(-12) cm3 molecule-1 s-1 (+/- 2-sigma). The only carbon-containing product observed by FTIR spectroscopy was FC(O)F. These results are discussed with respect to previous studies of peroxy radicals....

Sequential study on reactive blue 29 dye removal from aqueous solution by peroxy acid and single wall carbon nanotubes: experiment and theory

Directory of Open Access Journals (Sweden)

Jahangiri-Rad Mahsa

2013-01-01

Full Text Available Abstract The majority of anthraquinone dye released to the environment come from antrapogenic sources. Several techniques are available for dyes' removal. In this study removal of reactive blue 29 (RB29 by an advanced oxidation process sequenced with single wall carbon nanotubes was investigated. Advanced oxidation process was optimized over a period of 60 minutes by changing the ratio of acetic acid to hydrogen peroxide, the compounds which form peroxy acid. Reduction of 20.2% -56.4% of reactive blue 29 was observed when the ratio of hydrogen peroxide/acetic acid/dye changed from 344/344/1 to 344/344/0.08 at different times (60, 120 and 180 min. The optimum ratio of acetic acid/hydrogen peroxide/dye was found to be 344/344/0.16 over 60 min. The resultant then was introduced for further removal by single wall carbon nanotubes(SWCNTs as adsorbent. The adsorption of reactive blue 29 onto SWCNTs was also investigated. Langmuir, Freundlich and BET isotherms were determined and the results revealed that the adsorption of RB29 onto SWCNTs was well explained by BET model and changed to Freundlich isotherm when SWCNTs was used after the application of peroxy acid. Kinetic study showed that the equilibrium time for adsorption of RB 29 on to SWCNT is 4 h. Experiments were carried out to investigate adsorption kinetics, adsorbent capacity and the effect of solution pH on the removal of reactive blue29. The pseudo-second order kinetic equation could best describe the sorption kinetics. The most efficient pH for color removal (amongst pH=3, 5 and 8 was pH= 5. Further studies are needed to identify the peroxy acid degradation intermediates and to investigate their effects on SWCNTs.

Antimalarial activity of synthetic 1,2,4-trioxanes and cyclic peroxy ketals, a quantum similarity study

Science.gov (United States)

Gironés, X.; Gallegos, A.; Carbó-Dorca, R.

2001-12-01

In this work, the antimalarial activity of two series of 20 and 7 synthetic 1,2,4-trioxanes and a set of 20 cyclic peroxy ketals are tested for correlation search by means of Molecular Quantum Similarity Measures (MQSM). QSAR models, dealing with different biological responses (IC90, IC50 and ED90) of the parasite Plasmodium Falciparum, are constructed using MQSM as molecular descriptors and are satisfactorily correlated. The statistical results of the 20 1,2,4-trioxanes are deeply analyzed to elucidate the relevant structural features in the biological activity, revealing the importance of phenyl substitutions.

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

Directory of Open Access Journals (Sweden)

Oktavia Tri Wahyuni

2016-08-01

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

Treatment of an azo dye effluent by peroxi-coagulation and its comparison to traditional electrochemical advanced processes.

Science.gov (United States)

do Vale-Júnior, Edilson; da Silva, Djalma R; Fajardo, Ana S; Martínez-Huitle, Carlos A

2018-04-05

Peroxi-coagulation (PC) is an interesting new process that has not been widely studied in the literature. This work presents the application of this technology to treat an azo dye synthetic effluent, studying the effect of different parameters including initial pH, current density (j), initial dye concentration and supporting electrolyte. The two former variables significantly affected the colour removal of the wastewater, followed by the initial dye concentration and the kind of electrolyte, in a lesser extent. The optimum operating conditions achieved were initial pH of 3.0, j = 33.3 mA cm -2 , 100 mg L -1 of methyl orange (MO) and Na 2 SO 4 as supporting electrolyte. The performance of PC was also compared to other electrochemical advanced processes, under similar experimental conditions. Results indicate that the kinetic decay of the MO increases in the following order: electrocoagulation (EC) oxidation (EO) with electrogenerated H 2 O 2 oxidant character of the homogenous OH radicals generated by EF and PC approaches. The EO process with production of H 2 O 2 (EO-H 2 O 2 ) is limited by mass transport and the EC, as a separation method, takes longer times to achieve similar removal results. Energy requirements about 0.06 kWh g COD -1 , 0.09 kWh g COD -1 , 0.7 kWh g COD -1 and 0.1 kWh g COD -1 were achieved for PC, EF, EO-H 2 O 2 and EC, respectively. Degradation intermediates were monitored and carboxylic acids were detected for PC and EF processes, being rapidly removed by the former technology. PC emerges as a promising and competitive alternative for wastewaters depollution, among other oxidative approaches. Copyright © 2018 Elsevier Ltd. All rights reserved.

One-electron oxidation of BD84, an ellipticine antitumor derivative

International Nuclear Information System (INIS)

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

1991-01-01

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

Total phenolic and phytosterol compounds and the radical scavenging activity of germinated Australian sweet lupin flour.

Science.gov (United States)

Rumiyati; Jayasena, Vijay; James, Anthony P

2013-12-01

In addition to their favourable nutritional profile, legumes also contain a range of bioactive compounds such as phenolic compounds and phytosterols which may protect against chronic diseases including cancer and cardiovascular disease. Germination of some legume seeds has been previously reported to increase the concentration of the bioactive compounds. In this study, the effect of germination of Australian Sweet Lupin (ASL) seeds for 9 days on the concentration of some bioactive compounds and the radical scavenging activity in the resulting flour was determined. The concentration of total phenolic compounds in methanolic extracts of germinated ASL flour was determined using Folin Ciocalteu reagent and phytosterols in oil extracts were analyzed by gas-liquid chromatography. The methanolic and oil extracts were also used to determine radical scavenging activity toward 2,2-diphenyl-1-picrylhydrazyl. In the methanolic extracts of germinated ASL flour, phenolic contents and the antioxidant activity were significantly increased following germination (700 and 1400 %, respectively). Analysis of the oil extracts of germinated ASL flour revealed that the concentration of phytosterols and the antioxidant activity were also increased significantly compared to ungerminated ASL flour (300 and 800 %, respectively). The relative proportion of phytosterols in germinated ASL flour was: β-sitosterol (60 %), stigmasterol (30 %) and campesterol (10 %). Germination increases the concentration of bioactive compounds and the radical scavenging activity in the germinated ASL flour.

Ten-year results of a randomized clinical trial comparing radical mastectomy and total mastectomy with or without radiation

International Nuclear Information System (INIS)

Fisher, B.; Redmond, C.; Fisher, E.R.

1985-01-01

In 1971 a randomized trial was begun to compare alternative local and regional treatments of breast cancer, all of which employ breast removal. Life-table estimates were obtained for 1665 women enrolled in the study for a mean of 126 months. There were no significant differences among three groups of patients with clinically negative auxillary nodes, with respect to disease-free survival, distant-disease-free survival, or overall survival (about 57%) at 10 years. The patients were treated by radical mastectomy, total (simple) mastectomy without auxillary dissection but with regional irradiation, or total mastectomy without irradiation plus auxillary dissection only if nodes were subsequently positive. Similarly, no differences, were observed between patients with clinically positive nodes treated by radical mastectomy or by total mastectomy without auxillary dissection but with regional irradiation. Survival at 10 years was about 38% in both groups. Our findings indicate that the location of a breast tumor does not influence the prognosis and that irradiation of internal mammary nodes in patients with inner-quadrant lesions does not improve survival. The data also demonstrate that the results obtained at five years accurately predict the outcome at 10 years. It was concluded that the variations of local and regional treatment used in this study are not important in determining survival of patients with breast cancer. 25 references, 6 figures, 1 table

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

Preoperative radiochemotherapy and radical surgery in comparison with radical surgery alone

International Nuclear Information System (INIS)

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

1994-01-01

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

Investigation of reactions and species dominating low temperature combustion - Final report

Energy Technology Data Exchange (ETDEWEB)

Radi, P.; Knopp, G.; Johnson, M.; Boedi, A.; Gerber, T.

2009-12-15

This report for the Swiss Federal Office of Energy (SFOE) presents the results of work done at the Paul Scherrer Institute (PSI) in Switzerland. The project 'Investigation of reactions and species dominating low temperature combustion' involves the characterisation of species that govern ignition. A base established for the spectroscopic investigation of peroxy radicals is discussed. The two-fold aim of this project is discussed which includes the measurement of molecular features such as binding energies and dissociation patterns of well-studied and spectroscopically accessible molecules and radicals as well as the application of the measurement techniques to alkyl peroxy radicals. This was done in order to improve the database of a class of molecules playing a dominant role in combustion and atmospheric chemistry. Several experimental techniques that are to be developed to achieve these aims are looked at. Achievements made are discussed and future work to be carried out is noted.

Formation, Evaporation, and Hydrolysis of Organic Nitrates from Nitrate Radical Oxidation of Monoterpenes

Science.gov (United States)

Ng, N. L.; Takeuchi, M.; Eris, G.; Berkemeier, T.; Boyd, C.; Nah, T.; Xu, L.

2017-12-01

Organic nitrates play an important role in the cycling of NOx and secondary organic aerosol (SOA) formation, yet their formation mechanisms and fates remain highly uncertain. The interactions of biogenic VOCs with NO3 radicals represent a direct way for positively linking anthropogenic and biogenic emissions. Results from ambient studies suggest that organic nitrates have a relatively short lifetime, though corresponding laboratory data are limited. SOA and organic nitrates produced at night may evaporate the following morning due to increasing temperatures or dilution of semi-volatile compounds. Once formed, organic nitrates can also undergo hydrolysis in the presence of particle water. In this work, we investigate the formation, evaporation, and hydrolysis of organic nitrates generated from the nitrate radical oxidation of a-pinene, b-pinene, and limonene. Experiments are conducted in the Georgia Environmental Chamber facility (GTEC) under dry and humid conditions and different temperatures. Experiments are also designed to probe different peroxy radical pathways (RO2+HO2 vs RO2+NO3). Speciated gas-phase and particle-phase organic nitrates are continuously monitored by a Filter Inlet for Gases and AEROsols High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (FIGAERO-HR-ToF-CIMS). Bulk aerosol composition is measured by a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). A large suite of highly oxygenated gas- and particle-phase organic nitrates are formed rapidly. We find a resistance to aerosol evaporation when it is heated. The extent of organic nitrate hydrolysis in the humid experiments is evaluated. The dynamics of the speciated organic nitrates over the course of the experiments will also be discussed. Results from this chamber study provide fundamental data for understanding the dynamics of organic nitrate aerosols over its atmospheric lifetime.

Robots drive the German radical prostatectomy market: a total population analysis from 2006 to 2013.

Science.gov (United States)

Groeben, C; Koch, R; Baunacke, M; Wirth, M P; Huber, J

2016-12-01

To assess trends in the distribution of patients for radical prostatectomy in Germany from 2006 to 2013 and the impact of robotic surgery on annual caseloads. We hypothesized that the advent of robotics and the establishment of certified prostate cancer centers caused centralization in the German radical prostatectomy market. Using remote data processing we analyzed the nationwide German billing data from 2006 to 2013. We supplemented this database with additional hospital characteristics like the prostate cancer center certification status. Inclusion criteria were a prostate cancer diagnosis combined with radical prostatectomy. Hospitals with certification or a surgical robot in 2009 were defined as 'early' group. Linear covariant-analytic models were applied to describe trends over time. Annual radical prostatectomy numbers declined from 28 374 (2006) to 21 850 (2013). High-volume hospitals (⩾100 cases) decreased from 87 (22.0%) in 2006 to 43 (10.4%) in 2013. Low-volume hospitals (200 cases per year contrary to the overall trend (Pdecentralization of radical prostatectomy in Germany. The driving force for this development might consist in the overall decline of radical prostatectomy numbers. The most important factor for achieving higher caseloads was the presence of a robotic system. In order to optimize outcomes of radical prostatectomy additional health policy measures might be necessary.

The nature of the initiating centres for grafting in air-irradiated perfluoro polymers

International Nuclear Information System (INIS)

Bozzi, A.; Chapiro, A.

1987-01-01

Grafting of acrylic acid on polytetrafluoroethylene has been performed using films of the polymer gamma-irradiated in air and then treated with aqueous acrylic acid. It is concluded that the initiating centres are peroxides POOP', where P' is a small perfluorinated fragment, and also trapped peroxy radicals PO 2 radical which undergo deoxygenation. Homopolymerization is suppressed by polymerization inhibitors. (author)

Sticking of HO2 on fatty acids aggregates

Science.gov (United States)

Vardanega, Delphine; Briquez, Stéphane; Duflot, Denis; Monnerville, Maurice; Toubin, Céline

2015-04-01

Models of atmospheric chemistry are widely used to perform projections of future changes in the chemical composition of the global troposphere, including changes in climate related greenhouse gases and aerosol particles. However, large uncertainties are still associated with the chemistry implemented in these models, which in turn can lead to inaccurate long-term predictions. The proposed work seeks to improve our understanding of the oxidative capacity of the atmosphere, which drives the lifetime of trace gases, and therefore atmospheric composition. Recent measurements [1] of free radicals made in forested environments characterized by low levels of nitrogen oxides (NOx = NO and NO2) indicate that current models of atmospheric chemistry tend to overestimate the concentration of peroxy radicals (HO2 and RO2). An overestimation of peroxy radicals is an important issue since these radicals are the main precursors of the hydroxyl radical (OH), the most important atmospheric oxidant during daytime. This issue could lead to a significant overestimation of the oxidative capacity of the global atmosphere since more than 86% of the Earth surface is covered by forests, oceans, and polar regions. An analysis of this dataset indicates that the missing sink could be due to an underestimation of the rates of RO2+HO2 reactions, and/or the uptake of peroxy radicals onto aerosol particles. A thorough evaluation of scientific studies published in the literature shows that there is a lack of kinetic and mechanistic data to correctly assess the contribution of these two loss pathways of peroxy radicals in low NOx environments. Classical molecular dynamics simulations, using the Gromacs package [2], are performed to study the interaction of HO2 with organic (carboxylic acid) aerosols. The effect of the presence of water molecules on the surface are also be investigated. These calculations provide theoretical values for observable quantities such as uptake and mass accommodation

Radical Transversal Lightlike Submanifolds of Indefinite Para-Sasakian Manifolds

OpenAIRE

Shukla S.S.; Yadav Akhilesh

2014-01-01

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

A novel automated direct measurement method for total antioxidant capacity using a new generation, more stable ABTS radical cation.

Science.gov (United States)

Erel, Ozcan

2004-04-01

To develop a novel colorimetric and automated direct measurement method for total antioxidant capacity (TAC). A new generation, more stable, colored 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid radical cation (ABTS(*+)) was employed. The ABTS(*+) is decolorized by antioxidants according to their concentrations and antioxidant capacities. This change in color is measured as a change in absorbance at 660 nm. This process is applied to an automated analyzer and the assay is calibrated with Trolox. The novel assay is linear up to 6 mmol Trolox equivalent/l, its precision values are lower than 3%, and there is no interference from hemoglobin, bilirubin, EDTA, or citrate. The method developed is significantly correlated with the Randox- total antioxidant status (TAS) assay (r = 0.897, P total antioxidant capacity.

Informal Conference on Photochemistry Held in Atlanta, Georgia on 26 April-1 May, 1992

Science.gov (United States)

1992-05-01

of the kinetics of such reactions. We have measured rate constants for the neopentyl peroxy radical, generating the alkyl radical by laser flash... glycol diacetate) > Ketones(acetone.acetophenone) > Ethers(tetrahydrofuran. dioxane). Nltrlles(acetonltrlle).Halogenated hydrocarbons (carbon...the best solvent to synthesis of CBDA. especially ethyl acetate (Y63% /KW Hr) and ethylene glycol diacetate (Y55,/lW Hr).i (2) TEMPERATURE CBDA yield

Barrierless Reactions with Loose Transition States Govern the Yields and Lifetimes of Organic Nitrates Derived from Isoprene

Science.gov (United States)

The chemical reaction mechanism of NO addition to two β and δ isoprene hydroxy–peroxy radical isomers is examined in detail using density functional theory, coupled cluster methods, and the energy resolved master equation formalism to provide estimates of rate co...

Mid-infrared quantum cascade laser spectroscopy probing of the ...

Indian Academy of Sciences (India)

Aparajeo Chattopadhyay

2018-05-07

May 7, 2018 ... cm3 molecule. −1 s. −1 ... Quantum cascade laser; time-resolved mid-infrared spectroscopy; transient absorption; peroxy radicals .... peak of the laser emission profile. .... cal with O2 is a termolecular reaction (Eq. 3) and the.

Bran data of total flavonoid and total phenolic contents, oxygen radical absorbance capacity, and profiles of proanthocyanidins and whole grain physical traits of 32 red and purple rice varieties

Directory of Open Access Journals (Sweden)

Ming-Hsuan Chen

2016-09-01

Full Text Available Phytochemicals in red and purple bran rice have potential health benefit to humans. We determined the phytochemicals in brans of 32 red and purple global rice varieties. The description of the origin and physical traits of the whole grain (color, length, width, thickness and 100-kernel weight of this germplasm collection are provided along with data of total flavonoid and total phenolic contents, oxygen radical absorbance capacity and total proanthocyanidin contents. The contents and proportions of individual oligomers, from degree of polymerization of monomers to 14-mers, and polymers in bran of these 32 rice varieties are presented (DOI: http://dx.doi.org/10.1016/j.foodchem.2016.04.004 [1]. Keywords: Purple rice, Red rice, Black rice, Proanthocyanidins, Tannins, Flavonoids, Rice bran

Fluorinated cellular polypropylene films with time-invariant excellent surface electret properties by post-treatments

International Nuclear Information System (INIS)

An Zhenlian; Mao Mingjun; Yao Junlan; Zhang Yewen; Xia Zhongfu

2010-01-01

In this work, to improve the electret properties of cellular polypropylene films, they were fluorinated and post-treated with nitrous oxide and by isothermal crystallization. Surface electret properties of the samples were investigated by thermally stimulated discharge current measurements, and their compositions and structures were analysed by attenuated total reflection infrared spectroscopy and wide angle x-ray diffraction, respectively. Time-dependent deterioration of surface electret properties was observed for the fluorinated samples without the nitrous oxide post-treatment. However, deterioration did not occur for the fluorinated samples post-treated with nitrous oxide, and time-invariant excellent surface electret properties or deep surface charge traps were obtained by the combined post-treatments of the fluorinated samples with nitrous oxide and by isothermal crystallization. Based on the analyses of composition and structure of the treated samples, the deterioration was clarified to be due to a trace of oxygen in the reactive mixture, which led to the formation of peroxy RO 2 . radicals in the fluorinated surface layer. The time invariability of surface electret properties was owing to the rapid termination of the peroxy RO 2 . radicals by nitrous oxide. And the deep surface charge traps resulted from the isothermal crystallization treatment which led to an increase in the efficient charging interface between the crystallite and amorphous region and its property change.

Peroxy acetyl nitrate intercalibration. Final report. Step EV4V-CT90-0222

Energy Technology Data Exchange (ETDEWEB)

Krognes, T; Toupance, G; Glavas, S [and others

1994-06-01

The report deals with intercalibration of PAN (peroxy acetyl nitrate). PAN is a highly reactive and thermally unstable photo oxidant. It is formed in the atmosphere when a mixture of nitrogen oxides and organic compounds is irradiated by sunlight. It is an important reservoir for nitrogen oxides in the atmosphere. PAN interferes with many types of NO{sub x} monitors. In large cities and industrial areas PAN is an important component of photochemical ``smog``. It may cause irritation of respiratory organs, and in some cases cause plant damage. One country (Italy) presently has passed legislation that includes PAN among the air quality parameters that shall be monitored in polluted areas. Good monitoring and calibration methods are required to fulfill the purpose of such legislation. The emission of nitrogen oxides (NO{sub x}) is subjected to international treaties. To control the effect of such treaties, monitoring and modelling of NO{sub x} components is required. PAN is not the major component, but a significant part of this picture in central European areas. In arctic areas, PAN is a major component of NO{sub v}, and a large contributor to NO{sub x}. 6 figs., 2 tabs.

Isoprene photochemistry over the Amazon rainforest.

Science.gov (United States)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R; Rivera-Rios, Jean C; Seco, Roger; Bates, Kelvin H; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N; Kim, Saewung; Goldstein, Allen H; Guenther, Alex B; Manzi, Antonio O; Souza, Rodrigo A F; Springston, Stephen R; Watson, Thomas B; McKinney, Karena A; Martin, Scot T

2016-05-31

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4-0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (Amazon rainforest.

Kinetics of free radical reactions in irradiated crystalline L-leucine

International Nuclear Information System (INIS)

Dole, M.; Mahdavi, M.

1983-01-01

Four aspects of the radiation chemistry of crystalline L-leucine are presented. They are as follows: the transformation of one type of free radical into another as observed by following the ESR spectrum of individual peaks in the initial stages of the free radical decay at room or higher temperatures after a gamma irradiation at 77K; the catalytic effect of hydrogen gas in significantly accelerating the free radical decay; the unexpected effect of argon gas in decreasing the rate of the free radical decay; and the accurate agreement of the decay data with the diffusion controlled second order Waite equation when the latter is expressed in the linear form. The major free radical which exists in irradiated L-leucine gives rise to a spectrum of 8 Doublets for a total of 16 lines. Numbering the peaks from the least intense to the strongest, peaks numbers 3, 4, 6, and 7, initially increase in intensity before decreasing while peak number 5 rapidly decreases. However, during this initial period the total free radical concentration as measured by the total moment of the ESR spectrum decreases. The kinetics of these effects are discussed. (author)

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

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

Postradiation destruction of dextran in solutions

International Nuclear Information System (INIS)

Bondarenko, N.T.; Sharpatyj, V.A.

1989-01-01

Methods of pH-metry, UV absorption and ESR spectroscopy were used to study the oxidation destruction of dextran solutions, stored in the air after gamma irradiation ( 60 Co) bydoses of up to 200 kGy. It is shown that polymer destruction under mentioned conditions is initiated by hydroperoxide decomposition with successive radical transformation into peroxides. Experimentally observed periodical change of acidity of irradiated dextran solutions is also explained by transformations of peroxy radicals

Mechanism of antioxidant interaction on polymer oxidation by thermal and radiation ageing

International Nuclear Information System (INIS)

Seguchi, Tadao; Tamura, Kiyotoshi; Shimada, Akihiko; Sugimoto, Masaki; Kudoh, Hisaaki

2012-01-01

The mechanism of polymer oxidation by radiation and thermal ageing was investigated for the life evaluation of cables installed in radiation environments. The antioxidant as a stabilizer was very effective for thermal oxidation with a small content in polymers, but was not effective for radiation oxidation. The ionizing radiation induced the oxidation to result in chain scission even at low temperature, because the free radicals were produced and the antioxidant could not stop the oxidation of radicals with the chain scission. A new mechanism of antioxidant effect for polymer oxidation was proposed. The effect of antioxidant was not the termination of free radicals in polymer chains such as peroxy radicals, but was the depression of initial radical formation in polymer chains by thermal activation. The antioxidant molecule was assumed to delocalize the activated energy in polymer chains by the Boltzmann statics (distribution) to result in decrease in the probability of radical formation at a given temperature. The interaction distance (delocalization volume) by one antioxidant molecule was estimated to be 5–10 nm by the radius of sphere in polymer matrix, though the value would depend on the chemical structure of antioxidant. - Highlights: ► Interaction of antioxidant on polymer oxidation is discussed for thermal and radiation ageings. ► Antioxidant is very effective for thermal oxidation, but not for radiation induced oxidation. ► Interaction of antioxidant is not the termination reaction of radicals on polymers. ► Antioxidant is supposed to reduce the provability of polymer radical formation by thermal activation. ► Mechanism of polymer oxidation may not be chain reaction via peroxy radical and hydro-peroxide.

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

Science.gov (United States)

Dong, Guohui; Ai, Zhihui; Zhang, Lizhi

2014-12-01

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

Radical chemistry at a rural site (Wangdu) in the North China Plain: observation and model calculations of OH, HO2 and RO2 radicals

Science.gov (United States)

Tan, Zhaofeng; Fuchs, Hendrik; Lu, Keding; Hofzumahaus, Andreas; Bohn, Birger; Broch, Sebastian; Dong, Huabin; Gomm, Sebastian; Häseler, Rolf; He, Lingyan; Holland, Frank; Li, Xin; Liu, Ying; Lu, Sihua; Rohrer, Franz; Shao, Min; Wang, Baolin; Wang, Ming; Wu, Yusheng; Zeng, Limin; Zhang, Yinsong; Wahner, Andreas; Zhang, Yuanhang

2017-01-01

production at high NOx found in this study is consistent with the results from other field campaigns in urban environments, which underlines the need for better understanding of the peroxy radical chemistry for high NOx conditions.

Autoxidation of hydrazones. Some new insights.

Science.gov (United States)

Harej, Maja; Dolenc, Darko

2007-09-14

Autoxidation of hydrazones is a generally occurring reaction, leading mostly to the formation of alpha-azohydroperoxides. All structural kinds of hydrazones, having at least one hydrogen atom on nitrogen, are prone to autoxidation; however, there are marked differences in the rate of the reaction. Hydrazones of aliphatic ketones are 1-2 orders of magnitude more reactive than analogous derivatives of aromatic ketones. Even less reactive are the hydrazones of chalcones, which function also as efficient inhibitors of autoxidation of other hydrazones. These differences can be attributed to the reduction of the rate of the addition of oxygen to a hydrazonyl radical, which is a reversible reaction. In the case of conjugated ketones, it becomes endothermic, making this elementary step slow down and the chain termination reactions become important. Substituents influence the stability of hydrazonyl radicals and, consequently, the bond dissociation energies of the N-H bonds. In acetophenone phenylhydrazones, the substituents placed on the ring of hydrazine moiety exhibit a higher effect (Hammett rho = -2.8) than those on the ketone moiety (rho = -0.82), which denotes higher importance of the structure with spin density concentrated on nitrogen in delocalized hydrazonyl radical. Electronic effects of the substituents also affect the transition state for the abstraction of hydrogen atom by electrophilic peroxy radicals; NBO analysis display a negative charge transfer of about 0.4 eu from hydrazone to a peroxy radical in the transition state.

Oxidation of benzene by radiolytically produced OH radicals. [x rays

Energy Technology Data Exchange (ETDEWEB)

Klein, G W; Schuler, R H [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA)

1978-01-01

The radiolysis of N/sub 2/O saturated-aqueous solutions of benzene-/sup 14/C has been examined using radio-liquid chromatographic methods to follow the quantitative aspects of the reactions of hydroxycyclohexadienyl radicals. In the absence of a radical oxidant, at least five important products are produced. The total yield of 5.8 observed for the incorporation of benzene into products accounts for essentially all of the radicals initially produced from the water. Dimeric products predominate with a total yield of 4.1. Phenol is produced with a yield of only 0.8 indicating a disproportionation/combination ratio for hydroxycyclohexadienyl radicals of < = 0.4. In the presence of 2mM ferricyanide the hydroxycyclohexadienyl radicals are quantitatively oxidized to phenol with no trace (< 1%) remaining of dimeric or other high molecular weight products. The initial yield for phenol formation (6.0 molecules/100 eV) provides a measure for OH production in N/sub 2/O saturated aqueous solutions.

Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling.

Science.gov (United States)

Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas

2017-07-19

Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.

Polyphenolic Compounds and Free Radical Scavenging Activity in Eight Lamiaceae Herbs of Manipur

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Sandhyarani Devi KHOMDRAM

2011-05-01

Full Text Available Eight plants of Lamiaceae under subfamily Nepetoideae found in Manipur, India were selected for estimation of their polyphenolic compounds and free radical scavenging activity which is expressed on dry weight basis. In this present study, the total phenol and flavonoid contents as well as the free radical scavenging activity were studied using spectrophotometric method. The total phenol content was determined based on Folin-Ciocalteau reagent, flavonoid was determined by aluminium chloride spectrophotometric method and tannin by Folin Dennis Method. The free radical scavenging activity was determined by using DPPH radical which is expressed as IC50 (μg/ml. The total phenolic content varied from 21.39±0.927 to 46.28±0.543 mg/g, flavonoids content in the selected samples varied from 13.30±0.684 to 26.03±0.217 mg/g and tannin content varied from 8.72±0.160 to 17.04±0.206 mg/g. The free radical scavenging activity among the selected samples varied from 11.67±0.221 to 38.29±0.532 μg/ml. The correlation between the free radical scavenging activity with total phenol content (R2=0.511, with flavonoids (R2=0.241 and with tannin (R2=0.690 was calculated and maximum correlation value was found between tannin content and the free radical scavenging activity of the plant samples. The result supports that tannins were more responsible for free radical scavenging activity in the presently selected plants.

Total phenolic content, radical scavenging properties, and essential oil composition of Origanum species from different populations.

Science.gov (United States)

Dambolena, José S; Zunino, María P; Lucini, Enrique I; Olmedo, Rubén; Banchio, Erika; Bima, Paula J; Zygadlo, Julio A

2010-01-27

The aim of this work was to compare the antiradical activity, total phenol content (TPC), and essential oil composition of Origanum vulgare spp. virens, Origanum x applii, Origanum x majoricum, and O. vulgare spp. vulgare cultivated in Argentina in different localities. The experiment was conducted in the research station of La Consulta (INTA-Mendoza), the research station of Santa Lucia (INTA-San Juan), and Agronomy Faculty of National University of La Pampa, from 2007 to 2008. The composition of the essential oils of oregano populations was independent of cultivation conditions. In total, 39 compounds were identified in essential oils of oregano from Argentina by means of GC-MS. Thymol and trans-sabinene hydrate were the most prominent compounds, followed by gamma-terpinene, terpinen-4-ol, and alpha-terpinene. O. vulgare vulgare is the only Origanum studied which is rich in gamma-terpinene. Among tested oregano, O. x majoricum showed the highest essential oil content, 3.9 mg g(-1) dry matter. The plant extract of O. x majoricum had greater total phenol content values, 19.36 mg/g dry weight, than the rest of oregano studied. To find relationships among TPC, free radical scavenging activity (FRSA), and climate variables, canonical correlations were calculated. The results obtained allow us to conclude that 70% of the TPC and FRSA variability can be explained by the climate variables (R(2) = 0.70; p = 8.3 x 10(-6)), the temperature being the most important climatic variable.

Fast beam studies of free radical photodissociation

Energy Technology Data Exchange (ETDEWEB)

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

1993-12-01

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

Quality assessment of coffee beans with ESR and gamma-ray irradiation

International Nuclear Information System (INIS)

Ikeya, Motoji; Baffa, F.O.; Mascarenhas, Sergio

1989-01-01

Peroxy radical formation in raw coffee beans of different qualities and origins from all over the world has been studied with electron spin resonance (ESR) analysis. The γ-ray equivalent absorbed dose (ED) which creates the same concentration of radicals is obtained by the additive γ-ray irradiation of the coffee beans. The ED and the cup quality is somewhat inversely related suggesting that the peroxidation of the unsaturated fatty acid is somewhat indicative of the degree of the aromatic decomposition and rancidity. (author)

Synthesis and Characterization of Titanium Supported on High Order Nanoporous Silica and Application for Direct Oxidation of Benzene to Phenol

OpenAIRE

Alireza Badiei; Javad Gholami; Yeganeh Khaniani

2009-01-01

Direct oxidation of benzene to phenol in liquid phase by H2O2 peroxide was examined over Ti/ LUS-1 catalyst in methanol and acetic acid as solvents. The maximum yield and selectivity of the phenol produced was obtained in the presence of acetic acid. It can be attributed to the stabilization of H2O2 as peroxy acetic acid species in the radical mechanism for this reaction. Acetic acid interacts with hydrogen peroxide over Ti/LUS-1 and produces acetoxy radicals.

Synthesis and Characterization of Titanium Supported on High Order Nanoporous Silica and Application for Direct Oxidation of Benzene to Phenol

Directory of Open Access Journals (Sweden)

Alireza Badiei

2009-01-01

Full Text Available Direct oxidation of benzene to phenol in liquid phase by H2O2 peroxide was examined over Ti/ LUS-1 catalyst in methanol and acetic acid as solvents. The maximum yield and selectivity of the phenol produced was obtained in the presence of acetic acid. It can be attributed to the stabilization of H2O2 as peroxy acetic acid species in the radical mechanism for this reaction. Acetic acid interacts with hydrogen peroxide over Ti/LUS-1 and produces acetoxy radicals.

A Comparative Study of the Radical-scavenging Activity of the Phenolcarboxylic Acids Caffeic Acid, p-Coumaric Acid, Chlorogenic Acid and Ferulic Acid, With or Without 2-Mercaptoethanol, a Thiol, Using the Induction Period Method

Directory of Open Access Journals (Sweden)

Seiichiro Fujisawa

2008-10-01

Full Text Available Phenolcarboxylic acid antioxidants do not act in vivo as radical-scavengers in isolation, but rather together with GSH (glutathione, a coantioxidant, they constitute an intricate antioxidant network. Caffeic acid, p-coumaric acid, ferulic acid and chlorogenic acid with or without 2-mercaptoethanol (ME, as a substitute for GSH, was investigated by the induction period (IP method for polymerization of methyl methacrylate (MMA initiated by thermal decomposition of 2,2'-azobisisobutyronitrile (AIBN, a source of alkyl radicals, R. and benzoyl peroxide (BPO, a source of peroxy radicals, PhCOO. using differential scanning calorimetry (DSC. Upon PhCOO. radical scavenging, the stoichiometric factors (n, number of free radical trapped by one mole of antioxidant for caffeic acid, ferulic acid, p-coumaric acid and chlorogenic acid were 2.4, 1.8, 1.7 and 0.9, whereas upon R. radical scavenging, the corresponding values were 1.3, 1.2, 1.0 and 0.8, respectively. Antioxidants with n values close to 2 suggest the stepwise formation of semiquinone radicals and quinones. By contrast, those with n values close to 1 suggest the formation of dimers after single-electron oxidation, possibly due to recombination of corresponding aryloxy radicals. The ratio of the rate constant of inhibition to that of propagation (kinh/kp declined in the order chlorogenic acid > p-coumaric acid > ferulic acid > caffeic acid. The ratio of the observed IP for the phenolcarboxylic acid/2-mercapto-ethanol (ME mixture (1:1 molar ratio (A to the calculated IP (the simple sum of phenol acid antioxidant and ME (B was investigated. Upon R. scavenging, the caffeic acid or p-coumaric acid/ME mixture was A/B > 1, particularly the former was 1.2, suggesting a synergic effect. By contrast, upon PhCOO. scavenging, the corresponding mixture was A/B < 1, particularly the latter was 0.7, suggesting an antagonistic effect. Upon both radicals scavenging, the A/B for the ferulic acid or chlorogenic acid

Isoprene photochemistry over the Amazon rainforest

Science.gov (United States)

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; Rivera-Rios, Jean C.; Seco, Roger; Bates, Kelvin H.; Artaxo, Paulo; Duvoisin, Sergio; Keutsch, Frank N.; Kim, Saewung; Goldstein, Allen H.; Guenther, Alex B.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Springston, Stephen R.; Watson, Thomas B.; McKinney, Karena A.

2016-01-01

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK + MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. A value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). This abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest. PMID:27185928

Atmospheric chemistry of hydrofluorocarbons and hydrochlorofluorocarbons

Energy Technology Data Exchange (ETDEWEB)

Sehested, J

1995-03-01

Pulse radiolysis coupled with a time resolved UV absorption detection system and a FTIR spectrometer coupled to a 140 l reaction chamber was used to study the degradation of HCFCs and HFCs in the atmosphere. Reaction rates for a series of reactions of HFCs and HCFCs were investigated: F + RH, R + O{sub 2} + RO{sub 2} + NO, and RO{sub 2} + NO{sub 2} + M, together with UV absorption spectra of the halogenated alkyl (R) and halogenated alkyl peroxy radicals (RO{sub 2}). The products following the self reactions for RO{sub 2} radicals for RO{sub 2} = CF{sub 3}CF{sub 2}O{sub 2}, CF{sub 2}HCF{sub 2}O{sub 2}, CF{sub 3}CH{sub 2}O{sub 2}, CFH{sub 2}CFHO{sub 2}, CF{sub 3}O{sub 2}, and CF{sub 3}C(O)O{sub 2} were investigated by the FTIR setup. The results show that the self reaction of halogenated peroxy radicals give the alkoxy radical, RO, as product. The atmospheric fate of these radicals were C-C bond cleavage for CF{sub 3}CF{sub 2}O, CHF{sub 2}CF{sub 2}O, CFH{sub 2}CHFO, and CF{sub 3}C(O)O; while CF{sub 3}CH{sub 2}O radicals rect with O{sub 2} to give CF{sub 3}CHO and HO{sub 2}. the reaction between CFH{sub 2}O{sub 2} and HO{sub 2} was shown to give 29{+-}7 % CH{sub 2}FCOOH and 72{+-}11 % HCOF as the carbon containing products. (Abstract Truncated)

Psychopathology according to behaviorism: a radical restatement.

Science.gov (United States)

Pérez-Alvarez, Marino

2004-11-01

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

Waste water processing with radiation; destruction of organic pollution in water

International Nuclear Information System (INIS)

Micic, O.

1977-06-01

The mechanism of phenol degradation in irradiated aqueous solutions has been studied by means of pulse radiolysis and kinetic absorption spectrometry. G(-phenol) value depends on the dose rate, phenol concentration and the presence of oxygen in solution. The phenol peroxy radical formed during radiolysis is unstable and does not initiate chain reactions. It is the O 2 - radical that reacts with phenol to initiate an autodegradation chain. Rate constants for individual steps in the chain reaction scheme have been determined in both de-aerated and oxygenated solutions

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

Directory of Open Access Journals (Sweden)

Zhuowei Xue

2016-05-01

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

Free Radical Scavenging Properties of Annona squamosa

Science.gov (United States)

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

2017-10-26

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

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

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?

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

Science.gov (United States)

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

2016-04-01

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

Radicalization In Pakistan And The Spread Of Radical Islam In Pakistan

Directory of Open Access Journals (Sweden)

Bahir ahmad

2015-08-01

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

Antioxidant Activities of Total Pigment Extract from Blackberries

Directory of Open Access Journals (Sweden)

Jiechao Liu

2005-01-01

Full Text Available Total pigment has been extracted from blackberries and its antioxidant activity against lipid peroxidation and scavenging capacities towards superoxide anion radicals, hydroxyl radicals and nitrite in different in vitro systems have been investigated. The total pigment extract from blackberries (TPEB exhibited strong antioxidant activity against lipid peroxidation in a linoleic acid model system and scavenging capacities towards superoxide anion radicals, generated by a pyrogallol autoxidation system or by an illuminating riboflavin system, hydroxyl radicals generated by Fenton reaction, and nitrite. Furthermore, the antioxidant activities were correlated with the concentrations of the TPEB. In the test concentration range, the maximum inhibition percentage against linoleic acid peroxidation was 98.32 % after one week’s incubation, and the maximum scavenging percentages for the free radicals and nitrite inhibition in the above reactive systems reached 90.48, 96.48, 93.58 and 98.94 %, respectively. The TPEB is a natural, edible colorant with excellent antioxidant activities and health benefits and it seems to be applicable in both healthy food and medicine.

Early enteral nutrition and total parenteral nutrition on the nutritional status and blood glucose in patients with gastric cancer complicated with diabetes mellitus after radical gastrectomy.

Science.gov (United States)

Wang, Junli; Zhao, Jiamin; Zhang, Yanling; Liu, Chong

2018-07-01

Effects of early enteral nutrition (EEN) or total parenteral nutrition (TPN) support on nutritional status and blood glucose in patients with gastric cancer complicated with diabetes mellitus after radical gastrectomy were investigated. One hundred and twenty-nine patients with gastric cancer complicated with diabetes mellitus type 2 admitted to the First People's Hospital of Jinan (Jinan, China), from June 2012 to June 2016 were selected into the study. According to different nutrition support pathways, these patients were randomly divided into the EEN group and the TPN group. The improvement of nutritional indexes, postoperative complications, gastrointestinal function recovery and perioperative blood glucose fluctuation were compared between the two groups. On the 4th day after operation, the improvement levels of total bilirubin (TBL), alanine aminotransferase (ALT), aspartate transaminase (AST), total protein (TP), prealbumin (PAB), hemoglobin (HGB) and weight (Wt) in the EEN group were significantly higher than those in the conventional group (P0.05). No patients had complications in the EEN group, while a total of 29 patients in the TPN group suffered adverse reactions, indicating that the incidence rate of complications in the EEN group was significantly lower than that in the TPN group (Pnutrition for patients with gastric cancer complicated with diabetes mellitus after radical gastrectomy, which is worthy of clinical promotion as it maintains good nutritional status, produces few postoperative complications and keeps the blood glucose level stable, by which the postoperative evacuation time is early, the hospitalization time is short and the cost is low.

Contemporary open and robotic radical prostatectomy practice patterns among urologists in the United States.

Science.gov (United States)

Lowrance, William T; Eastham, James A; Savage, Caroline; Maschino, A C; Laudone, Vincent P; Dechet, Christopher B; Stephenson, Robert A; Scardino, Peter T; Sandhu, Jaspreet S

2012-06-01

We describe current trends in robotic and open radical prostatectomy in the United States after examining case logs for American Board of Urology certification. American urologists submit case logs for initial board certification and recertification. We analyzed logs from 2004 to 2010 for trends and used logistic regression to assess the impact of urologist age on robotic radical prostatectomy use. A total of 4,709 urologists submitted case logs for certification between 2004 and 2010. Of these logs 3,374 included 1 or more radical prostatectomy cases. Of the urologists 2,413 (72%) reported performing open radical prostatectomy only while 961 (28%) reported 1 or more robotic radical prostatectomies and 308 (9%) reported robotic radical prostatectomy only. During this 7-year period we observed a large increase in the number of urologists who performed robotic radical prostatectomy and a smaller corresponding decrease in those who performed open radical prostatectomy. Only 8% of patients were treated with robotic radical prostatectomy by urologists who were certified in 2004 while 67% underwent that procedure in 2010. Median age of urologists who exclusively performed open radical prostatectomy was 43 years (IQR 38-51) vs 41 (IQR 35-46) for those who performed only robotic radical prostatectomy. While the rate was not as high as the greater than 85% industry estimate, 67% of radical prostatectomies were done robotically among urologists who underwent board certification or recertification in 2010. Total radical prostatectomy volume almost doubled during the study period. These data provide nonindustry based estimates of current radical prostatectomy practice patterns and further our understanding of the evolving surgical treatment of prostate cancer. Copyright © 2012 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Enhanced Oxidation of Isoprene and Monoterpenes in High and Low NOx Conditions

Science.gov (United States)

Tokarek, T. W.; Gilman, J.; Lerner, B. M.; Koss, A.; Yuan, B.; Taha, Y. M.; Osthoff, H. D.; Warneke, C.; De Gouw, J. A.

2015-12-01

In the troposphere, the photochemical oxidation of volatile organic compounds (VOCs) is primarily initiated by their reactions with the hydroxyl radical (OH) which yields peroxy radicals (HO2 and RO2). Concentrations of OH and the rates of VOC oxidation depend on the efficiency of peroxy radical recycling to OH. Radical recycling mainly occurs through reaction of HO2 with NO to produce NO2 and, ultimately, ozone (O3). Hence, the rate of VOC oxidation is dependent on NOx (=NO+NO2) concentration. The Shale Oil and Natural Gas Nexus (SONGNEX) campaign was conducted from March 17 to April 29, 2015 with the main goal of identifying and quantifying industrial sources of pollutants throughout the United States, in particular those associated with the production of oil and natural gas. In this work, a case study of biogenic VOC oxidation within and outside a power plant plume in the Haynesville basin near the border of Texas and Louisiana is presented. Isoprene, monoterpenes and their oxides were measured by H3O+ chemical ionization mass spectrometry (H3O+ CIMS) in high time resolution (1 s). Further, an improved Whole Air Sampler (iWAS) was used to collect samples for post-flight analysis by gas chromatography mass spectrometric detection (GC-MS) and yielded speciated quantification of biogenic VOCs. The monoterpene oxide to monoterpene ratio follows the spatial extent of the plume as judged by another tracer (NOx), tracking the enhancement of oxidation rates by NOx. The observations are rationalized with the aid of box modeling using the Master Chemical Mechanism (MCM).

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...

Effect of storage conditions on graft of polypropylene non-woven fabric induced by electron beam

Energy Technology Data Exchange (ETDEWEB)

Lee, Jin Young; Jeun, Joon Pyo; Kang, Phil Hyun [Radiation Research Dvision for Industry and Environment, Korea Atomic Energy Research Institute, Jeongeup(Korea, Republic of)

2015-05-15

In this study, we fabricated effect of storage conditions on graft of polypropylene (PP) non-woven fabric induced by electron beam. The electron beam irradiations on PP non-woven fabric were carried out over a range of irradiation doses from 25 to 100 kGy to make free radicals on fabric surface. The radical measurement was established by electron spin resonance (ESR) for confirming the changes of the alkyl radical and peroxy radical according to effect of storage time, storage temperature and atmosphere. It was observed that the free radicals were increased with irradiation dose and decreased with storage time due to the continuous oxidation. However, the radical extinction was significantly delayed due to reduced mobility of radicals at extremely low temperature. The degree of graft based on the analysis of ESR was investigated. The conditions of graft reaction were set at a temperature: 60 degrees Celcius, reaction time: 6 hours and styrene monomer concentration: 20 wt%.

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)

Phytochemical Screening and Free Radical Scavenging Activities of ...

African Journals Online (AJOL)

Total phenolic, total flavonoid and proanthocyanidin contents were 65, 0.07 and 2.38 mg/g of powdered plant material for AF fruits, and 12, 51.35, 19.5 mg/g of powdered plant material for AF leaves as gallic acid, rutin and catechin equivalents respectively. Conclusion: AF leaves are five times more potent as a free radical ...

Radical pancreatectomy: postoperative evaluation by CT

Energy Technology Data Exchange (ETDEWEB)

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

1984-10-01

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

Radical pancreatectomy: postoperative evaluation by CT

International Nuclear Information System (INIS)

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

1984-01-01

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

In vitro free radical scavenging activity of ethanolic extract of the whole plant of Evolvulus alsinoides (L.) L.

Science.gov (United States)

Gomathi, Duraisamy; Ravikumar, Ganesan; Kalaiselvi, Manokaran; Vidya, Balasubramaniam; Uma, Chandrasekar

2015-06-01

To identify the free radical scavenging activity of ethanolic extract of Evolvulus alsinoides. The free radical scavenging activity was evaluated by in vitro methods like reducing power assay, total antioxidant activity, 2,2-diphenyl-1-picrylhydrazyl (DPPH) reduction, superoxide radical scavenging activity, 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS(+)) scavenging activity, hydroxyl radical scavenging assay, and nitric oxide radical scavenging assay, which were studied by using ascorbic acid as standard. The extract showed significant activities in all antioxidant assays compared with the reference antioxidant ascorbic acid. The total antioxidant activity as well as the reducing power was also found to increase in a dose-dependent manner. Evolvulus alsinoides may act as a chemopreventive agent, providing antioxidant properties and offering effective protection from free radicals.

Analysis of Hydroperoxides in solid Polyethylene by NMR and EPR Spectroscopy

International Nuclear Information System (INIS)

Assink, Roger A.; Celina, Mathias C.; Dunbar, Timothy D.; Alam, Todd M.; Clough, Roger Lee; Gillen, Kenneth T.

2000-01-01

The authors have shown that the hydroperoxide species in γ-irradiated 13 C-polyethylene can be directly observed by 13 C MAS NMR spectroscopy. The experiment was performed without the need for special sample preparation such as chemical derivatization or dissolution. Annealing experiments were employed to study the thermal decomposition of the hydroperoxide species and to measure an activation energy of 98 kJ/mol. EPR spectroscopy suggests that residual polyenyl and alkylperoxy radicals are predominantly trapped in interracial or crystalline regions, while the peroxy radicals observed after UV-photolysis of hydroperoxides are in amorphous regions

Airborne observations of total RONO2: new constraints on the yield and lifetime of isoprene nitrates

Directory of Open Access Journals (Sweden)

W. H. Brune

2009-02-01

Full Text Available Formation of isoprene nitrates (INs is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (ΣANs, NO2, total peroxy nitrates (ΣPNs, HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the lower free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%, (8%, 2.5 h, 79% and (12%, 95 min, 67%. The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that

The role of bromine and chlorine chemistry for arctic ozone depletion events in Ny-Ålesund and comparison with model calculations

Directory of Open Access Journals (Sweden)

M. Martinez

1999-07-01

Full Text Available During the Arctic Tropospheric Ozone Chemistry (ARCTOC campaigns at Ny-Ålesund, Spitsbergen, the role of halogens in the depletion of boundary layer ozone was investigated. In spring 1995 and 1996 up to 30 ppt bromine monoxide were found whenever ozone decreased from normal levels of about 40 ppb. Those main trace gases and others were specifically followed in the UV-VIS spectral region by differential optical absorption spectroscopy (DOAS along light paths running between 20 and 475 m a.s.l.. The daily variation of peroxy radicals closely followed the ozone photolysis rate J(O3(O1D in the absence of ozone depletion most of the time. However, during low ozone events this close correlation was no longer found because the measurement of radicals by chemical amplification (CA turned out to be sensitive to peroxy radicals and ClOx. Large CA signals at night can sometimes definitely be assigned to ClOx and reached up to 2 ppt. Total bromine and iodine were both stripped quantitatively from air by active charcoal traps and measured after neutron activation of the samples. Total bromine increased from background levels of about 15 ppt to a maximum of 90 ppt during an event of complete ozone depletion. For the spring season a strong source of bromine is identified in the pack ice region according to back trajectories. Though biogenic emission sources cannot be completely ruled out, a primary activation of halogenides by various oxidants seems to initiate an efficient autocatalytic process, mainly driven by ozone and light, on ice and perhaps on aerosols. Halogenides residing on pack ice surfaces are continuously oxidised by hypohalogenous acids releasing bromine and chlorine into the air. During transport and especially above open water this air mixes with upper layer pristine air. As large quantities of bromine, often in the form of BrO, have been observed at polar sunrise also around Antarctica, its release seems to be a natural phenomenon. The

Hearing Status after Radical Mastoidectomy without Tympanoplasty.

Science.gov (United States)

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

2017-12-01

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

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)

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.

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.

Radiolytic degradation of paracetamol in dilute aqueous solution

International Nuclear Information System (INIS)

Szabo, L.; Toth, T.; Homlok, R.; Takacs, E.; Wojnarovits, L.

2011-01-01

Complete text of publication follows. Paracetamol or with name acetaminophen is widely used as analgesic and antipyretic drug. Due to its heavy use it is regularly detected in the surface waters. The degradation of the compound formerly was studied in several advanced oxidation processes (UV/H 2 O 2 , UV/TiO 2 , electrochemical oxidation, ozonation). Here we report on the radiolytic degradation. In the experimental work we combined a wide variety of techniques. For the investigation of the intermediates pulse radiolysis, for end-product experiments (decolouration, mineralization) gamma irradiation were used together with UV-Vis spectroscopy, HPLC separation (with diode array and MS-MS detection), chemical oxygen demand, total organic carbon content and toxicity measurements. · OH radicals are the main oxidative species during irradiation. They add to the aromatic ring producing hydroxycyclohexadienyl type radicals. These radicals either transform to hydroxy-paracetamol stable products in several reaction steps, or after water elimination transform to semi-iminoquinone radical. The reaction of hydroxycyclohexadienyl radicals with O 2 yields peroxi radicals. The latter radicals may eliminate HO 2 · or undergo ring opening and transformation, first to different carboxylic acids, and finally (mineralization) to CO 2 , H 2 O and NH 3 or NO 2 . Paracetamol has a relatively low toxicity. In 10 -3 mol dm -3 DCF solution after irradiation some products (e.g. hydroquinone, acetamide) are more toxic than paracetamol. By increasing the dose the toxicity suddenly decreases. It seems that the toxic products are highly sensitive to irradiation treatment.

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.

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...

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.

Kombucha Tea Ameliorates Trichloroethylene Induced Hepatic Damages in Rats via Inhibition of Oxidative Stress and Free Radicals Induction

International Nuclear Information System (INIS)

Gharib, O.A.; Gharib, M.A.

2008-01-01

Kombucha Tea (KT) is reported to exhibit a wide variety of biological effects, including antioxidant. Evidence shows the important role of oxidative stress in the hepatic damage. The aim of this study is to investigate the possible protective effects of oral administration of KT in rats with trichloroethylene (TCE)-induced damage for ten consecutive days. Hepatic damage was evaluated by measuring total free radicals levels, biochemical and histological examinations. Serum gamma glutamyl transferase (GGT) activity (the hepatic damage marker), total protein, albumin and globulin as well as malonaldehyde (MDA), glutathione (GSH) content, nitric oxide (NO) concentration were evaluated in liver tissue homogenates. Total free radicals concentration in blood was examined by electron spin resonance (ESR). Total protein, DNA concentration, cell number and cell size in liver tissues were also examined. The rats orally administrated with TCE for ten days indicates hepatic damage changes, an increase in blood total free radicals concentration was observed, serum GGT activity, liver MDA, NO levels, total protein and decreased GSH content, DNA concentration and cell number. This accompanied with an increase in cell size of liver tissues, whereas KT reversed these effects. Furthermore, KT inhibits the concentration of total free radicals in blood and decreasing the increment of MDA and NO concentration. Histological studies reveal partial healing in those rats treated by KT after oral administration with TCE. The present results suggest that KT ameliorates TCE induced hepatic damage in rats probably due to its content of glucuronic, acetic acid and B vitamins via inhibition of oxidative stress and total free radicals

Total and ionization cross sections of electron scattering by fluorocarbons

International Nuclear Information System (INIS)

Antony, B K; Joshipura, K N; Mason, N J

2005-01-01

Electron impact total cross sections (50-2000 eV) and total ionization cross sections (threshold to 2000 eV) are calculated for typical plasma etching molecules CF 4 , C 2 F 4 , C 2 F 6 , C 3 F 8 and CF 3 I and the CF x (x 1-3) radicals. The total elastic and inelastic cross sections are determined in the spherical complex potential formalism. The sum of the two gives the total cross section and the total inelastic cross section is used to calculate the total ionization cross sections. The present total and ionization cross sections are found to be consistent with other theories and experimental measurements, where they exist. Our total cross section results for CF x (x = 1-3) radicals presented here are first estimates on these 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...

Spectroscopic studies of neutral and chemically oxidized species of β-carotene, lycopene and norbixin in CH2Cl2: Fluorescence from intermediate compounds

International Nuclear Information System (INIS)

Alwis, D.D.D.H; Chandrika, U.G.; Jayaweera, P.M.

2015-01-01

Radical cations, dications and oxidized intermediate species of three carotenoids, namely, β-carotene, lycopene and norbixin, were generated in CH 2 Cl 2 solutions via chemical oxidation using anhydrous FeCl 3 . UV–vis, fluorescence and fluorescence-excitation spectroscopic studies were performed to understand and compare the nature of intermediate species generated during the chemical oxidation process and subsequent degradation. The intense emission observed at 550 nm can be assigned to the S 2 →S 0 (1 1 B u →1 1 A g ) transition of the carotenoid molecules. The 350 nm excitation during the oxidation process for β-carotene, lycopene and norbixin exhibit intense fluorescence peaks at 492 nm, 493 nm and 500 nm, respectively. These peaks are assigned to intermediate peroxy/epoxy compounds of the three molecules that are formed with molecular oxygen prior to the formation of oxidized short-chain stable compounds. - Highlights: • Fluorescence and UV–vis studies on β-carotene, lycopene and norbixin. • Oxidation, induced by FeCl 3 in CH 2 Cl 2 shows blue shifted fluorescence peaks. • Fluorescence peaks were assigned to intermediate peroxy/epoxy forms of carotenoids. • The D0→D3 transition of radical cations are observed in the near IR region

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

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.

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.

Radical-scavenging-linked antioxidant activities of extracts from black chokeberry and blueberry cultivated in Korea.

Science.gov (United States)

Hwang, Seok Joon; Yoon, Won Byong; Lee, Ok-Hwan; Cha, Seung Ju; Kim, Jong Dai

2014-03-01

The objective of this study was to investigate the radical-scavenging-linked antioxidant properties of the extracts from black chokeberry and blueberry cultivated in Korea. The 70% ethanol extracts were prepared from black chokeberry and blueberry, and evaluated for total phenolic content, total flavonoid content, total proanthocyanidin content, and antioxidative activities, using various in vitro assays, such as DPPH(2,2-diphenyl-1-picrylhydrazyl), ABTS(2,2-azino-bis-(3-ethylenebenzothiozoline-6-sulphonic acid)) radical-scavenging activity, FRAP(ferric-reducing antioxidant power) and reducing power. The major phenolic compounds, including cyanidin-3-galactoside, cyanidin-3-arabinoside, neochlorogenic acid, procyanidin B1, were analysed by HPLC with a photodiode array detector. Results showed that total phenol, flavonoid and proanthocyanidin contents of black chokeberry extract were higher than those of blueberry extract. In addition, black chokeberry extract exhibited higher free radical-scavenging activity and reducing power than did blueberry extract. Cyanidin-3-galactoside was identified as a major phenolic compound, with considerable content in black chokeberry, that correlated with its higher antioxidant and radical-scavenging effects. These results suggest that black chokeberry extracts could be considered as a good source of natural antioxidants and functional food ingredients. Copyright © 2013 Elsevier Ltd. All rights reserved.

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)

Quantification of Phenolic Compounds and In Vitro Radical Scavenging Abilities with Leaf Extracts from Two Varieties of Psidium guajava L.

Science.gov (United States)

Camarena-Tello, Julio César; Martínez-Flores, Héctor Eduardo; Garnica-Romo, Ma Guadalupe; Padilla-Ramírez, José Saúl; Saavedra-Molina, Alfredo; Alvarez-Cortes, Osvaldo; Bartolomé-Camacho, María Carmen; Rodiles-López, José Octavio

2018-02-27

Guava leaf ( Psidium guajava L.) extracts are used in both traditional medicine and the pharmaceutical industry. The antioxidant compounds in P. guajava leaves can have positive effects including anti-inflammatory, anti-hyperglycemic, hepatoprotective, analgesic, anti-cancer effects, as well as protecting against cardiovascular diseases. In the present study, phenolic compounds and in vitro antioxidant capacity were measured in extracts obtained with polar and non-polar solvents from leaves of two varieties of guava, Calvillo Siglo XXI and Hidrozac. The quantity of total phenolics and total flavonoids were expressed as equivalents of gallic acid and quercetin, respectively. Hydroxyl radical, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and Oxygen Radical Absorbance Capacity using fluorescein (ORAC-FL) in vitro tests were used to assess the radical scavenging abilities of the extracts. The total phenolics were higher in the aqueous fraction of the variety Calvillo Siglo XXI, while in the Hidrozac variety total phenolics were higher in the acetone and chloroform fractions. Total flavonoids were higher in all fractions in the variety Calvillo Siglo XXI. Total phenolics showed a highly positive correlation for ORAC-FL, and a moderately positive correlation with hydroxyl radicals. Finally, total flavonoids showed a slightly positive correlation for ORAC-FL and hydroxyl radicals. Both varieties of guava leaf extract showed excellent antioxidant properties.

Quantification of Phenolic Compounds and In Vitro Radical Scavenging Abilities with Leaf Extracts from Two Varieties of Psidium guajava L.

Directory of Open Access Journals (Sweden)

Julio César Camarena-Tello

2018-02-01

Full Text Available Guava leaf (Psidium guajava L. extracts are used in both traditional medicine and the pharmaceutical industry. The antioxidant compounds in P. guajava leaves can have positive effects including anti-inflammatory, anti-hyperglycemic, hepatoprotective, analgesic, anti-cancer effects, as well as protecting against cardiovascular diseases. In the present study, phenolic compounds and in vitro antioxidant capacity were measured in extracts obtained with polar and non-polar solvents from leaves of two varieties of guava, Calvillo Siglo XXI and Hidrozac. The quantity of total phenolics and total flavonoids were expressed as equivalents of gallic acid and quercetin, respectively. Hydroxyl radical, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS, 2,2-diphenyl-1-picrylhydrazyl (DPPH, and Oxygen Radical Absorbance Capacity using fluorescein (ORAC-FL in vitro tests were used to assess the radical scavenging abilities of the extracts. The total phenolics were higher in the aqueous fraction of the variety Calvillo Siglo XXI, while in the Hidrozac variety total phenolics were higher in the acetone and chloroform fractions. Total flavonoids were higher in all fractions in the variety Calvillo Siglo XXI. Total phenolics showed a highly positive correlation for ORAC-FL, and a moderately positive correlation with hydroxyl radicals. Finally, total flavonoids showed a slightly positive correlation for ORAC-FL and hydroxyl radicals. Both varieties of guava leaf extract showed excellent antioxidant properties.

Quantification of Phenolic Compounds and In Vitro Radical Scavenging Abilities with Leaf Extracts from Two Varieties of Psidium guajava L.

Science.gov (United States)

Martínez-Flores, Héctor Eduardo; Garnica-Romo, Ma. Guadalupe; Padilla-Ramírez, José Saúl; Saavedra-Molina, Alfredo; Alvarez-Cortes, Osvaldo; Bartolomé-Camacho, María Carmen; Rodiles-López, José Octavio

2018-01-01

Guava leaf (Psidium guajava L.) extracts are used in both traditional medicine and the pharmaceutical industry. The antioxidant compounds in P. guajava leaves can have positive effects including anti-inflammatory, anti-hyperglycemic, hepatoprotective, analgesic, anti-cancer effects, as well as protecting against cardiovascular diseases. In the present study, phenolic compounds and in vitro antioxidant capacity were measured in extracts obtained with polar and non-polar solvents from leaves of two varieties of guava, Calvillo Siglo XXI and Hidrozac. The quantity of total phenolics and total flavonoids were expressed as equivalents of gallic acid and quercetin, respectively. Hydroxyl radical, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), 2,2-diphenyl-1-picrylhydrazyl (DPPH), and Oxygen Radical Absorbance Capacity using fluorescein (ORAC-FL) in vitro tests were used to assess the radical scavenging abilities of the extracts. The total phenolics were higher in the aqueous fraction of the variety Calvillo Siglo XXI, while in the Hidrozac variety total phenolics were higher in the acetone and chloroform fractions. Total flavonoids were higher in all fractions in the variety Calvillo Siglo XXI. Total phenolics showed a highly positive correlation for ORAC-FL, and a moderately positive correlation with hydroxyl radicals. Finally, total flavonoids showed a slightly positive correlation for ORAC-FL and hydroxyl radicals. Both varieties of guava leaf extract showed excellent antioxidant properties. PMID:29495514

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

Impact of metabolic syndrome on early recovery of continence after robot-assisted radical prostatectomy.

Science.gov (United States)

Nishikawa, Masatomo; Watanabe, Hiromitsu; Kurahashi, Toshifumi

2017-09-01

To evaluate the impact of metabolic syndrome on the early recovery of urinary continence after robot-assisted radical prostatectomy. The present study included a total of 302 consecutive Japanese patients with clinically localized prostate cancer who underwent robot-assisted radical prostatectomy. In this study, postoperative urinary continence was defined as no leak or the use of a security pad. The continence status was assessed by interviews before and 1 and 3 months after robot-assisted radical prostatectomy. Metabolic syndrome was defined as follows: body mass index ≥25 kg/m 2 and two or more of the following: hypertension, diabetes mellitus and dyslipidemia. The effect of the presence of metabolic syndrome on the continence status of these patients was retrospectively examined. A total of 116 (38.4%) and 203 (67.2%) of the 302 patients were continent at 1 and 3 months after robot-assisted radical prostatectomy, respectively. A total of 31 (10.3%) patients were judged to have metabolic syndrome. Despite the operative time being longer in patients with metabolic syndrome, no significant differences were observed in the remaining preoperative, intraoperative or postoperative variables between patients with or without metabolic syndrome. On multivariate logistic regression analysis, metabolic syndrome and the duration of hospitalization were significantly correlated with the 1-month continence status. Similarly, metabolic syndrome and estimated blood loss during surgery were independent predictors of continence rates at 3 months after robot-assisted radical prostatectomy. These findings suggest that the presence of metabolic syndrome could have a significant impact on the early recovery of urinary continence after robot-assisted radical prostatectomy. © 2017 The Japanese Urological Association.

Nitrate radical oxidation of γ-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields

Science.gov (United States)

Slade, Jonathan H.; de Perre, Chloé; Lee, Linda; Shepson, Paul B.

2017-07-01

Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/-3) %, total ON yield = 14(+3/-2) %, and SOA yield ≤ 10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography-mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.

Quality of life in advanced maxillary sinus cancer after radical versus conservative maxillectomy.

Science.gov (United States)

Liu, Liting; Liu, Dan; Guo, Qiyun; Shen, Bin

2013-07-01

A study of patients with advanced maxillary sinus cancer who underwent radical or conservative maxillectomy was performed to show the differences between the 2 groups in patients' survival rate and quality of life (QOL). A total of 61 advanced maxillary sinus cancer patients from Weifang People's Hospital in China were traced: 27 radical maxillectomy and 34 conservative maxillectomy. Survival rate was compared between the 2 groups. Quality of life assessments were performed at the time of preoperation as well as 6, 12, and 18 months after the operation. Measures included the University of Washington-QOL scale (UW-QOL) and the Hospital Anxiety and Depression Scale. The UW-QOL scale scores of the composite score, appearance, activity, recreation, swallowing, speech, and chewing in the conservative surgical group were much higher than those in the radical surgical group. However, there is no big difference in total survival rate between these 2 groups. Also, no significant difference can be seen in the scores of pain, employment, and shoulder between the 2 groups. At the 6-month follow-up, the radical maxillectomy had more effects on anxiety than the conservative maxillectomy, while they are almost equally effective on depression. The 12-month and 18-month follow-ups showed that the radical maxillectomy made a greater impact on both anxiety and depression than the conservative maxillectomy. Conservative maxillectomy is more effective than radical maxillectomy to preserve the QOL of patients with advanced maxillary sinus cancer.

Aging effect on radiation-induced degradation of polypropylene

International Nuclear Information System (INIS)

Imai, M.; Sekiguchi, M.; Tabei, M.; Yamada, Y.; Shimizu, H.

1995-01-01

PP sheets and films were irradiated with γ-ray and with high energy electron beam. The mechanical degradation, decay of peroxy radical and the variation of molecular weight with storage time were measured. The variation of molecular weight corresponded to mechanical degradation. The molecular weight of sheet sample at which elongation falls to zero was much higher than that of film sample. The relation between mechanical degradation and sample thickness was discussed. (author)

Comparison between Two Bromine Containing Free Radical Initiators in PRESAGE®

Energy Technology Data Exchange (ETDEWEB)

Park, Hyeonsuk; Ryu, Dongmin; Ye, Sung-Joon [Seoul National University, Seoul (Korea, Republic of)

2016-10-15

PRESAGE® is an optically clear 3-D polyurethane dosimeter which contains a halogenated carbon as a free radical initiator and leucomalachite dye. The change of the optical density is known to be linear with respect to the absorbed dose and the sensitivity is related to the carbon–halogen bond dissociation energy of the free radical initiator. Although there are some studies regarding free radical initiators and dye materials, there’s a lack of reports about the effect of other elements like LMG solvent which can be added when there’s a difficulty mixing materials. Also, there are some studies about comparison between free radicals with different kind of halogen atoms but there’s a lack of studies of comparison between initiators with the same halogen atom. In this experiments, two kinds of halocarbon free radical initiator with the same halogen atom (bromine) as well as the effect of the LMG solvent were studied to use the dosimeter as a therapeutic purpose. Effective atomic numbers were also calculated. The initiators with the same halogen atom, CBr{sub 4} and C{sub 2}H{sub 2}Br{sub 4}, reacted totally differently. CBr{sub 4} was more sensitive to the radiation and emitted maximum 4 times more free radicals upon irradiation with no additional effective atomic number but the absorbance after irradiation was highly variable with time. For stable measurement, C{sub 2}H{sub 2}Br{sub 4} would be more appropriate as a free radical initiator.

Comprehensive measurements of atmospheric OH reactivity and trace species within a suburban forest near Tokyo during AQUAS-TAMA campaign

Science.gov (United States)

Ramasamy, Sathiyamurthi; Nagai, Yoshihide; Takeuchi, Nobuhiro; Yamasaki, Shohei; Shoji, Koki; Ida, Akira; Jones, Charlotte; Tsurumaru, Hiroshi; Suzuki, Yuhi; Yoshino, Ayako; Shimada, Kojiro; Nakashima, Yoshihiro; Kato, Shungo; Hatakeyama, Shiro; Matsuda, Kazuhide; Kajii, Yoshizumi

2018-07-01

Total OH reactivity, which gives the instantaneous loss rate of OH radicals due to reactive species, is an invaluable technique to understand regional air quality, as it gives the overall reactivity of the air mass, the fraction of each trace species reactive to OH, the fraction of missing sinks, O3 formation potential, etc. Total OH reactivity measurement was conducted in a small suburban forest located ∼30 km from Tokyo during the air quality study at field museum TAMA (AQUAS-TAMA) campaign in early autumn 2012 and summer 2013. The average measured OH reactivities during that autumn and summer were 7.4 s-1 and 11.4 s-1, respectively. In summer, isoprene was the major contributor, accounting for 28.2% of the OH reactivity, as a result of enhanced light-dependent biogenic emission, whereas NO2 was major contributor in autumn, accounting for 19.6%, due to the diminished contribution from isoprene as a result of lower solar strength. Higher missing OH reactivity 34% was determined in summer, and linear regression analysis showed that oxygenated VOCs could be the potential candidates for missing OH reactivity. Lower missing OH reactivity 25% was determined in autumn and it was significantly reduced (11%) if the interference of peroxy radicals to the measured OH reactivity were considered.

Photodissociation of anisole and absolute photoionization cross-section of the phenoxy radical.

Science.gov (United States)

Xu, Hong; Pratt, S T

2013-11-21

We have studied the photodissociation dynamics of anisole (C6H5OCH3) at 193 nm and determined the absolute photoionization cross-section of the phenoxy radical at 118.2 nm (10.486 eV) relative to the known cross-section of the methyl radical. Even at this energy, there is extensive fragmentation of the phenoxy radical upon photoionization, which is attributed to ionizing transitions that populate low-lying excited electronic states of the cation. For phenoxy radicals with less than ∼1 eV of internal energy, we find a cross-section for the production of the phenoxy cation of 14.8 ± 3.8 Mb. For radicals with higher internal energy, dissociative ionization is the dominant process, and for internal energies of ∼2.7-3.7 eV, we find a total cross-section (photoionization plus dissociative ionization) of 22.3 ± 4.1 Mb. The results are discussed relative to the recently reported photoionization cross-section of phenol.

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.

Serum total anti-oxidant capacity of some Nigerian cigarette smokers

African Journals Online (AJOL)

Abstract. Cigarette smoke has been reported to contain free radicals. The interaction of these free radicals with the body defense system and associated health risk among Nigerian smokers have remained scarcely investigated despite the high numbers of smokers in our society. This study thus, investigates the serum total ...

Radiolysis of paracetamol in dilute aqueous solution

Science.gov (United States)

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

2012-09-01

Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O2 is c.a. 10%. The efficiency is 2-3 times higher in the presence of O2 due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily.

Radiation Chemistry of Xenon Trioxide, Xenate and Perxenate and Photochemistry of Perxenate - A Pulse Radiolysis and Laser Flash-Photolysis Study

DEFF Research Database (Denmark)

Kläning, U. K.; Sehested, Knud; Wolff, T.

1982-01-01

O2–6 are assumed. HXeO3 and H3XeO2–6 are formed in reactions of the hydrated electron with XeO3 and HXeO3–6, respectively. HXeO4 and H3XeO2–7 are formed in reactions of the hydroxyl radical with XeO3 and HXeO3–6 in which the hydroxyl radical adds to a ligand oxygen atom to form peroxy compounds. HXe......O2–5 is formed in a reaction with the hydroxyl radical anion in which the hydroxyl radical anion adds to the xenon atom and by photolysis of HXeO3–6: HXeO3–6 [graphic omitted] HXeO2–5+ O–. XeV, XeVII and XeIX and corresponding iodine species in the oxidation states four, six and eight have similar...

In vitro antioxidant evaluation and total phenolics of methanolic leaf extracts of Nyctanthes arbor-tristis L.

Science.gov (United States)

Michael, J Savarimuthu; Kalirajan, A; Padmalatha, C; Singh, A J A Ranjit

2013-09-01

To investigate the in vitro antioxidant activity and total phenolic content of the methanolic leaf extract of Nyctanthes arbor-tristis L. (NA). The sample was tested using five in vitro antioxidant methods (1, 1-diphenyl-2-picryl hydrazine radical scavenging activity (DPPH), hydroxyl radical-scavenging activity (-OH), nitric oxide scavenging activity (NO), superoxide radical-scavenging activity, and total antioxidant activity) to evaluate the in vitro antioxidant potential of NA and the total phenolic content (Folin-Ciocalteu method). The extract showed good free radical scavenging property which was calculated as an IC50 value. IC50 (Half maximal inhibitory concentration) of the methanolic extract was found to be 57.93 μg·mL(-1) for DPPH, 98.61 μg·mL(-1) for -OH, 91.74 μg·mL(-1) for NO, and 196.07 μg·mL(-1) for superoxide radical scavenging activity. Total antioxidant capacity of the extract was found to be (1198 ± 24.05) mg ascorbic acid for the methanolic extract. Free radical scavenging activity observed in the extracts of NA showed a concentration-dependent reaction. The in vitro scavenging tested for free radicals was reported to be due to high phenolic content in the leaf extract. The leaf extract of NA showed the highest total phenolic content with a value of 78.48 ± 4.2 equivalent mg TAE/g (tannic acid equivalent). N. arbor-tristis leaf extract exhibited potent free radical scavenging activity. The finding suggests that N. arbor-tristis leaves could be a potential source of natural antioxidant. Copyright © 2013 China Pharmaceutical University. Published by Elsevier B.V. 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.

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.

Total Peroxy Nitrates (ΣPNs in the atmosphere: the Thermal Dissociation-Laser Induced Fluorescence (TD-LIF technique and comparisons to speciated PAN measurements

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B. W. LaFranchi

2010-05-01

Full Text Available Peroxyacetyl nitrate (PAN and its chemical analogues are increasingly being quantified in the ambient atmosphere by thermal dissociation (TD followed by detection of either the peroxyacyl radical or the NO2 product. Here we present details of the technique developed at University of California, Berkeley which detects the sum of all peroxynitrates (ΣPNs via laser-induced fluorescence (LIF of the NO2 product. We review the various deployments and compare the Berkeley ΣPNs measurements with the sums of PAN and its homologue species detected individually by other instruments. The observed TD-LIF ΣPNs usually agree to within 10% with the summed individual species, thus arguing against the presence of significant concentrations of unmeasured PAN-type compounds in the atmosphere, as suggested by some photochemical mechanisms. Examples of poorer agreement are attributed to a sampling inlet design that is shown to be inappropriate for high NOx conditions. Interferences to the TD-LIF measurements are described along with strategies to minimize their effects.

Radiolytic degradation of paracetamol in dilute aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Szabo, L [Hungarian Academy of Sciences, Budapest (Hungary). Inst. of Isotopes; Budapest University of Technology and Economics, Budapest (Hungary); Toth, T [Budapest University of Technology and Economics, Budapest (Hungary); Homlok, R; Takacs, E; Wojnarovits, L [Hungarian Academy of Sciences, Budapest (Hungary). Inst. of Isotopes

2011-07-01

Complete text of publication follows. Paracetamol or with name acetaminophen is widely used as analgesic and antipyretic drug. Due to its heavy use it is regularly detected in the surface waters. The degradation of the compound formerly was studied in several advanced oxidation processes (UV/H{sub 2}O{sub 2}, UV/TiO{sub 2}, electrochemical oxidation, ozonation). Here we report on the radiolytic degradation. In the experimental work we combined a wide variety of techniques. For the investigation of the intermediates pulse radiolysis, for end-product experiments (decolouration, mineralization) gamma irradiation were used together with UV-Vis spectroscopy, HPLC separation (with diode array and MS-MS detection), chemical oxygen demand, total organic carbon content and toxicity measurements. {sup {center_dot}O}H radicals are the main oxidative species during irradiation. They add to the aromatic ring producing hydroxycyclohexadienyl type radicals. These radicals either transform to hydroxy-paracetamol stable products in several reaction steps, or after water elimination transform to semi-iminoquinone radical. The reaction of hydroxycyclohexadienyl radicals with O{sub 2} yields peroxi radicals. The latter radicals may eliminate HO{sub 2}{sup {center_dot}} or undergo ring opening and transformation, first to different carboxylic acids, and finally (mineralization) to CO{sub 2}, H{sub 2}O and NH{sub 3} or NO{sub 2}. Paracetamol has a relatively low toxicity. In 10{sup -3} mol dm{sup -3} DCF solution after irradiation some products (e.g. hydroquinone, acetamide) are more toxic than paracetamol. By increasing the dose the toxicity suddenly decreases. It seems that the toxic products are highly sensitive to irradiation treatment.

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.

Surgical, oncological, and obstetrical outcomes after abdominal radical trachelectomy - a systematic literature review.

Science.gov (United States)

Pareja, René; Rendón, Gabriel J; Sanz-Lomana, Carlos Millán; Monzón, Otto; Ramirez, Pedro T

2013-10-01

Radical trachelectomy is a standard treatment for selected patients with early-stage cervical cancer. Outcomes are well established for vaginal radical trachelectomy (VRT), but not for abdominal radical trachelectomy (ART). We searched MEDLINE, EMBASE, and CINAHL (October 1997 through October 2012) using the terms: uterine cervix neoplasms, cervical cancer, abdominal radical trachelectomy, vaginal radical trachelectomy, fertility sparing, and fertility preservation. We included original articles, case series, and case reports. Excluded were review articles, articles with duplicate patient information, and articles not in English. We identified 485 patients. Ages ranged from 6 to 44 years. The most common stage was IB1 (331/464; 71%), and the most common histologic subtype was squamous cell carcinoma (330/470; 70%). Operative times ranged from 110 to 586 min. Blood loss ranged from 50 to 5568 mL. Three intraoperative complications were reported. Forty-seven patients (10%) had conversion to radical hysterectomy. One hundred fifty-five patients (35%) had a postoperative complication. The most frequent postoperative complication was cervical stenosis (n=42; 9.5%). The median follow-up time was 31.6 months (range, 1-124). Sixteen patients (3.8%) had disease recurrence. Two patients (0.4%) died of disease. A total of 413 patients (85%) were able to maintain their fertility. A total of 113 patients (38%) attempted to get pregnant, and 67 of them (59.3%) were able to conceive. ART is a safe treatment option in patients with early-stage cervical cancer interested in preserving fertility. Copyright © 2013 Elsevier Inc. All rights reserved.

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.

Higher measured than modeled ozone production at increased NOx levels in the Colorado Front Range

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B. C. Baier

2017-09-01

Full Text Available Chemical models must correctly calculate the ozone formation rate, P(O3, to accurately predict ozone levels and to test mitigation strategies. However, air quality models can have large uncertainties in P(O3 calculations, which can create uncertainties in ozone forecasts, especially during the summertime when P(O3 is high. One way to test mechanisms is to compare modeled P(O3 to direct measurements. During summer 2014, the Measurement of Ozone Production Sensor (MOPS directly measured net P(O3 in Golden, CO, approximately 25 km west of Denver along the Colorado Front Range. Net P(O3 was compared to rates calculated by a photochemical box model that was constrained by measurements of other chemical species and that used a lumped chemical mechanism and a more explicit one. Median observed P(O3 was up to a factor of 2 higher than that modeled during early morning hours when nitric oxide (NO levels were high and was similar to modeled P(O3 for the rest of the day. While all interferences and offsets in this new method are not fully understood, simulations of these possible uncertainties cannot explain the observed P(O3 behavior. Modeled and measured P(O3 and peroxy radical (HO2 and RO2 discrepancies observed here are similar to those presented in prior studies. While a missing atmospheric organic peroxy radical source from volatile organic compounds co-emitted with NO could be one plausible solution to the P(O3 discrepancy, such a source has not been identified and does not fully explain the peroxy radical model–data mismatch. If the MOPS accurately depicts atmospheric P(O3, then these results would imply that P(O3 in Golden, CO, would be NOx-sensitive for more of the day than what is calculated by models, extending the NOx-sensitive P(O3 regime from the afternoon further into the morning. These results could affect ozone reduction strategies for the region surrounding Golden and possibly other areas that do not comply with national ozone

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

Dementia and memory improvement due to histological changes in the brain hippocampus and hormone secretion of brain by lecithin administration

OpenAIRE

GU, Yeun-Hwa; YAMASHITA, Takenori; KANG, Ki-Mun

2014-01-01

Abstract : In this study, senescence accelerated mice (SAMP8 male, 8w), were used for the study of spatial recognition ability. We studied the effects on the brain hippocampus by administering lecithin (500 mg/kg, po). As compared to sham control group, the peroxy radical was inhibited significant in the lecithin administration group. The brain peroxidized fat level had a tendency to decrease was found in the lecithin group. Also, in the intracerebral serotonin concentration, was increased in...

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

Transmandibular approach to total maxillectomy

OpenAIRE

Tiwari, R. M.

2001-01-01

Total Maxillectomy through transfacial approach has been practiced in the treatment of Cancer for more than a decade. Its role in T3 - T4 tumors extending posteriorly through gthe bony wall is questionable, since an oncological radical procedure is often not possible. Recurrences in the infratemporal fossa are common. Despite the addition of radiotherapy five year survivals have not significantly improved. Transmandibular approach to Total Maxillectomy overcomes this shortcoming by including ...

A model for plasma modification of polypropylene using atmospheric pressure discharges

CERN Document Server

Dorai, R

2003-01-01

Atmospheric pressure plasmas are commonly used to improve the wetting and adhesion properties of polymers. In spite of their use, the mechanisms for achieving these properties are unclear. In this regard, we report on a computational investigation of the gas phase and surface kinetics during humid-air corona treatment of polypropylene (PP) and the resulting modification of its surface properties while varying energy deposition, relative humidity (RH), web speed, and gas temperature. Using results from a global plasma chemistry model validated against experiments, we found that increasing energy deposition increased the densities of alcohol, carbonyl, acid, and peroxy radicals on the PP surface. In doing so, significant amounts of gas phase O sub 3 and N sub x O sub y are produced. Increasing the RH increased the production of peroxy and acid groups, while decreasing those of alcohol and carbonyl groups. Production of O sub 3 decreased while that of HNO sub 3 increased. Increasing the temperature decreased the...

Free radical scavenging activity and secondary metabolites from in vitro cultures of Sanicula graveolens.

Science.gov (United States)

Cheel, José; Schmeda-Hirschmann, Guillermo; Jordan, Miguel; Theoduloz, Cristina; Rodríguez, Jaime A; Gerth, André; Wilken, Dirk

2007-01-01

An in vitro propagation system was developed to obtain shoot and root cultures from the Andean spice Sanicula graveolens (Apiaceae). Propagation of shoots, roots and plantlets was achieved by the temporary immersion system. The free radical scavenging effect of the methanol/water (7:3 v/v) extracts was determined by the discoloration of the 1,1-diphenyl-2-picrylhydrazyl radical (DPPH). Total phenolic, flavonoid, chlorogenic acid (CA) and quercetin 3-O-glucoside content in the samples was assessed by spectrophotometry and DAD-HPLC analysis, respectively. On a dry weight basis, the crude extracts showed total phenolic values ranging from 3.57 to 6.93%, with highest content for the root culture sample. Total flavonoid content ranged from 1.23 to 2.23% and was lower for the root culture. Chlorogenic acid and neochlorogenic acid were identified by TLC in all samples. Highest free radical scavenging effect was observed for the root culture which also presented the highest CA content. Two of the shoot culture samples, with similar IC50 values in the DPPH discoloration assay, also presented close quercetin-3-O-glucoside content.

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...

In vitro free radical scavenging activity of Ixora coccinea L

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Moni Rani Saha

2008-06-01

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

Change in chemical constituents and free radical-scavenging activity during Pear (Pyrus pyrifolia) cultivar fruit development.

Science.gov (United States)

Cho, Jeong-Yong; Lee, Sang-Hyun; Kim, Eun Hee; Yun, Hae Rim; Jeong, Hang Yeon; Lee, Yu Geon; Kim, Wol-Soo; Moon, Jae-Hak

2015-01-01

Changes in chemical constituent contents and DPPH radical-scavenging activity in fruits of pear (Pyrus pyrifolia) cultivars during the development were investigated. The fruits of seven cultivars (cv. Niitaka, Chuhwangbae, Wonhwang, Hwangkeumbae, Hwasan, Manpungbae, and Imamuraaki) were collected at 15-day intervals after day 20 of florescence. Vitamins (ascorbic acid and α-tocopherol), arbutin, chlorogenic acid, malaxinic acid, total caffeic acid, total flavonoids, and total phenolics were the highest in immature pear fruit on day 20 after florescence among samples at different growth stages. All of these compounds decreased gradually in the fruit during the development. Immature pear fruit on day 35 or 50 after florescence exhibited higher free radical-scavenging activity than that at other times, although activities were slightly different among cultivars. The chemical constituent contents and free radical-scavenging activity were largely different among immature fruits of the pear cultivars, but small differences were observed when they matured.

The role of bromine and chlorine chemistry for arctic ozone depletion events in Ny-Ålesund and comparison with model calculations

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M. Martinez

Full Text Available During the Arctic Tropospheric Ozone Chemistry (ARCTOC campaigns at Ny-Ålesund, Spitsbergen, the role of halogens in the depletion of boundary layer ozone was investigated. In spring 1995 and 1996 up to 30 ppt bromine monoxide were found whenever ozone decreased from normal levels of about 40 ppb. Those main trace gases and others were specifically followed in the UV-VIS spectral region by differential optical absorption spectroscopy (DOAS along light paths running between 20 and 475 m a.s.l.. The daily variation of peroxy radicals closely followed the ozone photolysis rate J(O₃(O¹D in the absence of ozone depletion most of the time. However, during low ozone events this close correlation was no longer found because the measurement of radicals by chemical amplification (CA turned out to be sensitive to peroxy radicals and ClO_x. Large CA signals at night can sometimes definitely be assigned to ClO_x and reached up to 2 ppt. Total bromine and iodine were both stripped quantitatively from air by active charcoal traps and measured after neutron activation of the samples. Total bromine increased from background levels of about 15 ppt to a maximum of 90 ppt during an event of complete ozone depletion. For the spring season a strong source of bromine is identified in the pack ice region according to back trajectories. Though biogenic emission sources cannot be completely ruled out, a primary activation of halogenides by various oxidants seems to initiate an efficient autocatalytic process, mainly driven by ozone and light, on ice and perhaps on aerosols. Halogenides residing on pack ice surfaces are continuously oxidised by hypohalogenous acids releasing bromine and chlorine into the air. During transport and especially above open water this air mixes with upper layer pristine air. As large quantities of bromine, often in the form of BrO, have been observed at polar sunrise also around Antarctica, its release

Deviations from the O3-NO-NO2 photo-stationary state in Delhi, India

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Chate, Dilip M.; Ghude, Sachin D.; Beig, Gurfan; Mahajan, Anoop S.; Jena, Chinmay; Srinivas, Reka; Dahiya, Anita; Kumar, Nandini

2014-10-01

A network of air quality and weather monitoring stations was set-up across Delhi, India, under the System of Air quality Forecasting And Research (SAFAR) project. The objective of this network was to enable better understanding of air quality in terms of atmospheric chemistry, emissions and forecasting in Delhi, one of the largest metropolises in the world. In this study, we focus on the O3-NO-NO2-triad Photo Stationary State (PSS), and investigate site-specific deviations in the Leighton Ratio (Φ) during a short period in 2012 (1-31 December). Large variations were observed in the NO ( 1) were also observed occasionally, and these data were used to estimate the total peroxy radical (PO2) mixing ratios. This is the first estimate of PO2 reported for the city of Delhi and compares well with the results in the literature.

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.

Production of Peroxy Nitrates in Boreal Biomass Burning Plumes over Canada During the BORTAS Campaign

Science.gov (United States)

Busilacchio, Marcella; Di Carlo, Piero; Aruffo, Eleonora; Biancofiore, Fabio; Salisburgo, Cesare Dari; Giammaria, Franco; Bauguitte, Stephane; Lee, James; Moller, Sarah; Hopkins, James;

Production of peroxy nitrates in boreal biomass burning plumes over Canada during the BORTAS campaign

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M. Busilacchio

2016-03-01

Full Text Available The observations collected during the BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS campaign in summer 2011 over Canada are analysed to study the impact of forest fire emissions on the formation of ozone (O3 and total peroxy nitrates ∑PNs, ∑ROONO2. The suite of measurements on board the BAe-146 aircraft, deployed in this campaign, allows us to calculate the production of O3 and of  ∑PNs, a long-lived NOx reservoir whose concentration is supposed to be impacted by biomass burning emissions. In fire plumes, profiles of carbon monoxide (CO, which is a well-established tracer of pyrogenic emission, show concentration enhancements that are in strong correspondence with a significant increase of concentrations of ∑PNs, whereas minimal increase of the concentrations of O3 and NO2 is observed. The ∑PN and O3 productions have been calculated using the rate constants of the first- and second-order reactions of volatile organic compound (VOC oxidation. The ∑PN and O3 productions have also been quantified by 0-D model simulation based on the Master Chemical Mechanism. Both methods show that in fire plumes the average production of ∑PNs and O3 are greater than in the background plumes, but the increase of ∑PN production is more pronounced than the O3 production. The average ∑PN production in fire plumes is from 7 to 12 times greater than in the background, whereas the average O3 production in fire plumes is from 2 to 5 times greater than in the background. These results suggest that, at least for boreal forest fires and for the measurements recorded during the BORTAS campaign, fire emissions impact both the oxidized NOy and O3,  but (1 ∑PN production is amplified significantly more than O3 production and (2 in the forest fire plumes the ratio between the O3 production and the ∑PN production is lower than the ratio evaluated in the background air masses, thus confirming that the

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.

AKTIVITAS ANTIOKSIDAN DAN KADAR FENOLIK TOTAL DARI GANGGANG MERAH (Gracilaria verrucosa L. [Antioxidant Activity and Total Phenolic Content of Red Sea Weed (Gracilaria verrucosa L.

Directory of Open Access Journals (Sweden)

Lydia Ninan Lestario*

2008-12-01

Full Text Available The aims of this study were to compare the antioxidant activity and the total phenolic content of red sea weed (Gracilaria verrucosa L. from extract of methanol, ethanol, acetone, chloroform and hexane; and the correlation between total phenolic content and the antioxidant activity of each extract; then to determine the chlorophyll a, chlorophyll b, and carotene content of each extract and their correlation with the free radical scavenging activity as well. The antioxidant activity were measured by free radical scavenging method with DPPH and by reducing power method with K4Fe(CN6 as standard, whereas the total phenolic content was measured by Folin Ciocalteu method with gallic acid as standard. Chlorophyll a, chlorophyll b, and carotene were determined by spectrophotometric method based on Lambert-Beer law. The data of antioxidant activity and total phenolic content were statistically analyzed by Randomized Completely Block Design (RCBD with five kinds of solvents as treatments and five replications. Honestly Significant Difference Test (HSDT was used to compare the difference of treatments; whereas the chlorophyll a, chlorophyll b, and carotene content were not statistically analyzed since they were only supplement data. The results showed that the highest of the antioxidant activity by free radical scavenging method was found in acetone extract : 43.43% (BHT: 84.15%; whereas by reducing power method was found in chloroform extract : 0.1756 meq K4Fe(CN6/g extract (BHT : 6.1767 meq K4Fe(CN6/g extract; and the highest of the total phenolic content was also found in acetone extract : 45.29 mg /g extract. There were close correlation between phenolic content and antioxidant activity both by free radical scavenging method and by reducing power method with r (coefficient correlation respectivelly 0.89 and 0.91.Chlorophyll a and carotene had also close correlation with the free radical scaveging activity, but not for chlorophyll b.

Predicting an optimal outcome after radical prostatectomy: the trifecta nomogram.

Science.gov (United States)

Eastham, James A; Scardino, Peter T; Kattan, Michael W

2008-06-01

The optimal outcome after radical prostatectomy for clinically localized prostate cancer is freedom from biochemical recurrence along with the recovery of continence and erectile function, a so-called trifecta. We evaluated our series of open radical prostatectomy cases to determine the likelihood of this outcome and develop a nomogram predicting the trifecta. We reviewed the records of patients undergoing open radical prostatectomy for clinical stage T1c-T3a prostate cancer at our center during 2000 to 2006. Men were excluded if they received preoperative hormonal therapy, chemotherapy or radiation therapy, if pretreatment prostate specific antigen was more than 50 ng/ml, or if they were impotent or incontinent before radical prostatectomy. A total of 1,577 men were included in the study. Freedom from biochemical recurrence was defined as post-radical prostatectomy prostate specific antigen less than 0.2 ng/ml. Continence was defined as not having to wear any protective pads. Potency was defined as erection adequate for intercourse upon most attempts with or without phosphodiesterase-5 inhibitor. Mean patient age was 58 years and mean pretreatment prostate specific antigen was 6.4 ng/ml. A trifecta outcome (cancer-free status with recovery of continence and potency) was achieved in 62% of patients. In a nomogram developed to predict the likelihood of the trifecta baseline prostate specific antigen was the major predictive factor. Area under the ROC curve for the nomogram was 0.773 and calibration appeared excellent. A trifecta (optimal) outcome can be achieved in most men undergoing radical prostatectomy. The nomogram permits patients to estimate preoperatively their likelihood of an optimal outcome after radical prostatectomy.

Finding the radical of an algebra of linear transformations

NARCIS (Netherlands)

Cohen, A.M.; Ivanyos, G.; Wales, D.B.

1997-01-01

We present a method that reduces the problem of computing the radical of a matrix algebra over an arbitrary field to solving systems of semilinear equations. The complexity of the algorithm, measured in the number of arithmetic operations and the total number of the coefficients passed to an oracle

Radical constructivism: Between realism and solipsism

Science.gov (United States)

Martínez-Delgado, Alberto

2002-11-01

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

Spectroscopic studies of neutral and chemically oxidized species of β-carotene, lycopene and norbixin in CH{sub 2}Cl{sub 2}: Fluorescence from intermediate compounds

Energy Technology Data Exchange (ETDEWEB)

Alwis, D.D.D.H [Department of Chemistry, The Open University of Sri Lanka, Nawala (Sri Lanka); Department of Chemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka); Chandrika, U.G. [Department of Biochemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka); Jayaweera, P.M., E-mail: pradeep@sjp.ac.lk [Department of Chemistry, University of Sri Jayewardenepura, Nugegoda (Sri Lanka)

2015-02-15

Radical cations, dications and oxidized intermediate species of three carotenoids, namely, β-carotene, lycopene and norbixin, were generated in CH{sub 2}Cl{sub 2} solutions via chemical oxidation using anhydrous FeCl{sub 3}. UV–vis, fluorescence and fluorescence-excitation spectroscopic studies were performed to understand and compare the nature of intermediate species generated during the chemical oxidation process and subsequent degradation. The intense emission observed at 550 nm can be assigned to the S{sub 2}→S{sub 0} (1{sup 1}B{sub u}→1{sup 1}A{sub g}) transition of the carotenoid molecules. The 350 nm excitation during the oxidation process for β-carotene, lycopene and norbixin exhibit intense fluorescence peaks at 492 nm, 493 nm and 500 nm, respectively. These peaks are assigned to intermediate peroxy/epoxy compounds of the three molecules that are formed with molecular oxygen prior to the formation of oxidized short-chain stable compounds. - Highlights: • Fluorescence and UV–vis studies on β-carotene, lycopene and norbixin. • Oxidation, induced by FeCl{sub 3} in CH{sub 2}Cl{sub 2} shows blue shifted fluorescence peaks. • Fluorescence peaks were assigned to intermediate peroxy/epoxy forms of carotenoids. • The D0→D3 transition of radical cations are observed in the near IR region.

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

Science.gov (United States)

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

2015-11-01

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

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

Science.gov (United States)

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

2009-07-01

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

Search for high mass dilepton resonances in pp collisions at {radical}(s)=7 TeV with the ATLAS experiment

Energy Technology Data Exchange (ETDEWEB)

Aad, G [Fakultaet fuer Mathematik und Physik, Albert-Ludwigs-Universitaet, Freiburg i.Br. (Germany); Abbott, B [Homer L. Dodge Department of Physics and Astronomy, University of Oklahoma, Norman, OK (United States); Abdallah, J [Institut de Fisica d' Altes Energies and Universitat Autonoma de Barcelona and ICREA, Barcelona (Spain); Abdelalim, A A [Section de Physique, Universite de Geneve, Geneva (Switzerland); Abdesselam, A [Department of Physics, Oxford University, Oxford (United Kingdom); Abdinov, O [Institute of Physics, Azerbaijan Academy of Sciences, Baku (Azerbaijan); Abi, B [Department of Physics, Oklahoma State University, Stillwater, OK (United States); Abolins, M [Department of Physics and Astronomy, Michigan State University, East Lansing, MI (United States); Abramowicz, H [Raymond and Beverly Sackler School of Physics and Astronomy, Tel Aviv University, Tel Aviv (Israel); Abreu, H [LAL, Univ. Paris-Sud and CNRS/IN2P3, Orsay (France); Acerbi, E [INFN Sezione di Milano (Italy); Dipartimento di Fisica, Universita di Milano, Milano (Italy); Acharya, B S [INFN Gruppo Collegato di Udine (Italy); ICTP, Trieste [Italy; Adams, D L [Physics Department, Brookhaven National Laboratory, Upton, NY (United States); Addy, T N [Department of Physics, Hampton University, Hampton, VA (United States); Adelman, J [Department of Physics, Yale University, New Haven, CT (United States); Aderholz, M [Max-Planck-Institut fuer Physik (Werner-Heisenberg-Institut), Muenchen (Germany); Adomeit, S [Fakultaet fuer Physik, Ludwig-Maximilians-Universitaet Muenchen, Muenchen (Germany); Adragna, P [Department of Physics, Queen Mary University of London, London (United Kingdom); Adye, T [Particle Physics Department, Rutherford Appleton Laboratory, Didcot (United Kingdom); Aefsky, S [Department of Physics, Brandeis University, Waltham, MA (United States)

2011-06-13

This Letter presents a search for high mass e{sup +}e{sup -} or {mu}{sup +}{mu}{sup -} resonances in pp collisions at {radical}(s)=7 TeV at the LHC. The data were recorded by the ATLAS experiment during 2010 and correspond to a total integrated luminosity of {approx}40 pb{sup -1}. No statistically significant excess above the Standard Model expectation is observed in the search region of dilepton invariant mass above 110 GeV. Upper limits at the 95% confidence level are set on the cross section times branching ratio of Z{sup '} resonances decaying to dielectrons and dimuons as a function of the resonance mass. A lower mass limit of 1.048 TeV on the Sequential Standard Model Z{sup '} boson is derived, as well as mass limits on Z{sup *} and E{sub 6}-motivated Z{sup '} models.

Teaching Semantic Radicals Facilitates Inferring New Character Meaning in Sentence Reading for Nonnative Chinese Speakers

Directory of Open Access Journals (Sweden)

Thi Phuong Nguyen

2017-10-01

Full Text Available This study investigates the effects of teaching semantic radicals in inferring the meanings of unfamiliar characters among nonnative Chinese speakers. A total of 54 undergraduates majoring in Chinese Language from a university in Hanoi, Vietnam, who had 1 year of learning experience in Chinese were assigned to two experimental groups that received instructional intervention, called “old-for-new” semantic radical teaching, through two counterbalanced sets of semantic radicals, with one control group. All of the students completed pre- and post-tests of a sentence cloze task where they were required to choose an appropriate character that fit the sentence context among four options. The four options shared the same phonetic radicals but had different semantic radicals. The results showed that the pre-test and post-test score increases were significant for the experimental groups, but not for the control group. Most importantly, the experimental groups successfully transferred the semantic radical strategy to figure out the meanings of unfamiliar characters containing semantic radicals that had not been taught. The results demonstrate the effectiveness of teaching semantic radicals for lexical inference in sentence reading for nonnative speakers, and highlight the ability of transfer learning to acquire semantic categories of sub-lexical units (semantic radicals in Chinese characters among foreign language learners.

Salvage robotic radical prostatectomy

Directory of Open Access Journals (Sweden)

Samuel D Kaffenberger

2014-01-01

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

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.

Natural Products Garlic Oil and Vitamin E, Control Radiation Induced Disorders of Lipid and Carbohydrate Metabolism in Rats

International Nuclear Information System (INIS)

Ragab, E.A.; Ashry, O.M.

2004-01-01

Increased level of lipid peroxides in various tissues of irraiated animals, may play a crucial role in determining the pathogenesis of radiation exposure. Many of the damaging effects of ionizing radiation are mediated by reactive free radicals. The efficacy of oral treatment of rats with garlic oil (100 mg/kg body weight) for ten days and intraperitoneal administration of vitamin E (100mg/kg body wt.) two hours before whole body gamma irradiation (7Gy), was examine on certain biochemical parameters. The data obtained revealed that, radiation exposure caused increase in serum malondialdehyde level (indicating lipid peroxiation accompanied by increase in serum total lipid, trigacylglycerol, cholesterol an low density lipoprotein with significant decrease in high density lipoprotein. Radiation exposure also induced significant elevation in serum glucose level, liver glycogen and liver glucose 6-phosphatase activity level. Administration of the natural product (garlic oil) and /or vitamin E ameliorates the radiation inuced disturbances in lipid and carbohydrate metabolism. The study confirmed the beneficial role of the used antioxidative agents as recommended radioprotectors due to their ability of scavenging free radicals produced by ionizing radiation or oxidative stress

Investigation of OxProduction Rates in the Mexico City Metropolitan Area during MILAGRO

Science.gov (United States)

Dusanter, S.; Molina, L. T.; Stevens, P. S.

2009-12-01

Understanding the oxidative capacity of the atmosphere and the formation of secondary pollutants are important issues in atmospheric chemistry. For instance, the photochemical production of tropospheric ozone (O3) is of particular interest due to its detrimental effects on both human health and agricultural ecosystems. A detailed characterization of tropospheric O3 production rates will help in the development of effective control strategies. The 2006 Mexico City Metropolitan Area field campaign (MCMA-2006) was one of four components of MILAGRO (Megacity Initiative: Local And Global Research Observations) intended to collect information on the impact of megacity emissions on local, regional and global scales. In this presentation, rates of production of Ox (Ox = O3 + NO2) species during MCMA-2006 at the supersite T0 (Instituto Mexicano del Petroleo) will be presented using different approaches based on measured and modeled concentrations of ROx (OH + HO2 + RO2) radicals. In addition, we will examine both the reactivity of OH and the contribution of specific peroxy radicals to the oxidation rate of NO to estimate the contribution of groups of VOCs (alkanes, alkenes, aromatics, oxygenated and biogenic VOCs) to the total production rate of Ox species.

Gleason Score Correlation Between Prostate Biopsy and Radical Prostatectomy Specimens

Directory of Open Access Journals (Sweden)

Erdem Öztürk

2018-04-01

Full Text Available Objective: Prostate cancer is the most common malignancy in men and the second cause of cancer-related mortality. Prostate biopsy and the Gleason score guide treatment decisions in prostate cancer. Several studies have investigated the correlation between biopsy scores and radical prostatectomy specimen scores. We also evaluated the correlation of Gleason scores of these specimens in our patient series. Materials and Methods: We retrospectively reviewed the data of 468 men who were diagnosed with prostate cancer and underwent radical prostatectomy between 2008 and 2017. Patients’ age, prostate-specific antigen levels at diagnosis, and prostate biopsy and radical prostatectomy specimen Gleason scores were recorded. Upgrading and downgrading were defined as increase or decrease of Gleason score of radical prostate specimen compared to Gleason score of prostate biopsy. Results: A total of 442 men diagnosed with prostate cancer were included in the study. The mean age of the patients was 62.62±6.26 years (44-84 years and mean prostate specific antigen level was 9.01±6.84 ng/mL (1.09-49 ng/mL. Prostate biopsy Gleason score was 7 in 27 (6.1% men. Radical prostatectomy specimen Gleason score was 7 in 62 (14% men. Gleason correlation was highest in the 240 patients (71.6% with score <7 and was lowest in the 31 (38.75% patients with score =7. Conclusion: This study demonstrated that the discordance rate between Gleason scores of prostate biopsy and radical prostatectomy specimens was 35.7%.

Muonium and muonic radicals

International Nuclear Information System (INIS)

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

1985-01-01

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

Population-based assessment of racial/ethnic differences in utilization of radical cystectomy for patients diagnosed with bladder cancer.

Science.gov (United States)

Williams, Stephen B; Huo, Jinhai; Kosarek, Christopher D; Chamie, Karim; Rogers, Selwyn O; Williams, Michele A; Giordano, Sharon H; Kim, Simon P; Kamat, Ashish M

2017-07-01

Radical cystectomy is a surgical treatment for recurrent non-muscle-invasive and muscle-invasive bladder cancer; however, many patients may not receive this treatment. A total of 27,578 patients diagnosed with clinical stage I-IV bladder cancer from 1 January 2007 to 31 December 2013 were identified from the Surveillance, Epidemiology, and End Results (SEER) registry database. We used multivariable regression analyses to identify factors predicting the use of radical cystectomy and pelvic lymph node dissection. Cox proportional hazards models were used to analyze survival outcomes. A total of 1,693 (6.1%) patients with bladder cancer underwent radical cystectomy. Most patients (92.4%) who underwent radical cystectomy also underwent pelvic lymph node dissection. When compared with white patients, non-Hispanic blacks were less likely to undergo a radical cystectomy [odds ratio (OR) 0.79, 95% confidence interval (CI) 0.64-0.96, p = 0.019]. Moreover, recent year of surgery 2013 versus 2007 (OR 2.32, 95% CI 1.90-2.83, p groups diagnosed with bladder cancer, especially among older, non-Hispanic black patients.

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

DEFF Research Database (Denmark)

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

1996-01-01

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

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

International Nuclear Information System (INIS)

Williams, T.F.

1982-01-01

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

Muonium-containing vinyl radicals

International Nuclear Information System (INIS)

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

1987-01-01

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

Radicals in arithmetic

NARCIS (Netherlands)

W.J. Palenstijn (Willem Jan)

2014-01-01

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

Analytic amplitudes for hadronic forward scattering and the Heisenberg ln{sup 2} s behaviour of total cross sections

Energy Technology Data Exchange (ETDEWEB)

Nicolescu, Basarab [LPNHE, Unite de Recherche des Universites Paris 6 et Paris 7, associee au CNRS, Theory Group, Universite Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05 (France)

2004-07-01

We consider several classes of analytic parametrizations of hadronic scattering amplitudes (the COMPETE analysis), and compare their predictions to all available forward data (pp, {pi}p, Kp, {gamma}p, {gamma}{gamma}, {sigma}p). Although these parametrizations are very close for {radical}s {>=} 9 GeV, it turns out that they differ markedly at low energy, where a universal Pomeron term {approx} ln{sup 2} s enables one to extend the fit down to {radical}s = 4 GeV. We present predictions on the total cross sections and on the ratio of the real part to the imaginary part of the elastic amplitude ({rho} parameter) for present and future pp colliders, and on total cross sections for {gamma}p {yields} hadrons at cosmic-ray energies and for it{gamma}{gamma} {yields} hadrons up to {radical}s = 1 TeV. The ln{sup 2} s behaviour of total cross sections, first obtained by Heisenberg 50 years ago, receives now increased interest both on phenomenological and theoretical levels. We present a modification of the Heisenberg's model in connection with the presence of glueballs and we show that it leads to a realistic description of all existing hadron total cross-sections data, in agreement with the COMPETE analysis.

Charge transport kinetics in a robust radical-substituted polymer/nanocarbon composite electrode

Science.gov (United States)

Sato, Kan; Oyaizu, Kenichi; Nishide, Hiroyuki

We have reported a series of organic radical-substituted polymers as new-type charge storage and transport materials which could be used for energy related devices such as batteries and solar cells. Redox-active radical moieties introduced to the non-conjugated polymer backbones enable the rapid electron transfer among the adjacent radical sites, and thus large diffusive flux of electrical charge at a bulk scale. Here we present the elucidated charge transport kinetics in a radical polymer/single-walled carbon nanotube (SWNT) composite electrode. The synergetic effect of electrical conduction by a three-dimensional SWNT network and electron self-exchange reaction by radical polymers contributed to the 105-fold (per 1 g of added SWNT) boosting of electrochemical reactions and exceptionally large current density (greater than 1 A/cm2) as a rechargeable electrode. A totally organic-based secondary battery with a submicron thickness was fabricated to demonstrate the splendid electrochemical performances. Grants-in-Aid for Scientific Research (No. 24225003, 15J00888) and the Leading Graduate Program in Science and Engineering, from the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT).

Multiple free-radical scavenging capacity in serum

Science.gov (United States)

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

2012-01-01

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

Radicals in arithmetic

NARCIS (Netherlands)

Palenstijn, Willem Jan

2014-01-01

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

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

Directory of Open Access Journals (Sweden)

Ken Reidy

2018-03-01

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

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

Free radical scavenging activities of pigment extract from Hibiscus ...

African Journals Online (AJOL)

AJL

2012-01-05

Jan 5, 2012 ... molecules by getting electrons from them (Lien et al.,. 2008; Perry et al., ... of the filtrate was adjusted to 80% with 95% ethanol. The ..... Free Radical bio. Med. ... Antioxidant properties of banana flower of two cultivars in China using 2 ... total phenolic contents in peel and pulp of Chinese jujube (Ziziphus.

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.

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

Science.gov (United States)

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

2017-12-01

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

Patients undergoing radical prostatectomy have a better survival than the background population

DEFF Research Database (Denmark)

Andreas Røder, Martin; Brasso, Klaus; Drimer Berg, Kasper

2013-01-01

underwent radical prostatectomy. Patients were followed prospectively per protocol. No patients were lost to follow-up. Overall and cause-specific survival were described using Kaplan-Meier plots. Standardized relative survival and mortality ratio were calculated based on expected survival in the age......INTRODUCTION: The objective of this study was to investigate standardised relative survival and mortality ratio for patients undergoing radical prostatectomy for localized prostate cancer at our institution. MATERIAL AND METHODS: Between 1995 and 2010, a total of 1,350 consecutive patients......-matched Danish population using the methods and macros described by Dickmann. The country-specific population mortality rates used for calculation of the expected survival were based on data from The Human Mortality Database. RESULTS: The median follow-up was 3.4 years (range: 0-14.3 years). A total of 59 (4...

Youth De-Radicalization: A Canadian Framework

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Hafal (Haval Ahmad

2017-09-01

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

Radical cystectomy: Analysis of postoperative course

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Jeremić Dimitrije

2010-01-01

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

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

Science.gov (United States)

El-Agamey, Ali; McGarvey, David J

2016-01-01

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

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

Taking a radical position: Evidence for position specific radical representations in Chinese character recognition using masked priming ERP

Directory of Open Access Journals (Sweden)

I-Fan eSu

2012-09-01

Full Text Available In the investigation of orthographic representation of Chinese characters, one question that has stimulated much research is whether radicals (character components are specified for spatial position in a character (e.g. Ding, Peng, & Taft, 2004; Tsang & Chen, 2009. Differing from previous work, component or radical position information in this study is conceived in terms of relative frequency across different positions of characters containing it. A lexical decision task in a masked priming paradigm focusing on radicals with preferred position of occurrence was conducted. A radical position that encompasses more characters than other positions was identified to be the preferred position of a particular radical. The prime that was exposed for 96ms might share a radical with the target in the same or different positions. Moreover, the shared radical appeared either in its preferred or non-preferred position in the target. While response latencies only revealed the effect of graphical similarity, both effects of graphical similarity and radical position preference were found in the ERP results. The former effect was reflected in greater positivity in occipital P1 and greater negativity in N400 for radicals in different positions in prime and target characters. The latter effect manifested as greater negativity in occipital N170 and greater positivity in frontal P200 in the same time window elicited by radicals in their non-preferred position. Equally interesting was the reversal of the effect of radical position preference in N400 with greater negativity associated with radicals in preferred position. These findings identify the early ERP components associated with activation of position-specific radical representations in the orthographic lexicon, and reveal the change in the nature of competition from processing at the radical level to the lexical level.

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

Kinetics and mechanism of elementary chemical processes of importance in combustion. Periodic report 2 for the period October 1986 - April 1987

International Nuclear Information System (INIS)

Munk, J.; Pagsberg, P.; Ratajczak, E.; Sillesen, A.

1987-04-01

UV-spectra of vinyl and propargyl radicals have been recorded employing the technique of pulse radiolysis combined with time resolved UV-absorption spectroscoppy. The kinetics of vinyl radiocals was studied by monitoring the transient absorption signals in the range of 215-230 nm. In the presence of oxygen we observed the build-up of strong transient absorption signals at 230nm. Based on analysis of the spectral and kinetic features we have tentatively assigned the new absorption band to the vinyl peroxy radical. Propargyl radicals were produced by the argon sensitized radiolysis of propargyl bromide. In addition to the well-known absorption band at 332 nm we have observed a much stronger band with a maximum at 250 nm. The observed second order decay kinetics is accounted for by the combination reactions 2 C x H x -> products and C 3 H 3 + Br -> C 3 H 3 Br. (EG)

Radical radiotherapy for T3 laryngeal cancers

International Nuclear Information System (INIS)

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

1996-01-01

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

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

Gnosticism and Radical Feminism

DEFF Research Database (Denmark)

Cahana, Jonathan

2016-01-01

and radical feminism would easily fall under this definition. There is, however, one major difference: since radical feminism is a relatively recent phenomenon which also benefited from modern modes of text production and preservation, almost all of the sources are still with us. This, in turn, may allow us...... to use radical feminism to make certain aspects of ancient Gnosticism re-emerge from their long submersion, provided that enough similarities can be independently drawn between the two phenomena to merit such a comparison. This paper therefore presents a comparison between concepts and positions...

Radical's view of sciences

International Nuclear Information System (INIS)

Mittal, J.P.

2004-01-01

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

Harmonic Scalpel versus Electrocautery Dissection in Modified Radical Mastectomy for Breast Cancer: A Meta-Analysis.

Science.gov (United States)

Huang, Jinbo; Yu, Yinghua; Wei, Changyuan; Qin, Qinghong; Mo, Qinguo; Yang, Weiping

2015-01-01

Despite the common use of conventional electrocautery in modified radical mastectomy for breast cancer, the harmonic scalpel is recently emerging as a dominant surgical instrument for dissection and haemostasis, which is thought to reduce the morbidity, such as seroma and blood loss. But the results of published trials are inconsistent. So we made the meta-analysis to assess the intraoperative and postoperative endpoints among women undergoing modified radical mastectomy with harmonic scalpel or electrocautery. A comprehensive literature search of case-control studies from PubMed, MEDLINE, EMBASE and Cochrane Library databases involving modified radical mastectomy with harmonic scalpel or electrocautery was performed. We carried out a meta-analysis of primary endpoints including postoperative drainage, seroma development, intraoperative blood loss and secondly endpoints including operative time and wound complications. We used odds ratios (ORs) with 95% confidence intervals (CIs) to evaluate the effect size for categorical outcomes and standardised mean differences (SMDs) for continuous outcomes. A total of 11 studies with 702 patients were included for this meta-analysis. There was significant difference in total postoperative drainage (SMD: -0.74 [95%CI: -1.31, -0.16]; Pelectrocautery in modified radical mastectomy for breast cancer. No difference was found as for operative time between harmonic scalpel dissection and standard electrocautery (SMD: 0.04 [95%CI: -0.41, 0.50]; P = 0.85). Compared to standard electrocautery, harmonic scalpel dissection presents significant advantages in decreasing postoperative drainage, seroma development, intraoperative blood loss and wound complications in modified radical mastectomy for breast cancer, without increasing operative time. Harmonic scalpel can be recommended as a preferential surgical instrument in modified radical mastectomy.

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....

Singlet Oxygen and Free Radical Reactions of Retinoids and Carotenoids—A Review

Science.gov (United States)

Truscott, T. George

2018-01-01

We report on studies of reactions of singlet oxygen with carotenoids and retinoids and a range of free radical studies on carotenoids and retinoids with emphasis on recent work, dietary carotenoids and the role of oxygen in biological processes. Many previous reviews are cited and updated together with new data not previously reviewed. The review does not deal with computational studies but the emphasis is on laboratory-based results. We contrast the ease of study of both singlet oxygen and polyene radical cations compared to neutral radicals. Of particular interest is the switch from anti- to pro-oxidant behavior of a carotenoid with change of oxygen concentration: results for lycopene in a cellular model system show total protection of the human cells studied at zero oxygen concentration, but zero protection at 100% oxygen concentration. PMID:29301252

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

Science.gov (United States)

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

1991-03-01

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

Metal-Diazo Radicals of α-Carbonyl Diazomethanes

Science.gov (United States)

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-03-01

Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

Reaction between protein radicals and other biomolecules

DEFF Research Database (Denmark)

Østdal, H.; Davies, M.J.; Andersen, Henrik Jørgen

2002-01-01

The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2....... Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid...

Phytochemical screening, free radical scavenging, antioxidant activity and phenolic content of Dodonaea viscosa

Directory of Open Access Journals (Sweden)

Riaz Tauheeda

2012-01-01

Full Text Available The purpose of this study was to evaluate the antioxidant potential of Dodonaea viscosa Jacq. Methanolic extract of the plant was dissolved in distilled water and partitioned with n-hexane, chloroform, ethyl acetate and nbutanol sequentially. Phytochemical screening showed presence of phenolics, flavonoides and cardiac glycosides in large amount in chloroform, ethyl acetate and n-butanol fraction. The antioxidant potential of all these fractions and remaining aqueous fraction was evaluated by four methods: 1,1-Diphenyl-2-picrylhydrazyl (DPPH free radical scavenging activity, total antioxidant activity, Ferric Reducing Antioxidant Power (FRAP assay and ferric thiocyanate assay along with determination of their total phenolics. The results revealed that ethyl acetate soluble fraction exhibited highest percent inhibition of DPPH radical as compared to other fractions. It showed 81.14 ± 1.38% inhibition of DPPH radical at a concentration of 60 μg/ml. The IC50 of this fraction was found to be 33.95 ± 0.58 μg/ml, relative to butylated hydroxytoluene (BHT, having IC50 of 12.54 ± 0.89 μg/mL. It also showed highest FRAP value (380.53 ± 0.74 μM of trolox equivalents as well as highest total phenolic contents (208.58 ± 1.83 GAE μg/g and highest value of inhibition of lipid peroxidation (58.11 ± 1.49% at concentration of 500 μg/ml as compared to the other studied fractions. The chloroform fraction showed highest total antioxidant activity i.e.1.078 ± 0.59 (eq. to BHT.

Formation of long-lived radicals on proteins by radical transfer from heme enzymes--a common process?

DEFF Research Database (Denmark)

Ostdal, H; Andersen, H J; Davies, Michael Jonathan

1999-01-01

concentrations were observed after limited digestion, although this effect was less marked with the HRP/H2O2/BSA system than with Fe(III)Mb/H2O2/BSA, consistent with different modes of radical transfer. More extensive digestion of BSA decreased the radical concentration to levels below those detected with native...... investigated using horseradish peroxidase (HRP)/H2O2, in the presence and absence of added tyrosine. Incubation of HRP with H2O2 and bovine or human serum albumins, in the presence and absence of tyrosine, gave long-lived albumin-derived radicals as detected by EPR spectroscopy. Evidence has been obtained...... for these albumin radicals being located on buried tyrosine residues on the basis of blocking experiments. The effect of protein conformation on radical transfer has been investigated using partial proteolytic digestion prior to protein oxidation. With HRP/H2O2/BSA and Fe(III)Mb/H2O2/BSA increased radical...

Flavonoid, hesperidine, total phenolic contents and antioxidant ...

African Journals Online (AJOL)

Additionally, the antioxidant activities were also determined by ferric reducing antioxidant power (FRAP) and 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical scavenging activity. C. hystrix had the highest flavonoid and total phenolic contents while C. aurantifolia had the highest hesperidine content. The antioxidant activity of ...

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

Energy Technology Data Exchange (ETDEWEB)

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

1990-01-01

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

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

International Nuclear Information System (INIS)

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

1990-01-01

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

Eddy covariance fluxes of acyl peroxy nitrates (PAN, PPN and MPAN above a Ponderosa pine forest

Directory of Open Access Journals (Sweden)

G. M. Wolfe

2009-01-01

Full Text Available During the Biosphere Effects on AeRosols and Photochemistry EXperiment 2007 (BEARPEX-2007, we observed eddy covariance (EC fluxes of speciated acyl peroxy nitrates (APNs, including peroxyacetyl nitrate (PAN, peroxypropionyl nitrate (PPN and peroxymethacryloyl nitrate (MPAN, above a Ponderosa pine forest in the western Sierra Nevada. All APN fluxes are net downward during the day, with a median midday PAN exchange velocity of −0.3 cm s⁻¹; nighttime storage-corrected APN EC fluxes are smaller than daytime fluxes but still downward. Analysis with a standard resistance model shows that loss of PAN to the canopy is not controlled by turbulent or molecular diffusion. Stomatal uptake can account for 25 to 50% of the observed downward PAN flux. Vertical gradients in the PAN thermal decomposition (TD rate explain a similar fraction of the flux, suggesting that a significant portion of the PAN flux into the forest results from chemical processes in the canopy. The remaining "unidentified" portion of the net PAN flux (~15% is ascribed to deposition or reactive uptake on non-stomatal surfaces (e.g. leaf cuticles or soil. Shifts in temperature, moisture and ecosystem activity during the summer – fall transition alter the relative contribution of stomatal uptake, non-stomatal uptake and thermochemical gradients to the net PAN flux. Daytime PAN and MPAN exchange velocities are a factor of 3 smaller than those of PPN during the first two weeks of the measurement period, consistent with strong intra-canopy chemical production of PAN and MPAN during this period. Depositional loss of APNs can be 3–21% of the gross gas-phase TD loss depending on temperature. As a source of nitrogen to the biosphere, PAN deposition represents approximately 4–19% of that due to dry deposition of nitric acid at this site.

Free radicals in an Adamantane matrix. XI. Electron paramagnetic resonance study of conformations in the β-halo-tert-butyl radicals

International Nuclear Information System (INIS)

Lloyd, R.V.; Wood, D.E.

1975-01-01

The β-halo-tert-butyl radicals were prepared by x-irradiation of the corresponding isobutyl halides in an adamantane matrix at 77 0 K and their conformations were determined by analysis of their EPR spectra. The radicals are nonplanar at the radical site, the fluoro and chloro radicals trans eclipsed and the bromo and iodo radicals gauche staggered with respect to the relative orientation of the carbon halogen bond and the direction of the singly occupied orbital. Vibration-rotation motions about the favored conformation are much larger for the fluoro radical than for the others. The rate of interconversion of the inequivalent methylene protons is approximately 1.5 x 10 9 sec -1 for the bromo radical at 202 0 K while it is too slow to measure for the iodo radical at the same temperature. The barrier to interconversion has a lower limit of 3 kcal/mol for the bromo radical and higher than that for the iodo radical. The halogen and proton hfsc in gauss and the g values for the XCH 2 C(CH 3 ) 2 radicals are: 19 F = 103.7, CH 2 = 10.4, CH 3 = 23.3, g = 2.0030 at 214 K; 35 Cl = 19.5, CH 2 = 6.3, CH 3 = 21.1, g = 2.0042 at 215 K; 81 Br = 6.7, CH 2 = 21.4, 42.7, CH 3 = 21.4, g = 2.0010 at 202 K; 127 I = 7.0, CH 2 = 21.9, 43.8, CH 3 = 21.9, g = 2.0009 at 208 K. The fluoro radical decays to nonradical products above 318 0 K, the chloro radical converts to 2-methyl allyl radical above 306 0 K, the bromo radical converts to tert-butyl radical by exchange with a matrix proton (or deuteron) at 209 0 K as does the iodo radical above 225 0 K. Photolysis with a Xe lamp converts the bromo and iodo radicals to nonradical products in less than the experimental time constant of 0.3 sec. The hypothesis is put forward that the nonplanarity and high barrier to rotation observed explain the retention of stereochemical configuration in reactions involving β-chloro, β-bromo, and β-iodo alkyl radicals. (auth)

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

Science.gov (United States)

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

2015-10-30

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

Development and validation of a simple high performance thin layer chromatography method combined with direct 1,1-diphenyl-2-picrylhydrazyl assay to quantify free radical scavenging activity in wine.

Science.gov (United States)

Agatonovic-Kustrin, Snezana; Morton, David W; Yusof, Ahmad P

2016-04-15

The aim of this study was to: (a) develop a simple, high performance thin layer chromatographic (HPTLC) method combined with direct 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay to rapidly assess and compare free radical scavenging activity or anti-oxidant activity for major classes of polyphenolics present in wines; and (b) to investigate relationship between free radical scavenging activity to the total polyphenolic content (TPC) and total antioxidant capacity (TAC) in the wine samples. The most potent free radical scavengers that we tested for in the wine samples were found to be resveratrol (polyphenolic non-flavonoid) and rutin (flavonoid), while polyphenolic acids (caffeic acid and gallic acid) although present in all wine samples were found to be less potent free radical scavengers. Therefore, the total antioxidant capacity was mostly affected by the presence of resveratrol and rutin, while total polyphenolic content was mostly influenced by the presence of the less potent free radical scavengers gallic and caffeic acids. Copyright © 2015 Elsevier Ltd. All rights reserved.

17.9.3 Radical cations of diazo compounds

Science.gov (United States)

Davies, A. G.

This document is part of Subvolume E2 `Phosphorus-Centered Radicals, Radicals Centered on Other Heteroatoms, Organic Radical Ions' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

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

International Nuclear Information System (INIS)

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

1997-01-01

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

Radical-Local Teaching and Learning

DEFF Research Database (Denmark)

Hedegaard, Mariane; Chaiklin, Seth

Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded in the l......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...... radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem...

Electronic structure of Co islands grown on the {radical}3 x {radical}3-Ag/Ge(111) surface

Energy Technology Data Exchange (ETDEWEB)

Huang, Xiao-Lan; Chou, Chi-Hao; Lin, Chun-Liang; Tomaszewska, Agnieszka; Fu, Tsu-Yi, E-mail: phtifu@phy.ntnu.edu.tw

2011-09-30

By means of room temperature scanning tunneling spectroscopy (RT STS), we have studied the electronic structure of two different Ag/Ge(111) phases as well as Co islands grown on the {radical}3 x {radical}3-Ag/Ge (111) forming either {radical}13 x {radical}13 or 2 x 2 patterns. The spectrum obtained from 4 x 4-Ag/Ge(111) structure shows the existence of a shoulder at 0.7 V which is also present in the electronic structure of the Ge(111)-c2 x 8 and indicates donation of Ge electrons to electronic states of the Ag-driven phase. However, this fact is not supported by the electronic spectrum taken from the {radical}3 x {radical}3-Ag/Ge (111). The complexity of the Co-{radical}13 x {radical}13 islands bonding with the substrate is mirrored by a large number of peaks in their electronic spectra. The spectra obtained from the Co-2 x 2 islands which had grown on the step differ from those taken from Co-2 x 2 islands located along the edge of the terrace by a number of peaks at negative sample bias. This discrepancy is elucidated in terms of dissimilarities of Co-substrate interaction accompanying Co islands growth on different areas of the stepped surface.

Understanding political radicalization: The two-pyramids model.

Science.gov (United States)

McCauley, Clark; Moskalenko, Sophia

2017-04-01

This article reviews some of the milestones of thinking about political radicalization, as scholars and security officials struggled after 9/11 to discern the precursors of terrorist violence. Recent criticism of the concept of radicalization has been recognized, leading to a 2-pyramids model that responds to the criticism by separating radicalization of opinion from radicalization of action. Security and research implications of the 2-pyramids model are briefly described, ending with a call for more attention to emotional experience in understanding both radicalization of opinion and radicalization of action. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Orgasm after radical prostatectomy

NARCIS (Netherlands)

Koeman, M; VanDriel, MF; Schultz, WCMW; Mensink, HJA

Objective To evaluate the ability to obtain and the quality of orgasm after radical prostatectomy, Patients and methods The orgasms experienced after undergoing radical prostatectomy were evaluated in 20 men (median age 65 years, range 56-76) using a semi-structured interview and a self-administered

O Behaviorismo Radical como filosofia da mente Radical Behaviorism as philosophy of mind

Directory of Open Access Journals (Sweden)

Carlos Eduardo Lopes

2003-01-01

Full Text Available O Behaviorismo Radical de B. F. Skinner é constantemente acusado de eliminar a mente de sua explicação do comportamento humano. Uma análise do livro The Concept of Mind, de Gilbert Ryle, sugere a possibilidade de defender a existência de uma mente relacional, diferente da categoria de existência da mente defendida em interpretações cartesianas (mente substancial. A análise de alguns textos de Skinner sugere que o conceito de uma mente relacional também pode ser defendido no Behaviorismo Radical. Esse fato, culminaria na possibilidade de que, além de filosofia da Ciência do Comportamento, o Behaviorismo Radical, também pode ser uma filosofia da mente, o que traria conseqüências ao estudo e à aplicação da Análise do Comportamento.B. F. Skinner's Radical Behaviorism has been repeatedly accused of eliminating the mind from its explanation of human behavior. An analysis of Gilbert Ryle's book, The Concept of Mind, suggests the possibility of defending the existence of a relational mind, different from the category of existence of mind defended in Cartesian interpretations (substantial mind. The analysis of some texts of Skinner suggests that the concept of a relational mind can also be defended in Radical Behaviorism. This fact would lead to the possibility that, beyond a philosophy of Behavior Science, Radical Behaviorism may also be a philosophy of mind, which would bring consequences to the study and application of Analysis of Behavior.

Robot-assisted radical cystectomy with intracorporeal neobladder diversion: The Karolinska experience.

Science.gov (United States)

Collins, Justin W; Sooriakumaran, P; Sanchez-Salas, R; Ahonen, R; Nyberg, T; Wiklund, N P; Hosseini, A

2014-07-01

The aim of this report is to describe our surgical technique of totally intracorporeal robotic assisted radical cystectomy (RARC) with neobladder formation. Between December 2003 and March 2013, a total of 147 patients (118 male, 29 female) underwent totally intracorporeal RARC for urinary bladder cancer. We also performed a systematic search of Medline, Embase and PubMed databases using the terms RARC, robotic cystectomy, robot-assisted, totally intracorporeal RARC, intracorporeal neobladder, intracorporeal urinary diversion, oncological outcomes, functional outcomes, and complication rates. The mean age of our patients was 64 years (range 37-87). On surgical pathology 47% had pT1 or less disease, 27% had pT2, 16% had pT3 and 10% had pT4. The mean number of lymph nodes removed was 21 (range 0-60). 24% of patients had lymph node positive dAQ1isease. Positive surgical margins occurred in 6 cases (4%). Mean follow-up was 31 months (range 4-115 months). Two patients (1.4%) died within 90 days of their operation. Using Kaplan-Meier analysis, overall survival and cancer specific survival at 60 months was 68% and 69.6%, respectively. 80 patients (54%) received a continent diversion with totally intracorporeal neobladder formation. In the neobladder subgroup median total operating time was 420 minutes (range 265-760). Daytime continence and satisfactory sexual function or potency at 12 months ranged between 70-90% in both men and women. Our experience with totally intracorporeal RARC demonstrates acceptable oncological and functional outcomes that suggest this is a viable alternative to open radical cystectomy.

Muonium radicals in benzene-styrene mixtures

International Nuclear Information System (INIS)

Ng, B.W.; Stadlbauer, J.W.; Walker, D.C.

1984-01-01

Muonium radicals were observed through their μ + SR precession frequencies in high transverse magnetic fields in pure benzene, pure styrene and their mixtures, all as liquids at room temperature. In benzene-styrene mixtures, the radicals obtained in each pure liquid are both present, so no slow (10 -9 -10 -5 s) intermolecular exchange occurs; but strong selectivity was found with the formation of the radical from styrene being about eight-times more probable than the radical from benzene. (Auth.)

Does robotic assistance confer an economic benefit during laparoscopic radical nephrectomy?

Science.gov (United States)

Yang, David Y; Monn, M Francesca; Bahler, Clinton D; Sundaram, Chandru P

2014-09-01

While robotic assisted radical nephrectomy is safe with outcomes and complication rates comparable to those of the pure laparoscopic approach, there is little evidence of an economic or clinical benefit. From the 2009 to 2011 Nationwide Inpatient Sample database we identified patients 18 years old or older who underwent radical nephrectomy for primary renal malignancy. Robotic assisted and laparoscopic techniques were noted. Patients treated with the open technique and those with evidence of metastatic disease were excluded from analysis. Descriptive statistics were performed using the chi-square and Mann-Whitney tests, and the Student t-test. Multiple linear regression was done to examine factors associated with increased hospital costs and charges. We identified 24,312 radical nephrectomy cases for study inclusion, of which 7,787 (32%) were performed robotically. There was no demographic difference between robotic assisted and pure laparoscopic radical nephrectomy cases. Median total charges were $47,036 vs $38,068 for robotic assisted vs laparoscopic surgery (p robotic assisted surgery were $15,149 compared to $11,735 for laparoscopic surgery (p robotic assistance conferred an estimated $4,565 and $11,267 increase in hospital costs and charges, respectively, when adjusted for adapted Charlson comorbidity index score, perioperative complications and length of stay (p Robotic assisted radical nephrectomy results in increased medical expense without improving patient morbidity. Assuming surgeon proficiency with pure laparoscopy, robotic technology should be reserved primarily for complex surgeries requiring reconstruction. Traditional laparoscopic techniques should continue to be used for routine radical nephrectomy. Copyright © 2014 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

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

Science.gov (United States)

Jayatilaka, Nayana; Nelson, William H.

2008-01-01

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

Laparoscopic radical cystectomy: key points

Directory of Open Access Journals (Sweden)

D. V. Perlin

2018-01-01

Full Text Available Background. Radical cystectomy remains the golden standard for treatment of muscle invasive bladder cancer. Objective: to duplicate with highest accuracy the open radical cystectomy procedure, which we successfully utilized earlier in our clinic, in the of laparoscopic conditions in order to preserve the advantages of minimally invasive procedures and retain the reliability of the tried and tested open surgery.Materials and methods. In the report were included 35 patients (27 men and 8 women with bladder cancer, who underwent laparoscopic radical cystectomy in Volgograd Regional Center of Urology and Nephrology between April 2013 and March 2016. Only the patients who had been submitted to full intracorporal ileal conduits were included.Results. The mean operative time was 378 minutes, the mean blood loss was 285 millilitres, the mean length of hospital stay was 12.4 days, only 20 % of patients required the narcotic anesthetics. The postoperative complication rate was 11.4 %. However, the majority of the patients were successfully treated with minimally invasive procedures. Generally, our results were similar to other reported studies.Conclusion. Laparoscopic radical cystectomy is a safe and efficient modality of treatment of bladder cancer. However, it needs more procedures and longer observation period to establish laparoscopic radical cystectomy as an alternative to open radical cystectomy.

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

Directory of Open Access Journals (Sweden)

Mojtaba Bozorg

2017-05-01

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

Computational study of hydrogen shifts and ring-opening mechanisms in α-pinene ozonolysis products

DEFF Research Database (Denmark)

Kurtén, Theo; Rissanen, Matti P.; Mackeprang, Kasper

2015-01-01

, sterically unhindered) H-shifts of all four peroxy radicals formed in the ozonolysis of α-pinene using density functional (ωB97XD) and coupled cluster [CCSD(T)-F12] theory. In contrast to the related but chemically simpler cyclohexene ozonolysis system, none of the calculated H-shifts have rate constants...... products in the α-pinene ozonolysis system, additional ring-opening reaction mechanisms breaking the cyclobutyl ring are therefore needed. We further investigate possible uni- and bimolecular pathways for opening the cyclobutyl ring in the α-pinene ozonolysis system....

Sources of HO x and production of ozone in the upper troposphere over the United States

OpenAIRE

Jaeglé, L.; Jacob, Daniel James; Brune, W. H.; Tan, D.; Faloona, I. C.; Weinheimer, A. J.; Ridley, B. A.; Campos, T. L.; Sachse, G. W.

1998-01-01

The sources of HOx (OH+peroxy radicals) and the associated production of ozone at 8–12 km over the United States are examined by modeling observations of OH, HO2, NO, and other species during the SUCCESS aircraft campaign in April–May 1996. The HOx concentrations measured in SUCCESS are up to a factor of 3 higher than can be calculated from oxidation of water vapor and photolysis of acetone. The highest discrepancy was seen in the outflow of a convective storm. We show that convective injecti...

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.

Radical chemistry of artemisinin

Energy Technology Data Exchange (ETDEWEB)

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

2011-12-29

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

Radical chemistry of artemisinin

Science.gov (United States)

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

2010-12-01

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

Radical chemistry of artemisinin

International Nuclear Information System (INIS)

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

2010-01-01

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

Radical chemistry of artemisinin

Energy Technology Data Exchange (ETDEWEB)

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

2010-12-29

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

Oxygen free radicals in rheumatoid arthritis

NARCIS (Netherlands)

P. Biemond (Pieter)

1986-01-01

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

Free radicals in health and disease

International Nuclear Information System (INIS)

Gonet, B.

1993-01-01

Free radicals appear in the cells as the result of exogenic factors (ionizing radiation, UV) or reactions naturally occurring in the cell. Free radical reactions may cause destruction of macromolecules (DNA, lipids, proteins). Free radical pathology is important in many diseases and aging processes in organisms

Antioxidant, Cytotoxic Activities and Total Phenolic Content of Four Indonesian Medicinal Plants

Directory of Open Access Journals (Sweden)

Waras Nurcholis

2017-03-01

Full Text Available The crude ethanol extracts of four Indonesian medicinal plants namely Curcuma xanthorrhiza Roxb.,Phyllanthus niruri Linn., Andrographis paniculata Ness., and Curcuma aeruginosa Roxb. wereexamined for their antioxidant (radical scavenging activity using 2, 2-diphenyl-2-picrylhydrazyl(DPPH free radical and cytotoxicity using brine shrimp lethality test (BSLT. The total phenoliccontent was used the Folin-Ciocalteu method. IC50 values for DPPH radical scavenging activityranged from 14.5 to 178.5 μg/ml, with P. niruri having the lowest value and therefore the mostpotent, and C. aeruginosa having the highest value. LC50 values for BSLT ranged from 210.3 to593.2 μg/ml, with C. xanthorrhiza and A. paniculata having the lowest and highest values,respectively. The total phenolic content of the Indonesian plants ranged from 133.0 ±3.7 to863.3±54.7 mg tannic acid equivalent per 1 g extract, with C. aeruginosa and P. niruri having thelowest and highest values, respectively. A positive correlation between free radical scavengingactivity and the content of phenolic compounds was found in the four of Indonesian medicinal plants.

Ultraviolet photodissociation dynamics of the benzyl radical.

Science.gov (United States)

Song, Yu; Zheng, Xianfeng; Lucas, Michael; Zhang, Jingsong

2011-05-14

Ultraviolet (UV) photodissociation dynamics of jet-cooled benzyl radical via the 4(2)B(2) electronically excited state is studied in the photolysis wavelength region of 228 to 270 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance enhanced multiphoton ionization (REMPI) techniques. In this wavelength region, H-atom photofragment yield (PFY) spectra are obtained using ethylbenzene and benzyl chloride as the precursors of benzyl radical, and they have a broad peak centered around 254 nm and are in a good agreement with the previous UV absorption spectra of benzyl. The H + C(7)H(6) product translational energy distributions, P(E(T))s, are derived from the H-atom TOF spectra. The P(E(T)) distributions peak near 5.5 kcal mol(-1), and the fraction of average translational energy in the total excess energy, , is ∼0.3. The P(E(T))s indicate the production of fulvenallene + H, which was suggested by recent theoretical studies. The H-atom product angular distribution is isotropic, with the anisotropy parameter β ≈ 0. The H/D product ratios from isotope labeling studies using C(6)H(5)CD(2) and C(6)D(5)CH(2) are reasonably close to the statistical H/D ratios, suggesting that the H/D atoms are scrambled in the photodissociation of benzyl. The dissociation mechanism is consistent with internal conversion of the electronically excited benzyl followed by unimolecular decomposition of the hot benzyl radical on the ground state.

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

Science.gov (United States)

Jagiella, Stefan; Zabel, Friedhelm

2008-04-07

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

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

Science.gov (United States)

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

2013-02-01

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

Free 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

Resonance Raman study of benzyl radical

DEFF Research Database (Denmark)

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

1992-01-01

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

Radical-Local Teaching and Learning

DEFF Research Database (Denmark)

Hedegaard, Mariane; Chaiklin, Seth

radical-local teaching and learning approach. The first half of the book introduces the idea of radical-local teaching and learning and develops the theoretical background for this perspective, drawing on the cultural-historical research tradition, particularly from Vygotsky, El'konin, Davydov......, and Aidarova. The second half of the book addresses the central concern of radical-local teaching and learning - how to relate educational practices to children's specific historical and cultural conditions. The experiment was conducted for an academic year in an afterschool programme in the East Harlem......Radical-Local Teaching and Learning presents a theoretical perspective for analyzing and planning educational programmes for schoolchildren. To realize both general societal interests and worthwhile personal development, the content of educational programmes for children must be grounded...

What is Radical Behaviorism? A Review of Jay Moore's Conceptual Foundations of Radical Behaviorism

Science.gov (United States)

Baum, William M

2011-01-01

B. F. Skinner founded both radical behaviorism and behavior analysis. His founding innovations included: a versatile preparation for studying behavior; explicating the generic nature of stimulus and response; a pragmatic criterion for defining behavioral units; response rate as a datum; the concept of stimulus control; the concept of verbal behavior; and explicating the explanatory power of contingencies. Besides these achievements, however, Skinner also made some mistakes. Subsequent developments in radical behaviorist thought have attempted to remedy these mistakes. Moore's book presents a “party line” version of radical behaviorism. It focuses narrowly on a few of Skinner's concepts (mostly mentalism and verbal behavior) and contains no criticism of his mistakes. In fact, Moore adds a few mistakes of his own manufacture; for example, he insists that the mental realm does not exist—an unprovable and distracting assertion. The book's portrayal of behavior analysis would have been current around 1960; it mentions almost none of the developments since then. It also includes almost no developments in radical behaviorism since Skinner. Moore's book would give an unwary reader a highly distorted picture of contemporary behavior analysis and radical behaviorism.

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

Science.gov (United States)

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

2016-01-01

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

The Games Radicals Play: Special Issue on Free Radicals and Radical Ions

Directory of Open Access Journals (Sweden)

John C. Walton

2015-02-01

Full Text Available Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and arrangements appearing on the scene are even more interesting. Some of these are ephemeral and enjoy only a brief appearance, others are retro-types reappearing in new guises, still others are genuinely new and “go viral” in the scientific world. This Special Issue of Molecules contains the observations and reflections of a select group of chemists and physicists fascinated by this spectacle. It contains an eclectic mix reflecting on new modes and advances as well as on permutations and combinations that revive mature themes. [...

Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.

Science.gov (United States)

Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning

2015-05-13

An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

Bibliographies on radiation chemistry

International Nuclear Information System (INIS)

Greenstock, C.L.; Ross, A.B.; Helman, W.P.

1981-01-01

This bibliography lists about 400 papers dealing solely with the production and reactivity of superoxide radical anions in irradiated aqueous and organic liquids. Only papers dealing with quantitative mechanistic, spectroscopic or kinetic data have been included. The listing was prepared by searching the RCDC bibliographic data base with SELECT keywords O 2 - or HO 2 and aqueous solution. The key words radicals (oxygen), peroxy radicals, pulse radiolysis, flash radiolysis, esr and gamma rays were also used. Additional relevant references were obtained from inspection of reviews, individual author indexes and cited references. The present bibliography excludes solid and gas phase studies, and also technical, government and in-house reports, theses, patents and some symposia proceedings. Several references prior to 1960 have been added, and the list should be reasonably comprehensive from 1965-1980. The listing is in chronological order, according to year of publication in the categories Photochemistry, Radiation Chemistry, Other, and Reviews. (author)

Free radical scavenging activity and lipid peroxidation inhibition of Hypericum helianthemoides (spach Boiss

Directory of Open Access Journals (Sweden)

Soheila Moein

2015-06-01

Full Text Available Antioxidants are compounds that obstruct the oxidation of macromolecules in the body. In general, there are two categories of antioxidants, natural and synthetic. Recently, interest has been increased considerably for obtaining new natural antioxidants. In this study, the scavenging of free radicals such as DPPH, NO and OH by Hypericum helianthemoides extract was evaluated. Also, the antioxidant properties of this extract were evaluated by FRAP, FTC methods and determination phenolic compounds. The plant was collected from north of Fars Province and plant extraction was obtained using ethanol. In DPPH radical scavenging, different concentrations of the Hypericum extract were added to DPPH radical. In hydroxyl radical scavenging, Fenton reaction mixture, TCA and TBA were mixed with Hypericum extract. In nitric radical scavenging, nitropruside was mixed with Hypericum extract and then sulphanilic acid, naphthylene diamine were added. In determination of phenolic compounds, Folin-ciocalteu and sodium carbonate were added to Hypericum extract. In DPPH radical scavenging, the IC50 of Hypericum extract (309.35±6.5μg/ml was higher than the antioxidant standards, BHT (IC50=81.9±2.6 μg/ml and quercetin (IC50=60.04±6.48 μg/ml. The highest scavenging of hydroxyl radicals was observed in Hypericum extract (70.3±0.8%, 125 μg/ml. In gallic acid it was (73.8±3.3%. In 200 μg/ml of Hypericum extract scavenged NO radical (85.2±2.7%. In FRAP method, the IC50 of this extract was 109.7±10.5 μg/ml. In FTC method, the inhibition of lipid peroxidation by Hypericum extract, BHT and ascorbic acid were 59.2±2.2, 66.9±0.15, 64.06±0.02 respectively. Total phenol of the plant extract was 3±0.4 mg/g.

Radical-pair based avian magnetoreception

Science.gov (United States)

Procopio, Maria; Ritz, Thorsten

2014-03-01

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

Fast beam studies of free radical photodissociation

Energy Technology Data Exchange (ETDEWEB)

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

1993-11-01

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

Fast beam studies of free radical photodissociation

International Nuclear Information System (INIS)

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

1993-11-01

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

A population-based study of the use and outcome of radical radiotherapy for invasive bladder cancer

International Nuclear Information System (INIS)

Hayter, Charles R.R.; Paszat, Lawrence F.; Groome, Patti A.; Schulze, Karleen; Mackillop, William J.

1999-01-01

Purpose: The objective of this study is to describe the use and outcome of radical radiotherapy for bladder cancer in the province of Ontario, Canada, between 1982 and 1994. Methods: Electronic records of invasive bladder cancer (ICD code 188) from the Ontario Cancer Registry were linked to surgical records from all Ontario hospitals and radiotherapy (RT) records from all Ontario cancer centers. We identified cases receiving radical RT by selecting RT records containing 'bladder' or 'pelvis' anatomic region codes and a radical or curative intent code (or dose > 39.5 Gy if intent missing). We identified cases receiving salvage total cystectomy by selecting total cystectomy procedure codes occurring at any time beyond 4 months from the start of radical RT. We used life table methods to compute the following: the time from diagnosis to radical RT, the time from radical RT to salvage cystectomy, overall and cause-specific survival from radical radiotherapy to death, and overall and cause-specific survival from salvage cystectomy to death. We modeled the factors associated with time to death, time to cystectomy conditional on survival, and time to cystectomy or death, whichever came first, using Cox proportional hazards regression. Results: From the 20,906 new cases of bladder cancer diagnosed in Ontario from 1982 to 1994, we identified 1,372 cases treated by radical radiotherapy (78% male, 22% female; mean age 69.8 years). The median interval to start of radical RT from diagnosis was 13.4 weeks. Ninety-three percent of patients were treated on high-energy linacs, and the most common dose/fractionation scheme was 60 Gy/30 (31% of cases). Five-year survival rates were as follows: bladder cancer cause-specific, 41%; overall, 28%; cystectomy-free, 25%; bladder cancer cause-specific following salvage cystectomy, 36%; overall following salvage cystectomy, 28%. Factors associated with a higher risk of death and a poorer cystectomy-free survival were histology (squamous or

Phase II prospective randomized trial of weight loss prior to radical prostatectomy.

Science.gov (United States)

Henning, Susanne M; Galet, Colette; Gollapudi, Kiran; Byrd, Joshua B; Liang, Pei; Li, Zhaoping; Grogan, Tristan; Elashoff, David; Magyar, Clara E; Said, Jonathan; Cohen, Pinchas; Aronson, William J

2017-12-04

Obesity is associated with poorly differentiated and advanced prostate cancer and increased mortality. In preclinical models, caloric restriction delays prostate cancer progression and prolongs survival. We sought to determine if weight loss (WL) in men with prostate cancer prior to radical prostatectomy affects tumor apoptosis and proliferation, and if WL effects other metabolic biomarkers. In this Phase II prospective trial, overweight and obese men scheduled for radical prostatectomy were randomized to a 5-8 week WL program consisting of standard structured energy-restricted meal plans (1200-1500 Kcal/day) and physical activity or to a control group. The primary endpoint was apoptotic index in the radical prostatectomy malignant epithelium. Secondary endpoints were proliferation (Ki67) in the radical prostatectomy tissue, body weight, body mass index (BMI), waist to hip ratio, body composition, and serum PSA, insulin, triglyceride, cholesterol, testosterone, estradiol, leptin, adiponectin, interleukin 6, interleukin 8, insulin-like growth factor 1, and IGF binding protein 1. In total 23 patients were randomized to the WL intervention and 21 patients to the control group. Subjects in the intervention group had significantly more weight loss (WL:-3.7 ± 0.5 kg; Control:-1.6 ± 0.5 kg; p = 0.007) than the control group and total fat mass was significantly reduced (WL:-2.1 ± 0.4; Control: 0.1 ± 0.3; p = 0.015). There was no significant difference in apoptotic or proliferation index between the groups. Among the other biomarkers, triglyceride, and insulin levels were significantly decreased in the WL compared with the control group. In summary, this short-term WL program prior to radical prostatectomy resulted in significantly more WL in the intervention vs. the control group and was accompanied by significant reductions in body fat mass, circulating triglycerides, and insulin. However, no significant changes were observed in malignant

Radically enhanced molecular recognition

KAUST Repository

Trabolsi, Ali

2009-12-17

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

Radically enhanced molecular recognition

KAUST Repository

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

2009-01-01

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

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

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

Directory of Open Access Journals (Sweden)

Xieshun Wang

2017-12-01

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

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.

Quantification of hydroxyl radical produced during phacoemulsification.

Science.gov (United States)

Gardner, Jonathan M; Aust, Steven D

2009-12-01

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

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

Radical parametrectomy after 'cut-through' hysterectomy in low-risk early-stage cervical cancer: Time to consider this procedure obsolete.

Science.gov (United States)

Pareja, Rene; Echeverri, Lina; Rendon, Gabriel; Munsell, Mark; Gonzalez-Comadran, Mireia; Sanabria, Daniel; Isla, David; Frumovitz, Michael; Ramirez, Pedro T

2018-03-01

The goal of this study is to identify predictive factors in patients with a diagnosis of early-stage cervical cancer after simple hysterectomy in order to avoid a radical parametrectomy. A retrospective review was performed of all patients who underwent radical parametrectomy and bilateral pelvic lymphadenectomy at MD Anderson Cancer Center and at the Instituto de Cancerologia Las Americas in Medellin, Colombia from December 1999 to September 2017. We sought to determine the outcomes in patients diagnosed with low-risk factors (squamous, adenocarcinoma or adenosquamous lesions<2cm in size, and invading<10mm) undergoing radical parametrectomy and pelvic lymphadenectomy. A total of 30 patients were included in the study. The median age was 40.4years (range; 26-60) and median body mass index (BMI) was 26.4kg/m 2 (range; 17.7-40.0). A total 22 patients had tumors<1cm and 8 had tumors between 1 and 2cm. A total of 6 (33%) of 18 patients had evidence of lymph-vascular invasion (LVSI). No radical parametrectomy specimen had residual tumor, involvement of the parametrium, vaginal margin positivity, or lymph node metastasis. None of the patients received adjuvant therapy. After a median follow-up of 99months (range; 6-160) only one patient recurred. Radical parametrectomy may be avoided in patients with low-risk early-stage cervical cancer detected after a simple hysterectomy. Rates of residual disease (parametrial or vaginal) and the need for adjuvant treatments or recurrences are very low. Copyright © 2018 Elsevier Inc. All rights reserved.

O conceito de mal radical The concept of radical evil

Directory of Open Access Journals (Sweden)

Adriano Correia

2005-01-01

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

Preparing polymer brushes on polytetrafluoroethylene films by free radical polymerization

International Nuclear Information System (INIS)

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

2006-01-01

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

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

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

Reactions of carbonate radical with cobalt(II) aminopolycarboxylates

International Nuclear Information System (INIS)

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

1992-01-01

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

An efficient quantum mechanical method for radical pair recombination reactions.

Science.gov (United States)

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

2016-12-28

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

Self-Terminating, Oxidative Radical Cyclizations

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Uta Wille

2004-05-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-07-01

Organic molecules chemisorbed on surfaces hold the perspective of surface functionalization. The 1,4-butanedithiol radical chemisorbed at the Au(111) or Au(100) surface serves as a model system for the S-Au molecule-substrate bond. Density functional total-energy calculations have been carried out for the chemisorption of the radical on the unreconstructed Au surfaces, which are both known to be stabilized under electrochemical conditions. Local minima with close-by energies indicate multi-valley potential-energy surfaces, which originate from the interplay between the two S-Au adsorbate-substrate bonds and the internal degrees of freedom of the butanedithiol radical. Diffusion paths of the radical on both Au surfaces have been calculated within DFT using VASP. The diffusion barriers for translation and rotation of the radical differ. They can be fine-tuned by varying the applied potential in the electrochemical cell. This is considered theoretically by inspecting the variation of the dipole moment along the reaction paths. Consequences for the dynamics of succeeding diffusion hops are discussed.

A preliminary oncologic outcome and postoperative complications in patients undergoing robot-assisted radical cystectomy: Initial experience

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Satoru Muto

2017-05-01

Full Text Available Purpose: Robot-assisted radical cystectomy (RARC was originally intended to replace open radical cystectomy (ORC as a minimally invasive surgery for patients with invasive bladder cancer. The purpose of this study was to evaluate the advantages of robotic surgery, comparing perioperative and oncologic outcomes between RARC and ORC. Materials and Methods: Between June 2012 and August 2016, 49 bladder cancer patients were given a radical cystectomy, 21 robotically and 28 by open procedure. We compared the clinical variables between the RARC and ORC groups. Results: In the RARC group, the median estimated blood loss (EBL during cystectomy, total EBL, operative time during cystectomy, and total operative time were 0 mL, 457.5 mL, 199 minutes, and 561 minutes, respectively. EBL during cystectomy (p<0.001, total EBL (p<0.001, and operative time during cystectomy (p=0.003 in the RARC group were significantly lower compared with the ORC group. Time to resumption of a regular diet (p<0.001 and length of stay (p=0.017 were also significantly shorter compared with the ORC group. However, total operative time in the RARC group (median, 561 minutes was significantly longer compared with the ORC group (median, 492.5 minutes; p=0.015. Conclusions: This Japanese study presented evidence that RARC yields benefits in terms of BL and time to regular diet, while consuming greater total operative time. RARC may be a minimally invasive surgical alternative to ORC with less EBL and shorter length of stay.

Extraction method for high free radical scavenging activity of Siamese neem tree flowers

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Worarat Chaisawangwong

2009-10-01

Full Text Available Siamese neem tree (Azadirachta indica A. Juss. var. siamensis Valeton is a medicinal plant found in Thailand. Youngleaves and young flowers of this plant are commonly consumed as a bitter tonic vegetable. The flowers are also used fortreatment of fever. The flower extract has been reported to exhibit in vitro free radical scavenging activity and can inhibitlipid peroxidation of bronchogenic cancer cell line. Active compounds in the flowers are flavonoids such as rutin andquercetin. The content of these compounds in the crude extract depends on the method of extraction. Therefore, the appropriateextraction method promoting high yield of total flavonoids and high free radical scavenging activity was investigated inthis study. Six different extraction methods, i.e. maceration, percolation, decoction, soxhlet extraction, ultrasonic extraction(UE, and microwave assisted extraction (MA were carried out for extracting dried powder of Siamese neem tree young flowers. The solvent used for maceration, percolation, and soxhlet extraction was 50% ethanol, while distilled water was used for decoction and MA, and both solvents were used for UE. The content of crude extract, free radical scavenging activity, and total flavonoids content of each extract were investigated and compared. Comparing the various extraction methods, decoction provided an extract containing a high amount of total flavonoids (17.54 mgRE/g extract and promoting the highest scavenging activity at EC50 11.36 g/ml. Decoction is also simple, cheap, and convenient and could be used in developing countries. Thus, it should be the recommended extraction method for the flowers of Siamese neem tree for furtherdevelopment of antioxidant pharmaceutical preparations.

Surgical complications of radical retropubic prostatectomy: A single institutional experience of seven years

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Neeraj K Goyal

2007-01-01

Full Text Available Aim: To determine the surgical complications of open retropubic radical prostatectomy. Materials and Methods: Fifty-nine cases of localized prostate cancer underwent retropubic radical prostatectomy in our department in the last seven years. Standard technique of open retropubic radical prostatectomy as described by Walsh was used. During follow-up cancer control and quality of life indices (potency and urinary continence were noted. Result: Postoperative recovery of all patients except one was excellent. This patient required cardio-respiratory support and nine units of blood transfusion. Forty-nine out of 52 patients were continent, two had stress incontinence and one was totally incontinent at one year. Bladder neck contracture was present in eight out of 52 patients at one year. Forty-five patients were impotent at one year with or without oral tablet sildenafil. Cancer control was present in 45 out of 52 cases. Seven cases had biochemical failure at one year. Conclusion: Though retropubic radical prostatectomy is the standard treatment for early prostate cancer it is not without complications. It has a steep learning curve. More number of cases and refinement in technique is required to achieve world-class results.

Free radical scavenging potential and HPTLC analysis of Indigofera tinctoria linn (Fabaceae

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Sakthivel Srinivasan

2016-04-01

Full Text Available The objective of this study was to evaluate the free radical scavenging potential and high performance thin layer chromatography (HPTLC fingerprinting of Indigofera tinctoria (I. tinctoria. Phytochemical analysis was carried out using standard methods, and free radical scavenging activity of the plant was determined using 2,2-diphenyl-1-picrylhydrazy (DPPH, nitric oxide (NO and superoxide anion (O2− radical scavenging capacities. HPTLC plate was kept in CAMAG TLC Scanner 3 and the Rf values at fingerprint data were recorded by WINCATS software. Aqueous extract of I. tinctoria reliably showed the total phenolics (267.2±2.42 mg/g, flavonoids (75.43±3.36 mg/g and antioxidants (349.11±8.04 mg/g. The extract was found to have DPPH (52.08%, NO (23.12% and O2− (26.79% scavenging activities at the concentration of 250 μg/mL and the results were statistically significant compared with ascorbic acid standard (p<0.05. HPTLC results confirmed that the extract contained several potential active components such as phenols, flavonoids, saponins and terpenoids as the slides revealed multi-colored bands of varying intensities. This study confirmed that the plant had multipotential antioxidant and free radicals scavenging activities.

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.)

Near-Infrared Free-Radical and Free-Radical-Promoted Cationic Photopolymerizations by In-Source Lighting Using Upconverting Glass.

Science.gov (United States)

Kocaarslan, Azra; Tabanli, Sevcan; Eryurek, Gonul; Yagci, Yusuf

2017-11-13

A method is presented for the initiation of free-radical and free-radical-promoted cationic photopolymerizations by in-source lighting in the near-infrared (NIR) region using upconverting glass (UCG). This approach utilizes laser irradiation of UCG at 975 nm in the presence of fluorescein (FL) and pentamethyldiethylene triamine (PMDETA). FL excited by light emitted from the UCG undergoes electron-transfer reactions with PMDETA to form free radicals capable of initiating polymerization of methyl methacrylate. To execute the corresponding free-radical-promoted cationic polymerization of cyclohexene oxide, isobutyl vinyl ether, and N-vinyl carbazole, it was necessary to use FL, dimethyl aniline (DMA), and diphenyliodonium hexafluorophosphate as sensitizer, coinitiator, and oxidant, respectively. Iodonium ions promptly oxidize DMA radicals formed to the corresponding cations. Thus, cationic polymerization with efficiency comparable to the conventional irradiation source was achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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)

Redox properties of free radicals

International Nuclear Information System (INIS)

Neta, P.

1981-01-01

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

Hot wire radicals and reactions

International Nuclear Information System (INIS)

Zheng Wengang; Gallagher, Alan

2006-01-01

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

Effect of modified surgical method on subcutaneous hydrops of patients with breast cancer after modified radical mastectomy

OpenAIRE

Yan Li; Hua-Feng Pan; Gui-Lan Sun

2016-01-01

Objective: Through prospective randomized clinical study,to observe the preventive effect of improved surgical method to subcutaneous hydrops after modified radical mastec tomy. Method: A total of 80 cases of patients who have done modified radical mastectomy were selected, and randomly divided them into study group (40 cases) and control group (40 cases), then adopted different surgical methods as followed respectively, to observe the daily drainage volume at the first 3 d after ...

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

DEFF Research Database (Denmark)

Souto, Manuel; Bendixen, Dan; Jensen, Morten

2016-01-01

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

Changes in the amino acid profiles and free radical scavenging activities of Tenebrio molitor larvae following enzymatic hydrolysis.

Science.gov (United States)

Tang, Yujiao; Debnath, Trishna; Choi, Eun-Ju; Kim, Young Wook; Ryu, Jung Pyo; Jang, Sejin; Chung, Sang Uk; Choi, Young-Jin; Kim, Eun-Kyung

2018-01-01

Tenebrio molitor (T. molitor) larvae provide food at low environmental cost and contribute positively to livelihoods. In this research, we compared the amino acids compositions and antioxidant activities of various extracts of T. molitor to enhance their quality as food. For the comparison, distilled water extracts, enzymatic hydrolysates, and condensed enzymatic hydrolysates of T. molitor larvae were prepared. Their amino acids (AAs) profiles and antioxidant activities, including ferric-reducing antioxidant power, oxygen radical absorption capacity, and DPPH, hydroxyl radical, and hydrogen peroxide radical scavenging properties assay were analyzed. DW extracts had the lowest AAs contents and antioxidant activity compared with enzymatic extracts. Condensed hydrolysates with a combination of alcalase and flavourzyme (C-A+F) exhibited the highest levels of total free AAs (11.1759 g/100 g). C-A+F produced higher total hydrolyzed AAs (32.5292 g/100 g) compared with the other groups. The C-A+F possessed the strongest antioxidant activity. Notably, the antioxidant activities of the hydrolysates and the total hydrolyzed AAs amount were correlated. Taken together, our findings showed that C-A+F was a promising technique for obtaining extracts of T. molitor larvae with antioxidant activity as potential nutritious functional food.

Harmonic Scalpel versus Electrocautery Dissection in Modified Radical Mastectomy for Breast Cancer: A Meta-Analysis.

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Jinbo Huang

Full Text Available Despite the common use of conventional electrocautery in modified radical mastectomy for breast cancer, the harmonic scalpel is recently emerging as a dominant surgical instrument for dissection and haemostasis, which is thought to reduce the morbidity, such as seroma and blood loss. But the results of published trials are inconsistent. So we made the meta-analysis to assess the intraoperative and postoperative endpoints among women undergoing modified radical mastectomy with harmonic scalpel or electrocautery.A comprehensive literature search of case-control studies from PubMed, MEDLINE, EMBASE and Cochrane Library databases involving modified radical mastectomy with harmonic scalpel or electrocautery was performed. We carried out a meta-analysis of primary endpoints including postoperative drainage, seroma development, intraoperative blood loss and secondly endpoints including operative time and wound complications. We used odds ratios (ORs with 95% confidence intervals (CIs to evaluate the effect size for categorical outcomes and standardised mean differences (SMDs for continuous outcomes.A total of 11 studies with 702 patients were included for this meta-analysis. There was significant difference in total postoperative drainage (SMD: -0.74 [95%CI: -1.31, -0.16]; P< 0.01, seroma development[OR: 0.49 (0.34, 0.70; P < 0.01], intraoperative blood loss(SMD: -1.14 [95%CI: -1.81,-0.47]; P < 0.01 and wound complications [OR: 0.38 (0.24, 0.59; P < 0.01] between harmonic scalpel dissection and standard electrocautery in modified radical mastectomy for breast cancer. No difference was found as for operative time between harmonic scalpel dissection and standard electrocautery (SMD: 0.04 [95%CI: -0.41, 0.50]; P = 0.85.Compared to standard electrocautery, harmonic scalpel dissection presents significant advantages in decreasing postoperative drainage, seroma development, intraoperative blood loss and wound complications in modified radical mastectomy for

Free radicals trapped in polyethylene matrix

International Nuclear Information System (INIS)

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

1977-01-01

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

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

Science.gov (United States)

Herrling, Thomas; Jung, Katinka; Fuchs, Jürgen

2008-05-01

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

Outcome of postoperative radiotherapy following radical prostatectomy: a single institutional experience

Energy Technology Data Exchange (ETDEWEB)

Lee, Sea Won; Chung, Mi Joo; Jeong, Song Mi; Kim, Sung Hwan; Lee, Jong Hoon [Dept.of Radiation Oncology, St. Vincent' s Hospital, The Catholic University of Korea College of Medicine, Suwon (Korea, Republic of); Hwang, Tae Kon; Hong, Sung Hoo; Lee, Ji Youl; Jang, Hong Seok [Seoul St. Mary' s Hospital, The Catholic University of Korea College of Medicine, Seoul (Korea, Republic of); Yoon, Sei Chul [Dept.of Radiation Oncology, Bucheon St. Mary' s Hospital, The Catholic University of Korea College of Medicine, Bucheon (Korea, Republic of)

2014-09-15

This single institutional study is aimed to observe the outcome of patients who received postoperative radiotherapy after radical prostatectomy. A total of 59 men with histologically identified prostate adenocarcinoma who had received postoperative radiation after radical prostatectomy from August 2005 to July 2011 in Seoul St. Mary's Hospital of the Catholic University of Korea, was included. They received 45-50 Gy to the pelvis and boost on the prostate bed was given up to total dose of 63-72 Gy (median, 64.8 Gy) in conventional fractionation. The proportion of patients given hormonal therapy and the pattern in which it was given were analyzed. Primary endpoint was biochemical relapse-free survival (bRFS) after radiotherapy completion. Secondary endpoint was overall survival (OS). Biochemical relapse was defined as a prostate-specific antigen level above 0.2 ng/mL. After median follow-up of 53 months (range, 0 to 104 months), the 5-year bRFS of all patients was estimated 80.4%. The 5-year OS was estimated 96.6%. Patients who were given androgen deprivation therapy had a 5-year bRFS of 95.1% while the ones who were not given any had that of 40.0% (p < 0.01). However, the statistical significance in survival difference did not persist in multivariate analysis. The 3-year actuarial grade 3 chronic toxicity was 1.7% and no grade 3 acute toxicity was observed. The biochemical and toxicity outcome of post-radical prostatectomy radiotherapy in our institution is favorable and comparable to those of other studies.

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

Salvage radiotherapy for prostate-specific antigen relapse after radical prostatectomy for prostate cancer. A single-center experience

International Nuclear Information System (INIS)

Yoshida, Takahiro; Nakayama, Masashi; Suzuki, Osamu

2011-01-01

The aim of this study was to investigate the efficacy and prognostic factors of salvage radiotherapy for prostate-specific antigen relapse after radical prostatectomy for prostate cancer at a single center in Japan. A retrospective review of the medical records of 51 patients who underwent salvage radiotherapy for prostate-specific antigen relapse after radical prostatectomy was carried out. Salvage radiotherapy was undergone for the single indication of at least two consecutive prostate-specific antigen elevations >0.1 ng/ml. Salvage radiotherapy was delivered to the prostatic bed at a total dose of 60 or 64 Gy. Late toxicity was scored according to the Common Terminology Criteria for Adverse Events 3.0. A total dose of 60 and 64 Gy were administered to 26 and 25 patients, respectively. The median prostate-specific antigen level at the initiation of radiotherapy was 0.29 ng/ml (range, 0.11-1.10 ng/ml). With a median follow-up of 57.3 months (range, 9.9-134.0 months), the prostate-specific antigen relapse-free rate at 5 years was 50.7%. Multivariate analysis using Cox's proportional hazards regression model revealed that the Gleason score at radical prostatectomy ≥8 significantly predicted prostate-specific antigen relapse after salvage radiotherapy (hazard ratio 4.531; 95% confidence interval 1.413-14.535; P=0.011). The prostate-specific antigen relapse-free rate at 5 years in the Gleason score at radical prostatectomy ≤7 and at radical prostatectomy ≥8 was 62.7 and 15.4%, respectively. Salvage radiotherapy was effective for prostate-specific antigen relapse after radical prostatectomy with tolerable toxicities in Japanese patients. A high Gleason score seemed to be a poor prognostic factor. (author)

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)

Radical carbonylations using a continuous microflow system

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Takahide Fukuyama

2009-07-01

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

Abstraction of iodine from aromatic iodides by alkyl radicals: steric and electronic effects.

Science.gov (United States)

Dolenc, Darko; Plesnicar, Bozo

2006-10-13

Abstraction of the iodine atom from aryl iodides by alkyl radicals takes place in some cases very efficiently despite the unfavorable difference in bond dissociation energies of C-I bonds in alkyl and aryl iodides. The abstraction is most efficient in iodobenzenes, ortho-substituted with bulky groups. The ease of abstraction can be explained by the release of steric strain during the elimination of the iodine atom. The rate of abstraction correlates fairly well with the strain energy, calculated by density functional theory (DFT) and Hartree-Fock (HF) methods as a difference in the total energy of ortho and para isomers. However, besides the steric bulk, the presence of some other functional groups in an ortho substituent also influences the rate. The stabilization of the transition state, resembling a 9-I-2 iodanyl radical, by electron-withdrawing groups seems to explain a positive sign of the Hammett rho value in the radical abstraction of halogen atoms.

Radical-Mediated Enzymatic Polymerizations

Science.gov (United States)

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

2016-01-01

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

Role of the NO3 radicals in oxidation processes in the eastern Mediterranean troposphere during the MINOS campaign

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M. Vrekoussis

2004-01-01

Full Text Available During the MINOS campaign (28 July-18 August 2001 the nitrate (NO3 radical was measured at Finokalia station, on the north coast of Crete in South-East Europe using a long path (10.4 km Differential Optical Absorption Spectroscopy instrument (DOAS. Hydroxyl (OH radical was also measured by a Chemical Ionization Mass-Spectrometer (Berresheim et al., 2003. These datasets represent the first simultaneous measurements of OH and NO3 radicals in the area. NO3 radical concentrations ranged from less than 3x107 up to 9x108 radicals· cm-3 with an average nighttime value of 1.1x108 radicals· cm-3. The observed NO3 mixing ratios are analyzed on the basis of the corresponding meteorological data and the volatile organic compound (VOC observations which were measured simultaneously at Finokalia station. The importance of the NO3 radical chemistry relatively to that of OH in the dimethylsulfide (DMS and nitrate cycles is also investigated. The observed NO3 levels regulate the nighttime variation of DMS. The loss of DMS by NO3 during night is about 75% of that by OH radical during day. NO3 and nitrogen pentoxide (N2O5 reactions account for about 21% of the total nitrate (HNO3(g+NO-3(g production.

Allylthioketone Mediated Free Radical Polymerization of Methacrylates

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Feng Zhong

2017-11-01

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

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)

Generation and propagation of radical reactions on proteins

DEFF Research Database (Denmark)

Hawkins, C L; Davies, Michael Jonathan

2001-01-01

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

Optical and magnetic resonance measurements of a segmented poly(ester urethane)

International Nuclear Information System (INIS)

Cooke, D.W.; Muenchausen, R.E.; Bennett, B.L.; Orler, E.B.; Wrobleski, D.A.; Smith, M.E.; Jahan, M.S.; Thomas, D.E.

1999-01-01

X-ray-induced damage in Estane(registered trademark)5703 has been studied by luminescence, optical absorption and electron spin resonance techniques in the temperature interval ∼10-300 K. Molecular motion of the polymer soft segment, as determined by viscoelastic measurements, is correlated with features in the glow curve, indicating charge detrapping via thermal destruction of cavity traps. Spectral emission is characterized by four Lorentzian bands with maxima at 2.38, 2.55, 2.74 and 2.93 eV, which are attributed to triplet-to-singlet electronic transitions of the phenyl group in the polymer hard segment. Absorption peaks at 3.97, 4.29 and 4.46 eV are also assigned to transitions within this group. Several radicals with overlapping resonances are induced at 35 K, which, with increasing temperature, evolve into the relatively stable peroxy free-radical at room temperature

Radical scavenging activity of crude polysaccharides from Camellia sinensis

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Yang Fan

2011-01-01

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

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.

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.

The formation of highly oxidized multifunctional products in the ozonolysis of cyclohexene

DEFF Research Database (Denmark)

Rissanen, Matti P.; Kurtén, Theo; Sipilä, Mikko

2014-01-01

ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO3 -)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including...... of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1...

Some reactions of oxidizing radicals with enzymes in aqueous solution

International Nuclear Information System (INIS)

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

1979-01-01

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

Measurements of total OH reactivity during PROPHET-AMOS 2016

Science.gov (United States)

Rickly, P.; Sakowski, J.; Bottorff, B.; Lew, M.; Stevens, P. S.; Sklaveniti, S.; Locoge, N.; Dusanter, S.

2017-12-01

As one of the main oxidant in the atmosphere, the hydroxyl radical (OH) initiates the oxidation of volatile organic compounds that can lead to the formation of ozone and secondary organic aerosols. Understanding both the sources and sinks of OH is therefore important to address issues related to air quality and climate change. Measurements of total OH reactivity can provide an important test of our understanding of the OH radical budget. Recent measurements of total reactivity in many environments have been greater than calculated based on the measured concentration of VOCs, suggesting that important OH sinks in these environments are not well characterized. Measurements of total OH reactivity were performed in a forested environment during the PROPHET - AMOS field campaign (Program for Research on Oxidants: PHotochemisty, Emissions, and Transport - Atmospheric Measurements of Oxidants in Summer) using the Comparative Reactivity Method (CRM) and the Total OH Loss Rate Method (TOHLM). The site is characterized by large emissions of isoprene and monoterpenes and low anthropogenic influence. Measurements of total OH reactivity using these two techniques agree to within their respective uncertainties, giving confidence in the measured OH reactivity. In addition, measurements of trace gases (VOCs, NOx, O3) were used to perform a comprehensive apportionment of OH sinks. These measurements are used in a chemical model using the Master Chemical Mechanism to calculate the expected OH reactivity. The results will be compared to previous measurements of total OH reactivity at this site.

Long-lived gas-phase radicals from combustion

Energy Technology Data Exchange (ETDEWEB)

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

1989-04-20

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

[Research progress on free radicals in human body].

Science.gov (United States)

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

2016-08-10

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

Deciphering free-radical code of radiation effects

International Nuclear Information System (INIS)

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

2007-01-01

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

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.

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 Antioxidant Capacities and Total Phenolic Contents of Some Medicinal Plants in Iran

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Ali Mirzaei

2011-12-01

Full Text Available Background & Objectives: Free radicals are highly reactive molecules may cause great damage to cell membranes and DNA and Result in inducing oxidation DNA mutations leading to cancer, degenerative, and other diseases. Plant antioxidant derived may be preventive of free radical damages. Methods & Materials: The Stems and flower sample of plants air-dried, finely ground and were extracted by ethanol: water (70:30 for 48 h. Extracts were filtered and dried under vacuum. The antioxidant activity of five ethanolic extract of medicinal plants (Descurainia Sophia, Plantago major, Trachyspermum copticum L, Coriandrum sativum and Trigonella foenum-graecum from Iran were analysed by five different methods [1,1-diphenyl-2-picrylhydrazyl (DPPH radical, 2,2,azinobis-3-ethylbenzthiazoline-6-sulphonic acid (ABTS radical cation, Ferric-reducing antioxidant power assay (FRAP, phosphomolybdenum (PMB and reducing power (RP]. In addition, for determination of antioxidant components total phenolic content was also analyzed. Results: The total phenolic content of medicinal plant ranges from 74 to 154.3 mg Gallic acid/g extract as measured by the Folin–Ciocalteau method. Values of DPPH varied from 15.5 to 19.6 µmol trolex/g. FRAP ranged from 124.2 to 753 µmol of Fe(II/g extract. Antioxidant activity of the Plantago major was always higher compared to the other plants extracts values of total phenols content and antioxidant capacity by DPPH, ABTS, FRAP, (154.33 mg GAE/g, 1856 µmol trolox, 750 µmol trolox and 1169 µmol of Fe(II/g, extract respectively. The range of total antioxidant activity by phosphomolybdenum method was 513.3 to 870 µmol trolox/g. The reducing ability of the tested extracts was between 0.31-1.26. Plantago majorwas also highest activity in both tests. Conclusion: This study clearly demonstrated that Plantago major crude extract exhibit significant antioxidant activity.

Free radical scavenging injectable hydrogels for regenerative therapy

Energy Technology Data Exchange (ETDEWEB)

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

2017-02-01

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

Free radical scavenging injectable hydrogels for regenerative therapy

International Nuclear Information System (INIS)

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

2017-01-01

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

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

Science.gov (United States)

Caldwell, Charles R

2003-07-30

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

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

NARCIS (Netherlands)

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

2011-01-01

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

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

NARCIS (Netherlands)

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

2011-01-01

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

Cation radicals of xanthophylls.

Science.gov (United States)

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

2007-10-01

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

Determining the local origin of hydroxyl radical generation during phacoemulsification.

Science.gov (United States)

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

2011-06-01

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

Radiolysis of paracetamol in dilute aqueous solution

International Nuclear Information System (INIS)

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

2012-01-01

Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O 2 is c.a. 10%. The efficiency is 2–3 times higher in the presence of O 2 due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily. - Highlights: ► Paracetamol is easily degraded in aqueous solution by low dose irradiation. ► Main degradation products are hydroxylated molecules, acetamide and hydroquinone. ► Toxicity of solutions goes through a maximum as a function of dose.

Radiolysis of paracetamol in dilute aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Szabo, Laszlo [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Budapest University of Technology and Economics, Budapest (Hungary); Toth, Tuende [Budapest University of Technology and Economics, Budapest (Hungary); Homlok, Renata [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Takacs, Erzsebet [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Wojnarovits, Laszlo [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary)

2012-09-15

Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O{sub 2} is c.a. 10%. The efficiency is 2-3 times higher in the presence of O{sub 2} due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily. - Highlights: Black-Right-Pointing-Pointer Paracetamol is easily degraded in aqueous solution by low dose irradiation. Black-Right-Pointing-Pointer Main degradation products are hydroxylated molecules, acetamide and hydroquinone. Black-Right-Pointing-Pointer Toxicity of solutions goes through a maximum as a function of dose.

Violent Radicalization in Europe

DEFF Research Database (Denmark)

Dalgaard-Nielsen, Anja

2010-01-01

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

Application of ABTS radical cation for selective on-line detection of radical scavengers in HPLC eluates

NARCIS (Netherlands)

Koleva, [No Value; Niederlander, HAG; van Beek, TA

2001-01-01

The radical cation 2,2 ' -azinobis-(3 -ethylbenzothiazoline-6-sulfonate), (ABTS(.+)) was utilized in an on-line HPLC method for the detection of radical scavengers in complex matrixes. The HPLC-separated analytes react postcolumn with the preformed ABTS(.+), and the induced bleaching is detected as

The first report of a muoniated free radical formed from reaction of Mu with Br2

International Nuclear Information System (INIS)

Ghandi, Khashayar; Cottrell, Stephen P.; Fleming, Donald; Johnson, Clive

2006-01-01

In this paper, we report preliminary data for the first direct evidence of a free radical formed from Mu reactivity with Br 2 in the gas phase, in N 2 moderator at a total pressure of 3 bar. A new experimental setup and target vessel for μSR studies of reactive compounds, such as the halogens and hydrogen halides, suitable as well for RF measurements, is described. The experimental data, obtained from a longitudinal field repolarization curve, yields a hfc of 1770 MHz. We tentatively identify this as the [BrMuBr] radical, a non-conventional bond system, arising from the combination of a van der Waals interaction and dynamics on a repulsive surface. Studies of the dynamics and hfcs of possible radicals, which in principal could form, are also outlined here

Critical appraisal of outcomes following open radical prostatectomy.

Science.gov (United States)

Galvin, David J; Eastham, James A

2009-05-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2010-07-01

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

Radical Sustainable Innovation of office buildings

DEFF Research Database (Denmark)

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

2017-01-01

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

User involvement competence for radical innovation

DEFF Research Database (Denmark)

Lettl, Christopher

2007-01-01

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

User involvement competence for radical innovation

DEFF Research Database (Denmark)

Lettl, Christopher

2007-01-01

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

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

Science.gov (United States)

Witwicki, Maciej; Jezierska, Julia

2012-06-01

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

Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

Science.gov (United States)

Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

2017-09-28

High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

Hydroxyl radical reactivity with diethylhydroxylamine

International Nuclear Information System (INIS)

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

1977-01-01

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

Isolation and characterisation of in vitro and cellular free radical scavenging peptides from corn peptide fractions.

Science.gov (United States)

Wang, Liying; Ding, Long; Wang, Ying; Zhang, Yan; Liu, Jingbo

2015-02-16

Corn gluten meal, a corn processing industry by-product, is a good source for the preparation of bioactive peptides due to its special amino acid composition. In the present study, the in vitro and cellular free radical scavenging activities of corn peptide fractions (CPFs) were investigated. Results indicated that CPF1 (molecular weight less than 1 kDa) and CPF2 (molecular weight between 1 and 3 kDa) exhibited good hydroxyl radical, superoxide anion radical and 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonicacid) diammonium salt (ABTS) radical scavenging activity and oxygen radical absorbance capacity (ORAC). Meanwhile, the in vitro radical scavenging activity of CPF1 was slightly higher than that of CPF2. Both CPF1 and CPF2 also exhibited significant cytoprotective effects and intracellular reactive oxygen species scavenging activity in Caco-2 cells exposed to hydrogen peroxide (H2O2). The amino acid composition analysis revealed that the CPF were rich in hydrophobic amino acids, which comprised of more than 45% of total amino acids. An antioxidant peptide sequence of Tyr-Phe-Cys-Leu-Thr (YFCLT) was identified from CPF1 using matrix-assisted laser desorption/ionization time-of-flight/time-of-flight mass spectrometry (MALDI TOF/TOF MS). The YFCLT exhibited excellent ABTS radical scavenging activity with a 50% effective concentration (EC50) value of 37.63 µM, which was much lower than that of Trolox. In conclusion, corn gluten meal might be a good source to prepare antioxidant peptides.

Radical dematerialization and degrowth

Science.gov (United States)

Kallis, Giorgos

2017-05-01

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

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.

Cytotoxicity, Total Phenolic Contents and Antioxidant Activity of the ...

African Journals Online (AJOL)

The leaves of Annona muricata were extracted using ethanol and the extracts were evaluated for cytotoxicity using Brine Shrimp Lethality Assay, total phenolic content (TPC) and antioxidant activity using DPPH radical scavenging assay. The crude extract showed 73.33 % mortality at 1000 μg/mL concentration and its ...

Radical vs. Conservative Surgical Treatment of Hepatic Hydatid Cyst: A 10- Year Experience

Directory of Open Access Journals (Sweden)

M Ghaemi

2009-07-01

Full Text Available Introduction: Hepatic hydatid cyst is caused by echinococcosis granulosis. It is a major health problem in endemic areas. The modern treatment of hydatid cysts of the liver varies from surgical intervention to percutaneous drainage or medical therapy. A high rate of complications following percutaneous drainage, and ineffectiveness of medical therapy have shown not to be the definitive treatments for the disease. Thus, surgery is still the best choice for the treatment of hydatid cyst of the liver. Surgical treatment methods can be divided into radical and conservative approaches. There is controversy regarding efficacy of the two surgical methods. In this study, we aimed to present a retrospective evaluation of the two surgical methods in patients treated for the hepatic hydatid cyst. Methods: This retrospective study reviewed medical records of 135 patients who underwent surgery for hepatic hydatid cyst from 1997 to 2007. Surgery comprised conservative methods (evacuation of the cyst content and excision of the inner cyst layers and radical methods (total excision of the cyst and removal of its outer layer. Results: One hundred thirty five patients underwent liver surgery. Conservative surgery was performed for 71 (53%, whereas, the remaining 64 patients (47% underwent radical surgery. Postoperative complications were 28% and 19%, respectively. Recurrence of the cyst in the conservative and radical surgery groups was noted to be 12.5 and 1.5%, respectively. The mean length of hospital stay was shorter in the radical surgery group (5 vs. 15 days. Conclusion: Radical surgery may be the preferred treatment for the hepatic hydatid cyst because of its low rate of postoperative complications and recurrence, as well as short hospital stay. Selection of the most appropriate treatment depends on the size, number, and location of the cyst(s, and presence of cystobiliary communications, and the availability of an experienced surgeon.

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.

Biochemistry and pathology of radical-mediated protein oxidation

DEFF Research Database (Denmark)

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

1997-01-01

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

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

NARCIS (Netherlands)

Demant, F.; de Graaf, B.

2010-01-01

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

Determination of the barrier height for acetyl radical dissociation from acetyl chloride photodissociation at 235 nm using velocity map imaging.

Science.gov (United States)

Tang, Xiaonan; Ratliff, Britni J; FitzPatrick, Benjamin L; Butler, Laurie J

2008-12-18

This work uses velocity map imaging to determine the barrier height for acetyl radical, CH3CO, dissociation to CH3 + CO. Photodissociation of acetyl chloride at 235 nm generates acetyl radicals with an internal energy distribution spanning this barrier. We determine the velocity and internal energy distribution of all nascent acetyl radicals, stable and unstable, by measuring the velocities of the Cl(2P3/2) and Cl(2P1/2) cofragments. These Cl cofragments are detected with 2 + 1 resonance-enhanced multiphoton ionization (REMPI) in a spin-orbit branching ratio Cl(2P3/2):Cl(2P1/2) of 3.3 +/- 0.2. Using 157 nm photoionization, we then detect the recoil velocities of the energetically stable acetyl radicals. The radicals and momentum matched Cl atoms evidence parallel angular distributions. Comparison of the total recoil translational energy distribution P(E(T)) for all radicals to that obtained from the detection of stable radicals yields an onset for dissociation at a translational energy of 25.0 +/- 0.4 kcal/mol. From this onset we can calculate the barrier height for CH3CO --> CH3 + CO, but this relies on prior determinations of the C-Cl bond energy of acetyl chloride. Using an experimental bond dissociation energy of 83.4 +/- 0.2 kcal/mol yields a dissociation barrier of 14.2 +/- 0.5 kcal/mol. Our data evidence that a portion of the acetyl radicals formed with total internal energy above the barrier are stable due to the partitioning of energy into rotation during the C-Cl bond fission of the precursor. Thus, the internal energy onset for dissociation is not as sharp as was assumed in prior determinations of the barrier. The experimentally determined onset is compared with that predicted from electronic structure calculations at the G3//B3LYP and CCSD(T) levels of theory.

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

NARCIS (Netherlands)

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

2013-01-01

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

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...

Comparison of ChemicalComposition and Free Radical Scavenging Ability of Glycosidically Bound andFree Volatiles from Bosnian Pine (Pinus heldreichii Christ. var. leucodermis

Directory of Open Access Journals (Sweden)

Mladen Milos

2007-03-01

Full Text Available The results obtained show that Bosnian pine is richin glycosidically bound volatile compounds with strong free radical scavengingproperties. Since volatiles can be released from nonvolatile glycosideprecursors, these compounds can be considered as a hidden potential source ofantioxidant substances and may contribute to the total free radical scavengingability of Bosnian pine.

Radical prostatectomy, sparing of the seminal vesicles, and painful orgasm.

Science.gov (United States)

Mogorovich, Andrea; Nilsson, Andreas E; Tyritzis, Stavros I; Carlsson, Stefan; Jonsson, Martin; Haendler, Leif; Nyberg, Tommy; Steineck, Gunnar; Wiklund, N Peter

2013-05-01

Erectile dysfunction has been widely investigated as the major factor responsible for sexual bother in patients after radical prostatectomy (RP); painful orgasm (PO) is one element of this bother, but little is known about its prevalence and its effects on sexual health. This study aims to investigate the prevalence of PO and to identify potential risk factors. A total of 1,411 consecutive patients underwent open (radical retropubic prostatectomy) or robot-assisted laparoscopic RP between 2002 and 2006. The patients were asked to complete a study-specific questionnaire. Of a total of 145 questions, 5 dealt with the orgasmic characteristics. The questionnaire was also administered to a comparison group of 442 persons, matched for age and area of residency. The response rate was 91% (1,288 patients). A total of 143 (11%) patients reported PO. Among the 834 men being able to have an orgasm, the prevalence was 18% vs. 6% in the comparison group (relative risk [RR] 2.8, 95% confidence interval [CI] 1.7-4.5). When analyzed as independent variables, bilateral seminal vesicle (SV)-sparing approach (RR 2.33, 95% CI 1.0-5.3, P = 0.045) and age <60 years were significantly related to the presence of PO (95% CI 0.5-0.9, P = 0.019). After adjustment for age, bilateral SV-sparing still remained a significant predictor for occurrence of PO. We found that PO occurs significantly more often in patients undergoing bilateral SV-sparing RP when compared with age-matched comparison population. © 2013 International Society for Sexual Medicine.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-05-28

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

The Rise of Radicals in Bioinorganic Chemistry

OpenAIRE

Gray, Harry B.; Winkler, Jay R.

2016-01-01

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

Radical prostatectomy. Results and indications

International Nuclear Information System (INIS)

Jacqmin, D.

1997-01-01

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

Responsibility for radical change in addressing climate change

NARCIS (Netherlands)

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

2015-01-01

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

Sensitivity to grid resolution in the ability of a chemical transport model to simulate observed oxidant chemistry under high-isoprene conditions

Directory of Open Access Journals (Sweden)

K. Yu

2016-04-01

Full Text Available Formation of ozone and organic aerosol in continental atmospheres depends on whether isoprene emitted by vegetation is oxidized by the high-NOx pathway (where peroxy radicals react with NO or by low-NOx pathways (where peroxy radicals react by alternate channels, mostly with HO2. We used mixed layer observations from the SEAC4RS aircraft campaign over the Southeast US to test the ability of the GEOS-Chem chemical transport model at different grid resolutions (0.25°  ×  0.3125°, 2°  ×  2.5°, 4°  ×  5° to simulate this chemistry under high-isoprene, variable-NOx conditions. Observations of isoprene and NOx over the Southeast US show a negative correlation, reflecting the spatial segregation of emissions; this negative correlation is captured in the model at 0.25°  ×  0.3125° resolution but not at coarser resolutions. As a result, less isoprene oxidation takes place by the high-NOx pathway in the model at 0.25°  ×  0.3125° resolution (54 % than at coarser resolution (59 %. The cumulative probability distribution functions (CDFs of NOx, isoprene, and ozone concentrations show little difference across model resolutions and good agreement with observations, while formaldehyde is overestimated at coarse resolution because excessive isoprene oxidation takes place by the high-NOx pathway with high formaldehyde yield. The good agreement of simulated and observed concentration variances implies that smaller-scale non-linearities (urban and power plant plumes are not important on the regional scale. Correlations of simulated vs. observed concentrations do not improve with grid resolution because finer modes of variability are intrinsically more difficult to capture. Higher model resolution leads to decreased conversion of NOx to organic nitrates and increased conversion to nitric acid, with total reactive nitrogen oxides (NOy changing little across model resolutions. Model concentrations in the

Effect of heavy ion irradiation on sucrose radical production

International Nuclear Information System (INIS)

Nakagawa, Kouichi; Sato, Yukio

2004-01-01

We investigated sucrose radicals produced by heavy-ion irradiation with various LETs (linear energy transfer) and the possibility for a sucrose ESR (electron spin resonance) dosimeter. The obtained spectral pattern was the same as that for helium (He) ions, carbon (C) ions, neon (Ne) ions, argon (Ar) ions, and iron (Fe) ions. Identical spectra were measured after one year, but the initial intensities decreased by a few percent when the samples were kept in ESR tubes with the caps at ambient temperature. The total spin concentration obtained by heavy-ion irradiation had a linear relation with the absorbed dose, and correlated logarithmically with the LET. Qualitative ESR analyses showed that the production of sucrose radicals depended on both the particle identity and the LET at the same dose. The production of spin concentration by He ions was the most sensitive to LET. Empirical relations between the LET and the spin yield for various particles imply that the LET at a certain dose can be estimated by the spin concentration. (authors)

An Appreciation of Free Radical Chemistry

Indian Academy of Sciences (India)

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

Treatment results of adjuvant radiotherapy and salvage radiotherapy after radical prostatectomy for prostate cancer

International Nuclear Information System (INIS)

Wadasaki, Koichi; Kaneyasu, Yuko; Kenjo, Masahiro; Matsuura, Kanji; Murakami, Yuji; Hashimoto, Yasutoshi; Ito, Katsuhide; Kiriu, Hiroshi; Ito, Atsushi

2007-01-01

The indications for and the efficacy of radiation therapy after radical operation for patients with prostate cancer are not clear. We analyzed the treatment results of adjuvant radiotherapy and salvage radiotherapy after radical prostatectomy. Between September 1997 and November 2004, 57 patients received adjuvant radiotherapy or salvage radiotherapy after radical prostatectomy. Fifteen patients received radiation therapy because of positive margins and/or extracapsular invasion in surgical specimens (adjuvant group). Forty-two patients received radiation therapy because of rising prostate-specific antigen (PSA) during follow-up (salvage group). Radiation therapy was delivered to the fossa of the prostate±seminal vesicles by a three-dimensional (3-D) conformal technique to a total dose of 60-66 Gy (median, 60 Gy). Biochemical control was defined as the maintenance of a PSA level of less than 0.2 ng/ml. The median follow-up period after radiation therapy was 33 months (range, 12-98 months). Three-year biochemical control rates were 87% for the adjuvant group and 61% for the salvage group. For patients in the salvage group treated without hormone therapy, the preradiation PSA value was the most significant factor for the biochemical control rate. The 3-year biochemical control rate was 93% in patients whose preradiation PSA was 0.5 ng/ml or less and 29% in patients whose preradiation PSA was more than 0.5 ng/ml. No severe adverse effects (equal to or more than grade 3) were seen in treated patients. Radiation therapy after radical prostatectomy seemed to be effective for adjuvant therapy and for salvage therapy in patients with a preradiation PSA of 0.5 ng/ml or less. Also, radiation to the fossa of the prostate±seminal vesicles, to a total dose of 60-66 Gy, using a three-dimensional (3-D) conformal technique, seemed to be safe. (author)

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

Interactions between simple radicals and water

International Nuclear Information System (INIS)

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

2008-01-01

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

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

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

Perioperative and mid-term oncologic outcomes of robotic assisted radical cystectomy with totally intracorporeal neobladder: Results of a propensity score matched comparison with open cohort from a single-centre series.

Science.gov (United States)

Simone, Giuseppe; Tuderti, Gabriele; Misuraca, Leonardo; Anceschi, Umberto; Ferriero, Mariaconsiglia; Minisola, Francesco; Guaglianone, Salvatore; Gallucci, Michele

2018-04-17

In this study, we compared perioperative and oncologic outcomes of patients treated with either open or robot-assisted radical cystectomy and intracorporeal neobladder at a tertiary care center. The institutional prospective bladder cancer database was queried for "cystectomy with curative intent" and "neobladder". All patients underwent robot-assisted radical cystectomy and intracorporeal neobladder or open radical cystectomy and orthotopic neobladder for high-grade non-muscle invasive bladder cancer or muscle invasive bladder cancer with a follow-up length ≥2 years were included. A 1:1 propensity score matching analysis was used. Kaplan-Meier method was performed to compare oncologic outcomes of selected cohorts. Survival rates were computed at 1,2,3 and 4 years after surgery and the log rank test was applied to assess statistical significance between the matched groups. Overall, 363 patients (299 open and 64 robotic) were included. Open radical cystectomy patients were more frequently male (p = 0.08), with higher pT stages (p = 0.003), lower incidence of urothelial histologies (p = 0.05) and lesser adoption of neoadjuvant chemotherapy (open radical cystectomy cases (all p ≥ 0.22). Open cohort showed a higher rate of perioperative overall complications (91.3% vs 42.2%, p 0.001). At Kaplan-Meier analysis robotic and open cohorts displayed comparable disease-free survival (log-rank p = 0.746), cancer-specific survival (p = 0.753) and overall-survival rates (p = 0.909). Robot-assisted radical cystectomy and intracorporeal neobladder provides comparable oncologic outcomes of open radical cystectomy and orthotopic neobladder at intermediate term survival analysis. Copyright © 2018 Elsevier Ltd, BASO ~ The Association for Cancer Surgery, and the European Society of Surgical Oncology. All rights reserved.

In vitro callus culture of Heliotropium indicum Linn. for assessment of total phenolic and flavonoid content and antioxidant activity.

Science.gov (United States)

Kumar, Muthusamy Senthil; Chaudhury, Shibani; Balachandran, Srinivasan

2014-12-01

The total phenolic and flavonoid content and percentage of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging activity of callus and in vivo plant parts of Heliotropium indicum Linn. were estimated. Murashige and Skoog (MS) basal medium supplemented with α-naphthaleneacetic acid (NAA) 2.0 mg/l with benzyladenine (BA) 0.5 mg/l showed the highest amount of callus biomass (1.87 g/tube). The morphology of callus was significantly different according to the plant growth regulators and their concentrations used in the medium. The highest amount of total phenolic (21.70 mg gallic acid equivalent per gram (GAE/g)) and flavonoid (4.90 mg quercetin equivalent per gram (QE/g)) content and the maximum percentage (77.78 %) of radical scavenging activity were estimated in the extract of inflorescence. The synergistic effect of NAA (2.0 mg/l) and BA (0.5 mg/l) enhances the synthesis of total phenolic (9.20 mg GAE/g) and flavonoid (1.25 mg QE/g) content in the callus tissue. The callus produced by the same concentration shows 45.24 % of free radical scavenging activity. While comparing the various concentrations of NAA with 2,4-dichlorophenoxyacetic acid (2,4-D) for the production of callus biomass, total phenolic and flavonoid content and free radical scavenging activity, all the concentrations of NAA were found to be superior than those of 2,4-D.

The first report of a muoniated free radical formed from reaction of Mu with Br{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Ghandi, Khashayar [Department of Chemistry, Mount Allison University, 63C York Street, Sackville (Canada)]. E-mail: kghandi@mta.ca; Cottrell, Stephen P. [ISIS, CCLRC Rutherford Appleton Laboratory, Chilton (United Kingdom); Fleming, Donald [Department of Chemistry, University of British Columbia and TRIUMF, Vancouver, NB E4L 1G8 (Canada); Johnson, Clive [ISIS, CCLRC Rutherford Appleton Laboratory, Chilton (United Kingdom)

2006-03-31

In this paper, we report preliminary data for the first direct evidence of a free radical formed from Mu reactivity with Br{sub 2} in the gas phase, in N{sub 2} moderator at a total pressure of 3 bar. A new experimental setup and target vessel for {mu}SR studies of reactive compounds, such as the halogens and hydrogen halides, suitable as well for RF measurements, is described. The experimental data, obtained from a longitudinal field repolarization curve, yields a hfc of 1770 MHz. We tentatively identify this as the [BrMuBr] radical, a non-conventional bond system, arising from the combination of a van der Waals interaction and dynamics on a repulsive surface. Studies of the dynamics and hfcs of possible radicals, which in principal could form, are also outlined here.

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.

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

Total Synthesis of 15-F2t-Isoprostane by Using a New Oxidative Cyclization of Distonic Radical Anions as the Key Step

Czech Academy of Sciences Publication Activity Database

Jahn, Ullrich; Dinca, E.

2009-01-01

Roč. 15, č. 1 (2009), s. 58-62 ISSN 0947-6539 Grant - others:DFG(DE) Ja896/3-1 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclization * electron transfer * prostanoids * radical ions Subject RIV: CC - Organic Chemistry Impact factor: 5.382, year: 2009

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)

Enhancing production through optimisation of DPPH and radical ...

African Journals Online (AJOL)

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

TECHNICAL CHARACTERISTICS OF RADICAL PROSTATECTOMY FOR EARLY CONTINENCE RECOVERY

Directory of Open Access Journals (Sweden)

V. A. Perepechay

2014-07-01

Full Text Available The paper presents the technical characteristics of radical prostatectomy (RPE for early continence recovery in patients with prostate cancer. Restoration of the fascial structures of the small pelvis after RPE has been found to promote early urinary continence recovery. A method for total restoration of the fascial structures of the small pelvis (an operation after A. Tewari and a procedure for performing posterior suspension of urethrocystic neoanastomosis in Denonvilliers’ fascia length deficit are considered, which show the similar results in the time of continence recovery.

Hydroxyl-radical induced dechlorination of pentachlorophenol in water

International Nuclear Information System (INIS)

He Yongke; Wu Jilan; Fang Xingwang; Sonntag, C. von

1998-01-01

The hydroxyl-radical induced dechlorination of pentachlorophenol (PCP) in water has been investigated pulse radiolytically. Hydroxyl radicals react with PCP by both electron transfer and addition. The former process results in pentachlorophenoxyl radicals (PCP-O), the latter process followed by rapid HCl elimination gives birth to deprotonated hydroxytetrachlorophenoxyl radicals ( - O-TCP-O). These phenoxyl radicals exhibit maximum absorption around 452 nm, which hinders the proper estimation of the ratio of the two processes. However, these two processes cause different changes in conductivity. In basic solution, the electron transfer causes a conductivity increase due to the formation of OH - whereas an addition followed by HCl elimination results in a conductivity decrease. The concurrence of these two processes reduces the relative variation in conductivity, from which about 53% electron transfer is deduced

Exploring the Theories of Radicalization

Directory of Open Access Journals (Sweden)

Maskaliūnaitė Asta

2015-12-01

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

Superoxide radical (O2-) reactivity with respect to glutathione

International Nuclear Information System (INIS)

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

1984-01-01

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

3D analysis of high ozone production rates observed during the ESCOMPTE campaign

Science.gov (United States)

Coll, Isabelle; Pinceloup, Stéphanie; Perros, Pascal E.; Laverdet, Gérard; Le Bras, Georges

2005-03-01

The development of environmental policies to reduce the ozone levels around large agglomerations requires a good understanding of the development of ozone episodes. In particular, it is necessary to know the location and photochemical activity of the plume where ozone is formed. Measurement campaigns make it possible not only to characterize the concentration fields of ozone and its precursors but also to identify the zones of strong ozone production, by means of specific measurements and kinetic calculations. The combination of the observation-based data with numerical simulations allows to better characterize photochemical pollution. This paper presents a study carried out within the ESCOMPTE program and based on the determination of ozone production rates by experimental and numerical methods: ground measurements of peroxy radicals, NO x at a rural site, airborne measurements of NO X and O 3, Eulerian modeling. The reported case is of particular interest since it corresponds to an episode with very different photochemical situations. The diurnal variations of the peroxy radical concentration are analyzed in relation to those of ozone and its precursors. Ozone production rates— P(O 3)-are studied over one particular day. The results show particularly high concentrations of RO 2+HO 2 at ground level (up to 200 pptv) under the influence of the urban and industrial plume, but also highlight very high production rates of ozone (60 to 80 ppbv h -1) a few tens of kilometers from the sources. The results show satisfactory agreement between the various approaches. Modeling provides a four-dimensional (4D) description of the plumes, in particular the relation between the ozone precursor concentrations and P(O 3) on the ground.

Observational constraints on the global atmospheric budget of ethanol

Directory of Open Access Journals (Sweden)

V. Naik

2010-06-01

Full Text Available Energy security and climate change concerns have led to the promotion of biomass-derived ethanol, an oxygenated volatile organic compound (OVOC, as a substitute for fossil fuels. Although ethanol is ubiquitous in the troposphere, our knowledge of its current atmospheric budget and distribution is limited. Here, for the first time we use a global chemical transport model in conjunction with atmospheric observations to place constraints on the ethanol budget, noting that additional measurements of ethanol (and its precursors are still needed to enhance confidence in our estimated budget. Global sources of ethanol in the model include 5.0 Tg yr⁻¹ from industrial sources and biofuels, 9.2 Tg yr⁻¹ from terrestrial plants, ~0.5 Tg yr⁻¹ from biomass burning, and 0.05 Tg yr⁻¹ from atmospheric reactions of the ethyl peroxy radical (C₂H₅O₂ with itself and with the methyl peroxy radical (CH₃O₂. The resulting atmospheric lifetime of ethanol in the model is 2.8 days. Gas-phase oxidation by the hydroxyl radical (OH is the primary global sink of ethanol in the model (65%, followed by dry deposition (25%, and wet deposition (10%. Over continental areas, ethanol concentrations predominantly reflect direct anthropogenic and biogenic emission sources. Uncertainty in the biogenic ethanol emissions, estimated at a factor of three, may contribute to the 50% model underestimate of observations in the North American boundary layer. Current levels of ethanol measured in remote regions are an order of magnitude larger than those in the model, suggesting a major gap in understanding. Stronger constraints on the budget and distribution of ethanol and OVOCs are a critical step towards assessing the impacts of increasing the use of ethanol as a fuel.

Investigating Atmospheric Oxidation with Molecular Dynamics Imaging and Spectroscopy

Science.gov (United States)

Merrill, W. G.; Case, A. S.; Keutsch, F. N.

2013-06-01

Volatile organic compounds (VOCs) in the Earth's atmosphere constitute trace gas species emitted primarily from the biosphere, and are the subject of inquiry for a variety of air quality and climate studies. Reactions intiated (primarily) by the hydroxyl radical (OH) lead to a myriad of oxygenated species (OVOCs), which in turn are prone to further oxidation. Investigations of the role that VOC oxidation plays in tropospheric chemistry have brought to light two troubling scenarios: (1) VOCs are responsible in part for the production of two EPA-regulated pollutants---tropospheric ozone and organic aerosol---and (2) the mechanistic details of VOC oxidation remain convoluted and poorly understood. The latter issue hampers the implementation of near-explicit atmospheric simulations, and large discrepancies in OH reactivity exist between measurements and models at present. Such discrepancies underscore the need for a more thorough description of VOC oxidation. Time-of-flight measurements and ion-imaging techniques are viable options for resolving some of the mechanistic and energetic details of VOC oxidation. Molecular beam studies have the advantage of foregoing unwanted bimolecular reactions, allowing for the characterization of specific processes which must typically compete with the complex manifold of VOC oxidation pathways. The focus of this work is on the unimolecular channels of organic peroxy radical intermediates, which are necessarily generated during VOC oxidation. Such intermediates may isomerize and decompose into distinct chemical channels, enabling the unambiguous detection of each pathway. For instance, a (1 + 1') resonance enhanced multiphoton ionization (REMPI) scheme may be employed to detect carbon monoxide generated from a particular unimolecular process. A number of more subtle mechanistic details may be explored as well. By varying the mean free path of the peroxy radicals in a flow tube, the role of collisional quenching in these unimolecular

Reactions of melatonin with radicals in deoxygenated aqueous solution

International Nuclear Information System (INIS)

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

1998-01-01

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

Physicochemical characterisation and radical-scavenging activity of Cucurbitaceae seed oils.

Science.gov (United States)

Jorge, Neuza; da Silva, Ana Carolina; Malacrida, Cassia Roberta

2015-01-01

Oils extracted from Cucurbitaceae seeds were characterised for their fatty acid and tocopherol compositions. In addition, some physicochemical characteristics, total phenolic contents and the radical-scavenging activities were determined. Oil content amounted to 23.9% and 27.1% in melon and watermelon seeds, respectively. Physicochemical characteristics were similar to those of other edible oils and the oils showed significant antioxidant activities. Fatty acid composition showed total unsaturated fatty acid content of 85.2-83.5%, with linoleic acid being the dominant fatty acid (62.4-72.5%), followed by oleic acid (10.8-22.7%) and palmitic acid (9.2-9.8%). The oils, especially watermelon seed oil, showed high total tocopherol and phenolic contents. The γ-tocopherol was the predominant tocopherol in both oils representing 90.9 and 95.6% of the total tocopherols in melon and watermelon seed oils, respectively. The potential utilisation of melon and watermelon seed oils as a raw material for food, chemical and pharmaceutical industries appears to be favourable.

Rate constants for the reaction of OH radicals with 1-chloroalkanes at 295 K

DEFF Research Database (Denmark)

Markert, F.; Nielsen, O.J.

1992-01-01

The rate constants for the reaction of OH radicals with a series of 1-chloroalkanes were measured at 295 K and at a total pressure of 1 atm. The rate constants were obtained by using the absolute technique of pulse radiolysis combined with kinetic UV-spectroscopy. The results are discussed in terms...

Sulfate radical-based water treatment in presence of chloride: formation of chlorate, inter-conversion of sulfate radicals into hydroxyl radicals and influence of bicarbonate.

Science.gov (United States)

Lutze, Holger V; Kerlin, Nils; Schmidt, Torsten C

2015-04-01

Sulfate radical (SO4(-)) based oxidation is discussed as a potential water treatment option and is already used in ground water remediation. However, the complex SO4(-) chemistry in various matrices is poorly understood. In that regard, the fast reaction of SO4(-) with Cl(-) is of high importance since Cl(-) belongs to the main constituents in aqueous environments. This reaction yields chlorine atoms (Cl) as primary products. Cl initiate a cascade of subsequent reactions with a pH dependent product pattern. At low pH ( 5 Cl mainly react with water yielding hydroxyl radicals. Thus, at moderate Cl(-) concentrations (mM range) the SO4(-)-based process may be converted into a conventional (hydroxyl radical -based) advanced oxidation process. The conversion of SO4(-) into OH, however, is interrupted in presence of bicarbonate by scavenging of Cl. Copyright © 2014. Published by Elsevier Ltd.

Free radical scavenging injectable hydrogels for regenerative therapy.

Science.gov (United States)

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

2017-02-01

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

IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

Science.gov (United States)

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

2013-01-01

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

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

Evidence of free radical and antioxidant activity in Spirodela exposed to metallic and metal oxide nanoparticles: potential for protein and lipid damage

CSIR Research Space (South Africa)

Thwala, Melusi

2012-04-01

Full Text Available the quantities of free radicals (H202, total ROS/RNS), antioxidant activity (catalase, superoxide disrnutasc, and total antioxidam capacity) were analyzed. Oxidative stress has been suggested as a significant route of toxicity induction by engineered...

Flavonoids as scavengers of nitric oxide radical.

NARCIS (Netherlands)

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

1995-01-01

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

Radical radiation therapy for prostate cancer in Japan. A patterns of care study report

International Nuclear Information System (INIS)

Nakamura, Katsumasa; Mitsuhashi, Norio

2003-01-01

The patterns of radical radiation therapy for prostate cancer are unclear in Japan. A Patterns of Care Study was performed throughout Japan to examine the patterns of radiation therapy for prostate cancer. From 1999 to 2000, extramural audits were performed on 50 randomly selected institutions (∼7% of all institutions in Japan). Detailed information was collected on a total of 311 prostate cancer patients without evidence of distant metastases, who were treated by radiation therapy between 1996 and 1998. Of these 311 patients, 162 treated radically using photon beams were analyzed in this study. Eighty percent of the patients had high-risk diseases defined as T3 or T4 tumors, a pretreatment prostate-specific antigen level >20 ng/ml or poorly differentiated adenocarcinoma. Androgen ablation was performed in 85.8% of patients and the median duration of hormonal therapy before and after radiation therapy was 5.3 and 21.4 months, respectively. The median total dose of radiation therapy to the prostate was 65.0 Gy (range: 20-74 Gy). The 3-year overall and biochemical relapse-free survival rates were 86.7 and 86.1%, respectively. Late toxicity was mild, with only nine patients (5.6%) exhibiting grade 2 late morbidity. The majority of the patients who received radical radiation therapy in Japan have high-risk disease. Androgen ablation plus radiation therapy was commonly used to treat these patients and resulted in high rates of initial control with a low risk of complications. (author)

Progress on resonance ionization detection of combustion radicals

International Nuclear Information System (INIS)

Cool, T.A.

1994-01-01

Selective laser ionization techniques are used in our laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames. The progress made on the following three separate experiments during the past year is briefly described in this report. Flame Radical Concentration Measurements with VUV Spectroscopy; observation of hyperfine quantum beats in cyanogen; and the spectroscopy of the ClCO radical

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

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.

Alkyl Radicals as Hydrogen Bond Acceptors: Computational Evidence

DEFF Research Database (Denmark)

Hammerum, Steen

2009-01-01

Spectroscopic, energetic and structural information obtained by DFT and G3-type computational studies demonstrates that charged proton donors can form moderately strong hydrogen bonds to simple alkyl radicals. The presence of these bonds stabilizes the adducts and modifies their structure......, and gives rise to pronounced shifts of IR stretching frequencies and to increased absorption intensities. The hydrogen bond acceptor properties of alkyl radicals equal those of many conventional acceptors, e.g., the bond length changes and IR red-shifts suggest that tert-butyl radicals are slightly better...... acceptors than formaldehyde molecules, while propyl radicals are as good as H2O. The hydrogen bond strength appears to depend on the proton affinity of the proton donor and on the ionization energy of the acceptor alkyl radical, not on the donor-acceptor proton affinity difference, reflecting...