Enzymic aromatization of 6-alkyl-substituted androgens, potent competitive and mechanism-based inhibitors of aromatase.

PubMed Central

Numazawa, M; Yoshimura, A; Oshibe, M

1998-01-01

To gain insight into the relationships between the aromatase inhibitory activity of 6-alkyl-substituted androgens, potent competitive inhibitors, and their ability to serve as a substrate of aromatase, we studied the aromatization of a series of 6alpha- and 6beta-alkyl (methyl, ethyl, n-propyl, n-pentyl and n-heptyl)-substituted androst-4-ene-3,17-diones (ADs) and their androsta-1,4-diene-3,17-dione (ADD) derivatives with human placental aromatase, by gas chromatography-mass spectrometry. Among the inhibitors examined, ADD and its 6alpha-alkyl derivatives with alkyl functions less than three carbons long, together with 6beta-methyl ADD, are suicide substrates of aromatase. All of the steroids, except for 6beta-n-pentyl ADD and its n-heptyl analogue as well as 6beta-n-heptyl AD, were found to be converted into the corresponding 6-alkyl oestrogens. The 6-methyl steroids were aromatized most efficiently in each series, and the aromatization rate essentially decreased in proportion to the length of the 6-alkyl chains in each series, where the 6alpha-alkyl androgens were more efficient substrates than the corresponding 6beta isomers. The Vmax of 6alpha-methyl ADD was approx. 2.5-fold that of the natural substrate AD and approx. 3-fold that of the parent ADD. On the basis of this, along with the facts that the rates of a mechanism-based inactivation of aromatase by ADD and its 6alpha-methyl derivative are similar, it is implied that alignment of 6alpha-methyl ADD in the active site could favour the pathway leading to oestrogen over the inactivation pathway, compared with that of ADD. The relative apparent Km values for the androgens obtained in this study are different from the relative Ki values obtained previously, indicating that there is a difference between the ability to serve as an inhibitor and the ability to serve as a substrate in the 6-alkyl androgen series. PMID:9405288

40 CFR 799.5025 - Testing consent orders for mixtures without Chemical Abstracts Service Registry Numbers.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Required test FR citation Di(heptyl, nonyl, undecyl) phthalate (D711P) as a mixture of the following six substances: (1) diheptyl phthalate (branched and linear isomers), CAS No. 68515-44-6 Environmental effects. January 9, 1989. (2) dinonyl phthalate (branched and linear isomers), CAS No. 68515-45-7 ......do Do. (3...

40 CFR 799.5025 - Testing consent orders for mixtures without Chemical Abstracts Service Registry Numbers.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Required test FR citation Di(heptyl, nonyl, undecyl) phthalate (D711P) as a mixture of the following six substances: (1) diheptyl phthalate (branched and linear isomers), CAS No. 68515-44-6 Environmental effects. January 9, 1989. (2) dinonyl phthalate (branched and linear isomers), CAS No. 68515-45-7 ......do Do. (3...

40 CFR 799.5025 - Testing consent orders for mixtures without Chemical Abstracts Service Registry Numbers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Required test FR citation Di(heptyl, nonyl, undecyl) phthalate (D711P) as a mixture of the following six substances: (1) diheptyl phthalate (branched and linear isomers), CAS No. 68515-44-6 Environmental effects. January 9, 1989. (2) dinonyl phthalate (branched and linear isomers), CAS No. 68515-45-7 ......do Do. (3...

40 CFR 799.5025 - Testing consent orders for mixtures without Chemical Abstracts Service Registry Numbers.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Required test FR citation Di(heptyl, nonyl, undecyl) phthalate (D711P) as a mixture of the following six substances: (1) diheptyl phthalate (branched and linear isomers), CAS No. 68515-44-6 Environmental effects. January 9, 1989. (2) dinonyl phthalate (branched and linear isomers), CAS No. 68515-45-7 ......do Do. (3...

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2013 CFR

2013-10-01

...-Amyl methyl ether (Methyl tert-pentyl ether) C Amyl methyl ketone, see Methyl amyl ketone D Animal and... heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone n-Butyl propionate C Butyl stearate III... alcohol (all isomers) C Diisobutylene B Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate...

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2014 CFR

2014-10-01

... Amyl methyl ketone, see Methyl amyl ketone D Animal and Fish oils, n.o.s. D (see also Oil, edible, or...-Butyl formate D n-Butyl formate @D Butyl heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone... Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate, see Dialkyl(C7-C13) phthalates Diisononyl...

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2012 CFR

2012-10-01

... Amyl methyl ketone, see Methyl amyl ketone D Animal and Fish oils, n.o.s. D (see also Oil, edible, or...-Butyl formate D n-Butyl formate @D Butyl heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone... Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate, see Dialkyl(C7-C13) phthalates Diisononyl...

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2011 CFR

2011-10-01

... Amyl methyl ketone, see Methyl amyl ketone D Animal and Fish oils, n.o.s. D (see also Oil, edible, or...-Butyl formate D n-Butyl formate @D Butyl heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone... Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate, see Dialkyl(C7-C13) phthalates Diisononyl...

46 CFR 30.25-1 - Cargoes carried in vessels certificated under the rules of this subchapter.

Code of Federal Regulations, 2010 CFR

2010-10-01

... Amyl methyl ketone, see Methyl amyl ketone D Animal and Fish oils, n.o.s. D (see also Oil, edible, or...-Butyl formate D n-Butyl formate @D Butyl heptyl ketone [C] Butyl methyl ketone, see Methyl butyl ketone... Diisobutyl ketone D Diisobutyl phthalate B Diisodecyl phthalate, see Dialkyl(C7-C13) phthalates Diisononyl...

Molecular Signature of Pseudomonas aeruginosa with Simultaneous Nanomolar Detection of Quorum Sensing Signaling Molecules at a Boron-Doped Diamond Electrode

NASA Astrophysics Data System (ADS)

Buzid, Alyah; Shang, Fengjun; Reen, F. Jerry; Muimhneacháin, Eoin Ó.; Clarke, Sarah L.; Zhou, Lin; Luong, John H. T.; O'Gara, Fergal; McGlacken, Gerard P.; Glennon, Jeremy D.

2016-07-01

Electroanalysis was performed using a boron-doped diamond (BDD) electrode for the simultaneous detection of 2-heptyl-3-hydroxy-4-quinolone (PQS), 2-heptyl-4-hydroxyquinoline (HHQ) and pyocyanin (PYO). PQS and its precursor HHQ are two important signal molecules produced by Pseudomonas aeruginosa, while PYO is a redox active toxin involved in virulence and pathogenesis. This Gram-negative and opportunistic human pathogen is associated with a hospital-acquired infection particularly in patients with compromised immunity and is the primary cause of morbidity and mortality in cystic fibrosis (CF) patients. Early detection is crucial in the clinical management of this pathogen, with established infections entering a biofilm lifestyle that is refractory to conventional antibiotic therapies. Herein, a detection procedure was optimized and proven for the simultaneous detection of PYO, HHQ and PQS in standard mixtures, biological samples, and P. aeruginosa spiked CF sputum samples with remarkable sensitivity, down to nanomolar levels. Differential pulse voltammetry (DPV) scans were also applicable for monitoring the production of PYO, HHQ and PQS in P. aeruginosa PA14 over 8 h of cultivation. The simultaneous detection of these three compounds represents a molecular signature specific to this pathogen.

40 CFR 60.667 - Chemicals affected by subpart NNN.

Code of Federal Regulations, 2012 CFR

2012-07-01

... fractions n-Butane 106-97-8 1,4-Butanediol 110-63-4 Butanes, mixed 1-Butene 106-98-9 2-Butene 25167-67-3 Butenes, mixed n-Butyl acetate 123-86-4 Butyl acrylate 141-32-2 n-Butyl alcohol 71-36-3 sec-Butyl alcohol... Diethanolamine 111-42-2 Diethylbenzene 25340-17-4 Diethylene glycol 111-46-6 Di-n-heptyl-n-nonyl undecyl...

[Gene deletion and functional analysis of the heptyl glycosyltransferase (waaF) gene in Vibrio parahemolyticus O-antigen cluster].

PubMed

Zhao, Feng; Meng, Songsong; Zhou, Deqing

2016-02-04

To construct heptyl glycosyltransferase gene II (waaF) gene deletion mutant of Vibrio parahaemolyticus, and explore the function of the waaF gene in Vibrio parahaemolyticus. The waaF gene deletion mutant was constructed by chitin-based transformation technology using clinical isolates, and then the growth rate, morphology and serotypes were identified. The different sources (O3, O5 and O10) waaF gene complementations were constructed through E. coli S17λpir strains conjugative transferring with Vibrio parahaemolyticus, and the function of the waaF gene was further verified by serotypes. The waaF gene deletion mutant strain was successfully constructed and it grew normally. The growth rate and morphology of mutant were similar with the wild type strains (WT), but the mutant could not occurred agglutination reaction with O antisera. The O3 and O5 sources waaF gene complementations occurred agglutination reaction with O antisera, but the O10 sources waaF gene complementations was not. The waaF gene was related with O-antigen synthesis and it was the key gene of O-antigen synthesis pathway in Vibrio parahaemolyticus. The function of different sources waaF gene were not the same.

Functional Amyloids Keep Quorum-sensing Molecules in Check*

PubMed Central

Seviour, Thomas; Hansen, Susan Hove; Yang, Liang; Yau, Yin Hoe; Wang, Victor Bochuan; Stenvang, Marcel R.; Christiansen, Gunna; Marsili, Enrico; Givskov, Michael; Chen, Yicai; Otzen, Daniel E.; Nielsen, Per Halkjær; Geifman-Shochat, Susana; Kjelleberg, Staffan; Dueholm, Morten S.

2015-01-01

The mechanism by which extracellular metabolites, including redox mediators and quorum-sensing signaling molecules, traffic through the extracellular matrix of biofilms is poorly explored. We hypothesize that functional amyloids, abundant in natural biofilms and possessing hydrophobic domains, retain these metabolites. Using surface plasmon resonance, we demonstrate that the quorum-sensing (QS) molecules, 2-heptyl-3-hydroxy-4(1H)-quinolone and N-(3-oxododecanoyl)-l-homoserine lactone, and the redox mediator pyocyanin bind with transient affinity to functional amyloids from Pseudomonas (Fap). Their high hydrophobicity predisposes them to signal-amyloid interactions, but specific interactions also play a role. Transient interactions allow for rapid association and dissociation kinetics, which make the QS molecules bioavailable and at the same time secure within the extracellular matrix as a consequence of serial bindings. Retention of the QS molecules was confirmed using Pseudomonas aeruginosa PAO1-based 2-heptyl-3-hydroxy-4(1H)-quinolone and N-(3-oxododecanoyl)-l-homoserine lactone reporter assays, showing that Fap fibrils pretreated with the QS molecules activate the reporters even after sequential washes. Pyocyanin retention was validated by electrochemical analysis of pyocyanin-pretreated Fap fibrils subjected to the same washing process. Results suggest that QS molecule-amyloid interactions are probably important in the turbulent environments commonly encountered in natural habitats. PMID:25586180

Molecular Signature of Pseudomonas aeruginosa with Simultaneous Nanomolar Detection of Quorum Sensing Signaling Molecules at a Boron-Doped Diamond Electrode

PubMed Central

Buzid, Alyah; Shang, Fengjun; Reen, F. Jerry; Muimhneacháin, Eoin Ó; Clarke, Sarah L.; Zhou, Lin; Luong, John H. T.; O’Gara, Fergal; McGlacken, Gerard P.; Glennon, Jeremy D.

2016-01-01

Electroanalysis was performed using a boron-doped diamond (BDD) electrode for the simultaneous detection of 2-heptyl-3-hydroxy-4-quinolone (PQS), 2-heptyl-4-hydroxyquinoline (HHQ) and pyocyanin (PYO). PQS and its precursor HHQ are two important signal molecules produced by Pseudomonas aeruginosa, while PYO is a redox active toxin involved in virulence and pathogenesis. This Gram-negative and opportunistic human pathogen is associated with a hospital-acquired infection particularly in patients with compromised immunity and is the primary cause of morbidity and mortality in cystic fibrosis (CF) patients. Early detection is crucial in the clinical management of this pathogen, with established infections entering a biofilm lifestyle that is refractory to conventional antibiotic therapies. Herein, a detection procedure was optimized and proven for the simultaneous detection of PYO, HHQ and PQS in standard mixtures, biological samples, and P. aeruginosa spiked CF sputum samples with remarkable sensitivity, down to nanomolar levels. Differential pulse voltammetry (DPV) scans were also applicable for monitoring the production of PYO, HHQ and PQS in P. aeruginosa PA14 over 8 h of cultivation. The simultaneous detection of these three compounds represents a molecular signature specific to this pathogen. PMID:27427496

Dynamic adsorption properties of n-alkyl glucopyranosides determine their ability to inhibit cytolysis mediated by acoustic cavitation.

PubMed

Sostaric, Joe Z; Miyoshi, Norio; Cheng, Jason Y; Riesz, Peter

2008-10-09

Suspensions of human leukemia (HL-60) cells readily undergo cytolysis when exposed to ultrasound above the acoustic cavitation threshold. However, n-alkyl glucopyranosides (hexyl, heptyl, and octyl) completely inhibit ultrasound-induced (1057 kHz) cytolysis (Sostaric, et al. Free Radical Biol. Med. 2005, 39, 1539-1548). The efficacy of protection from ultrasound-induced cytolysis was determined by the n-alkyl chain length of the glucopyranosides, indicating that protection efficacy depended on adsorption of n-alkyl glucopyranosides to the gas/solution interface of cavitation bubbles and/or the lipid membrane of cells. The current study tests the hypothesis that "sonoprotection" (i.e., protection of cells from ultrasound-induced cytolysis) in vitro depends on the adsorption of glucopyranosides at the gas/solution interface of cavitation bubbles. To test this hypothesis, the effect of ultrasound frequency (from 42 kHz to 1 MHz) on the ability of a homologous series of n-alkyl glucopyranosides to protect cells from ultrasound-induced cytolysis was investigated. It is expected that ultrasound frequency will affect sonoprotection ability since the nature of the cavitation bubble field will change. This will affect the relative importance of the possible mechanisms for ultrasound-induced cytolysis. Additionally, ultrasound frequency will affect the lifetime and rate of change of the surface area of cavitation bubbles, hence the dynamically controlled adsorption of glucopyranosides to their surface. The data support the hypothesis that sonoprotection efficiency depends on the ability of glucopyranosides to adsorb at the gas/solution interface of cavitation bubbles.

The C-terminal ester of membrane anchored peptide ion channels affects anion transport.

PubMed

Djedovic, Natasha; Ferdani, Riccardo; Harder, Egan; Pajewska, Jolanta; Pajewski, Robert; Schlesinger, Paul H; Gokel, George W

2003-12-07

Five heptapeptide derivatives, [CH3(CH2)17]2NCOCH2OCH2CO-Gly-Gly-Gly-Pro-Gly-Gly-Gly-OR, in which R = ethyl, 2-propyl, heptyl, benzyl, and cyclohexylmethyl, were found to transport chloride anion through a phospholipid bilayer to varying extents dependent on the identity of R. It was concluded that the R group is a membrane anchor for the synthetic chloride channels.

Cummulative effects of a 9 phthalate mixture using DEHP, DiHP, DiBP, DBP, BBP, DCHP, D(hexyl)P,D(heptyl)P and DPeP on Charles River-Sprague Dawley (CR-SD) fetal rat testis testosterone(T) production and gene expression

EPA Science Inventory

In utero exposure to mixtures of 2 to 5 phthalate esters (PE) with similar modes of action have been shown to inhibit male reproductive development in a dose-additive fashion. Further when PE were administered to pregnant dams during the period of sexual differentiation, when rep...

2-heptyl-formononetin increases cholesterol and induces hepatic steatosis in mice.

PubMed

Andersen, Charlotte; Schjoldager, Janne G; Tortzen, Christian G; Vegge, Andreas; Hufeldt, Majbritt R; Skaanild, Mette T; Vogensen, Finn K; Kristiansen, Karsten; Hansen, Axel K; Nielsen, John

2013-01-01

Consumption of isoflavones may prevent adiposity, hepatic steatosis, and dyslipidaemia. However, studies in the area are few and primarily with genistein. This study investigated the effects of formononetin and its synthetic analogue, 2-heptyl-formononetin (C7F), on lipid and cholesterol metabolism in C57BL/6J mice. The mice were fed a cholesterol-enriched diet for five weeks to induce hypercholesterolemia and were then fed either the cholesterol-enriched diet or the cholesterol-enriched diet-supplemented formononetin or C7F for three weeks. Body weight and composition, glucose homeostasis, and plasma lipids were compared. In another experiment, mice were fed the above diets for five weeks, and hepatic triglyceride accumulation and gene expression and histology of adipose tissue and liver were examined. Supplementation with C7F increased plasma HDL-cholesterol thereby increasing the plasma level of total cholesterol. Supplementation with formononetin did not affect plasma cholesterol but increased plasma triglycerides levels. Supplementation with formononetin and C7F induced hepatic steatosis. However, formononetin decreased markers of inflammation and liver injury. The development of hepatic steatosis was associated with deregulated expression of hepatic genes involved in lipid and lipoprotein metabolism. In conclusion, supplementation with formononetin and C7F to a cholesterol-enriched diet adversely affected lipid and lipoprotein metabolism in C57BL/6J mice.

2-Heptyl-Formononetin Increases Cholesterol and Induces Hepatic Steatosis in Mice

PubMed Central

Andersen, Charlotte; Schjoldager, Janne G.; Tortzen, Christian G.; Vegge, Andreas; Hufeldt, Majbritt R.; Skaanild, Mette T.; Vogensen, Finn K.; Kristiansen, Karsten; Hansen, Axel K.; Nielsen, John

2013-01-01

Consumption of isoflavones may prevent adiposity, hepatic steatosis, and dyslipidaemia. However, studies in the area are few and primarily with genistein. This study investigated the effects of formononetin and its synthetic analogue, 2-heptyl-formononetin (C7F), on lipid and cholesterol metabolism in C57BL/6J mice. The mice were fed a cholesterol-enriched diet for five weeks to induce hypercholesterolemia and were then fed either the cholesterol-enriched diet or the cholesterol-enriched diet-supplemented formononetin or C7F for three weeks. Body weight and composition, glucose homeostasis, and plasma lipids were compared. In another experiment, mice were fed the above diets for five weeks, and hepatic triglyceride accumulation and gene expression and histology of adipose tissue and liver were examined. Supplementation with C7F increased plasma HDL-cholesterol thereby increasing the plasma level of total cholesterol. Supplementation with formononetin did not affect plasma cholesterol but increased plasma triglycerides levels. Supplementation with formononetin and C7F induced hepatic steatosis. However, formononetin decreased markers of inflammation and liver injury. The development of hepatic steatosis was associated with deregulated expression of hepatic genes involved in lipid and lipoprotein metabolism. In conclusion, supplementation with formononetin and C7F to a cholesterol-enriched diet adversely affected lipid and lipoprotein metabolism in C57BL/6J mice. PMID:23738334

Detection of the Pseudomonas Quinolone Signal (PQS) by cyclic voltammetry and amperometry using a boron doped diamond electrode.

PubMed

Zhou, Lin; Glennon, Jeremy D; Luong, John H T; Reen, F Jerry; O'Gara, Fergal; McSweeney, Christina; McGlacken, Gerard P

2011-10-07

2-Heptyl-3-hydroxy-4-quinolone, known as the Pseudomonas Quinolone Signal, is a key regulator of bacterial cooperative behaviour known as quorum sensing. A simple electrochemical strategy was employed for its sensitive detection using a bare boron-doped diamond electrode by cyclic voltammetry and amperometry. PQS (and potentially other quinolones) was then detected in cultures of P. aeruginosa pqsL(-) mutant strains. This journal is © The Royal Society of Chemistry 2011

NMR Reveals Double Occupancy of Quinone-type Ligands in the Catalytic Quinone Binding Site of the Na+-translocating NADH:Quinone Oxidoreductase from Vibrio cholerae*

PubMed Central

Nedielkov, Ruslan; Steffen, Wojtek; Steuber, Julia; Möller, Heiko M.

2013-01-01

The sodium ion-translocating NADH:quinone oxidoreductase (Na+-NQR) from the pathogen Vibrio cholerae exploits the free energy liberated during oxidation of NADH with ubiquinone to pump sodium ions across the cytoplasmic membrane. The Na+-NQR consists of four membrane-bound subunits NqrBCDE and the peripheral NqrF and NqrA subunits. NqrA binds ubiquinone-8 as well as quinones with shorter prenyl chains (ubiquinone-1 and ubiquinone-2). Here we show that the quinone derivative 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone (DBMIB), a known inhibitor of the bc1 and b6f complexes found in mitochondria and chloroplasts, also inhibits quinone reduction by the Na+-NQR in a mixed inhibition mode. Tryptophan fluorescence quenching and saturation transfer difference NMR experiments in the presence of Na+-NQR inhibitor (DBMIB or 2-n-heptyl-4-hydroxyquinoline N-oxide) indicate that two quinone analog ligands are bound simultaneously by the NqrA subunit with very similar interaction constants as observed with the holoenzyme complex. We conclude that the catalytic site of quinone reduction is located on NqrA. The two ligands bind to an extended binding pocket in direct vicinity to each other as demonstrated by interligand Overhauser effects between ubiquinone-1 and DBMIB or 2-n-heptyl-4-hydroxyquinoline N-oxide, respectively. We propose that a similar spatially close arrangement of the native quinone substrates is also operational in vivo, enhancing the catalytic efficiency during the final electron transfer steps in the Na+-NQR. PMID:24003222

Impact of ester promoieties on transdermal delivery of ketorolac.

PubMed

Liu, Kuo-Sheng; Hsieh, Pei-Wen; Aljuffali, Ibrahim A; Lin, Yin-Ku; Chang, Shu-Hao; Wang, Jhi-Joung; Fang, Jia-You

2014-03-01

Different types of ketorolac ester prodrugs incorporating tert-butyl (KT), benzyl (KB), heptyl (KH), and diketorolac heptyl (DKH) promoieties were synthesized for the comparison of percutaneous penetration. The prodrugs were characterized according to their melting point, capacity factor, lipophilicity, solubility in 30% ethanol/buffer, enzymatic hydrolysis, in vitro skin permeation, hair follicle accumulation, and in vivo skin tolerance. Interactions between the prodrugs and esterases were predicted by molecular docking. Both equimolar suspensions and saturated solutions in 30% ethanol/pH 7.4 buffer were employed as the applied dose. All of the prodrugs exhibited a lower melting point than ketorolac. The lipophilicity increased in the following order: ketorolac < KT < KB < KH < DKH. The prodrugs were rapidly hydrolyzed to the parent drug in esterase medium, skin homogenate, and plasma, with KT and KB exhibiting higher degradation rates. KT exhibited the highest skin permeation, followed by KB. The flux of KT and KB exceeded that of ketorolac by 2.5-fold and twofold, respectively. KH and DKH did not improve ketorolac permeation but exhibited a sustained release behavior. KT and KH revealed selective absorption into follicles and a threefold greater follicular uptake compared with ketorolac. KB, KH, and DKH slightly but significantly increased transepidermal water loss (TEWL) after consecutive administration for 7 days, whereas ketorolac and KT exhibited no influence on TEWL. According to the experimental results, it can be concluded that an optimal balance between lipophilicity and aqueous solubility is important in the design of a successful prodrug. The acceptable skin tolerance for safe application is also an important consideration. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Bacterial Infochemicals are Drivers of Algal Lysis

NASA Astrophysics Data System (ADS)

Whalen, K.; Deering, R.; Rowley, D. C.; El Gamal, A.; Schorn, M.; Moore, B. S.; Johnson, M. D.; Mincer, T. J.; Harvey, E.

2016-02-01

Processing of organic matter by bacteria forces oceanic biogeochemical cycles, food web structure and ultimately environmental stoichiometry. A newly emerging picture of the microbial loop suggests that bacteria are not merely passive recipients of dissolved organic matter (DOM) from phytoplankton exudate. Rather, heterotrophic bacteria can mediate the flow of DOM by actively producing soluble algicidal compounds. However, deciphering those chemical signals that determine these interactions has remained a challenge. Here, we report the isolation of 2-heptyl-4-quinolone (HHQ), released by Pseudoalteromonas piscicida, a marine gamma-proteobacteria isolated from plastic debris in the North Atlantic. Both 2-heptyl-3-hydroxy-4-quinolone and its immediate precursor, HHQ are known to function as antibiotics and quorum sensing signaling molecules with crucial roles in virulence, and apoptosis in eukaryotic cells (e.g. fungi and mammalian cells). Our ecologically-relevant screening of live cells and filtrate from P. piscicida cultures caused a significant decrease in the growth rate of the bloom-forming coccolithophore, Emiliania huxleyi. Bioassay-guided fraction of P. piscicida extracellular crude extracts identified HHQ, which induced mortality in three strains of E. huxleyi with an IC50 in the nanomolar range. In contrast, the marine chlorophyte, Dunaliella tertiolecta and diatom, Phaeodactylum tricornutum were unaffected by HHQ exposures (IC50 > 10 micromolar), but were susceptible to extracts of P. piscicida, indicating this bacterium may produce a cocktail of algicidal compounds specific to different phytoplankton guilds. The ability of HHQ to influence phytoplankton growth suggests that alkylquinolone-signaling molecules play a fundamental role in interkingdom interactions, ultimately influencing shifts in phytoplankton population dynamics. This study implicates a new role for HHQ beyond its importance in quorum sensing.

Boron-containing chlorins and tetraazaporphyrins: synthesis and cell uptake of boronated pyropheophorbide a derivatives.

PubMed

Ratajski, Michal; Osterloh, Jens; Gabel, Detlef

2006-03-01

The literature on the synthesis and the biological properties of boron-containing chlorins and phthalocyanines is reviewed. A series of homologous derivatives of pyropheophorbide A is described. The compounds contain the B(12)H(11)SH(2-) cluster attached to the single carboxyl group and vary in the length of the alkyl chain (methyl, propyl, pentyl, heptyl and nonyl) attached via an ether linkage to the former vinyl group. Cellular uptake was found for all derivatives except the nonyl sidechain. The compounds were moderately cell-toxic. Localization in lysosomes could be excluded; the compounds localized probably in the mitochondria.

Acute toxicity of 353-nonylphenol and its metabolites for zebrafish embryos.

PubMed

Kammann, Ulrike; Vobach, Michael; Wosniok, Werner; Schäffer, Andreas; Telscher, Andreas

2009-03-01

Nonylphenol (NP) can be detected in the aquatic environment all over the world. It is applied as a technical mixture of isomers of which 353-NP is the most relevant both in terms of abundance (about 20% of total mass) and endocrine potential. 353-NP is metabolised in sewage sludge. The aims of the present study were to determine and to compare the acute toxicity of t-NP, 353-NP and its metabolites as well as to discuss if the toxicity of 353-NP changes during degradation. 353-NP and two of its metabolites were synthesised. The zebrafish embryo test was performed according to standard protocols. Several lethal and non-lethal endpoints during embryonal development were reported. NOEL, LOEL and EC50 were calculated. All tested compounds caused lethal as well as non-lethal malformations during embryo development. 353-NP showed a higher toxicity (EC50 for lethal endpoints 6.7 mg/L) compared to its metabolites 4-(3.5-dimethyl-3-heptyl)-2-nitrophenol (EC50 13.3 mg/L) and 4-(3,5-dimethyl-3-heptyl)-2-bromophenol (EC50 27.1 mg/L). In surface water, concentrations of NP are far below the NOEC identified by the zebrafish embryo test. However, in soils and sewage sludge, concentrations may reach or even exceed these concentrations. Therefore, sludge-treated sites close to surface waters should be analysed for NP and its metabolites in order to detect an unduly high contamination due to runoff events. The results of the present study point out that the toxicity of 353-NP probably declines during metabolisation in water, sediment and soil, but does not vanish since the major metabolites exhibit a clear toxic potential for zebrafish embryos. Metabolites of environmental pollutants should be included in the ecotoxicological test strategy for a proper risk assessment.

Electron Transport in Paracoccus Halodenitrificans and the Role of Ubiquinone

NASA Technical Reports Server (NTRS)

Hochstein, L. I.; Cronin, S. E.

1983-01-01

The membrane-bound NADH oxidase of Paracoccus halodenitrificans was inhibited by dicoumarol, 2-n-heptyl-4-hydroxyquinoline-N-oxide (HQNO), and exposure to ultraviolet light (at 366 nm). When the membranes were extracted with n-pentane, NADH oxidase activity was lost. Partial restoration was achieved by adding the ubiquinone fraction extracted from the membranes. Succinate oxidation was not inhibited by dicoumarol or HQNO but was affected by ultraviolet irradiation or n-pentane extraction. However, the addition of the ubiquinone fraction to the n-pentane-extracted membranes did not restore enzyme activity. These observations suggested the reducing equivalents from succinate entered the respiratory chain on the oxygen side of the HQNO-sensitive site and probably did not proceed through a quinone.

Isolation of tert-alkylphenols from the products of alkylation of phenols

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nesterova, T.N.; Verevkin, S.P.; Rempel', R.D.

1987-08-10

The authors studied the conditions of isolation of tert-amyl-, hexyl-, heptyl-, octyl-, decyl-, and dodecylphenols, and tert-alkylcresols, alkylpyrocatechols, and alkylhydroquinones from alkylation products. The compounds were isolated in all cases from reaction mixtures obtained in presence of cation-exchange resins of the KU-2 type. A preliminary stage, flash evaporation of the reaction mass at 4-13 Pa for 5-15 min, is needed to prevent decomposition of tert-alkylphenols during their isolation from acid reaction mixtures by fractionation. Flash distillation of high-boiling tert-alkylphenols should be conducted in presence of a component lowering the boiling point of the mixture, added in 1:(0.5-1.0) weight ratio ofmore » original mixture to the component.« less

Electron transport in Paracoccus halodenitrificans and the role of Ubiquinone

NASA Technical Reports Server (NTRS)

Hochstein, L. I.; Cronin, S. E.

1984-01-01

The membrane-bound NADH oxidase of Paracoccus halodenitrificans was inhibited by dicoumarol, 2-n-heptyl-4-hydroxyquinoline-N-oxide (HQNO), and exposure to ultraviolet light (at 366 nm). When the membranes were extracted with n-pentane, NADH oxidase activity was lost. Partial restoration was achieved by adding the ubiquinone fraction extracted from the membranes. Succinate oxidation was not inhibited by dicoumarol or HQNO but was affected by ultraviolet irradiation or n-pentane extraction. However, the addition of the ubiquinone fraction to the n-pentane-extracted membranes did not restore enzyme activity. These observations suggested the reducing equivalents from succinate entered the respiratory chain on the oxygen side of the HQNO-sensitive site and probably did not proceed through a quinone.

Site-directed mutagenesis of conserved cysteine residues in NqrD and NqrE subunits of Na+-translocating NADH:quinone oxidoreductase.

PubMed

Fadeeva, M S; Bertsova, Y V; Verkhovsky, M I; Bogachev, A V

2008-02-01

Each of two hydrophobic subunits of Na+-translocating NADH:quinone oxidoreductase (NQR), NqrD and NqrE, contain a pair of strictly conserved cysteine residues within their transmembrane alpha-helices. Site-directed mutagenesis showed that substitutions of these residues in NQR of Vibrio harveyi blocked the Na+-dependent and 2-n-heptyl-4-hydroxyquinoline N-oxide-sensitive quinone reductase activity of the enzyme. However, these mutations did not affect the interaction of NQR with NADH and menadione. It was demonstrated that these conserved cysteine residues are necessary for the correct folding and/or the stability of the NQR complex. Mass and EPR spectroscopy showed that NQR from V. harveyi bears only a 2Fe-2S cluster as a metal-containing prosthetic group.

Enzymatic properties of the membrane-bound NADH oxidase system in the aerobic respiratory chain of Bacillus cereus.

PubMed

Kim, Man Suk; Kim, Young Jae

2004-11-30

Membranes prepared from Bacillus cereus KCTC 3674, grown aerobically on a complex medium, oxidized NADH exclusively, whereas deamino-NADH was little oxidized. The respiratory chain-linked NADH oxidase exhibited an apparent K(m) value of approximately 65 microM for NADH. The maximum activity of the NADH oxidase was obtained at about pH 8.5 in the presence of 0.1 M KCl (or NaCl). Respiratory chain inhibitor 2-heptyl-4-hydroxyquinoline-N-oxide (HQNO) inhibited the activity of the NADH oxidase by about 90% at a concentration of 40 microM. Interestingly, rotenone and capsaicin inhibited the activity of the NADH oxidase by about 60% at a concentration of 40 microM and the activity was also highly sensitive to Ag(+).

Respiration-linked proton translocation coupled to anaerobic reduction of manganese(IV) and iron(III) in Shewanella putrefaciens MR-1.

PubMed Central

Myers, C R; Nealson, K H

1990-01-01

An oxidant pulse technique, with lactate as the electron donor, was used to study respiration-linked proton translocation in the manganese- and iron-reducing bacterium Shewanella putrefaciens MR-1. Cells grown anaerobically with fumarate or nitrate as the electron acceptor translocated protons in response to manganese (IV), fumarate, or oxygen. Cells grown anaerobically with fumarate also translocated protons in response to iron(III) and thiosulfate, whereas those grown with nitrate did not. Aerobically grown cells translocated protons only in response to oxygen. Proton translocation with all electron acceptors was abolished in the presence of the protonophore carbonyl cyanide m-chlorophenylhydrazone (20 microM) and was partially to completely inhibited by the electron transport inhibitor 2-n-heptyl-4-hydroxyquinoline N-oxide (50 microM). PMID:2172208

Mass Spectra of Some Perfluoroalkyl and Perfluoroalkylether Substituted 1,2,4-Oxadiazoles

NASA Technical Reports Server (NTRS)

Paciorek, Kazimiera J. L.; Nakahara, James H.; Kratzer, Reinhold H.; Rosser, Robert W.

1977-01-01

Electron impact fragmentation patterns were obtained for 1,4-bis[(5-perfluoro-n-heptyl)-1,2,4-oxadiazolyl- benzene, its perfluoroalkylether substituted analogue, 3,5-bis(perfluoroalkyl)-, 3,5-bis(perfluoroalkylether)- and 3-perfluoroalkylether-5-perfluoroalkyl-1,2,4-oxadiazoles. In the compounds containing the phenylene group the molecular ion constituted the base peak; the main process was the breakdown of the oxadiazole ring with concurrent liberation of the perfluoroalkyl or perfluoroalkylether nitrile molecule; cleavage of the fluorinated chain ot to the oxadiazole ring was found to take place to a considerable degree. In the perfluorinated 1,2,4-oxadiazoles cleavage beta to the oxadiazole ring occurred preferentially; fragmentation of the ring itself took place to a limited degree only. The 3-perfluoroalkylether-5-perfluoroalkyl-1,2,4-oxadiazole appeared to undergo the primary beta-cleavage exclusively at the perfluoroalkylether sidechain.

Mesomorphic phase transitions of 3F7HPhF studied by complementary methods

NASA Astrophysics Data System (ADS)

Deptuch, Aleksandra; Jaworska-Gołąb, Teresa; Marzec, Monika; Pociecha, Damian; Fitas, Jakub; Żurowska, Magdalena; Tykarska, Marzena; Hooper, James

2018-02-01

Physical properties and the phase sequence of (S)-4‧-(1-methylheptyloxycarbonyl)biphenyl-4-yl 4-[7-(2,2,3,3,4,4,4-heptafluorobutoxy) heptyl-1-oxy]-2-fluorobenzoate exhibiting the liquid crystalline paraelectric smectic A*, ferroelectric smectic C* and antiferroelectric smectic CA* phases were studied by complementary methods in the temperature range from -125 to 120 °C. Differential scanning calorimetry measurements together with polarizing optical microscopy provided the phase sequence, including the glass transition and a cold crystallization. X-ray diffraction was used to obtain the unit-cell parameters of the crystal phase, as well as the layer thickness and correlation length in the liquid crystalline smectic phases. The tilt angle was found to reach 45°, as determined from the measurements of the layer thickness and molecular modeling. Relaxation processes in the smectic phases and the fragility parameter were studied using frequency-domain dielectric spectroscopy.

C-type natriuretic peptide modulates quorum sensing molecule and toxin production in Pseudomonas aeruginosa

PubMed Central

Blier, Anne-Sophie; Veron, Wilfried; Bazire, Alexis; Gerault, Eloïse; Taupin, Laure; Vieillard, Julien; Rehel, Karine; Dufour, Alain; Le Derf, Franck; Orange, Nicole; Hulen, Christian; Feuilloley, Marc G. J.

2011-01-01

Pseudomonas aeruginosa coordinates its virulence expression and establishment in the host in response to modification of its environment. During the infectious process, bacteria are exposed to and can detect eukaryotic products including hormones. It has been shown that P. aeruginosa is sensitive to natriuretic peptides, a family of eukaryotic hormones, through a cyclic nucleotide-dependent sensor system that modulates its cytotoxicity. We observed that pre-treatment of P. aeruginosa PAO1 with C-type natriuretic peptide (CNP) increases the capacity of the bacteria to kill Caenorhabditis elegans through diffusive toxin production. In contrast, brain natriuretic peptide (BNP) did not affect the capacity of the bacteria to kill C. elegans. The bacterial production of hydrogen cyanide (HCN) was enhanced by both BNP and CNP whereas the production of phenazine pyocyanin was strongly inhibited by CNP. The amount of 2-heptyl-4-quinolone (HHQ), a precursor to 2-heptyl-3-hydroxyl-4-quinolone (Pseudomonas quinolone signal; PQS), decreased after CNP treatment. The quantity of 2-nonyl-4-quinolone (HNQ), another quinolone which is synthesized from HHQ, was also reduced after CNP treatment. Conversely, both BNP and CNP significantly enhanced bacterial production of acylhomoserine lactone (AHL) [e.g. 3-oxo-dodecanoyl-homoserine lactone (3OC12-HSL) and butanoylhomoserine lactone (C4-HSL)]. These results correlate with an induction of lasI transcription 1 h after bacterial exposure to BNP or CNP. Concurrently, pre-treatment of P. aeruginosa PAO1 with either BNP or CNP enhanced PAO1 exotoxin A production, via a higher toxA mRNA level. At the same time, CNP led to elevated amounts of algC mRNA, indicating that algC is involved in C. elegans killing. Finally, we observed that in PAO1, Vfr protein is essential to the pro-virulent effect of CNP whereas the regulator PtxR supports only a part of the CNP pro-virulent activity. Taken together, these data reinforce the hypothesis that during infection natriuretic peptides, particularly CNP, could enhance the virulence of PAO1. This activity is relayed by Vfr and PtxR activation, and a general diagram of the virulence activation cascade involving AHL, HCN and exotoxin A is proposed. PMID:21511763

Henry's law constants measurements of the nonylphenol isomer 4(3‧,5‧-dimethyl-3‧-heptyl)-phenol, tertiary octylphenol and γ-hexachlorocyclohexane between 278 and 298 K

NASA Astrophysics Data System (ADS)

Xie, Zhiyong; Le Calvé, Stéphane; Feigenbrugel, Valérie; Preuß, Thomas G.; Vinken, Ralph; Ebinghaus, Ralf; Ruck, Wolfgang

2004-09-01

Henry's Law Constants (HLC, M atm-1) were determined for the diastereomeric mixture of the nonylphenol isomer 4(3‧,5‧-dimethyl-3‧-heptyl)-phenol diastereomers (NP353(+) and NP353(-)), tertiary octylphenol (t-OP) and γ-hexachlorocyclohexane (γ-HCH) in artificial seawater over a temperature range 278-298 K using a dynamic equilibrium system. Trace organic substances present in the gas phase were trapped by tandem XAD-2 cartridges and extracted with a soxhlet extractor. The extracts were derivatived with N,O-bis(trimethylsilyl)-trifluoroacetamide (BSTFA), and then analyzed with GC-MS in the selective ion mode. At 293 K and in artificial seawater, HLC (M atm-1) were found to be equal to: NP353(+), HLC=(483±169); NP353(-), HLC=(551±193); t-OP, HLC=(400±140); γ-HCH, HLC=(876±307). The obtained data were used to derive the following Van't Hoff expressions: ln HLC (NP353(+))=8.73 (±0.95)×(1000/T) -23.61 (±3.30); ln HLC (NP353(-))=8.61 (±0.91)×(1000/T)-23.08 (±3.18); ln HLC (t-OP)=9.03 (±1.40)×(1000/T)-24.83 (±4.86); ln HLC (γ-HCH)=6.17 (±1.08)×(1000/T)-14.28 (±3.75). The derived enthalpies of solvation for NP353(+), NP353(-), t-OP and γ-HCH are -72.6±7.9, -71.6±7.6, -75.1±11.5 and -51.3±9.0 kJ mol-1, respectively. The HLC measurements of γ-HCH, which was used as reference substance, were in good agreement with literature values and its corresponding derived enthalpy of solvation agrees well to the previous values reported in the literature. A reassessment of the air/water gas exchange based on experimentally derived HLC was made for the nonylphenol (NP) in the Lower Hudson River estuary (New York/New Jersey, USA) that was previously reported by Van Ry. A net atmospheric deposition was calculated for the gas exchange of NP in the Lower Bay (Ffw=0.13), and it nearly reaches the condition of equilibrium in the Upper Bay (Ffw=0.46).

Enabling the intestinal absorption of highly polar antiviral agents: ion-pair facilitated membrane permeation of zanamivir heptyl ester and guanidino oseltamivir.

PubMed

Miller, Jonathan M; Dahan, Arik; Gupta, Deepak; Varghese, Sheeba; Amidon, Gordon L

2010-08-02

Antiviral drugs often suffer from poor intestinal permeability, preventing their delivery via the oral route. The goal of this work was to enhance the intestinal absorption of the low-permeability antiviral agents zanamivir heptyl ester (ZHE) and guanidino oseltamivir (GO) utilizing an ion-pairing approach, as a critical step toward making them oral drugs. The counterion 1-hydroxy-2-naphthoic acid (HNAP) was utilized to enhance the lipophilicity and permeability of the highly polar drugs. HNAP substantially increased the log P of the drugs by up to 3.7 log units. Binding constants (K(11(aq))) of 388 M(-1) for ZHE-HNAP and 2.91 M(-1) for GO-HNAP were obtained by applying a quasi-equilibrium transport model to double-reciprocal plots of apparent octanol-buffer distribution coefficients versus HNAP concentration. HNAP enhanced the apparent permeability (P(app)) of both compounds across Caco-2 cell monolayers in a concentration-dependent manner, as substantial P(app) (0.8-3.0 x 10(-6) cm/s) was observed in the presence of 6-24 mM HNAP, whereas no detectable transport was observed without counterion. Consistent with a quasi-equilibrium transport model, a linear relationship with slope near 1 was obtained from a log-log plot of Caco-2 P(app) versus HNAP concentration, supporting the ion-pair mechanism behind the permeability enhancement. In the rat jejunal perfusion assay, the addition of HNAP failed to increase the effective permeability (P(eff)) of GO. However, the rat jejunal permeability of ZHE was significantly enhanced by the addition of HNAP in a concentration-dependent manner, from essentially zero without HNAP to 4.0 x 10(-5) cm/s with 10 mM HNAP, matching the P(eff) of the high-permeability standard metoprolol. The success of ZHE-HNAP was explained by its >100-fold stronger K(11(aq)) versus GO-HNAP, making ZHE-HNAP less prone to dissociation and ion-exchange with competing endogenous anions and able to remain intact during membrane permeation. Overall, this work presents a novel approach to enable the oral delivery of highly polar antiviral drugs, and provides new insights into the underlying mechanisms governing the success or failure of the ion-pairing strategy to increase oral absorption.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge.

PubMed

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D; Boettcher, Shannon W

2015-08-04

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg(-1) based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30-50 Wh kg(-1) is possible with optimization.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge

PubMed Central

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D.; Boettcher, Shannon W.

2015-01-01

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg−1 based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30–50 Wh kg−1 is possible with optimization. PMID:26239891

[IMMUNOCYTOCHEMICAL ANALYSIS OF THE DISTURBANCES IN THE STRUCTURE OF SYNAPTONEMAL COMPLEXES IN SPERMATOCYTE NUCLEI IN MICE UNDER EXPOSURE TO ROCKET FUEL COMPONENT].

PubMed

Lovinskaya, A V; Kolumbayeva, S Zh; Abilev, S K; Kolomiets, O L

2016-01-01

There was performed an assessment of genotoxic effects of rocket fuel component--unsymmetrical dimethylhydrazine (UDMH, heptyl)--on forming germ cells of male mice. Immunocytochemically there was studied the structure of meiotic nuclei at different times after the intraperitoneal administration of UDMH to male mice. There were revealed following types of disturbances of the structure of synaptonemal complexes (SCs) of meiotic chromosomes: single and multiple fragments of SCs associations of autosomes with a sex bivalent, atypical structure of the SCs with a frequency higher than the reference level. In addition, there were found the premature desinapsis of sex bivalents, the disorder offormation of the genital corpuscle and ring SCs. Established disorders in SCs of spermatocytes, analyzed at 38th day after the 10-days intoxication of animal by the component of rocket fuel, attest to the risk of permanent persistence of chromosomal abnormalities occurring in the pool of stem cells.

Lysine-containing cationic liposomes activate the NLRP3 inflammasome: Effect of a spacer between the head group and the hydrophobic moieties of the lipids.

PubMed

Li, Tianshu; He, Jieyan; Horvath, Gabor; Próchnicki, Tomasz; Latz, Eicke; Takeoka, Shinji

2018-02-01

Cationic lipids containing lysine head groups and ditetradecyl, dihexadecyl or dioctadecyl glutamate hydrophobic moieties with/without propyl, pentyl or heptyl spacers were applied for the preparation of cationic liposomes using a simple bath type-sonicator. The size distribution, zeta potential, cellular internalization, and cytotoxicity of the liposomes were characterized, and the innate immune stimulation, e.g., the NLRP3 inflammasome activation of human macrophages and THP-1 cells, was evaluated by the detection of IL-1β release. Comparatively, L3C14 and L5C14 liposomes, made from the lipids bearing lysine head groups, ditetradecyl hydrophobic chains and propyl or pentyl spacers, respectively, were the most potent to activate the NLRP3 inflammasome. The possible mechanism includes endocytosis of the cationic liposomes and subsequent lysosome rupture without significant inducement of reactive oxygen species production. In summary, we first disclosed the structural effect of cationic liposomes on the NLRP3 inflammasome activation, which gives an insight into the application of nanoparticles for improved immune response. Copyright © 2017 Elsevier Inc. All rights reserved.

Investigation of fabrication process for sub 20-nm dense pattern of non-chemically amplified electron beam resist based on acrylic polymers

NASA Astrophysics Data System (ADS)

Ochiai, Shunsuke; Takayama, Tomohiro; Kishimura, Yukiko; Asada, Hironori; Sonoda, Manae; Iwakuma, Minako; Hoshino, Ryoichi

2016-10-01

In this study, we examine exposure characteristics of a positive tone electron beam resist consisting of methyl α- chloroacrylate and α-methylstyrene by changing the development process conditions. 25/25 nm and 30/30 nm line-andspace (L/S) patterns (design value) are developed in amyl and heptyl acetates. The resist patterns developed at 0ºC for 120 s show the better shapes having the vertical sidewalls than those developed at 22 °C for 60 s. The dose margins of pattern formation for 0°C development become wider, although the sensitivities are lower. The effect of post exposure baking (PEB) on exposure characteristics is also investigated. Adding PEB process performed at 120°C for 2 min, the dose margin also becomes wider although the sensitivity is lower. 20/20 nm L/S patterns are fabricated by using PEB and/or 0°C development. Though the required exposure dose is larger, the resist pattern is improved by PEB and/or 0°C development. The formation of 35 nm pitch pattern is also presented.

Characterization of three bioenergetically active respiratory terminal oxidases in the cyanobacterium Synechocystis sp. strain PCC 6803.

PubMed

Pils, D; Schmetterer, G

2001-09-25

Synechocystis sp. PCC 6803 contains three respiratory terminal oxidases (RTOs): cytochrome c oxidase (Cox), quinol oxidase (Cyd), and alternate RTO (ARTO). Mutants lacking combinations of the RTOs were used to characterize these key enzymes of respiration. Pentachlorophenol and 2-heptyl-4-hydroxy-quinoline-N-oxide inhibited Cyd completely, but had little effect on electron transport to the other RTOs. KCN inhibited all three RTOs but the in vivo K(I) for Cox and Cyd was quite different (7 vs. 27 microM), as was their affinity for oxygen (K(M) 1.0 vs. 0.35 microM). ARTO has a very low respiratory activity. However, when uptake of 3-O-methylglucose, an active H+ co-transport, was used to monitor energization of the cytoplasmic membrane, ARTO was similarly effective as the other RTOs. As removal of the gene for cytochrome c(553) had the same effects as removal of ARTO genes, we propose that the ARTO might be a second Cox. The possible functions, localization and regulation of the RTOs are discussed.

Experimental and modeling study of fuel interactions with an alkyl nitrate cetane enhancer, 2-ethyl-hexyl nitrate

DOE PAGES

Goldsborough, S. S.; Johnson, M. V.; Banyon, C.; ...

2014-07-15

Our study investigates the autoignition behavior of two gasoline surrogates doped with an alkyl nitrate cetane enhancer, 2-ethyl-hexyl nitrate (2EHN) to better understand dopant interactions with the fuels, including influences of accelerating kinetic pathways and enhanced exothermicity. A primary reference fuel (PRF) blend of n-heptane/iso-octane, and a toluene reference fuel (TRF) blend of n-heptane/iso-octane/toluene are used where the aromatic fraction of the latter is set to 20% (liquid volume), while the content of n-heptane is adjusted so that the overall reactivity of the undoped fuels is similar, e.g., Anti-Knock Index (AKI) of similar to 91, Cetane Number (CN) similar tomore » 25. Doping levels of 0.1, 1.0 and 3.0% (liquid volume basis) are used where tests are conducted within a rapid compression machine (RCM) at a compressed pressure of 21 bar, covering temperatures from 675 to 1025 K with stoichiometric fuel-oxygen ratios at O-2 = 11.4%. At the experimental conditions, it is found that the doping effectiveness of 2EHN is fairly similar between the two fuels, though 2EHN is more effective in the aromatic blend at the lowest temperatures, while it is slightly more effective in the non-aromatic blend at intermediate temperatures. Furthermore, kinetic modeling of the experiments indicates that although some of the reactivity trends can be captured using a detailed model, the extents of predicted Cetane Number enhancement by 2EHN are too large, while differences in fuel interactions for the two fuels result in excessive stimulation of the non-aromatic blend. Sensitivity analysis using the kinetic model indicates that the CH 2O and CH 3O 2 chemistry are very sensitive to the dopant at all conditions. The rate of 2EHN decomposition is only important at low temperatures where its decomposition rate is slow due to the high activation energy of the reaction. At higher temperatures, dopant-derived 3-heptyl radicals are predicted to play an important role stimulating ignition. Finally, nitrogen chemistry is important through the 'NO - NO 2 loop' where this can generate substantial amounts of OH. But, at the highest doping levels the formation of methyl and ethyl nitrite, and nitric acid significantly competes with this so that less OH is generated and this constrains the reactivity enhancement of 2EHN.« less

Molecular architectures and functions of radical enzymes and their (re)activating proteins.

PubMed

Shibata, Naoki; Toraya, Tetsuo

2015-10-01

Certain proteins utilize the high reactivity of radicals for catalysing chemically challenging reactions. These proteins contain or form a radical and therefore named 'radical enzymes'. Radicals are introduced by enzymes themselves or by (re)activating proteins called (re)activases. The X-ray structures of radical enzymes and their (re)activases revealed some structural features of these molecular apparatuses which solved common enigmas of radical enzymes—i.e. how the enzymes form or introduce radicals at the active sites, how they use the high reactivity of radicals for catalysis, how they suppress undesired side reactions of highly reactive radicals and how they are (re)activated when inactivated by extinction of radicals. This review highlights molecular architectures of radical B12 enzymes, radical SAM enzymes, tyrosyl radical enzymes, glycyl radical enzymes and their (re)activating proteins that support their functions. For generalization, comparisons of the recently reported structures of radical enzymes with those of canonical radical enzymes are summarized here. © The Authors 2015. Published by Oxford University Press on behalf of the Japanese Biochemical Society. All rights reserved.

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

PubMed

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.

Incidence and location of positive surgical margin among open, laparoscopic and robot-assisted radical prostatectomy in prostate cancer patients: a single institutional analysis.

PubMed

Koizumi, Atsushi; Narita, Shintaro; Nara, Taketoshi; Takayama, Koichiro; Kanda, Sohei; Numakura, Kazuyuki; Tsuruta, Hiroshi; Maeno, Atsushi; Huang, Mingguo; Saito, Mitsuru; Inoue, Takamitsu; Tsuchiya, Norihiko; Satoh, Shigeru; Nanjo, Hiroshi; Habuchi, Tomonori

2018-06-19

To evaluate the positive surgical margin rates and locations in radical prostatectomy among three surgical approaches, including open radical prostatectomy, laparoscopic radical prostatectomy and robot-assisted radical prostatectomy. We retrospectively reviewed clinical outcomes at our institution of 450 patients who received radical prostatectomy. Multiple surgeons were involved in the three approaches, and a single pathologist conducted the histopathological diagnoses. Positive surgical margin rates and locations among the three approaches were statistically assessed, and the risk factors of positive surgical margin were analyzed. This study included 127, 136 and 187 patients in the open radical prostatectomy, laparoscopic radical prostatectomy and robot-assisted radical prostatectomy groups, respectively. The positive surgical margin rates were 27.6% (open radical prostatectomy), 18.4% (laparoscopic radical prostatectomy) and 13.4% (robot-assisted radical prostatectomy). In propensity score-matched analyses, the positive surgical margin rate in the robot-assisted radical prostatectomy was significantly lower than that in the open radical prostatectomy, whereas there was no significant difference in the positive surgical margin rates between robot-assisted radical prostatectomy and laparoscopic radical prostatectomy. In the multivariable analysis, PSA level at diagnosis and surgical approach (open radical prostatectomy vs robot-assisted radical prostatectomy) were independent risk factors for positive surgical margin. The apex was the most common location of positive surgical margin in the open radical prostatectomy and laparoscopic radical prostatectomy groups, whereas the bladder neck was the most common location in the robot-assisted radical prostatectomy group. The significant difference of positive surgical margin locations continued after the propensity score adjustment. Robot-assisted radical prostatectomy may potentially achieve the lowest positive surgical margin rate among three surgical approaches. The bladder neck was the most common location of positive surgical margin in robot-assisted radical prostatectomy and apex in open radical prostatectomy and laparoscopic radical prostatectomy. Although robot-assisted radical prostatectomy may contribute to the reduction of positive surgical margin, dissection of the bladder neck requires careful attention to avoid positive surgical margins.

Purification and characterization of antifungal phenazines from a fluorescent Pseudomonas strain FPO4 against medically important fungi.

PubMed

Gorantla, J N; Kumar, S Nishanth; Nisha, G V; Sumandu, A S; Dileep, C; Sudaresan, A; Kumar, M M Sree; Lankalapalli, R S; Kumar, B S Dileep

2014-09-01

The strain FPO4 was isolated from the rhizoplane of rice plant root and identified as a fluorescent Pseudomonas aeruginosa on the basis of 16S rDNA sequences and BLAST analysis. The extracellular metabolites produced by this strain were purified by silica gel column chromatography and isolated four pure compounds. Based on the spectral data the four compounds were identified as phenazin-1-ol, phenazine-1-carboxylic acid (PCA), 2-heptyl-3-hydroxyl-4(1H)-quinolone (PQS), and phenazine-1-carboxamide (PCN), respectively. Phenazin-1-ol and PCA were active against all the eight fungi tested. The highest activity of 4 μg/mL by PCA was recorded against Trichophyton rubrum, a human pathogen responsible for causing athlete's foot, jock itch, ringworm and fingernail fungus infections, followed by Candida albicans and Candida tropicalis. The activity of phenazin-1-ol, PCA against Candida spp. was found to be better than the standard antifungal agent amphotericin B. Furthermore, the present study reports the antimicrobial activity of the purified phenazines on major human pathogen, T. rubrum for the first time. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Pseudovibrio denitrificans strain Z143-1, a heptylprodigiosin-producing bacterium isolated from a Philippine tunicate.

PubMed

Sertan-de Guzman, Alice A; Predicala, Rey Z; Bernardo, Evelyn B; Neilan, Brett A; Elardo, Sheila P; Mangalindan, Gina C; Tasdemir, Deniz; Ireland, Chris M; Barraquio, Wilfredo L; Concepcion, Gisela P

2007-12-01

Microbial isolate Z143-1 found to be associated with an unidentified tunicate was characterized due to its significant antimicrobial activity. Z143-1 is similar to Pseudovibrio ascidiaceicola and Pseudovibrio denitrificans in morphological, physiological and biochemical characteristics, except for its ability to ferment glucose and produce a characteristic red pigment. Fatty acid methyl ester analysis revealed a predominance of the fatty acid 18:1 omega7c at 80.55%, at levels slightly lower than the Pseudovibrio denitrificans type strain DN34(T) (87.7%). The mol% G+C of Z143-1 is 54.02, relatively higher than the Pseudovibrio denitrificans type strain DN34(T) and Pseudovibrio ascidiaceicola with mol% G+C of 51.7 and 51.4, respectively. However, phylogenetic analysis of the 16S rRNA gene sequence of Z143-1 showed 100% similarity with the Pseudovibrio denitrificans type strain DN34(T). In this study, the bacterium Z143-1 is reported as a new strain of Pseudovibrio denitrificans. While there is no report of a secondary metabolite for Pseudovibrio denitrificans, Z143-1 produces the red pigment heptylprodigiosin, also known as 16-methyl-15-heptyl-prodiginine, which shows anti-Staphylococcus aureus activity.

Pseudomonas aeruginosa inhibits the growth of Cryptococcus species.

PubMed

Rella, Antonella; Yang, Mo Wei; Gruber, Jordon; Montagna, Maria Teresa; Luberto, Chiara; Zhang, Yong-Mei; Del Poeta, Maurizio

2012-06-01

Pseudomonas aeruginosa is a ubiquitous and opportunistic bacterium that inhibits the growth of different microorganisms, including Gram-positive bacteria and fungi such as Candida spp. and Aspergillus fumigatus. In this study, we investigated the interaction between P. aeruginosa and Cryptococcus spp. We found that P. aeruginosa PA14 and, to a lesser extent, PAO1 significantly inhibited the growth of Cryptococcus spp. The inhibition of growth was observed on solid medium by the visualization of a zone of inhibition of yeast growth and in liquid culture by viable cell counting. Interestingly, such inhibition was only observed when P. aeruginosa and Cryptococcus were co-cultured. Minimal inhibition was observed when cell-cell contact was prevented using a separation membrane, suggesting that cell contact is required for inhibition. Using mutant strains of Pseudomonas quinoline signaling, we showed that P. aeruginosa inhibited the growth of Cryptococcus spp. by producing antifungal molecules pyocyanin, a redox-active phenazine, and 2-heptyl-3,4-dihydroxyquinoline (PQS), an extracellular quorum-sensing signal. Because both P. aeruginosa and Cryptococcus neoformans are commonly found in lung infections of immunocompromised patients, this study may have important implication for the interaction of these microbes in both an ecological and a clinical point of view.

Modeling Alkyl p-Methoxy Cinnamate (APMC) as UV absorber based on electronic transition using semiempirical quantum mechanics ZINDO/s calculation

NASA Astrophysics Data System (ADS)

Salmahaminati; Azis, Muhlas Abdul; Purwiandono, Gani; Arsyik Kurniawan, Muhammad; Rubiyanto, Dwiarso; Darmawan, Arif

2017-11-01

In this research, modeling several alkyl p-methoxy cinnamate (APMC) based on electronic transition by using semiempirical mechanical quantum ZINDO/s calculation is performed. Alkyl cinnamates of C1 (methyl) up to C7 (heptyl) homolog with 1-5 example structures of each homolog are used as materials. Quantum chemistry-package software Hyperchem 8.0 is used to simulate the drawing of the structure, geometry optimization by a semiempirical Austin Model 1 algorithm and single point calculation employing a semiempirical ZINDO/s technique. ZINDO/s calculations use a defined criteria that singly excited -Configuration Interaction (CI) where a gap of HOMO-LUMO energy transition and maximum degeneracy level are 7 and 2, respectively. Moreover, analysis of the theoretical spectra is focused on the UV-B (290-320 nm) and UV-C (200-290 nm) area. The results show that modeling of the compound can be used to predict the type of UV protection activity depends on the electronic transition in the UV area. Modification of the alkyl homolog relatively does not change the value of wavelength absorption to indicate the UV protection activity. Alkyl cinnamate compounds are predicted as UV-B and UV-C sunscreen.

A Bacterial Quorum-Sensing Precursor Induces Mortality in the Marine Coccolithophore, Emiliania huxleyi.

PubMed

Harvey, Elizabeth L; Deering, Robert W; Rowley, David C; El Gamal, Abrahim; Schorn, Michelle; Moore, Bradley S; Johnson, Matthew D; Mincer, Tracy J; Whalen, Kristen E

2016-01-01

Interactions between phytoplankton and bacteria play a central role in mediating biogeochemical cycling and food web structure in the ocean. However, deciphering the chemical drivers of these interspecies interactions remains challenging. Here, we report the isolation of 2-heptyl-4-quinolone (HHQ), released by Pseudoalteromonas piscicida, a marine gamma-proteobacteria previously reported to induce phytoplankton mortality through a hitherto unknown algicidal mechanism. HHQ functions as both an antibiotic and a bacterial signaling molecule in cell-cell communication in clinical infection models. Co-culture of the bloom-forming coccolithophore, Emiliania huxleyi with both live P. piscicida and cell-free filtrates caused a significant decrease in algal growth. Investigations of the P. piscicida exometabolome revealed HHQ, at nanomolar concentrations, induced mortality in three strains of E. huxleyi. Mortality of E. huxleyi in response to HHQ occurred slowly, implying static growth rather than a singular loss event (e.g., rapid cell lysis). In contrast, the marine chlorophyte, Dunaliella tertiolecta and diatom, Phaeodactylum tricornutum were unaffected by HHQ exposures. These results suggest that HHQ mediates the type of inter-domain interactions that cause shifts in phytoplankton population dynamics. These chemically mediated interactions, and other like it, ultimately influence large-scale oceanographic processes.

Current Status of Robot-Assisted Radical Cystectomy: What is the Real Benefit?

PubMed

Takenaka, Atsushi

2015-09-01

In recent years, robot-assisted radical cystectomy has received attention worldwide as a useful procedure that helps to overcome the limitations of open radical cystectomy. We compared the surgical technique, perioperative and oncological outcomes, and learning curve of robot-assisted radical cystectomy with those of open radical cystectomy. The indications for robot-assisted radical cystectomy are identical to those of open radical cystectomy. Relative contraindications are due to patient positioning in the Trendelenburg position for long periods. Urinary diversion is performed either extracorporeally with a small skin incision or intracorporeally with a totally robotic-assisted maneuver. Accordingly, robot-assisted radical cystectomy can be performed safely with an acceptable operative time, little blood loss, and low transfusion rates. The lymph node yield and positive surgical margin rate were not significantly different between robot-assisted radical cystectomy and open radical cystectomy. The survival rates after robot-assisted radical cystectomy are estimated to be similar to that after open radical cystectomy. However, the recurrence pattern is different between robot-assisted radical cystectomy and open radical cystectomy, i.e., extrapelvic lymph node recurrence and peritoneal carcinomatosis were more frequently found in patients who underwent robot-assisted radical cystectomy than in those who underwent open radical cystectomy. Further validation is necessary to prove the feasibility of oncological control. A steep learning curve is one of the benefits of the new technique. The experience of only 50 robot-assisted radical prostatectomies is a minimum requirement for performing feasible robot-assisted radical cystectomy, and surgeons who have performed only 30 surgeries can reach an acceptable level of quality for robot-assisted radical cystectomy.

17.9.3 Radical cations of diazo compounds

NASA Astrophysics Data System (ADS)

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'.

The widetilde{A}←widetilde{X} ABSORPTION SPECTRUM OF 2-NITROOXYBUTYL PEROXY RADICAL

NASA Astrophysics Data System (ADS)

Eddingsaas, Nathan; Takematsu, Kana; Okumura, Mitchio

2009-06-01

The nitrate radical is an important atmospheric oxidant in the nighttime sky. Nitrate radicals react by addition to alkenes, and in the presence of oxygen form nitrooxyalkyl peroxy radicals. The peroxy radical formed from the reaction of 2-butene, nitrate radical, and oxygen was detected by cavity ringdown spectroscopy (CRDS) via its widetilde{A}←widetilde{X} electronic absorption spectrum. The widetilde{A}←widetilde{X} electronic transition is a bound-bound transition with enough structure to distinguish between different peroxy radicals as well as different conformers of the same peroxy radical. Two conformers of the nitrooxybutyl peroxy radical have been observed; the absorption features are red shifted from the same absorption features of sec-butyl peroxy radical. Calculations on the structure of nitrooxyalkyl peroxy radicals and general trends of the position of the widetilde{A}←widetilde{X} absorption transitions have also been performed and compared to those of unsubstituted peroxy radicals.

Multiple free-radical scavenging capacity in serum

PubMed Central

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

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species

NASA Astrophysics Data System (ADS)

Watts, Richard J.; Yu, Miao; Teel, Amy L.

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical + sulfate radical probe, and hexachloroethane as a reductant + nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole > > TCE > PCE > > nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion.

Kr-86 Ion-Beam Irradiation of Hydrated DNA: Free Radical and Unaltered Base Yields

PubMed Central

Becker, David; Adhikary, Amitava; Tetteh, Smedley T.; Bull, Arthur W.; Sevilla, Michael D.

2012-01-01

This work reports an ESR and product analysis investigation of Kr-86 ion-beam irradiation of hydrated DNA at 77 K. The irradiation results in the formation and trapping of both base radicals and sugar phosphate radicals (DNA backbone radicals). The absolute yields (G, μmol/J) of the base radicals are smaller than the yields found in similarly prepared γ-irradiated DNA samples, and the relative yields of backbone radicals relative to base radicals are much higher than that found in γ-irradiated samples. From these results, we have elaborated our radiation chemical model of the track structure for ion-beam irradiated DNA as it applies to krypton ion-beams. The base radicals, which are trapped as ion radicals or reversibly protonated or deprotonated ion radicals, are formed almost entirely in the track penumbra, a region in which radiation chemical effects are similar to those found in γ-irradiated samples. By comparing the yields of base radicals in ion-beam samples to the yields of the same radicals in γ-irradiated samples, the partition of energy between the low-LET region (penumbra) and the core is experimentally determined. The neutral sugar and other backbone radicals, which are not as susceptible to recombination as are ion radicals, are formed largely in the track core. The backbone radicals show a linear dose response up to very high doses. Unaltered base release yields in Kr-86 irradiated hydrated DNA are equal to sugar radical yields within experimental error limits, consistent with radiation-chemical processes in which all base release originates with sugar radicals. Two phosphorus-centered radicals from fragmentation of the DNA backbone are found in low yields. PMID:23106211

Kr-86 ion-beam irradiation of hydrated DNA: free radical and unaltered base yields.

PubMed

Becker, David; Adhikary, Amitava; Tetteh, Smedley T; Bull, Arthur W; Sevilla, Michael D

2012-12-01

This work reports an ESR and product analysis investigation of Kr-86 ion-beam irradiation of hydrated DNA at 77 K. The irradiation results in the formation and trapping of both base radicals and sugar phosphate radicals (DNA backbone radicals). The absolute yields (G, μmol/J) of the base radicals are smaller than the yields found in similarly prepared γ-irradiated DNA samples, and the relative yields of backbone radicals relative to base radicals are much higher than that found in γ-irradiated samples. From these results, we have elaborated our radiation chemical model of the track structure for ion-beam irradiated DNA as it applies to krypton ion-beams. The base radicals, which are trapped as ion radicals or reversibly protonated or deprotonated ion radicals, are formed almost entirely in the track penumbra, a region in which radiation chemical effects are similar to those found in γ-irradiated samples. By comparing the yields of base radicals in ion-beam samples to the yields of the same radicals in γ-irradiated samples, the partition of energy between the low-LET region (penumbra) and the core is experimentally determined. The neutral sugar and other backbone radicals, which are not as susceptible to recombination as are ion radicals, are formed largely in the track core. The backbone radicals show a linear dose response up to very high doses. Unaltered base release yields in Kr-86 irradiated hydrated DNA are equal to sugar radical yields within experimental error limits, consistent with radiation-chemical processes in which all base release originates with sugar radicals. Two phosphorus-centered radicals from fragmentation of the DNA backbone are found in low yields.

Addition products of alpha-tocopherol with lipid-derived free radicals.

PubMed

Yamauchi, Ryo

2007-01-01

The addition products of alpha-tocopherol with lipid-derived free radicals have been reviewed. Free radical scavenging reactions of alpha-tocopherol take place via the alpha-tocopheroxyl radical as an intermediate. If a suitable free radical is present, an addition product can be formed from the coupling of the free radical with the alpha-tocopheroxyl radical. The addition products of alpha-tocopherol with lipid-peroxyl radicals are 8a-(lipid-dioxy)-alpha-tocopherones, which are hydrolyzed to alpha-tocopherylquinone. On the other hand, the carbon-centered radicals of lipids prefer to react with the phenoxyl radical of alpha-tocopherol to form 6-O-lipid-alpha-tocopherol under anaerobic conditions. The addition products of alpha-tocopherol with peroxyl radicals (epoxylinoleoyl-peroxyl radicals) produced from cholesteryl ester and phosphatidylcholine were detected in the peroxidized human plasma using a high-sensitive HPLC procedure with postcolumn reduction and electrochemical detection. Thus, the formation of these addition products provides us with much information on the antioxidant function of vitamin E in biological systems.

Characteristics of Radical Reactions, Spin Rules, and a Suggestion for the Consistent Use of a Dot on Radical Species

ERIC Educational Resources Information Center

Wojnarovits, Laszlo

2011-01-01

In many chemical reactions, reactive radicals have been shown to be transient intermediates. The free radical character of a chemical species is often, but not always, indicated by adding a superscript dot to the chemical formula. A consistent use of this radical symbol on all species that have radical character is suggested. Free radicals have a…

Fragmentation of alpha-Radical Cations of Arginine-Containing Peptides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia; Yang, Zhibo; Ng, Dominic C.

2010-04-01

Fragmentation pathways of peptide radical cations, M+, with well-defined initial location of the radical site were explored using collision-induced dissociation (CID) experiments. Peptide radical cations were produced by gas-phase fragmentation of CoIII(salen)-peptide complexes [salen = N,N´-ethylenebis (salicylideneaminato)]. Subsequent hydrogen abstraction from the -carbon of the side chain followed by Ca-C bond cleavage results in the loss of a neutral side chain and formation of an a-radical cation with the radical site localized on the a-carbon of the backbone. Similar CID spectra dominated by radical-driven dissociation products were obtained for a number of a-radicals when the basic arginine side chain wasmore » present in the sequence. In contrast, proton-driven fragmentation dominates CID spectra of a-radicals produced via the loss of the arginine side chain. Our results suggest that in most cases radical migration precedes fragmentation of large peptide radical cations.« less

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species.

PubMed

Watts, Richard J; Yu, Miao; Teel, Amy L

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical+sulfate radical probe, and hexachloroethane as a reductant+nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole>TCE>PCE >nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion. Published by Elsevier B.V.

Radical distinction: Support for radical left and radical right parties in Europe.

PubMed

Rooduijn, Matthijs; Burgoon, Brian; van Elsas, Erika J; van de Werfhorst, Herman G

2017-12-01

Support for radical parties on both the left and right is on the rise, fueling intuition that both radicalisms have similar underpinnings. Indeed, existing studies show that radical left and right voters have overlapping positions and preferences. In this article, however, we focus on the differences in the voting bases of such parties. We show that radical left and right voters have sharply diverging ideological profiles. When it comes to the historical traditions of the 'left' and 'right', these voters differ radically from each other. Both groups express the traditions associated with their mainstream counterparts-particularly with respect to (non-)egalitarian, (non-)altruistic, and (anti-)cosmopolitan values. Such differences also explain why radical left voters tend to be more, not less, educated than mainstream or radical right voters.

A substrate radical intermediate in the reaction between ribonucleotide reductase from Escherichia coli and 2'-azido-2'-deoxynucleoside diphosphates.

PubMed

Sjöberg, B M; Gräslund, A; Eckstein, F

1983-07-10

The B2 subunit of ribonucleotide reductase from Escherichia coli contains a tyrosine radical which is essential for enzyme activity. In the reaction between ribonucleotide reductase and the substrate analogue 2'-azido-2'-deoxycytidine 5'-diphosphate a new transient radical is formed. The EPR characteristics of this new radical species are consistent with a localization of the unpaired electron at the sugar moiety of the nucleotide. The radical shows hyperfine couplings to a hydrogen and a nitrogen nucleus, the latter probably being part of the azide substituent. The formation of the nucleotide radical in this suicidal reaction is concomitant with the decay of the tyrosine radical of the B2 subunit. Kinetic data argue for a first (pseudosecond) order decay of the B2 radical via generation of the nucleotide radical followed by a slower first order decay of the nucleotide radical. End products in the reaction are cytosine and radical-free protein B2. In the reaction between bacteriophage T4 ribonucleotide reductase and 2'-azido-2'-deoxycytidine 5'-diphosphate an identical nucleotide radical is formed. The present results are consistent with the hypothesis that the appearance and structure of the transient radical mimic stages in the normal reaction pathway of ribonucleotide reductase, postulated to proceed via 3'-hydrogen abstraction and cation radical formation of the substrate nucleotide (Stubbe, J., and Ackles, D. (1980) J. Biol. Chem. 255, 8027-8030). The nucleotide radical described here might be equivalent to such a cation radical intermediate.

The Legitimization of the Radical Tradition in France, 1789-1901.

ERIC Educational Resources Information Center

Gough, Hugh

1988-01-01

Traces the development of radicalism from the 1789 French Revolution to the present. States that radical philosophy has its roots in rationalism and Enlightenment thought and was linked to positivism during the nineteenth century. Despite the failings of radicalism and the Radical Party, the radical tradition set precedents for current political…

Expanding Radical SAM Chemistry by Using Radical Addition Reactions and SAM Analogues.

PubMed

Ji, Xinjian; Li, Yongzhen; Xie, Liqi; Lu, Haojie; Ding, Wei; Zhang, Qi

2016-09-19

Radical S-adenosyl-l-methionine (SAM) enzymes utilize a [4Fe-4S] cluster to bind SAM and reductively cleave its carbon-sulfur bond to produce a highly reactive 5'-deoxyadenosyl (dAdo) radical. In almost all cases, the dAdo radical abstracts a hydrogen atom from the substrates or from enzymes, thereby initiating a highly diverse array of reactions. Herein, we report a change of the dAdo radical-based chemistry from hydrogen abstraction to radical addition in the reaction of the radical SAM enzyme NosL. This change was achieved by using a substrate analogue containing an olefin moiety. We also showed that two SAM analogues containing different nucleoside functionalities initiate the radical-based reactions with high efficiencies. The radical adduct with the olefin produced in the reaction was found to undergo two divergent reactions, and the mechanistic insights into this process were investigated in detail. Our study demonstrates a promising strategy in expanding radical SAM chemistry, providing an effective way to access nucleoside-containing compounds by using radical SAM-dependent reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radical distinction: Support for radical left and radical right parties in Europe

PubMed Central

Burgoon, Brian; van Elsas, Erika J; van de Werfhorst, Herman G

2017-01-01

Support for radical parties on both the left and right is on the rise, fueling intuition that both radicalisms have similar underpinnings. Indeed, existing studies show that radical left and right voters have overlapping positions and preferences. In this article, however, we focus on the differences in the voting bases of such parties. We show that radical left and right voters have sharply diverging ideological profiles. When it comes to the historical traditions of the ‘left’ and ‘right’, these voters differ radically from each other. Both groups express the traditions associated with their mainstream counterparts—particularly with respect to (non-)egalitarian, (non-)altruistic, and (anti-)cosmopolitan values. Such differences also explain why radical left voters tend to be more, not less, educated than mainstream or radical right voters. PMID:29187802

Structure of free radicals in irradiated acetyl-L-leucine single crystals at 77 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Almanov, G.A.; Bogdanchikov, G.A.; Usov, O.M.

1988-09-01

By using the EPR method, two types of radicals are observed, which are formed in acetyl-L-leucine single crystals irradiated at 77K. These are alkyl type radicals (CH/sub 3/)/sub 2/CCH/sub 2/CH(NHCOCH/sub 3/)COOH and peptide group radicals. When the crystals are defrozen to room temperatures, the radicals of the second type disappear without formation of paramagnetic particles. Two possible structures of the peptide group radicals were studied by the INDO method. On defreezing to room temperature, the alkyl group radical is retained, while the peptide radical disappears without formation of paramagnetic particles. For the protonated form of the anion-radical, a better agreementmore » is observed between the theoretically calculated and the experimentally obtained HFI constants. The quantum chemical analysis of the possible structures of the peptide group radicals indicates that the formation of the protonated form of the anion-radical is energetically favorable.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samskog, P.; Kispert, L.D.; Lund, A.

Four different alkoxy radicals were identified by ESR studies in x-ray irradiated single crystals of trehalose. The radical sites are O/sup prime//sub 2/(I), O/sub 2/(II), O/sup prime//sub 3/(III), and the probable ring oxygen O/sub 5/(IV). All alkoxy radicals exhibit one or two ..beta..-proton couplings. An additional coupling to a ..gamma.. proton for radical II is observed. The difference in the g/sub max/ value for the alkoxy radicals is discussed in terms of the type of hydrogen bonding involved. Two hydroxyalkyl radicals VI and VII were also produced at 77 K. Storage of crystals for one week results in decay ofmore » radicals I and II. Alkoxy radical II transform into a C/sub 6/-centered hydroxyalkyl radical V.« less

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

PubMed

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

2011-12-20

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

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

PubMed

Kamogawa, Erisa; Sueishi, Yoshimi

2014-03-01

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

Pilot study of radical hysterectomy versus radical trachelectomy on sexual distress.

PubMed

Brotto, Lori A; Smith, Kelly B; Breckon, Erin; Plante, Marie

2013-01-01

Radical trachelectomy, which leaves the uterus intact, has emerged as a desirable surgical option for eligible women with early-stage cervical cancer who wish to preserve fertility. The available data suggest excellent obstetrical outcomes with radical trachelectomy, and no differences in sexual responding between radical trachelectomy and radical hysterectomy. There is a need to examine the effect of radical hysterectomy on sexual distress given that it is distinct from sexual function. Participants were 34 women diagnosed with early-stage cervical cancer. The authors report 1-month postsurgery data for 29 women (radical hysterectomy group: n = 17, M age = 41.8 years; radical trachelectomy group: n = 12, M age = 31.8 years), and 6-month follow-up data on 26 women. Whereas both groups experienced an increase in sex-related distress immediately after surgery, distress continued to increase 6 months after surgery for the radical hysterectomy group but decreased in the radical trachelectomy group. There were no between-group differences in mood, anxiety, or general measures of health. The decrease in sex-related distress in the radical trachelectomy but not in the radical hysterectomy group suggests that the preservation of fertility may have attenuated sex-related distress. Care providers should counsel women exploring surgical options for cervical cancer about potential sex distress-related sequelae.

Standard Gibbs free energies of reactions of ozone with free radicals in aqueous solution: quantum-chemical calculations.

PubMed

Naumov, Sergej; von Sonntag, Clemens

2011-11-01

Free radicals are common intermediates in the chemistry of ozone in aqueous solution. Their reactions with ozone have been probed by calculating the standard Gibbs free energies of such reactions using density functional theory (Jaguar 7.6 program). O(2) reacts fast and irreversibly only with simple carbon-centered radicals. In contrast, ozone also reacts irreversibly with conjugated carbon-centered radicals such as bisallylic (hydroxycylohexadienyl) radicals, with conjugated carbon/oxygen-centered radicals such as phenoxyl radicals, and even with nitrogen- oxygen-, sulfur-, and halogen-centered radicals. In these reactions, further ozone-reactive radicals are generated. Chain reactions may destroy ozone without giving rise to products other than O(2). This may be of importance when ozonation is used in pollution control, and reactions of free radicals with ozone have to be taken into account in modeling such processes.

Physiological Concentrations of Ascorbate Cannot Prevent the Potentially Damaging Reactions of Protein Radicals in Humans.

PubMed

Nauser, Thomas; Gebicki, Janusz M

2017-09-18

The principal initial biological targets of free radicals formed under conditions of oxidative stress are the proteins. The most common products of the interaction are carbon-centered alkyl radicals which react rapidly with oxygen to form peroxyl radicals and hydroperoxides. All these species are reactive, capable of propagating the free radical damage to enzymes, nucleic acids, lipids, and endogenous antioxidants, leading finally to the pathologies associated with oxidative stress. The best chance of preventing this chain of damage is in early repair of the protein radicals by antioxidants. Estimate of the effectiveness of the physiologically significant antioxidants requires knowledge of the antioxidant tissue concentrations and rate constants of their reaction with protein radicals. Previous studies by pulse radiolysis have shown that only ascorbate can repair the Trp and Tyr protein radicals before they form peroxyl radicals under physiological concentrations of oxygen. We have now extended this work to other protein C-centered radicals generated by hydroxyl radicals because these and many other free radicals formed under oxidative stress can produce secondary radicals on virtually any amino acid residue. Pulse radiolysis identified two classes of rate constants for reactions of protein radicals with ascorbate, a faster one in the range (9-60) × 10 7 M -1 s -1 and a slow one with a range of (0.5-2) × 10 7 M -1 s -1 . These results show that ascorbate can prevent further reactions of protein radicals only in the few human tissues where its concentration exceeds about 2.5 mM.

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

PubMed

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

2016-12-01

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

[Lavoisier and radicals].

PubMed

Lafont, Olivier

2007-01-01

Lavoisier and his co-workers (Guyton de Morveau, Bertholet, Fourcroy) considered that acids were constituted of oxygen and of something else that they called radicals. These radicals were known in some cases, i.e. nitrogen for nitrous acid, carbon for carbonic acid, phosphorus for phosphoric acid. In the case of sulfur, the sulfuric radical could be associated with different quantities of oxigen leading to sulfuric or sulfurous acids. In other cases radicals remained unknown at the time i.e. muriatic radical for muriatic acid, or benzoyl radical for benzoic acid. It is interesting to notice that Lavoisier evoked the case of compound radicals constituted of different substances such as carbon and hydrogen.

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

PubMed

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 the peroxyl radical precursor used (water-soluble or lipid-soluble peroxyl radical precursors) has little influence on the yields and kinetics of the transients formed from the reaction of peroxyl radicals with carotenoids. In the context of the interest in carotenoids as radical scavenging antioxidants, the fates of the addition radicals (formed from the reaction of carotenoid with peroxyl radicals) and carotenoid radical cations are discussed. Copyright © 2015 Elsevier Inc. All rights reserved.

Pyrimidine Nucleobase Radical Reactivity in DNA and RNA.

PubMed

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.

Pyrimidine nucleobase radical reactivity in DNA and RNA

NASA Astrophysics Data System (ADS)

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.

Tuning spin-spin interactions in radical dendrimers.

PubMed

Vidal-Gancedo, José; Lloveras, Vega; Liko, Flonja; Pinto, Luiz F; Muñoz-Gómez, Jose L

2018-05-10

Two generations of phosphorous dendrimers were synthesized and fully functionalized with TEMPO radicals via acrylamido or imino group linkers to evaluate the impact of the linker substitution on the radical-radical interactions. A drastic change in the way that the radicals interacted among them was observed by EPR and CV studies: while radicals in Gn-imino-TEMPO dendrimers presented a strong spin-spin interaction, in the Gn-acrylamido-TEMPO ones they acted mainly as independent radicals. This shows that these interactions could be tuned by the solely substitution of the radical linker, opening the perspective of controlling and modulating the extension of these interactions depending on each application. The chemical properties of the linker strongly influence the spin-spin exchange between pendant radicals. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical properties which control selectivity and efficacy of aromatic N-oxide bioreductive drugs.

PubMed Central

Wardman, P.; Priyadarsini, K. I.; Dennis, M. F.; Everett, S. A.; Naylor, M. A.; Patel, K. B.; Stratford, I. J.; Stratford, M. R.; Tracy, M.

1996-01-01

Pulse radiolysis was used to generate radicals from one electron reduction of 1,2,4-benzotriazine-1,4-dioxides (derivatives of tirapazamine), and of imidazo [1,2-a]quinoxaline-4-oxides (analogues of RB90740), which have selective toxicity towards hypoxic cells. Radicals from the mono N-oxides (from the latter compounds) react with oxygen approximately 10-40 times faster than does the tirapazamine radical. Radicals from the tirapazamine analogues studied react with oxygen up to approximately 10 times slower than tirapazamine radicals. The quinoxaline N-oxide radicals are involved in prototropic equilibria with pK(a) values (5.5 to 7.4) spanning that reported for tirapazamine (6.0). Generation of radicals radiolytically in the presence of H donors (formate, 2-propanol, deoxyribose) indicate a chain reaction ascribed to H abstraction by the drug radical. The protonated drug radical is much more reactive than the radical anion (H abstraction rate constant approximately equal to 10(2) - 10(3) dm3 mol-1 s-1). Chain termination is ascribed to drug radical-radical reactions, i.e. radical stability in anoxia, with rate constants 2k approximately equal to 1 x 10(7) to 2 x 10(8) dm3 mol-1 s-1 at pH approximately 7.4. Estimates of the reduction potentials of the drug-radical couples in water at pH 7 for two of the mono-N-oxides were in the range-0.7 to 0.8 V vs NHE at pH 7. PMID:8763850

Solution Kinetics Database on the Web

National Institute of Standards and Technology Data Gateway

SRD 40 NDRL/NIST Solution Kinetics Database on the Web (Web, free access)   Data for free radical processes involving primary radicals from water, inorganic radicals and carbon-centered radicals in solution, and singlet oxygen and organic peroxyl radicals in various solvents.

Carnivorous pitcher plant uses free radicals in the digestion of prey.

PubMed

Chia, Tet Fatt; Aung, Hnin Hnin; Osipov, Anatoly N; Goh, Ngoh Khang; Chia, Lian Sai

2004-01-01

A study of the involvement of free oxygen radicals in trapping and digestion of insects by carnivorous plants was the main goal of the present investigation. We showed that the generation of oxygen free radicals by pitcher fluid of Nepenthes is the first step of the digestion process, as seen by EPR spin trapping assay and gel-electrophoresis. The EPR spectrum of N. gracilis fluid in the presence of DMPO spin trap showed the superposition of the hydroxyl radical spin adduct signal and of the ascorbyl radical signal. Catalase addition decreased the generation of hydroxyl radicals showing that hydroxyl radicals are generated from hydrogen peroxide, which can be derived from superoxide radicals. Gel-electrophoresis data showed that myosin, an abundant protein component of insects, can be rapidly broken down by free radicals and protease inhibitors do not inhibit this process. Addition of myoglobin to the pitcher plant fluid decreased the concentration of detectable radicals. Based on these observations, we conclude that oxygen free radicals produced by the pitcher plant aid in the digestion of the insect prey.

Radical constructivism: Between realism and solipsism

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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

2015-11-01

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

Metal-Diazo Radicals of α-Carbonyl Diazomethanes

PubMed Central

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-01-01

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. PMID:26960916

Metal-Diazo Radicals of α-Carbonyl Diazomethanes

NASA Astrophysics Data System (ADS)

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.

Metal-Diazo Radicals of α-Carbonyl Diazomethanes.

PubMed

Li, Feifei; Xiao, Longqiang; Liu, Lijian

2016-03-10

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 [Rh(I)Cl(cod)]2, [Co(II)(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 [Rh(I)Cl(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 peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

PubMed Central

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 in aqueous media. Biological implications of the minor free radical pathway are discussed in the context of ONOO− detection, using the boronate probes. PMID:21434648

Isoprene Peroxy Radical Dynamics.

PubMed

Teng, Alexander P; Crounse, John D; Wennberg, Paul O

2017-04-19

Approximately 500 Tg of 2-methyl-1,3-butadiene (isoprene) is emitted by deciduous trees each year. Isoprene oxidation in the atmosphere is initiated primarily by addition of hydroxyl radicals (OH) to C 4 or C 1 in a ratio 0.57 ± 0.03 (1σ) to produce two sets of distinct allylic radicals. Oxygen (O 2 ) adds to these allylic radicals either δ (Z or E depending on whether the allylic radical is cis or trans) or β to the OH group forming six distinct peroxy radical isomers. Due to the enhanced stability of the allylic radical, however, these peroxy radicals lose O 2 in competition with bimolecular reactions. In addition, the Z-δ hydroxy peroxy radical isomers undergo unimolecular 1,6 H-shift isomerization. Here, we use isomer-resolved measurements of the reaction products of the peroxy radicals to diagnose this complex chemistry. We find that the ratio of δ to β hydroxy peroxy radicals depends on their bimolecular lifetime (τ bimolecular ). At τ bimolecular ≈ 0.1 s, a transition occurs from a kinetically to a largely thermodynamically controlled distribution at 297 K. Thus, in nature, where τ bimolecular > 10 s, the distribution of isoprene hydroxy peroxy radicals will be controlled primarily by the difference in the relative stability of the peroxy radical isomers. In this regime, β hydroxy peroxy radical isomers comprise ∼95% of the radical pool, a much higher fraction than in the nascent (kinetic) distribution. Intramolecular 1,6 H-shift isomerization of the Z-δ hydroxy peroxy radical isomers produced from OH addition to C 4 is estimated to be ∼4 s -1 at 297 K. While the Z-δ isomer is initially produced in low yield, it is continually reformed via decomposition of the β hydroxy peroxy radicals. As a result, unimolecular chemistry from this isomer contributes about half of the atmospheric fate of the entire pool of peroxy radicals formed via addition of OH at C 4 for typical atmospheric conditions (τ bimolecular = 100 s and T = 25 C). In contrast, unimolecular chemistry following OH addition at C 1 is slower and less important.

Contemporary Open and Robotic Radical Prostatectomy Practice Patterns Among Urologists in the United States

PubMed Central

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.

2012-01-01

Purpose We describe current trends in robotic and open radical prostatectomy in the United States after examining case logs for American Board of Urology certification. Materials and Methods 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. Results 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. Conclusions 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. PMID:22498227

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

PubMed

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.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

Free Radical Reactions in Food.

ERIC Educational Resources Information Center

Taub, Irwin A.

1984-01-01

Discusses reactions of free radicals that determine the chemistry of many fresh, processed, and stored foods. Focuses on reactions involving ascorbic acid, myoglobin, and palmitate radicals as representative radicals derived from a vitamin, metallo-protein, and saturated lipid. Basic concepts related to free radical structure, formation, and…

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

PubMed

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

2015-03-01

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

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

PubMed

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

2014-12-01

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

An oxygen radical absorbance capacity-like assay that directly quantifies the antioxidant's scavenging capacity against AAPH-derived free radicals.

PubMed

Kohri, Shunji; Fujii, Hirotada; Oowada, Shigeru; Endoh, Nobuyuki; Sueishi, Yoshimi; Kusakabe, Miku; Shimmei, Masashi; Kotake, Yashige

2009-03-15

A new method is proposed for the evaluation of oxygen radical absorbance capacity (ORAC). The current fluorescence-based ORAC assay (ORAC-FL) is an indirect method that monitors the antioxidant's ability to protect the fluorescent probe from free radical-mediated damage, and an azo-radical initiator, AAPH (2,2-azobis(2-amidinopropane) dihydrochloride), has been used as a thermal free radical source. The new ORAC assay employs a short in situ photolysis of AAPH to generate free radicals. The electron paramagnetic resonance (EPR) spin trapping method was employed to identify and quantify AAPH radicals. In the presence of antioxidant, the level of AAPH radicals was decreased, and ORAC-EPR values were calculated following a simple kinetic formulation. Alkyl-oxy radical was identified as the sole decomposition product from AAPH; therefore, we concluded that ORAC-FL is the assay equivalent to alkyl-oxy radical scavenging capacity measurement. ORAC-EPR results for several antioxidants and human serum indicated that the overall tendency is in agreement with ORAC-FL, but absolute values showed significant discrepancies. ORAC-EPR is a rapid and simple method that is especially suitable for thermally labile biological specimens because the sample heating is not required for free radical production.

Lithium formate for EPR dosimetry: radiation-induced radical trapping at low temperatures.

PubMed

Krivokapić, André; Aalbergsjø, Siv G; De Cooman, Hendrik; Hole, Eli Olaug; Nelson, William H; Sagstuen, Einar

2014-05-01

Radiation-induced primary radicals in lithium formate. A material used in EPR dosimetry have been studied using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-Induced EPR (EIE) techniques. In this study, single crystals were X irradiated at 6-8 K and radical formation at these and higher temperatures were investigated. Periodic density functional theory calculations were used to assist in assigning the radical structures. Mainly two radicals are present at 6 K, the well-known CO2(•-) radical and a protonated electron-gain product. Hyperfine coupling tensors for proton and lithium interactions were obtained for these two radicals and show that the latter radical exists in four conformations with various degrees of bending at the radical center. Pairs of CO2(•-) radicals were also observed and the tensor for the electron-electron dipolar coupling was determined for the strongest coupled pair, which exhibited the largest spectral intensity. Upon warming, both the radical pairs and the reduction product decay, the latter apparently by a transient species. Above 200 K the EPR spectrum was mainly due to the CO2(•-) (mono) radicals, which were previously characterized as the dominant species present at room temperature and which account for the dosimetric EPR signal.

CYCLOOXYGENASE COMPETITIVE INHIBITORS ALTER TYROSYL RADICAL DYNAMICS IN PROSTAGLANDIN H SYNTHASE-2†

PubMed Central

Wu, Gang; Tsai, Ah-Lim; Kulmacz, Richard J.

2009-01-01

Reaction of prostaglandin H synthase (PGHS) isoforms 1 or 2 with peroxide forms a radical at Tyr385 that is required for cyclooxygenase catalysis, and another radical at Tyr504, whose function is unknown. Both tyrosyl radicals are transient and rapidly dissipated by reductants, suggesting that cyclooxygenase catalysis might be vulnerable to suppression by intracellular antioxidants. Our initial hypothesis was that the two radicals are in equilibrium and that their proportions and stability are altered upon binding of fatty acid substrate. As a test, we examined the effects of three competitive inhibitors (nimesulide, flurbiprofen and diclofenac) on the proportions and stability of the two radicals in PGHS-2 pretreated with peroxide. Adding nimesulide after ethyl peroxide led to some narrowing of the tyrosyl radical signal detected by EPR spectroscopy, consistent with a small increase in the proportion of the Tyr504 radical. Neither flurbiprofen nor diclofenac changed the EPR linewidth when added after peroxide. In contrast, the effects of cyclooxygenase inhibitors on the stability of the preformed tyrosyl radicals were dramatic. The half-life of total tyrosyl radical was 4.1 min in the control, >10 hr with added nimesulide, 48 min with flurbiprofen, and 0.8 min with diclofenac. Stabilization of the tyrosyl radicals was evident even at substoichiometric levels of nimesulide. Thus, the inhibitors had potent, structure-dependent, effects on the stability of both tyrosyl radicals. This dramatic modulation of tyrosyl radical stability by cyclooxygenase site ligands suggests a mechanism for regulating the reactivity of PGHS tyrosyl radicals with cellular antioxidants. PMID:19894761

Reduction of protein radicals by GSH and ascorbate: potential biological significance.

PubMed

Gebicki, Janusz M; Nauser, Thomas; Domazou, Anastasia; Steinmann, Daniel; Bounds, Patricia L; Koppenol, Willem H

2010-11-01

The oxidation of proteins and other macromolecules by radical species under conditions of oxidative stress can be modulated by antioxidant compounds. Decreased levels of the antioxidants glutathione and ascorbate have been documented in oxidative stress-related diseases. A radical generated on the surface of a protein can: (1) be immediately and fully repaired by direct reaction with an antioxidant; (2) react with dioxygen to form the corresponding peroxyl radical; or (3) undergo intramolecular long range electron transfer to relocate the free electron to another amino acid residue. In pulse radiolysis studies, in vitro production of the initial radical on a protein is conveniently made at a tryptophan residue, and electron transfer often leads ultimately to residence of the unpaired electron on a tyrosine residue. We review here the kinetics data for reactions of the antioxidants glutathione, selenocysteine, and ascorbate with tryptophanyl and tyrosyl radicals as free amino acids in model compounds and proteins. Glutathione repairs a tryptophanyl radical in lysozyme with a rate constant of (1.05±0.05)×10(5) M(-1) s(-1), while ascorbate repairs tryptophanyl and tyrosyl radicals ca. 3 orders of magnitude faster. The in vitro reaction of glutathione with these radicals is too slow to prevent formation of peroxyl radicals, which become reduced by glutathione to hydroperoxides; the resulting glutathione thiyl radical is capable of further radical generation by hydrogen abstraction. Although physiologically not significant, selenoglutathione reduces tyrosyl radicals as fast as ascorbate. The reaction of protein radicals formed on insulin, β-lactoglobulin, pepsin, chymotrypsin and bovine serum albumin with ascorbate is relatively rapid, competes with the reaction with dioxygen, and the relatively innocuous ascorbyl radical is formed. On the basis of these kinetics data, we suggest that reductive repair of protein radicals may contribute to the well-documented depletion of ascorbate in living organisms subjected to oxidative stress.

[Spectroscopic Diagnosis of Two-Dimensional Distribution of OH Radicals in Wire-Plate Pulsed Corona Discharge Reactor].

PubMed

Jiang, Jian-ping; Luo, Zhong-yang; Xuan, Jian-yong; Zhao, Lei; Fang, Meng-xiang; Gao, Xiang

2015-10-01

Pulsed corona discharge in atmosphere has been widely regarded as an efficient flue gas treatment technology for the generation of active radical species, such as the OH radicals. The spatial distribution of OH radicals generated by pulsed corona discharge plays an important role in decomposing pollutants. The two-dimensional (2-D) distribution of OH radicals of positive wire--plate pulsed corona discharge was detected using laser-induced fluorescence (LIF). The influence of relative humidity (RH) and oxygen concentration on the 2-D distribution of OH radicals were investigated. The results indicated that the 2-D distribution of OH radicals was characterized by a fan-shaped distribution from the wire electrode to plate electrode, and both the maximum values of vertical length and horizontal width of the fan area was less than 1 cm. The 2-D distribution area of OH radicals increased significantly with increasing the RH and the optimum condition was 65% RH. The optimal level of the oxygen concentration for the 2-D distribution area of OH radicals was 2%. The process of OH radical generation and 2-D distribution area of OH radicals were significantly interfered when the oxygen concentration was larger than 15%. The total quenching rate coefficients for different RH values and oxygen concentration in this study were used to calculate the fluorescence yield of OH radical. The fluorescence yield, which is the ratio between the emission rate (Einstein coefficient) and the sum of the emission rate and quenching rate, was used to normalize the 2-D distribution area of OH radicals. The fluorescence yield of OH radical decreased with increasing the RH and oxygen concentration linearly and rapidly. It was also found that compared with the RH, the influence of the oxygen concentration had more notable effect on the fluorescence yield of OH radical and 2-D distribution area of OH radicals.

Radical scavenger can scavenge lipid allyl radicals complexed with lipoxygenase at lower oxygen content.

PubMed

Koshiishi, Ichiro; Tsuchida, Kazunori; Takajo, Tokuko; Komatsu, Makiko

2006-04-15

Lipoxygenases have been proposed to be a possible factor that is responsible for the pathology of certain diseases, including ischaemic injury. In the peroxidation process of linoleic acid by lipoxygenase, the E,Z-linoleate allyl radical-lipoxygenase complex seems to be generated as an intermediate. In the present study, we evaluated whether E,Z-linoleate allyl radicals on the enzyme are scavenged by radical scavengers. Linoleic acid, the content of which was greater than the dissolved oxygen content, was treated with soya bean lipoxygenase-1 (ferric form) in the presence of radical scavenger, CmP (3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-N-oxyl). The reaction rate between oxygen and lipid allyl radical is comparatively faster than that between CmP and lipid allyl radical. Therefore a reaction between linoleate allyl radical and CmP was not observed while the dioxygenation of linoleic acid was ongoing. After the dissolved oxygen was depleted, CmP stoichiometrically trapped linoleate-allyl radicals. Accompanied by this one-electron redox reaction, the resulting ferrous lipoxygenase was re-oxidized to the ferric form by hydroperoxylinoleate. Through the adduct assay via LC (liquid chromatography)-MS/MS (tandem MS), four E,Z-linoleate allyl radical-CmP adducts corresponding to regio- and diastereo-isomers were detected in the linoleate/lipoxygenase system, whereas E,E-linoleate allyl radical-CmP adducts were not detected at all. If E,Z-linoleate allyl radical is liberated from the enzyme, the E/Z-isomer has to reach equilibrium with the thermodynamically favoured E/E-isomer. These data suggested that the E,Z-linoleate allyl radicals were not liberated from the active site of lipoxygenase before being trapped by CmP. Consequently, we concluded that the lipid allyl radicals complexed with lipoxygenase could be scavenged by radical scavengers at lower oxygen content.

Taking a Radical Position: Evidence for Position-Specific Radical Representations in Chinese Character Recognition Using Masked Priming ERP

PubMed Central

Su, I.-Fan; Mak, Sin-Ching Cassie; Cheung, Lai-Ying Milly; Law, Sam-Po

2012-01-01

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 et al., 2004; Tsang and 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 96 ms 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 event-related potential (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. PMID:23024634

Cyclooxygenase Reaction Mechanism of PGHS ------- Evidence for a Reversible Transition between a Pentadienyl Radical and a New Tyrosyl Radical by Nitric Oxide Trapping

PubMed Central

Lü, Jian-Ming; Rogge, Corina E.; Wu, Gang; Kulmacz, Richard J.; van der Donk, Wilfred A.; Tsai, Ah-lim

2011-01-01

Incubation of prostaglandin H synthase-1 (PGHS-1) under anaerobic conditions with peroxide and arachidonic acid leads to two major radical species: a pentadienyl radical and a radical with a narrow EPR spectrum. The proportions of the two radicals are sensitive to temperature, favoring the narrow radical species at 22 °C. The EPR characteristics of this latter radical are somewhat similar to the previously reported narrow-singlet tyrosine radical NS1a and are insensitive to deuterium labeling of AA. To probe the origin and structure of this radical, we combined EPR analysis with nitric oxide (NO) trapping of tyrosine and substrate derived radicals for both PGHS-1 and -2. Formation of 3-nitrotyrosine in the proteins was analyzed by immunoblotting, whereas NO adducts to AA and AA metabolites were analyzed by mass spectrometry and by chromatography of 14C-labeled products. The results indicate that both nitrated tyrosine residues and NO-AA adducts formed upon NO trapping. The NO-AA adduct was predominantly an oxime at C11 of AA with three conjugated double bonds, as indicated by absorption at 275 nm and by mass spectral analysis. This adduct amounted to 10% and 20% of the heme concentration of PGHS-1 and -2, respectively. For PGHS-1, the yield of NO-AA adduct matched the yield of the narrow radical signal obtained in parallel EPR experiments. High frequency EPR characterization of this narrow radical, reported in an accompanying paper, supports assignment to a new tyrosyl radical, NS1c, rather than an AA-based radical. To reconcile the results from EPR and NO-trapping studies, we propose that the NS1c is in equilibrium with an AA pentadienyl radical, and that the latter reacts preferentially with NO. PMID:21403766

Practicing Radical Pedagogy: Balancing Ideals with Institutional Constraints.

ERIC Educational Resources Information Center

Sweet, Stephen

1998-01-01

Describes radical pedagogy and observes that an overview of "Teaching Sociology" suggests that few teachers fully practice it. Argues that while professors are free to teach radical theory, radical pedagogy is hindered by institutional constraints. Concludes that radical teachers may benefit from remaining more within the confines imposed by their…

Leadership Styles for the Five Stages of Radical Change

DTIC Science & Technology

1998-04-01

radical change. This article continues prior work on radical change with theory and research on leadership style. The result is a model of radical...every stage of that process. Leadership style and organiza- tional change theory and re- search have ex- isted for de- cades, but have rarely con... Leadership Styles for the Five Stages of Radical Change 129 TUTORIAL LEADERSHIP STYLES FOR THE FIVE STAGES OF RADICAL CHANGE Dr. Kathleen K. Reardon

Electron spin resonance of gamma-irradiated poly/ethylene 2,6-naphthalene dicarboxylate/.

NASA Technical Reports Server (NTRS)

Rogowski, R. S.; Pezdirtz, G. F.

1971-01-01

The two types of radicals trapped in gamma-irradiated PEN 2,6 are identified by ESR as - O - CH - CH2 - O - (radical I) and a radical located on the naphthalene ring (radical II). The concentrations of the radicals in the gross polyer are 10 to 20% of I and 80 to 90% of II. Similar trapped radicals are established in beta-irradiated PET, a structurally related polymer.

Antioxidant vitamins and enzymatic and synthetic oxygen-derived free radical scavengers in the prevention and treatment of cardiovascular disease.

PubMed

Nayak, D U; Karmen, C; Frishman, W H; Vakili, B A

2001-01-01

Oxygen-derived free radical formation can lead to cellular injury and death. Under normal situations, the human body has a free radical scavenger system (catalase, superoxide dismutase) that can detoxify free radicals. Antioxidant vitamins and enzymatic and synthetic oxygen-derived free radical scavengers have been used clinically to prevent the formation of oxidized LDL and to prevent reperfusion injury, which is often caused by free radicals. In this article, the pathogenesis of free radical production and cell injury are discussed, and therapeutic approaches for disease prevention are presented.

Understanding political radicalization: The two-pyramids model.

PubMed

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).

The electron is a catalyst

NASA Astrophysics Data System (ADS)

Studer, Armido; Curran, Dennis P.

2014-09-01

The electron is an efficient catalyst for conducting various types of radical cascade reaction that proceed by way of radical and radical ion intermediates. But because electrons are omnipresent, catalysis by electrons often passes unnoticed. In this Review, a simple analogy between acid/base catalysis and redox catalysis is presented. Conceptually, the electron is a catalyst in much the same way that a proton is a catalyst. The 'electron is a catalyst' paradigm unifies mechanistically an assortment of synthetic transformations that otherwise have little or no apparent relationship. Diverse radical cascades, including unimolecular radical substitution reactions (SRN1-type chemistry), base-promoted homolytic aromatic substitutions (BHAS), radical Heck-type reactions, radical cross-dehydrogenative couplings (CDC), direct arene trifluoromethylations and radical alkoxycarbonylations, can all be viewed as electron-catalysed reactions.

Tar balls from Deep Water Horizon oil spill: environmentally persistent free radicals (EPFR) formation during crude weathering.

PubMed

Kiruri, Lucy W; Dellinger, Barry; Lomnicki, Slawo

2013-05-07

Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041-47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils.

Tar Balls from Deep Water Horizon Oil Spill: Environmentally Persistent Free Radicals (EPFR) Formation During Crude Weathering

PubMed Central

Kiruri, Lucy W.; Dellinger, Barry; Lomnicki, Slawo

2014-01-01

Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041−47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils. PMID:23510127

Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies.

PubMed

Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun

2016-07-13

Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions.

ESR studies on reactivity of protein-derived tyrosyl radicals formed by prostaglandin H synthase and ribonucleotide reductase.

PubMed

Lassmann, G; Curtis, J; Liermann, B; Mason, R P; Eling, T E

1993-01-01

Using ESR spectroscopy, the ability of enzyme inhibitors to quench protein-derived tyrosyl radicals was studied in two different enzymes, prostaglandin H synthase and ribonucleotide reductase. The prostaglandin H synthase inhibitors indomethacin, eugenol, and MK-410 effectively prevent the formation of tyrosyl radicals during the oxidation of arachidonic acid by prostaglandin H synthase from ram seminal vesicles. A direct reaction with preformed tyrosyl radicals was observed only with eugenol. The other prostaglandin H synthase inhibitors were ineffective. The ribonucleotide reductase inhibitors hydroxyurea and 4-hydroxyanisole, which effectively inactivate the tyrosyl radical in the active site of ribonucleotide reductase present in tumor cells, exhibit a different reactivity with tyrosyl radicals formed by prostaglandin H synthase. Hydroxyurea quenches preformed tyrosyl radicals in prostaglandin H synthase weakly, whereas 4-hydroxyanisole does not quench tyrosyl radicals in prostaglandin H synthase at all. Eugenol, which quenches preformed prostaglandin H synthase-derived tyrosyl radicals, also quenches the tyrosyl radical in ribonucleotide reductase. The results suggest that the reactivity of protein-linked tyrosyl radicals in ribonucleotide reductase and those formed during prostaglandin H synthase catalysis are very different and have unrelated roles in enzyme catalysis.

π vs σ-Radical States of One-Electron Oxidized DNA/RNA Bases: A Density Functional Theory Study

PubMed Central

Kumar, Anil; Sevilla, Michael D.

2013-01-01

As a result of their inherent planarity, DNA base radicals generated by one electron oxidation/reduction or bond cleavage form π- or σ-radicals. While most DNA base systems form π-radicals there are a number of nucleobase analogs such as one-electron oxidized 6-azauraci1, 6-azacytosine, and 2-thiothymine or one-electron reduced 5-bromouracil that form more reactive σ-radicals. Elucidating the availability of these states within DNA, base radical electronic structure is important to the understanding of the reactivity of DNA base radicals in different environments. In this work, we address this question by the calculation of the relative energies of π- and σ-radical states in DNA/RNA bases and their analogs. We used density functional theory B3LYP/6-31++G** method to optimize the geometries of π- and σ-radicals in Cs symmetry (i.e., planar) in the gas phase and in solution using the polarized continuum model (PCM). The calculations predict that σ- and π-radical states in one electron oxidized bases of thymine, T(N3-H)•, and uracil, U(N3-H)• are very close in energy, i.e., the π-radical is only ca. 4 kcal/mol more stable than the σ-radical. For the one electron oxidized radicals of cytosine, C•+, C(N4-H)•, adenine, A•+, A(N6-H)•, and guanine, G•+, G(N2-H)•, G(N1-H)• the π-radicals are ca. 16 to 41 kcal/mol more stable than their corresponding σ-radicals. Inclusion of solvent (PCM) is found to stabilize the π- over σ-radical of each of the systems. U(N3-H)• with three discrete water molecules in the gas phase, is found to form a three-electron σ bond between N3 atom of uracil and O atom of a water molecule but on inclusion of full solvation and discrete hydration the π-radical remains most stable.. PMID:24000793

π- vs σ-radical states of one-electron-oxidized DNA/RNA bases: a density functional theory study.

PubMed

Kumar, Anil; Sevilla, Michael D

2013-10-03

As a result of their inherent planarity, DNA base radicals generated by one-electron oxidation/reduction or bond cleavage form π- or σ-radicals. While most DNA base systems form π-radicals, there are a number of nucleobase analogues such as one-electron-oxidized 6-azauraci1, 6-azacytosine, and 2-thiothymine or one-electron reduced 5-bromouracil that form more reactive σ-radicals. Elucidating the availability of these states within DNA, base radical electronic structure is important to the understanding of the reactivity of DNA base radicals in different environments. In this work, we address this question by the calculation of the relative energies of π- and σ-radical states in DNA/RNA bases and their analogues. We used density functional theory B3LYP/6-31++G** method to optimize the geometries of π- and σ-radicals in Cs symmetry (i.e., planar) in the gas phase and in solution using the polarized continuum model (PCM). The calculations predict that σ- and π-radical states in one-electron-oxidized bases of thymine, T(N3-H)(•), and uracil, U(N3-H)(•), are very close in energy; i.e., the π-radical is only ca. 4 kcal/mol more stable than the σ-radical. For the one-electron-oxidized radicals of cytosine, C(•+), C(N4-H)(•), adenine, A(•+), A(N6-H)(•), and guanine, G(•+), G(N2-H)(•), G(N1-H)(•), the π-radicals are ca. 16-41 kcal/mol more stable than their corresponding σ-radicals. Inclusion of solvent (PCM) is found to stabilize the π- over σ-radical of each of the systems. U(N3-H)(•) with three discrete water molecules in the gas phase is found to form a three-electron σ bond between the N3 atom of uracil and the O atom of a water molecule, but on inclusion of full solvation and discrete hydration, the π-radical remains most stable.

Plasmid DNA-encapsulating liposomes: effect of a spacer between the cationic head group and hydrophobic moieties of the lipids on gene expression efficiency.

PubMed

Obata, Yosuke; Saito, Shunsuke; Takeda, Naoya; Takeoka, Shinji

2009-05-01

We have synthesized a series of cationic amino acid-based lipids having a spacer between the cationic head group and hydrophobic moieties and examined the influence of the spacer on a liposome gene delivery system. As a comparable spacer, a hydrophobic spacer with a hydrocarbon chain composed of 0, 3, 5, 7, or 11 carbons, and a hydrophilic spacer with an oxyethylene chain (10 carbon and 3 oxygen molecules) were investigated. Plasmid DNA (pDNA)-encapsulating liposomes were prepared by mixing an ethanol solution of the lipids with an aqueous solution of pDNA. The zeta potentials and cellular uptake efficiency of the cationic liposomes containing each synthetic lipid were almost equivalent. However, the cationic lipids with the hydrophobic spacer were subject to fuse with biomembrane-mimicking liposomes. 1,5-Dihexadecyl-N-lysyl-N-heptyl-l-glutamate, having a seven carbon atom spacer, exhibited the highest fusogenic potential among the synthetic lipids. Increased fusion potential correlated with enhanced gene expression efficiency. By contrast, an oxyethylene chain spacer showed low gene expression efficiency. We conclude that a hydrophobic spacer between the cationic head group and hydrophobic moieties is a key component for improving pDNA delivery.

Pseudomonas aeruginosa quorum sensing molecules correlate with clinical status in cystic fibrosis.

PubMed

Barr, Helen L; Halliday, Nigel; Cámara, Miguel; Barrett, David A; Williams, Paul; Forrester, Douglas L; Simms, Rebecca; Smyth, Alan R; Honeybourne, David; Whitehouse, Joanna L; Nash, Edward F; Dewar, Jane; Clayton, Andrew; Knox, Alan J; Fogarty, Andrew W

2015-10-01

Pseudomonas aeruginosa produces quorum sensing signal molecules that are potential biomarkers for infection.A prospective study of 60 cystic fibrosis patients with chronic P. aeruginosa, who required intravenous antibiotics for pulmonary exacerbations, was undertaken. Clinical measurements and biological samples were obtained at the start and end of the treatment period. Additional data were available for 29 of these patients when they were clinically stable.Cross-sectionally, quorum sensing signal molecules were detectable in the sputum, plasma and urine of 86%, 75% and 83% patients, respectively. They were positively correlated between the three biofluids. Positive correlations were observed for most quorum sensing signal molecules in sputum, plasma and urine, with quantitative measures of pulmonary P. aeruginosa load at the start of a pulmonary exacerbation. Plasma concentrations of 2-nonyl-4-hydroxy-quinoline (NHQ) were significantly higher at the start of a pulmonary exacerbation compared to clinical stability (p<0.01). Following the administration of systemic antibiotics, plasma 2-heptyl-4-hydroxyquinoline (p=0.02) and NHQ concentrations (p<0.01) decreased significantly.In conclusion, quorum sensing signal molecules are detectable in cystic fibrosis patients with pulmonary P. aeruginosa infection and are positively correlated with quantitative measures of P. aeruginosa. NHQ correlates with clinical status and has potential as a novel biomarker for P. aeruginosa infection. Copyright ©ERS 2015.

The role of the peripheral benzodiazepine receptor in photodynamic activity of certain pyropheophorbide ether photosensitizers: albumin site II as a surrogate marker for activity.

PubMed

Dougherty, Thomas J; Sumlin, Adam B; Greco, William R; Weishaupt, Kenneth R; Vaughan, Lurine A; Pandey, Ravindra K

2002-07-01

A study has been carried out to define the importance of the peripheral benzodiazepine receptor (PBR) as a binding site for a series of chlorin-type photosensitizers, pyropheophorbide-a ethers, the subject of a previous quantitative structure-activity relationship study by us. The effects of the PBR ligand PK11195 on the photodynamic activity have been determined in vivo for certain members of this series of alkyl-substituted ethers: two of the most active derivatives (hexyl and heptyl), the least active derivative (dodecyl [C12]) and one of intermediate activity (octyl [C8]). The photodynamic therapy (PDT) effect was inhibited by PK11195 for both of the most active derivatives, but no effect on PDT activity was found for the less active C12 or C8 ethers. The inhibitory effects of PK11195 were predicted by the binding of only the active derivatives to the benzodiazepine site on albumin, ie. human serum albumin (HSA)-Site II. Thus, as with certain other types of photosensitizers, it has been demonstrated with this series of pyropheophorbide ethers that in vitro binding to HSA-Site II is a predictor of both optimal in vivo activity and binding to the PBR in vivo.

Algicidal activity of marine Alteromonas sp. KNS-16 and isolation of active compounds.

PubMed

Cho, Ji Young

2012-01-01

The KNS-16 algicidal strain was isolated from a harmful alga bloom (HAB) area and identified as Alteromonas sp. based on 16S rDNA sequencing. The KNS-16 strain was found to control HABs by producing algicidal compounds in an indirect interaction. Four active compounds were isolated from KNS-16 culture, and their structures were analyzed by interpreting nuclear magnetic resonance and mass spectroscopy data. The structures were identified as 2-undecen-1'-yl-4-quinolone (1), 2-undecyl-4-quinolone (2), 3-hexyl-6-pentyl-4-hydroxyl-2H-pyran-2-one (3), and 6-heptyl-3-hexyl-4-hydroxyl-2H-pyran-2-one (4). Compound 1 was most active against HABs such as Heterosigma akashiwo, Cochlodinium polykrikoides, and Alexandrium tamarense with LC(50) values of 0.5-1.1 µg/mL. The four compounds exhibited high LC(50) values against aquaculture algae such as Tetaselmis suecica, Isochrysis galbana, and Pavlova lutheri at 39-66 µg/mL. Based on toxicity tests on the brine shrimp Artemia salina and the rotifer Brachionus rotundiformis, the four compounds showed ranges of 409-608 and 189-224 µg/mL of LC(50) for the two organisms, respectively. The LC(50) values for juvenile fish of Sebastes schlegelii were 284-304 µg/mL.

Pseudomonas aeruginosa quorum sensing molecules correlate with clinical status in cystic fibrosis

PubMed Central

Halliday, Nigel; Cámara, Miguel; Barrett, David A.; Williams, Paul; Forrester, Douglas L.; Simms, Rebecca; Smyth, Alan R.; Honeybourne, David; Whitehouse, Joanna L.; Nash, Edward F.; Dewar, Jane; Clayton, Andrew; Knox, Alan J.; Fogarty, Andrew W.

2015-01-01

Pseudomonas aeruginosa produces quorum sensing signal molecules that are potential biomarkers for infection. A prospective study of 60 cystic fibrosis patients with chronic P. aeruginosa, who required intravenous antibiotics for pulmonary exacerbations, was undertaken. Clinical measurements and biological samples were obtained at the start and end of the treatment period. Additional data were available for 29 of these patients when they were clinically stable. Cross-sectionally, quorum sensing signal molecules were detectable in the sputum, plasma and urine of 86%, 75% and 83% patients, respectively. They were positively correlated between the three biofluids. Positive correlations were observed for most quorum sensing signal molecules in sputum, plasma and urine, with quantitative measures of pulmonary P. aeruginosa load at the start of a pulmonary exacerbation. Plasma concentrations of 2-nonyl-4-hydroxy-quinoline (NHQ) were significantly higher at the start of a pulmonary exacerbation compared to clinical stability (p<0.01). Following the administration of systemic antibiotics, plasma 2-heptyl-4-hydroxyquinoline (p=0.02) and NHQ concentrations (p<0.01) decreased significantly. In conclusion, quorum sensing signal molecules are detectable in cystic fibrosis patients with pulmonary P. aeruginosa infection and are positively correlated with quantitative measures of P. aeruginosa. NHQ correlates with clinical status and has potential as a novel biomarker for P. aeruginosa infection. PMID:26022946

Stereostructure of a norbornane diexo-condensed 1,3-oxazine[2,3-a]isoindolone An X-ray study

NASA Astrophysics Data System (ADS)

Argay, Gy.; Kálmán, A.; Stájer, G.; Bernáth, G.

1994-12-01

The structure of 3,6-methano-12b-p-tolyl-2a,3,4,5,6,6a,7,12b-octahydro-2H-3,1-benzoxazino[2,3-a]isoindol-8-one (C23H23NO2, Mr = 345.42), prepared from 2-p-toluoylbenzoic acid and diexo-3-hydroxymethylbicyclo[2.2.1]heptyl-2-amine, has been established by X-ray crystallography from diffractometer data: it crystallizes in the triclinic space group Poverline1 with a = 8.186(2) Å, b = 8.683(2) Å, c = 13.324(5) Å, α = 83.46(4)°, β = 75.48(6)°, γ = 77.60(4)°, V = 893.6(4) Å3, Z = 2, Dc = 1.284 g cm-3 and μ(Cu Kα) = 0.641 mm-1. The structure was solved by direct methods and refined to R = 0.061 for 3685 observed reflections. The molecule exhibits diexo-annelation between the 1,3-oxazine ring and the norbornane moiety. The p-tolyl group and norbonane annelation hydrogens are trans and the 1,3-oxazine ring is fused to an almost planar γ-lactam ring. Consequently, the six-membered hetero ring assumes an irregular conformation among the canonical forms 1S6, 1T3 and B3,6.

Role of the Pseudomonas quinolone signal (PQS) in sensitising Pseudomonas aeruginosa to UVA radiation.

PubMed

Pezzoni, Magdalena; Meichtry, Martín; Pizarro, Ramón A; Costa, Cristina S

2015-01-01

One of the main stress factors that bacteria face in the environment is solar ultraviolet-A (UVA) radiation, which leads to lethal effects through oxidative damage. The aim of this work was to investigate the role of 2-heptyl-3-hydroxi-4-quinolone (the Pseudomonas quinolone signal or PQS) in the response of Pseudomonas aeruginosa to UVA radiation. PQS is an intercellular quorum sensing signal associated to membrane vesicles which, among other functions, regulates genes related to iron acquisition, forms stable complexes with iron and participates in oxidative phenomena. UVA exposure of the wild-type PAO1 strain and a pqsA mutant unable to produce PQS revealed a sensitising role for this signal. Research into the mechanism involved in this phenomenon revealed that catalase, an essential factor in the UVA defence, is not related to PQS-mediated UVA sensitivity. Absorption of UVA by PQS produced its own photo-degradation, oxidation of the probe 2',7'- dichlorodihydrofluorescein and generation of singlet oxygen and superoxide anion, suggesting that this signal could be acting as an endogenous photosensitiser. The results presented in this study could explain the high sensitivity to UVA of P. aeruginosa when compared to enteric bacteria. Copyright © 2014 Elsevier B.V. All rights reserved.

The Agr quorum-sensing system regulates fibronectin binding but not hemolysis in the absence of a functional electron transport chain.

PubMed

Pader, Vera; James, Ellen H; Painter, Kimberley L; Wigneshweraraj, Sivaramesh; Edwards, Andrew M

2014-10-01

Staphylococcus aureus is responsible for numerous chronic and recurrent infections, which are frequently associated with the emergence of small-colony variants (SCVs) that lack a functional electron transport chain. SCVs exhibit enhanced expression of fibronectin-binding protein (FnBP) and greatly reduced hemolysin production, although the basis for this is unclear. One hypothesis is that these phenotypes are a consequence of the reduced Agr activity of SCVs, while an alternative is that the lack of a functional electron transport chain and the resulting reduction in ATP production are responsible. Disruption of the electron transport chain of S. aureus genetically (hemB and menD) or chemically, using 2-n-heptyl-4-hydroxyquinoline N-oxide (HQNO), inhibited both growth and Agr activity and conferred an SCV phenotype. Supplementation of the culture medium with synthetic autoinducing peptide (sAIP) significantly increased Agr expression in both hemB mutant strains and S. aureus grown with HQNO and significantly reduced staphylococcal adhesion to fibronectin. However, sAIP did not promote hemolysin expression in hemB mutant strains or S. aureus grown with HQNO. Therefore, while Agr regulates fibronectin binding in SCVs, it cannot promote hemolysin production in the absence of a functional electron transport chain. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

The Agr Quorum-Sensing System Regulates Fibronectin Binding but Not Hemolysis in the Absence of a Functional Electron Transport Chain

PubMed Central

Pader, Vera; James, Ellen H.; Painter, Kimberley L.; Wigneshweraraj, Sivaramesh

2014-01-01

Staphylococcus aureus is responsible for numerous chronic and recurrent infections, which are frequently associated with the emergence of small-colony variants (SCVs) that lack a functional electron transport chain. SCVs exhibit enhanced expression of fibronectin-binding protein (FnBP) and greatly reduced hemolysin production, although the basis for this is unclear. One hypothesis is that these phenotypes are a consequence of the reduced Agr activity of SCVs, while an alternative is that the lack of a functional electron transport chain and the resulting reduction in ATP production are responsible. Disruption of the electron transport chain of S. aureus genetically (hemB and menD) or chemically, using 2-n-heptyl-4-hydroxyquinoline N-oxide (HQNO), inhibited both growth and Agr activity and conferred an SCV phenotype. Supplementation of the culture medium with synthetic autoinducing peptide (sAIP) significantly increased Agr expression in both hemB mutant strains and S. aureus grown with HQNO and significantly reduced staphylococcal adhesion to fibronectin. However, sAIP did not promote hemolysin expression in hemB mutant strains or S. aureus grown with HQNO. Therefore, while Agr regulates fibronectin binding in SCVs, it cannot promote hemolysin production in the absence of a functional electron transport chain. PMID:25092909

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

NASA Astrophysics Data System (ADS)

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

2016-07-01

Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H513CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H513CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg

2016-07-05

Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 us. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures upmore » to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 13CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 13CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

Kinetics and Near-Infrared Spectroscopy of Organic Peroxy Radicals

NASA Astrophysics Data System (ADS)

Smarte, M. D.; Okumura, M.

2016-12-01

Organic peroxy radicals are important intermediates in atmospheric chemistry with fates that control the rate of radical propagation in an oxidation mechanism. Laboratory methods for detecting peroxy radicals are essential to measuring precise rate constants that constrain these fates. In this work, we discuss the use of near-infrared cavity ringdown spectroscopy to detect organic peroxy radicals for the purpose of laboratory kinetics measurements. We focus on chlorine-substituted peroxy radicals generated in the oxidation of alkenes by chlorine, a minor tropospheric oxidant found in marine and coastal regions. Previous kinetics experiments on peroxy radicals have largely used UV absorption spectroscopy via the dissociative B-X transition. However, the spectra produced are featureless and exhibit substantial overlap; determining the concentration profile of an individual peroxy radical can be an arduous task. In our work, we probe the forbidden peroxy radical A-X transition in the near-infrared. While this approach requires overcoming small cross sections ( 10-21 cm2), the A state is bound and leads to structured absorption spectra that may be useful in constraining the kinetics of mixtures of organic peroxy radicals formed in the oxidation of complex hydrocarbons. Only a few kinetics studies utilizing the A-X transition exist in the literature and they are focused on small, unsubstituted species. This presentation explores the ability of the A-X transition to unravel the kinetics of more complex peroxy radicals in laboratory experiments using several example systems: (1) Determining rate constants for the self and cross reactions of β-chloroethylperoxy and HO2. (2) Detecting the second generation of peroxy radicals formed from alkoxy radical decomposition in the chlorine-initiated oxidation of 2-butene. (3) Observing different rates of reactivity with NO across the pool of peroxy radical isomers formed in the chlorine-initiated oxidation of isoprene.

Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase: direct evidence for products and pathways in low temperature benzene oxidation.

PubMed

Kirk, Benjamin B; Harman, David G; Kenttämaa, Hilkka I; Trevitt, Adam J; Blanksby, Stephen J

2012-12-28

The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium)phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me(3)N(+))C(6)H(4)˙ + O(2)] = 2.8 × 10(-11) cm(3) molecule(-1) s(-1), Φ = 4.9%; k(2)[((-)O(2)C)C(6)H(4)˙ + O(2)] = 5.4 × 10(-11) cm(3) molecule(-1) s(-1), Φ = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermodynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.

Characterization of the radical-scavenging reaction of 2-O-substituted ascorbic acid derivatives, AA-2G, AA-2P, and AA-2S: a kinetic and stoichiometric study.

PubMed

Takebayashi, Jun; Tai, Akihiro; Gohda, Eiichi; Yamamoto, Itaru

2006-04-01

The aim of this study was to characterize the antioxidant activity of three ascorbic acid (AA) derivatives O-substituted at the C-2 position of AA: ascorbic acid 2-glucoside (AA-2G), ascorbic acid 2-phosphate (AA-2P), and ascorbic acid 2-sulfate (AA-2S). The radical-scavenging activities of these AA derivatives and some common low molecular-weight antioxidants such as uric acid or glutathione against 1,1-diphenyl-picrylhydrazyl (DPPH) radical, 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) radical cation (ABTS+), or galvinoxyl radical were kinetically and stoichiometrically evaluated under pH-controlled conditions. Those AA derivatives slowly and continuously reacted with DPPH radical and ABTS+, but not with galvinoxyl radical. They effectively reacted with DPPH radical under acidic conditions and with ABTS+ under neutral conditions. In contrast, AA immediately quenched all species of radicals tested at all pH values investigated. The reactivity of Trolox, a water-soluble vitamin E analogue, was comparable to that of AA in terms of kinetics and stoichiometrics. Uric acid and glutathione exhibited long-lasting radical-scavenging activity against these radicals under certain pH conditions. The radical-scavenging profiles of AA derivatives were closer to those of uric acid and glutathione rather than to that of AA. The number of radicals scavenged by one molecule of AA derivatives, uric acid, or glutathione was equal to or greater than that by AA or Trolox under the appropriate conditions. These data suggest the potential usage of AA derivatives as radical scavengers.

ELECTRON SPIN RESONANCE STUDIES ON PEROXIDE RADICALS IN IRRADIATED POLYPROPYLENE (in German)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fischer, H.; Hellwege, K.-H.; Neudoerfl, P.

1963-06-01

Peroxide radicals are formed by oxidation of carbon radicals in irradiated isotactic polypropylene. An interpretation of their ESR spectra is given. The recombination of the peroxide radicals follows a chain reaction mechanism, which is derived from the reversibility of formation of peroxide radicals, the time dependence of their concentration, and from the oxygen consumption of samples containing peroxide radicals. The reactions are discussed in view of the radiation induced oxidative degradation of polypropylene. (auth)

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

PubMed

Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

2018-06-04

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions

NASA Astrophysics Data System (ADS)

Williams, Peggy E.; Marshall, David L.; Poad, Berwyck L. J.; Narreddula, Venkateswara R.; Kirk, Benjamin B.; Trevitt, Adam J.; Blanksby, Stephen J.

2018-06-01

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions.

Lexical processing of Chinese sub-character components: Semantic activation of phonetic radicals as revealed by the Stroop effect.

PubMed

Yeh, Su-Ling; Chou, Wei-Lun; Ho, Pokuan

2017-11-17

Most Chinese characters are compounds consisting of a semantic radical indicating semantic category and a phonetic radical cuing the pronunciation of the character. Controversy surrounds whether radicals also go through the same lexical processing as characters and, critically, whether phonetic radicals involve semantic activation since they can also be characters when standing alone. Here we examined these issues using the Stroop task whereby participants responded to the ink color of the character. The key finding was that Stroop effects were found when the character itself had a meaning unrelated to color, but contained a color name phonetic radical (e.g., "guess", with the phonetic radical "cyan", on the right) or had a meaning associated with color (e.g., "pity", with the phonetic radical "blood" on the right which has a meaning related to "red"). Such Stroop effects from the phonetic radical within a character unrelated to color support that Chinese character recognition involves decomposition of characters into their constituent radicals; with each of their meanings including phonetic radicals activated independently, even though it would inevitably interfere with that of the whole character. Compared with the morphological decomposition in English whereby the semantics of the morphemes are not necessarily activated, the unavoidable semantic activation of phonetic radicals represents a unique feature in Chinese character processing.

Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

PubMed

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 .

Social Radicalism as a Framework for Education.

ERIC Educational Resources Information Center

Nelson, Jack L.

This paper examines the nature of radicalism, proposes definitions and dimensions, and suggests the dynamics of radical thoughts and their interrelation with schools. A radical idea is one which is highly divergent from the normative values, behaviors, ideals or traditions of a culture at a point in time. This paper views radical ideas as…

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

PubMed

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

2017-11-01

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

Development of atomic radical monitoring probe and its application to spatial distribution measurements of H and O atomic radical densities in radical-based plasma processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takahashi, Shunji; Katagiri Engineering Co., Ltd., 3-5-34 Shitte Tsurumi-ku, Yokohama 230-0003; Takashima, Seigo

2009-09-01

Atomic radicals such as hydrogen (H) and oxygen (O) play important roles in process plasmas. In a previous study, we developed a system for measuring the absolute density of H, O, nitrogen, and carbon atoms in plasmas using vacuum ultraviolet absorption spectroscopy (VUVAS) with a compact light source using an atmospheric pressure microplasma [microdischarge hollow cathode lamp (MHCL)]. In this study, we developed a monitoring probe for atomic radicals employing the VUVAS with the MHCL. The probe size was 2.7 mm in diameter. Using this probe, only a single port needs to be accessed for radical density measurements. We successfullymore » measured the spatial distribution of the absolute densities of H and O atomic radicals in a radical-based plasma processing system by moving the probe along the radial direction of the chamber. This probe allows convenient analysis of atomic radical densities to be carried out for any type of process plasma at any time. We refer to this probe as a ubiquitous monitoring probe for atomic radicals.« less

Detection of peroxyl radicals from polluted air by free radical reaction combined with liquid chromatography signal amplification technique.

PubMed

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

2018-01-22

Free radicals play an important role in the oxidizing power of polluted air, the development of aging-related diseases, the formation of ozone, and the production of secondary particulate matter. The high variability of peroxyl radical concentration has prevented the detection of possible trends or distributions in the concentration of free radicals. We present a new method, free radical reaction combined with liquid chromatography photodiode array detection, for identifying and quantifying peroxyl radicals in polluted air. Functionalized graphene was used for loading peroxyl radicals and reactive molecules in air sampling system, which can facilitate reaction kinetics (charge transfers) between peroxyl radicals and reaction molecules. Separation was performed with and without a preliminary exposure of the polluted air sample to reactive molecule(s) system. The integral chromatographic peak areas before and after air sampling are used to quantify the atmospheric peroxyl radicals in polluted air. The utility of the new technique was tested with measurements carried out in the field. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative Degradation of Methyl Orange Solution by Fe-MKSF Catalyst: Identification of Radical Species

NASA Astrophysics Data System (ADS)

Abdullah, N. H.; Selamat, M. K. A.; Nasuha, N.; Hassan, H.; Zubir, N. A.

2018-06-01

Iron–immobilized montmorillonite KSF (Fe-MKSF) has been recognized as promising catalyst in degrading persistence organic contaminants. However, detailed mechanistic insight during the catalysis which involving the formation and identification of radical species were remained indeterminate due to complex reaction. Inspiring by this gap, iron-immobilized clay (Fe-MKSF) was synthesized and used as heterogeneous catalyst in the oxidative degradation of methyl orange (MO) solution. Identification of radical species were determined through the inclusion of different types of radical scavenging agent during the Fenton-like reaction at optimum condition. Interestingly, dominant radical species were found to be hydroperoxyl radicals (•OOH) which subsequently followed by hydroxyl radicals (•OH) during the catalysis. Based on the percentage of MO removal, it was suggested that approximately 88% of the •OOH radicals existed at the interface of catalyst while 39% presence in bulk solution. Meanwhile, the interface •OH radicals promoted 38% of MO removal, whilst 4% by the bulk •OH radicals. Hence, these findings have conveyed novel insight on detailed radicals’ identification as well as its’ interaction during the catalysis.

Biochemistry of free radicals: from electrons to tissues.

PubMed

Boveris, A

1998-01-01

Free radicals are chemical species with an unpaired electron in the outer valence orbitals. The unpaired electron makes them paramagnetic (physics) and relatively reactive (chemistry). The free radicals that are normal metabolites in aerobic biological systems have varied reactivities, ranging from the high reactivity of hydroxyl radical (t1/2 = 10(-9) s) to the low reactivity of melanins (t1/2 = days). The univalent reduction of oxygen that takes place in mammalian organs produces superoxide radicals at a rate of about 2% of the total oxygen uptake. The primary production of superoxide radicals sustains a free radical chain reaction involving a series of reactive oxygen species (hydrogen peroxide, hydroxyl and peroxyl radical and singlet oxygen). Nitric oxide is almost unreactive as free radical except for its termination reaction with superoxide radical to yield the strong oxidant peroxynitrite. Nitric oxide also reacts with ubiquinol in a redox reaction, with cytochrome oxidase competitively with oxygen, and oxymyoglobin and oxyhemoglobin displacing oxygen. Septic shock and endotoxemia produce muscle dysfunction and oxidative stress due to increased steady state concentrations of reactive oxygen and nitrogen species.

Synergistic effects of Lewis bases and substituents on the electronic structure and reactivity of boryl radicals.

PubMed

Lu, Dongmei; Wu, Chao; Li, Pengfei

2014-02-03

Boryl radicals have the potential for the development of new molecular entities and for application in new radical reactions. However, the effects of the substituents and coordinating Lewis bases on the reactivity of boryl radicals are not fully understood. By using first-principles methods, we investigated the spin-density distribution and reactivity of a series of boryl radicals with various substituents and Lewis bases. The substituents, along with the Lewis bases, only affect the radical reactivity when an unpaired electron is in the boron pz orbital, that is, for three-coordinate radicals. We found evidence of synergistic effects between the substituents and the Lewis bases that can substantially broaden the tunability of the reactivity of the boryl radicals. Among Lewis bases, pyridine and imidazol-2-ylidene show a similar capacity for stabilization by delocalizing the spin density. Electron-donating substituents, such as nitrogen, more efficiently stabilize boryl radicals than oxygen and carbon atoms. The reactivity of a boryl radical is always boron based, irrespective of the spin density on boron. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-band Electron Paramagnetic Resonance Investigation of Stable Organic Radicals Present under Cold Stratification in 'Fuji' Apple Seeds.

PubMed

Nakagawa, Kouichi; Matsumoto, Kazuhiro; Chaiserm, Nattakan; Priprem, Aroonsri

2017-01-01

We investigated stable organic radicals formed in response to cold stratification in 'Fuji' apple seeds using X-band (9 GHz) electron paramagnetic resonance (EPR) technique. This technique primarily detected two paramagnetic species in each seed. These two different radical species were assigned as a stable organic radical and Mn 2+ species based on the g values and hyperfine components. Signal from the stable radicals was noted at a g value of about 2.00 and was strong and relatively stable. Significant radical intensity changes were observed in apple seeds on refrigeration along with water supplementation. The strongest radical intensity and a very weak Mn 2+ signal were also observed for the seeds kept in moisture-containing sand in a refrigerator. Noninvasive EPR of the radicals present in each seed revealed that the stable radicals were located primarily in the seed coat. These results indicate that the significant radical intensity changes in apple seeds under refrigeration for at least 90 days followed by water supplementation for one week, can be related to cold stratification of the seeds.

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

PubMed

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

2014-09-30

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

A Stable Room-Temperature Luminescent Biphenylmethyl Radical.

PubMed

Ai, Xin; Chen, Yingxin; Feng, Yuting; Li, Feng

2018-03-05

There is only one family of room-temperature luminescent radicals, the triphenylmethyl radicals, to date. Herein, we synthesize a new stable room-temperature luminescent radical, (N-carbazolyl)bis(2,4,6-tirchlorophenyl)methyl radical (CzBTM), which has improved properties compared to the triphenylmethyl radicals. X-ray crystallography, electron paramagnetic resonance spectroscopy, and magnetic susceptibility measurements confirmed the radical structure. CzBTM shows room-temperature deep-red to near-infrared emission in various solutions. Both thermal and photo stability were significantly enhanced by the replacement of trichlorobenzene by the carbazole moiety. The electroluminescence results of CzBTM verify its potential application to circumvent the problem of triplet harvesting in traditional fluorescent OLEDs. A new family of stable luminescent radicals based on CzBTM is anticipated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

OH radical induced depolymerization of poly(methacrylic acid)

NASA Astrophysics Data System (ADS)

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

1999-05-01

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

Generation of radicals and antimalarial activity of dispiro-1,2,4-trioxolanes

NASA Astrophysics Data System (ADS)

Denisov, E. T.; Denisova, T. G.

2013-01-01

The kinetic schemes of the intramolecular oxidation of radicals generated from substituted dispiro-1,2,4-trioxolanes (seven compounds) in the presence of Fe2+ and oxygen were built. Each radical reaction was defined in terms of enthalpy, activation energy, and rate constant. The kinetic characteristics were calculated by the intersecting parabolas method. The competition between the radical reactions was considered. The entry of radicals generated by each compound into the volume was calculated. High antimalarial activity was found for 1,2,4-trioxolanes, which generated hydroxyl radicals. The structural features of trioxolanes responsible for the generation of hydroxyl radicals were determined.

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

PubMed

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

2015-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-06-01

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

Radicalization and Radical Catalysis of Biomass Sugars: Insights from First-principles Studies

PubMed Central

Yang, Gang; Zhu, Chang; Zou, Xianli; Zhou, Lijun

2016-01-01

Ab initio and density functional calculations are conducted to investigate the radicalization processes and radical catalysis of biomass sugars. Structural alterations due to radicalization generally focus on the radicalized sites, and radicalization affects H-bonds in D-fructofuranose more than in D-glucopyranose, potentially with outcome of new H-bonds. Performances of different functionals and basis sets are evaluated for all radicalization processes, and enthalpy changes and Gibbs free energies for these processes are presented with high accuracy, which can be referenced for subsequent experimental and theoretical studies. It shows that radicalization can be utilized for direct transformation of biomass sugars, and for each sugar, C rather than O sites are always preferred for radicalization, thus suggesting the possibility to activate C-H bonds of biomass sugars. Radical catalysis is further combined with Brønsted acids, and it clearly states that functionalization fundamentally regulates the catalytic effects of biomass sugars. In presence of explicit water molecules, functionalization significantly affects the activation barriers and reaction energies of protonation rather than dehydration steps. Tertiary butyl and phenyl groups with large steric hindrances or hydroxyl and amino groups resulting in high stabilities for protonation products drive the protonation steps to occur facilely at ambient conditions. PMID:27405843

Product yield-detected ESR on magnetic field-dependent photoreduction of quinones in SDS micellar solution

NASA Astrophysics Data System (ADS)

Okazaki, M.; Sakata, S.; Konaka, R.; Shiga, T.

1987-06-01

Transient free radicals in the magnetic field-dependent photoreduction of quinones (menadione or anthraquinone) in a sodium dodecyl sulfate (SDS) micellar solution, were converted to stable nitroxide radicals by the ``spin trapping'' technique with or without the microwave irradiation. Upon irradiating the microwave at 160 mW, the product yield (``spin adduct'' of the alkyl radical generated from SDS molecule) decreased by up to 14% at certain magnetic fields in a resonant manner. Although only one component of the postulated radical pair was converted to the spin adduct, the decrease in the yield as a function of external magnetic field revealed the ESR spectra of both component radicals of the radical pair, i.e., the semiquinone radical and the alkyl radical from SDS. This experiment not only gives the direct evidence for the radical pair model, but also suggests the possibility for this method to be applied in controlling the chemical reactions by the microwave. A simple calculation was made to simulate the observed ``product yield-detected ESR.'' Agreements were achieved semiquantitatively between the observed reductions in the spin adduct yields and those calculated. The estimated exchange interaction between the component radicals in the radical pair of the present systems was lower than 0.3 mT.

Efficient depletion of ascorbate by amino acid and protein radicals under oxidative stress.

PubMed

Domazou, Anastasia S; Zelenay, Viviane; Koppenol, Willem H; Gebicki, Janusz M

2012-10-15

Ascorbate levels decrease in organisms subjected to oxidative stress, but the responsible reactions have not been identified. Our earlier studies have shown that protein C-centered radicals react rapidly with ascorbate. In aerobes, these radicals can react with oxygen to form peroxyl radicals. To estimate the relative probabilities of the reactions of ascorbate with protein C- and O-centered radicals, we measured by pulse radiolysis the rate constants of the reactions of C-centered radicals in Gly, Ala, and Pro with O₂ and of the resultant peroxyl radicals with ascorbate. Calculations based on the concentrations of ascorbate and oxygen in human tissues show that the relative probabilities of reactions of the C-centered amino acid radicals with O₂ and ascorbate vary between 1:2.6 for the pituitary gland and 1:0.02 for plasma, with intermediate ratios for other tissues. The high frequency of occurrence of Gly, Ala, and Pro in proteins and the similar reaction rate constants of their C-centered radicals with O₂ and their peroxo-radicals with ascorbate suggest that our results are also valid for proteins. Thus, the formation of protein C- or O-centered radicals in vivo can account for the loss of ascorbate in organisms under oxidative stress. Copyright © 2012 Elsevier Inc. All rights reserved.

Acetyl radical generation in cigarette smoke: Quantification and simulations

NASA Astrophysics Data System (ADS)

Hu, Na; Green, Sarah A.

2014-10-01

Free radicals are present in cigarette smoke and can have a negative effect on human health. However, little is known about their formation mechanisms. Acetyl radicals were quantified in tobacco smoke and mechanisms for their generation were investigated by computer simulations. Acetyl radicals were trapped from the gas phase using 3-amino-2, 2, 5, 5-tetramethyl-proxyl (3AP) on solid support to form stable 3AP adducts for later analysis by high-performance liquid chromatography (HPLC), mass spectrometry/tandem mass spectrometry (MS-MS/MS) and liquid chromatography-mass spectrometry (LC-MS). Simulations were performed using the Master Chemical Mechanism (MCM). A range of 10-150 nmol/cigarette of acetyl radical was measured from gas phase tobacco smoke of both commercial and research cigarettes under several different smoking conditions. More radicals were detected from the puff smoking method compared to continuous flow sampling. Approximately twice as many acetyl radicals were trapped when a glass fiber particle filter (GF/F specifications) was placed before the trapping zone. Simulations showed that NO/NO2 reacts with isoprene, initiating chain reactions to produce hydroxyl radical, which abstracts hydrogen from acetaldehyde to generate acetyl radical. These mechanisms can account for the full amount of acetyl radical detected experimentally from cigarette smoke. Similar mechanisms may generate radicals in second hand smoke.

Free-radical reactions induced by OH-radical attack on cytosine-related compounds: a study by a method combining ESR, spin trapping and HPLC.

PubMed Central

Hiraoka, W; Kuwabara, M; Sato, F; Matsuda, A; Ueda, T

1990-01-01

Free-radical reactions induced by OH-radical attack on cytosine-related compounds were investigated by a method combining ESR, spin trapping with 2-methyl-2-nitrosopropane and high-performance liquid chromatography (HPLC). Cytidine, 2'-deoxycytidine, cytidine 3'-monophosphate, cytidine 5'-monophosphate, 2'-deoxycytidine 5'-monophosphate and their derivatives, of which 5,6-protons at the base moiety were replaced by deuterons, and polycytidylic acid (poly(C] were employed as samples. OH radicals were generated by X-irradiating an N2O-saturated aqueous solution. Five spin adducts were separated by HPLC. Examination of them by ESR spectroscopy and UV photospectrometry showed that spin adducts assigned to C5 and C6 radicals due to OH addition to the 5,6 double-bond, a deaminated form of the spin adduct derived from a C5 radical due to the cyclization reaction between C5' of the sugar and C6 of the base, and a spin adduct assigned to the C4' radical due to H abstraction by OH radicals were produced. From these results the sites of OH-radical attack and the subsequent radical reactions in cytosine-related compounds were clarified. PMID:2157193

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

PubMed

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

2015-06-10

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

Open conversion during minimally invasive radical prostatectomy: impact on perioperative complications and predictors from national data.

PubMed

Sharma, Vidit; Meeks, Joshua J

2014-12-01

Despite the increased use of minimally invasive radical prostatectomy, open conversion may occur due to surgical complications, surgeon inexperience or failure to progress. We used nationally representative data to quantify the impact of open conversion compared to nonconverted minimally invasive radical prostatectomy and open radical prostatectomy, and identify predictors of open conversion. Years 2004 to 2010 of the Nationwide Inpatient Sample were queried for patients who underwent radical prostatectomy to analyze the association of open conversion during minimally invasive radical prostatectomy with Clavien complications. Multivariate regression models yielded significant predictors of open conversion. From 2004 to 2010, 134,398 (95% CI 111,509-157,287) minimally invasive radical prostatectomies were performed with a 1.8% (95% CI 1.4-2.1) open conversion rate, translating to 2,360 (95% CI 2,001-2,720) conversions. Open conversion cases had a longer length of stay (4.17 vs 1.71 days, p <0.001) and higher hospital charges ($51,049 vs $37,418, p <0.001) than nonconverted cases. Of open conversion cases 45.2% experienced a complication vs 7.2% and 12.9% of minimally invasive radical prostatectomy and open radical prostatectomy cases, respectively (p <0.001). After adjusting for age and comorbidities, open conversion was associated with significantly increased odds of a Clavien grade 1, 2, 3 and 4 complication compared to nonconverted minimally invasive radical prostatectomy and open radical prostatectomy (OR range 2.913 to 15.670, p <0.001). Significant multivariate predictors of open conversion were obesity (OR 1.916), adhesions (OR 3.060), anemia (OR 5.692) and surgeon volume for minimally invasive radical prostatectomy less than 25 cases per year (OR 7.376) (all p <0.01). Open conversion during minimally invasive radical prostatectomy is associated with a higher than expected increase in complications compared to open radical prostatectomy and minimally invasive radical prostatectomy after adjusting for age and comorbidities. External validation of predictors of open conversion may prove useful in minimizing open conversion during minimally invasive radical prostatectomy. Copyright © 2014 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

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

PubMed

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 is proposed between aminocarboxylates and arylamine free radicals via the carboxylic group-linked tertiary nitrogen of the deprotonated amino acid derivatives. These findings may have significant implications for the biological fate of arylamine xenobiotic and drug free-radical metabolites.

Crystalline bipyridinium radical complexes and uses thereof

DOEpatents

Fahrenbach, Albert C.; Barnes, Jonathan C.; Li, Hao; Stoddart, J. Fraser; Basuray, Ashish Neil; Sampath, Srinivasan

2015-09-01

Described herein are methods of generating 4,4'-bipyridinium radical cations (BIPY.sup..cndot.+), and methods for utilizing the radical-radical interactions between two or more BIPY.sup..cndot.+ radical cations that ensue for the creation of novel materials for applications in nanotechnology. Synthetic methodologies, crystallographic engineering techniques, methods of physical characterization, and end uses are described.

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

ERIC Educational Resources Information Center

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…

Theoretical studies of alkyl radicals in the NaY and HY zeolites.

PubMed

Ghandi, Khashayar; Zahariev, Federico E; Wang, Yan Alexander

2005-08-18

Interplay of quantum mechanical calculations and experimental data on hyperfine coupling constants of ethyl radical in zeolites at several temperatures was engaged to study the geometries and binding energies and to predict the temperature dependence of hyperfine splitting of a series of alkyl radicals in zeolites for the first time. The main focus is on the hyperfine interaction of alkyl radicals in the NaY and HY zeolites. The hyperfine splitting for neutral free radicals and free radical cations is predicted for different zeolite environments. This information can be used to establish the nature of the muoniated alkyl radicals in the NaY and HY zeolites via muSR experiments. The muon hyperfine coupling constants of the ethane radical cation in these zeolites are very large with relatively little dependence on temperature. It was found that the intramolecular dynamics of alkyl free radicals are only weakly affected by their strong binding to zeolites. In contrast, the substrate binding has a significant effect on their intermolecular dynamics.

ERPs reveal sub-lexical processing in Chinese character recognition.

PubMed

Wu, Yan; Mo, Deyuan; Tsang, Yiu-Kei; Chen, Hsuan-Chih

2012-04-18

The present study used ERPs and a lexical decision task to explore the roles of position-general and position-specific radicals and their relative time courses in processing Chinese characters. Two types of radical frequency were manipulated: the number of characters containing a specific radical irrespective of position (i.e., radical frequency or RF) and the number of characters containing a specific radical at a particular position (i.e., position-specific radical frequency or PRF). The PRF effect was found to be associated with P150, P200, and N400, whereas the RF effect was associated with P200. These results suggest that both position-general and position-specific radicals could influence character processing, but the effect of position-specific radicals appeared earlier and lasted longer than that of position-general radicals. These findings are interpreted in terms of the specific orthographic properties of the sub-lexical components of Chinese characters. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Adolescent Radicalism and Family Socialization

ERIC Educational Resources Information Center

Christiansen, Niels; And Others

1976-01-01

Intention was to see if tendencies toward political and cultural radicalism could be identified as two separate dimensions of radicalism among adolescents and to study family characteristics which might explain a tendency toward radicalism. (Author/RK)

Ab initio molecular dynamics of the reactivity of vitamin C toward hydroxyl and HO₂/O⁻₂ radicals.

PubMed

Lespade, Laure

2017-11-21

Vitamin C is one of the most abundant exogenous antioxidants in the cell, and it is of the utmost importance to elucidate its mechanism of action against radicals. In this study, the reactivity of vitamin C toward OH and [Formula: see text] radicals in aqueous medium was analyzed by ab initio molecular dynamics using CPMD code. The simulations led to results similar to those of static studies or experiments for the pair of [Formula: see text] radicals but bring new insights for the reactivity with hydroxyl radical: the reaction takes place before the formation of an adduct and consists of two steps: first an electron is transferred to hydroxyl radical and then the ascorbyl radical loses a proton. Graphical Abstract Reactivity of vitamin C toward hydroxyl and [Formula: see text] radicals.

Total free radical species and oxidation equivalent in polluted air.

PubMed

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.

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

PubMed

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

2004-12-21

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

Elucidating the Charge Transfer Mechanism in Radical Polymer Thin Films

NASA Astrophysics Data System (ADS)

Mukherjee, Sanjoy; Boudouris, Bryan

The active role of polymers in organic electronics has attracted significant attention in recent decades. Beyond conventional conjugated polymers, recently radical polymers have received a great deal of consideration by the community. Radical polymers are redox-active macromolecules with non-conjugated backbones functionalized with persistent radical sites. Because of their nascent nature, many open questions regarding the physics of their solid-state charge transfer mechanism still exist. In order to address these questions, well-defined radical polymers were synthesized and blended in a manner such that there was tight control over the radical density within the conducting thin films. We demonstrate that the systematic manipulation of the radical-to-radical spacing in open-shell macromolecules leads to exponential changes in the macroscopic electrical conductivity, and temperature-independent charge transport behaviour. Thus, a clear picture emerges that charge transfer in radical polymers is dictated by a tunnelling mechanism between proximal sites. This behavior is consistent with a distinct mechanism similar to redox reactions in biological media, but is unique relative to transport in common conjugated polymers. These results constitute the first experimental insight into the mechanism of solid-state electrical conduction in radical polymers.

DFT and ENDOR Study of Bixin Radical Cations and Neutral Radicals on Silica-Alumina.

PubMed

Tay-Agbozo, Sefadzi S; Krzyaniak, Matthew D; Bowman, Michael K; Street, Shane; Kispert, Lowell D

2015-06-18

Bixin, a carotenoid found in annatto (Bixa orellana), is unique among natural carotenoids by being water-soluble. We stabilized free radicals from bixin on the surface of silica-alumina (Si-Al) and characterized them by pulsed electron-nuclear double resonance (ENDOR). DFT calculations of unpaired electron spin distribution for various bixin radicals predict the EPR hyperfine couplings. Least-square fitting of experimental ENDOR spectra by spectra calculated from DFT hyperfine couplings characterized the radicals trapped on Si-Al. DFT predicts that the trans bixin radical cation is more stable than the cis bixin radical cation by 1.26 kcal/mol. This small energy difference is consistent with the 26% trans and 23% cis radical cations in the ENDOR spectrum. The remainder of the ENDOR spectrum is due to several neutral radicals formed by loss of a H(+) ion from the 9, 9', 13, or 13' methyl group, a common occurrence in all water-insoluble carotenoids previously studied. Although carboxyl groups of bixin strongly affect its solubility relative to other natural carotenoids, they do not alter properties of its free radicals based on DFT calculations and EPR measurements which remain similar to typical water-insoluble carotenoids.

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

NASA Astrophysics Data System (ADS)

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.

STABLE FREE-RADICAL FORMS OF PLASMA PROTEINS OR SIMPLER RELATED STRUCTURES WHICH INDUCE BRAIN EXCITATORY EFFECTS

PubMed Central

Polis, B. David; Wyeth, John; Goldstein, Leonide; Graedon, Joe

1969-01-01

Stable free radicals have been prepared from purified plasma proteins, pituitary peptides, and simpler related structures like 5-OH tryptophan and melatonin by oxidation with the free-radical nitrosyl disulfonate in alkaline solution under controlled conditions. The presence of tyrosine or trytophan amino acid residues in the protein was found essential for free-radical formation. These red-colored, stable free radicals showed electron spin resonance spectra in aqueous solutions at room temperature and maintained this characteristic for weeks when stored at 5°C. Illumination, by visible light, of the free-radical proteins and peptides separated from excess nitrosyl disulfonate by salt fractionation or chromatography enhanced the free-radical concentration in the light. The increased signal decayed in the dark. Intravenous administration of the free-radical proteins or peptides into rabbits equipped with chronic cranial electrodes and sedated with a small dose of pentobarbital caused a sudden EEG arousal accompanied by behavioral changes indicative of brain excitation. Illumination of the free-radical compounds prior to administration enhanced the effects. Untreated control proteins or peptides had no effects. The observations are interpreted to suggest the involvement of free-radical structures in the transfer of energy in nervous tissue. PMID:4311379

Preparation of optically active bicyclodihydrosiloles by a radical cascade reaction

PubMed Central

Miyazaki, Koichiro; Yamane, Yu; Yo, Ryuichiro; Uno, Hidemitsu

2013-01-01

Summary Bicyclodihydrosiloles were readily prepared from optically active enyne compounds by a radical cascade reaction triggered by tris(trimethylsilyl)silane ((Me3Si)3SiH). The reaction was initiated by the addition of a silyl radical to an α,β-unsaturated ester, forming an α-carbonyl radical that underwent radical cyclization to a terminal alkyne unit. The resulting vinyl radical attacked the silicon atom in an SHi manner to give dihydrosilole. The reaction preferentially formed trans isomers of bicyclosiloles with an approximately 7:3 to 9:1 selectivity. PMID:23946827

Spatial distribution of CH3 and CH2 radicals in a methane rf discharge

NASA Astrophysics Data System (ADS)

Sugai, H.; Kojima, H.; Ishida, A.; Toyoda, H.

1990-06-01

Spatial distributions of neutral radicals CH3 and CH2 in a capacitively coupled rf glow discharge of methane were measured by threshold ionization mass spectrometry. A strong asymmetry of the density profile was found for the CH2 radical in the high-pressure (˜100 mTorr) discharge. In addition, comprehensive measurements of electron energy distribution, ionic composition, and radical sticking coefficient were made to use as inputs to theoretical modeling of radicals in the methane plasma. The model predictions agree substantially with the measured radical distributions.

Explanation to the difference in the ketyl radical formation yields of benzophenone and benzil

NASA Astrophysics Data System (ADS)

Okutsu, Tetsuo; Muramatsu, Hidenori; Horiuchi, Hiroaki; Hiratsuka, Hiroshi

2005-03-01

p Ka values of benzophenone ketyl and benzil ketyl radicals were determined as 9.4 and 12.4, respectively. We can successfully explain the difference in quantum yield of the proton transfer between benzophenone ketyl and benzil ketyl radicals by these values. Reaction enthalpies of the proton transfer are the same (-80 kJ mol -1) for these radicals, and the difference in p Ka value can be explained by that reaction entropies. Reaction entropies between two radicals are discussed by the possible structure of the radicals.

Enolization of acetone in superheated water detected via radical formation.

PubMed

Ghandi, Khashayar; Addison-Jones, Brenda; Brodovitch, Jean-Claude; McCollum, Brett M; McKenzie, Iain; Percival, Paul W

2003-08-13

Muoniated free radicals have been detected in muon-irradiated aqueous solutions of acetone at high temperatures and pressures. At temperatures below 250 degrees C, the radical product is consistent with muonium addition to the keto form of acetone. However, at higher temperatures, a different radical was detected, which is attributed to muonium addition to the enol form. Muon hyperfine coupling constants have been determined for both radicals over a wide range of temperatures, significantly extending the range of conditions under which these radicals and the keto-enol equilibrium have been studied.

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

NASA Astrophysics Data System (ADS)

Volkamer, R.; Sheehy, P.; Molina, L. T.; Molina, M. J.

2010-07-01

A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time-resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; the MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10-25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: Oxygenated VOC other than HCHO about 33%; HCHO and O3 photolysis each about 20%; O3/alkene reactions and HONO photolysis each about 12%, other sources <3%. Nitryl chloride photolysis could potentially contribute ~15% additional radicals, while NO2* + water makes - if any - a very small contribution (~2%). The peak radical production of ~7.5 107 molec cm-3 s-1 is found already at 10:00 a.m., i.e., more than 2.5 h before solar noon. O3/alkene reactions are indirectly responsible for ~33% of these radicals. Our measurements and analysis comprise a database that enables testing of the representation of radical sources and radical chain reactions in photochemical models. Since the photochemical processing of pollutants in the MCMA is radical limited, our analysis identifies the drivers for ozone and SOA formation. We conclude that reductions in VOC emissions provide an efficient opportunity to reduce peak concentrations of these secondary pollutants, because (1) about 70% of radical production is linked to VOC precursors; (2) lowering the VOC/NOx ratio has the further benefit of reducing the radical re-cycling efficiency from radical chain reactions (chemical amplification of radical sources); (3) a positive feedback is identified: lowering the rate of radical production from organic precursors also reduces that from inorganic precursors, like ozone, as pollution export from the MCMA caps the amount of ozone that accumulates at a lower rate inside the MCMA. Continued VOC reductions will in the future result in decreasing peak concentrations of ozone and SOA in the MCMA.

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

DOE PAGES

Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; ...

2016-07-05

Cycloheptatrienyl (tropyl) radical, C 7H 7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. In this study, the pyrolysis products resulting from C 7H 7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C 7H 7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals domore » not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C 7H 7) radicals but rather only benzyl (C 6H 5CH 2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C 6H 5CH 2, C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2. Finally, analysis of the temperature dependence for the pyrolysis of the isotopic species (C 6H 5CD 2, C 6D 5CH 2, and C 6H 5 13CH 2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buckingham, Grant T.; National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden Colorado 80401; Porterfield, Jessica P.

2016-07-07

Cycloheptatrienyl (tropyl) radical, C{sub 7}H{sub 7}, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C{sub 7}H{sub 7} were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C{sub 7}H{sub 7} are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize tomore » benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C{sub 7}H{sub 7}) radicals but rather only benzyl (C{sub 6}H{sub 5}CH{sub 2}). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C{sub 6}H{sub 5}CH{sub 2}, C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).« less

An in vivo ESR spin-trapping study: Free radical generation in rats from formate intoxication— role of the Fenton reaction

PubMed Central

Dikalova, Anna E.; Kadiiska, Maria B.; Mason, Ronald P.

2001-01-01

Electron spin resonance spectroscopy has been used to study free radical generation in rats with acute sodium formate poisoning. The in vivo spin-trapping technique was used with α-(4-pyridyl-1-oxide)-N-t-butylnitrone (POBN), which reacts with free radical metabolites to form radical adducts, which were detected in the bile and urine samples from Fischer rats. The use of [13C]-sodium formate and computer simulations of the spectra identified the 12-line spectrum as arising from the POBN/carbon dioxide anion radical adduct. The identification of POBN/⋅CO\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} \\begin{equation*}{\\mathrm{_{2}^{-}}}\\end{equation*}\\end{document} radical adduct provides direct electron spin resonance spectroscopy evidence for the formation of ⋅CO\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\setlength{\\oddsidemargin}{-69pt} \\begin{document} \\begin{equation*}{\\mathrm{_{2}^{-}}}\\end{equation*}\\end{document} radicals during acute intoxication by sodium formate, suggesting a free radical metabolic pathway. To study the mechanism of free radical generation by formate, we tested several known inhibitors. Both allopurinol, an inhibitor of xanthine oxidase, and aminobenzotriazole, a cytochrome P450 inhibitor, decreased free radical formation from formate, which may imply a dependence on hydrogen peroxide. In accord with this hypothesis, the catalase inhibitor 3-aminotriazole caused a significant increase in free radical formation. The iron chelator Desferal decreased the formation of free radicals up to 2-fold. Presumably, iron plays a role in the mechanism of free radical generation by formate via the Fenton reaction. The detection of formate free radical metabolites generated in vivo and the key role of the Fenton reaction in this process may be important for understanding the pathogenesis of both formate and methanol intoxication. PMID:11717423

Pulse radiolysis in model studies toward radiation processing

NASA Astrophysics Data System (ADS)

Von Sonntag, C.; Bothe, E.; Ulanski, P.; Deeble, D. J.

1995-02-01

Using the pulse radiolysis technique, the OH-radical-induced reactions of poly(vinyl alcohol) PVAL, poly(acrylic acid) PAA, poly(methacrylic acid) PMA, and hyaluronic acid have been investigated in dilute aqueous solution. The reactions of the free-radical intermediates were followed by UV-spectroscopy and low-angle laser light-scattering; the scission of the charged polymers was also monitored by conductometry. For more detailed product studies, model systems such as 2,4-dihydroxypentane (for PVAL) and 2,4-dimethyl glutaric acid (for PAA) was also investigated. With PVA, OH-radicals react predominantly by abstraction of an H-atom in α-position to the hydroxyl group (70%). The observed bimolecular decay rate constant of the PVAL-radicals decreases with time. This has been interpreted as being due to an initially fast decay of proximate radicals and a decrease of the probability of such encounters with time. Intramolecular crosslinking (loop formation) predominates at high doses per pulse. In the presence of O 2, peroxyl radicals are formed which in the case of the α-hydroxyperoxyl radicals can eliminate HO 2-radicals in competition with bimolecular decay processes which lead to a fragmentation of the polymer. In PAA, radicals both in α-position (characterized by an absorption near 300 nm) and in β-position to the carboxylate groups are formed in an approximately 1:2 ratio. The lifetime of the radicals increases with increasing electrolytic dissociation of the polymer. The β-radicals undergo a slow (intra- as well as intermolecular) H-abstraction yielding α-radicals, in competition to crosslinking and scission reactions. In PMA only β-radicals are formed. Their fragmentation has been followed by conductometry. In hyaluronic acid, considerable fragmeentation is observed even in the absence of oxygen which, in fact, has some protective effect against this process. Thus free-radical attack on this important biopolymer makes it especially vulnerable with respect to a reduction of its viscosity, and in rheumatic diseases this effect may be the reason for their painfulnes.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Influence of Smoking Puff Parameters and Tobacco Varieties on Free Radicals Yields in Cigarette Mainstream Smoke.

PubMed

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

2018-05-07

Cigarette smoke is a major exogenous source of free radicals, and the resulting oxidative stress is one of the major causes of smoking-caused diseases. Yet, many of the factors that impact free radical delivery from cigarettes remain unclear. In this study, we machine-smoked cigarettes and measured the levels of gas- and particulate-phase radicals by electron paramagnetic resonance (EPR) spectroscopy using standardized smoking regimens (International Organization of Standardization (ISO) and Canadian Intense (CI)), puffing parameters, and tobacco blends. Radical delivery per cigarette was significantly greater in both gas (4-fold) and particulate (6-fold) phases when cigarettes were smoked under the CI protocol compared to the ISO protocol. Total puff volume per cigarette was the major factor with radical production being proportional to total volume, regardless of whether volume differences were achieved by changes in individual puff volume or puff frequency. Changing puff shape (bell vs sharp vs square) or puff duration (1-5 s), without changing volume, had no effect on radical yields. Tobacco variety did have a significant impact on free radical production, with gas-phase radicals highest in reconstituted > burley > oriental > bright tobacco and particulate-phase radicals highest in burley > bright > oriental > reconstituted tobacco. Our findings show that modifiable cigarette design features and measurable user smoking behaviors are key factors determining free radical exposure in smokers.

Stabilization of Two Radicals with One Metal: A Stepwise Coupling Model for Copper-Catalyzed Radical–Radical Cross-Coupling

PubMed Central

Qi, Xiaotian; Zhu, Lei; Bai, Ruopeng; Lan, Yu

2017-01-01

Transition metal-catalyzed radical–radical cross-coupling reactions provide innovative methods for C–C and C–heteroatom bond construction. A theoretical study was performed to reveal the mechanism and selectivity of the copper-catalyzed C–N radical–radical cross-coupling reaction. The concerted coupling pathway, in which a C–N bond is formed through the direct nucleophilic addition of a carbon radical to the nitrogen atom of the Cu(II)–N species, is demonstrated to be kinetically unfavorable. The stepwise coupling pathway, which involves the combination of a carbon radical with a Cu(II)–N species before C–N bond formation, is shown to be probable. Both the Mulliken atomic spin density distribution and frontier molecular orbital analysis on the Cu(II)–N intermediate show that the Cu site is more reactive than that of N; thus, the carbon radical preferentially react with the metal center. The chemoselectivity of the cross-coupling is also explained by the differences in electron compatibility of the carbon radical, the nitrogen radical and the Cu(II)–N intermediate. The higher activation free energy for N–N radical–radical homo-coupling is attributed to the mismatch of Cu(II)–N species with the nitrogen radical because the electrophilicity for both is strong. PMID:28272407

Catalysts For Hydrogenation And Hydrosilylation Methods Of Making And Using The Same

DOEpatents

Dioumaev, Vladimir K.; Bullock, R. Morris

2004-05-18

A compound is provided including an organometallic complex represented by the formula I: wherein M is an atom of molybdenum or tangsten, Cp is substituted or unsubstituted cyclopentadienyl radical represented by the formula [C.sub.5 Q.sup.1 Q.sup.2 Q.sup.3 Q.sup.4 Q.sup.5 ], wherein Q.sup.1 to Q.sup.5 are independently selected from the group consisting of H radical, C.sub.1-20 hydrocarbyl radical, substituted hydrocarbyl radical, halogen radical, halogen-substituted hydrocarbyl radical, --OR, --C(O)R', --CO.sub.2 R', --SiR'.sub.3 and --NR'R", wherein R' and R" are independently selected from the group consisting of H radical, C.sub.1-20 hydrocarbyl radical, halogen radical, and halogen-substituted hydrocarbyl radical, wherein said Q.sup.1 to Q.sup.5 radicals are optionally linked to each other to form a stable bridging group, NHC is any N-heterocyclic carbene ligand, L is either any neutral electron donor ligand, wherein k is a number from 0 to 1 or L is an anionic ligand wherein k is 2, and A.sup.- is an anion. Processes using the organometallic complex as catalyst for hydrogenation of aldehydes and ketones are provided. Processes using the organometallic complex as catalyst for the hydrosilylation of aldehydes, ketones and esters are also provided.

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

PubMed

Irikura, Karl K

2013-03-14

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

Investigating the Distribution of Stable Paramagnetic Species in an Apple Seed Using X-Band EPR and EPR Imaging.

PubMed

Nakagawa, Kouichi; Epel, Boris

2017-03-01

This study investigated the location and distribution of paramagnetic species in apple seeds using electron paramagnetic resonance (EPR) and X-band (9 GHz) EPR imaging (EPRI). EPR primarily detected two paramagnetic species per measured seed. These two different radical species were assigned as stable radicals and Mn 2+ species based on the g values and hyperfine components. The signal from the stable radical was noted at g ≈ 2.00 and was strong and relatively stable. The subsequent noninvasive EPRI of the radical present in each seed revealed that the stable radicals were located primarily in the seed coat, with very few radicals observed in the cotyledon of the seed. These results indicate that the stable radical species were only found within the seed coat, and few radical species were found in other seed parts.

Oxidative stress, free radicals and protein peroxides.

PubMed

Gebicki, Janusz M

2016-04-01

Primary free radicals generated under oxidative stress in cells and tissues produce a cascade of reactive secondary radicals, which attack biomolecules with efficiency determined by the reaction rate constants and target concentration. Proteins are prominent targets because they constitute the bulk of the organic content of cells and tissues and react readily with many of the secondary radicals. The reactions commonly lead to the formation of carbon-centered radicals, which generally convert in vivo to peroxyl radicals and finally to semistable hydroperoxides. All of these intermediates can initiate biological damage. This article outlines the advantages of the application of ionizing radiations to studies of radicals, with particular reference to the generation of desired radicals, studies of the kinetics of their reactions and correlating the results with events in biological systems. In one such application, formation of protein hydroperoxides in irradiated cells was inhibited by the intracellular ascorbate and glutathione. Copyright © 2015 Elsevier Inc. All rights reserved.

Covalently Bound Nitroxyl Radicals in an Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hughes, Barbara K.; Braunecker, Wade A.; Bobela, David C.

2016-09-15

A series of covalent organic framework (COF) structures is synthesized that possesses a tunable density of covalently bound nitroxyl radicals within the COF pores. The highest density of organic radicals produces an electron paramagnetic resonance (EPR) signal that suggests the majority of radicals strongly interact with other radicals, whereas for smaller loadings the EPR signals indicate the radicals are primarily isolated but with restricted motion. The dielectric loss as determined from microwave absorption of the framework structures compared with an amorphous control suggests that free motion of the radicals is inhibited when more than 25% of available sites are occupied.more » The ability to tune the mode of radical interactions and the subsequent effect on redox, electrical, and optical characteristics in a porous framework may lead to a class of structures with properties ideal for photoelectrochemistry or energy storage.« less

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

NASA Astrophysics Data System (ADS)

Wink, David A.; Desrosiers, Marc F.

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

Ozone decomposition in aqueous acetate solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sehested, K.; Holcman, J.; Bjergbakke, E.

1987-01-01

The acetate radical ion reacts with ozone with a rate constant of k = (1.5 +/- 0.5) x 10Z dmT mol s . The products from this reaction are CO2, HCHO, and O2 . By subsequent reaction of the peroxy radical with ozone the acetate radical ion is regenerated through the OH radical. A chain decomposition of ozone takes place. It terminates when the acetate radical ion reacts with oxygen forming the unreactive peroxy acetate radical. The chain is rather short as oxygen is developed, as a result of the ozone consumption. The inhibiting effect of acetate on the ozonemore » decay is rationalized by OH scavenging by acetate and successive reaction of the acetate radical ion with oxygen. Some products from the bimolecular disappearance of the peroxy acetate radicals, however, react further with ozone, reducing the effectiveness of the stabilization.« less

The scavenging reactions of nitrogen dioxide radical and carbonate radical by tea polyphenol derivatives: a pulse radiolysis study

NASA Astrophysics Data System (ADS)

Miao, Jin-Ling; Wang, Wen-Feng; Pan, Jing-Xi; Lu, Chang-Yuan; Li, Rong-Qun; Yao, Si-De

2001-02-01

The reactions of tea polyphenol derivatives, including epicatechin (EC) and epigallocatechin gallate (EGCG), with nitrogen dioxide radical (NO 2rad ) and carbonate radical (CO 3rad - ) have been studied in detail using time-resolved pulse radiolysis technique. In all the cases, the corresponding phenoxyl radical was formed through electron transfer reaction. From the build-up kinetics of the phenoxyl radicals and the decay kinetics of CO 3rad - radical, the reaction rate constants of EC, EGCG with NO 2rad and CO 3rad - were determined to be 9.0×10 7, 1.2×10 8 and 5.6×10 8, 6.6×10 8 dm 3 mol -1 s -1, respectively. Therefore, tea polyphenol derivatives proved to be efficient scavengers of NO 2rad and CO 3rad - radicals.

Jet-Cooled Chlorofluorobenzyl Radicals: Spectroscopy and Mechanism

NASA Astrophysics Data System (ADS)

Yoon, Young; Lee, Sang

2016-06-01

Whereas the benzyl radical, a prototypic aromatic free radical, has been the subject of numerous spectroscopic studies, halo-substituted benzyl radicals have received less attention, due to the difficulties associated with production of radicals from precursors. In particular, chloro-substituted benzyl radicals have been much less studied because of the weak visible emission intensity and weak C-Cl bond dissociation energy. The jet-cooled chlorofluorobenzyl radicals were generated in a technique of corona excited supersonic jet expansion using a pinhole-type glass nozzle for the vibronic assignments and measurements of electronic energies of the D_1 → D_0 transition. The 2,4-,2.5-, and 2.6- chlorofluorobenzyl radicals were generated by corona discharge of corresponding precursors, chlorofluorotoluenes seeded in a large amount of helium carrier gas. The vibronic emission spectra were recorded with a long-path monochromator in the visible region. The emission spectra show the vibronic bands originating from two types of benzyl-type radicals, chlorofluorobenzyl and fluorobenzyl benzyl radicals, in which fluorobenzyl radicals were obtained by displacement of Cl by H produced by dissociation of methyl C-H bond. From the analysis of the spectra observed, we could determine the electronic energies in D_1 → D_0 transition and vibrational mode frequencies at the D_0 state of chlorofluorobenzyl radicals, which show the origin band of the electronic transition to be shifted to red region, comparing with the parental benzyl radical. From the quantitative analysis of the red-shift, it has been found that the additivity rule can be applied to dihalo-substituted benzyl radicals. In this presentation, the dissociation process of precursors in corona discharge is discussed in terms of bond dissociation energy as well as the spectroscopic analysis of the radicals. C. S. Huh, Y. W. Yoon, and S. K. Lee, J. Chem. Phys. 136, 174306 (2012). Y. W. Huh, S. Y. Chae, and S. K. Lee, Chem. Phys. Lett. 608, 6 (2014). Y. W. Yoon, S. Y. Chae, M. Lim, and S. K. Lee, Chem. Phys. Lett. 637, 148 (2015).

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

PubMed

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

2018-05-20

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

Magnetic field effects on coenzyme B12- and B6-dependent lysine 5,6-aminomutase: switching of the J-resonance through a kinetically competent radical-pair intermediate.

PubMed

Chen, Jun-Ru; Ke, Shyue-Chu

2018-05-09

The environmental magnetic field is beneficial to migratory bird navigation through the radical-pair mechanism. One of the continuing challenges in understanding how magnetic fields may perturb biological processes is that only a very few field-sensitive examples have been explored despite the prevalence of radical pairs in enzymatic reactions. We show that the reaction of adenosylcobalamin- and pyridoxal-5'-phosphate-dependent lysine 5,6-aminomutase proceeds via radical-pair intermediates and is magnetic field dependent. The 5'-deoxyadenosyl radical from adenosylcobalamin abstracts a C5(H) from the substrate to yield a {cob(ii)alamin - substrate} radical pair wherein the large spin-spin interaction (2J = 8000 gauss) locks the radical pair in a triplet state, as evidenced by electron paramagnetic resonance spectroscopy. Application of an external magnetic field in the range of 6500 to 8500 gauss triggers intersystem crossing to the singlet {cob(ii)alamin - substrate} radical-pair state. Spin-conserved H back-transfer from deoxyadenosine to the substrate radical yields a singlet {cob(ii)alamin-5'-deoxyadenosyl} radical pair. Spin-selective recombination to adenosylcobalamin decreased the enzyme catalytic efficiency kcat/Km by 16% at 7600 gauss. As a mechanistic probe, observation of magnetic field effects successfully demonstrates the presence of a kinetically significant radical pair in this enzyme. The study of a pronounced high-field level-crossing characteristic through an immobilized radical pair with a constant exchange interaction deepens our understanding of how a magnetic field may interact with an enzyme.

A pulse radiolysis study of the dynamics of ascorbic acid free radicals within a liposomal environment.

PubMed

Kobayashi, Kazuo; Seike, Yumiko; Saeki, Akinori; Kozawa, Takahiro; Takeuchi, Fusako; Tsubaki, Motonari

2014-10-06

The dynamics of free-radical species in a model cellular system are examined by measuring the formation and decay of ascorbate radicals within a liposome with pulse radiolysis techniques. Upon pulse radiolysis of an N2O-saturated aqueous solution containing ascorbate-loaded liposome vesicles, ascorbate radicals are formed by the reaction of OH(·) radicals with ascorbate in unilamellar vesicles exclusively, irrespective of the presence of vesicle lipids. The radicals are found to decay rapidly compared with the decay kinetics in an aqueous solution. The distinct radical reaction kinetics in the vesicles and in bulk solution are characterized, and the kinetic data are analyzed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The benzylperoxyl radical as a source of hydroxyl and phenyl radicals.

PubMed

Sander, Wolfram; Roy, Saonli; Bravo-Rodriguez, Kenny; Grote, Dirk; Sanchez-Garcia, Elsa

2014-09-26

The benzyl radical (1) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix-isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O2 is the benzylperoxyl radical (2), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]-H migration and subsequent cleavage of the O-O bond to produce a hydrogen-bonded complex between the hydroxyl radical and benzaldehyde (4). Prolonged photolysis produces the benzoyl radical (5) and water, which finally yield the phenyl radical (7), CO, and H2O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7. Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Screening of Potential Free Radicals Scavenger and Antibacterial Activities of Purwoceng (Pimpinella alpina Molk).

PubMed

Wahyuningrum, Retno; Utami, Pri Iswati; Dhiani, Binar Asrining; Kumalasari, Malikhah; Kusumawardani, Rizka Sari

2016-11-01

Purwoceng ( Pimpinella alpina Molk) is a traditional medicinal plant used for its aphrodisiac values. This plant was originated Dieng Plateu, Central Java, Indonesia. Purwoceng has been reported to contain steroid, flavonoids, glycoside, saponins, tannins, and phenolic. Based on secondary metabolite compounds of Purwoceng herbs, a research need to be done to determine the other potential free radicals scavenger and antibacterial activities of Purwoceng. The objectives of this research are to screen the potential free radicals scavenger activity of in vitro using DPPH (1,1 diphenyl-2-picryl-hydrazil) radicals and NO• (nitric oxide) radicals, and antibacterial activity of Purwoceng. The extraction is done by a maceration method with petroleum ether, ethyl acetate, and ethanol solvent, respectively. Free radicals scavenger test was performed using DPPH radicals and NO• radicals, while antibacterial activity screening was performed using agar diffusion test. The results showed that ethyl acetate extract of Purwoceng has free radical scavenger activity with IC50 53.07 ppm lower than butylated hydroxytoluene. Ethyl acetate extract and ethanol extract of Purwoceng have antibacterial activity against Staphyloccus aureus , Escherichia coli , and MG42 bacterial isolate.

Radical scavenging ability of some compounds isolated from Piper cubeba towards free radicals.

PubMed

Aboul-Enein, Hassan Y; Kładna, Aleksandra; Kruk, Irena

2011-01-01

The purpose of this study was to identify the antioxidant activity of 16 compounds isolated from Piper cubeba (CNCs) through the extent of their capacities to scavenge free radicals, hydroxyl radical (HO(•)), superoxide anion radical O•(2)(-) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH(•)), in different systems. Electron paramagnetic resonance (EPR) and 5,5-dimethyl-1-pyrroline-N-oxide, DMPO, as the spin trap, and chemiluminescence techniques were applied. Using the Fenton-like reaction [Fe(II) + H(2)O(2)], CNCs were found to inhibit DMPO-OH radical formation ranging from 5 to 57% at 1.25 mmol L(-1) concentration. The examined CNCs also showed a high DPPH antiradical activity (ranging from 15 to 99% at 5 mmol L(-1) concentration). Furthermore, the results indicated that seven of the 16 tested compounds may catalyse the conversion of superoxide radicals generated in the potassium superoxide/18-crown-6 ether system, thus showing superoxide dismutase-like activity. The data obtained suggest that radical scavenging properties of CNCs might have potential application in many plant medicines. Copyright © 2010 John Wiley & Sons, Ltd.

Quantification of hydroxyl radical produced during phacoemulsification.

PubMed

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.

Isolation and Characterization of the 2,2'-Azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) Radical Cation-Scavenging Reaction Products of Arbutin.

PubMed

Tai, Akihiro; Ohno, Asako; Ito, Hideyuki

2016-09-28

Arbutin, a glucoside of hydroquinone, has shown strong 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation-scavenging activity, especially in reaction stoichiometry. This study investigated the reaction mechanism of arbutin against ABTS radical cation that caused high stoichiometry of arbutin in an ABTS radical cation-scavenging assay. HPLC analysis of the reaction mixture of arbutin and ABTS radical cation indicated the existence of two reaction products. The two reaction products were purified and identified to be a covalent adduct of arbutin with an ABTS degradation fragment and 3-ethyl-6-sulfonate benzothiazolone. A time-course study of the radical-scavenging reactions of arbutin and the two reaction products suggested that one molecule of arbutin scavenges three ABTS radical cation molecules to generate an arbutin-ABTS fragment adduct as a final reaction product. The results suggest that one molecule of arbutin reduced two ABTS radical cation molecules to ABTS and then cleaved the third ABTS radical cation molecule to generate two products, an arbutin-ABTS fragment adduct and 3-ethyl-6-sulfonate benzothiazolone.

Electron spin resonance study of thermal instability reactions in jet fuels

NASA Technical Reports Server (NTRS)

Zeldes, H.; Livingston, R.

1984-01-01

Free radicals were studied by electron spin resonance (ESR) using model compounds that are representative of constituents of jet fuels. Radical formation was initiated with peroxides and hydroperoxides by using UV photolysis at and near room temperature and thermal initiation at higher temperatures. Both oxygen free and air saturated systems were studied. N-Dodecane was frequently used as a solvent, and a mixture of n-dodecyl radicals was made with a peroxide initiator in n-dodecane (free of oxygen) thermally at 212 C and photolytically at room temperature. Hydrogen abstraction from the 3,4,5 and 6-positions gives radicals that are sufficiently alike that their spectra are essentially superimposed. The radical formed by abstract of hydrogen from the 2-position gives a different spectrum. ESR parameters for these radicals were measured. The radical formed by abstraction of a primary hydrogen was not observed. Similar radicals are formed from n-decane. A variety of exploratory experiments were carried out with systems that give free radical spectra to which was added small amounts of 2,5-dimethylpyrrole.

Thiyl radicals and induction of protein degradation

PubMed Central

Schöneich, Christian

2016-01-01

Thiyl radicals are important intermediates in the redox biology and chemistry of thiols. These radicals can react via hydrogen transfer with various C-H bonds in peptides and proteins, leading to the generation of carbon-centered radicals, and, potentially, to irreversible protein damage. This review summarizes quantitative information on reaction kinetics and product formation, and discusses the significance of these reactions for protein degradation induced by thiyl radical formation. PMID:26212409

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singha, Subhash; Mohanty, Bedangadas; Netrakanti, Pawan Kumar

We compiled the experimentally measured p-bar/p ratio at midrapidity in p+p collisions from {radical}(s)=23 to 7000 GeV and compared it to various mechanisms of baryon production as implemented in the pythia, phojet, and Heavy Ion Jet Interaction Generator (HIJING)/B-B models. For the models studied with default settings, phojet has the best agreement with the measurements, pythia gives a higher value for {radical}(s)<200 GeV, and the ratios from HIJING/B-B are consistently lower for all the {radical}(s) studied. A comparison of the data to different mechanisms of baryon production as implemented in pythia shows that through a suitable tuning of the suppressionmore » of diquark-antidiquark pair production in the color field relative to quark-antiquark production and allowing the diquarks to split according to the popcorn scheme, a fairly reasonable description of the measured p-bar/p ratio for {radical}(s)<200 GeV is given. A comparison of the beam energy dependence of the p-bar/p ratio in p+p and nucleus-nucleus (A + A) collisions at midrapidity shows that the baryon production is significantly more for A + A collisions relative to p+p collisions for {radical}(s)<200 GeV. We also carry out a phenomenological fit to the y{sub beam} dependence of the p-bar/p ratio.« less

How Semantic Radicals in Chinese characters Facilitate Hierarchical Category-Based Induction.

PubMed

Wang, Xiaoxi; Ma, Xie; Tao, Yun; Tao, Yachen; Li, Hong

2018-04-03

Prior studies indicate that the semantic radical in Chinese characters contains category information that can support the independent retrieval of category information through the lexical network to the conceptual network. Inductive reasoning relies on category information; thus, semantic radicals may influence inductive reasoning. As most natural concepts are hierarchically structured in the human brain, this study examined how semantic radicals impact inductive reasoning for hierarchical concepts. The study used animal and plant nouns, organized in basic, superordinate, and subordinate levels; half had a semantic radical and half did not. Eighteen participants completed an inductive reasoning task. Behavioural and event-related potential (ERP) data were collected. The behavioural results showed that participants reacted faster and more accurately in the with-semantic-radical condition than in the without-semantic-radical condition. For the ERPs, differences between the conditions were found, and these differences lasted from the very early cognitive processing stage (i.e., the N1 time window) to the relatively late processing stages (i.e., the N400 and LPC time windows). Semantic radicals can help to distinguish the hierarchies earlier (in the N400 period) than characters without a semantic radical (in the LPC period). These results provide electrophysiological evidence that semantic radicals may improve sensitivity to distinguish between hierarchical concepts.

Well-Known Mediators of Selective Oxidation with Unknown Electronic Structure: Metal-Free Generation and EPR Study of Imide-N-oxyl Radicals.

PubMed

Krylov, Igor B; Kompanets, Mykhailo O; Novikova, Katerina V; Opeida, Iosip O; Kushch, Olga V; Shelimov, Boris N; Nikishin, Gennady I; Levitsky, Dmitri O; Terent'ev, Alexander O

2016-01-14

Nitroxyl radicals are widely used in chemistry, materials sciences, and biology. Imide-N-oxyl radicals are subclass of unique nitroxyl radicals that proved to be useful catalysts and mediators of selective oxidation and CH-functionalization. An efficient metal-free method was developed for the generation of imide-N-oxyl radicals from N-hydroxyimides at room temperature by the reaction with (diacetoxyiodo)benzene. The method allows for the production of high concentrations of free radicals and provides high resolution of their EPR spectra exhibiting the superhyperfine structure from benzene ring protons distant from the radical center. An analysis of the spectra shows that, regardless of the electronic effects of the substituents in the benzene ring, the superhyperfine coupling constant of an unpaired electron with the distant protons at positions 4 and 5 of the aromatic system is substantially greater than that with the protons at positions 3 and 6 that are closer to the N-oxyl radical center. This is indicative of an unusual character of the spin density distribution of the unpaired electron in substituted phthalimide-N-oxyl radicals. Understanding of the nature of the electron density distribution in imide-N-oxyl radicals may be useful for the development of commercial mediators of oxidation based on N-hydroxyimides.

Effect of copper oxide concentration on the formation and persistency of environmentally persistent free radicals (EPFRs) in particulates.

PubMed

Kiruri, Lucy W; Khachatryan, Lavrent; Dellinger, Barry; Lomnicki, Slawo

2014-02-18

Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼ 2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75-1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed--from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively.

Ground and Excited-Electronic-State Dissociations of Hydrogen-Rich and Hydrogen-Deficient Tyrosine Peptide Cation Radicals

NASA Astrophysics Data System (ADS)

Viglino, Emilie; Lai, Cheuk Kuen; Mu, Xiaoyan; Chu, Ivan K.; Tureček, František

2016-09-01

We report a comprehensive study of collision-induced dissociation (CID) and near-UV photodissociation (UVPD) of a series of tyrosine-containing peptide cation radicals of the hydrogen-rich and hydrogen-deficient types. Stable, long-lived, hydrogen-rich peptide cation radicals, such as [AAAYR + 2H]+● and several of its sequence and homology variants, were generated by electron transfer dissociation (ETD) of peptide-crown-ether complexes, and their CID-MS3 dissociations were found to be dramatically different from those upon ETD of the respective peptide dications. All of the hydrogen-rich peptide cation radicals contained major (77%-94%) fractions of species having radical chromophores created by ETD that underwent photodissociation at 355 nm. Analysis of the CID and UVPD spectra pointed to arginine guanidinium radicals as the major components of the hydrogen-rich peptide cation radical population. Hydrogen-deficient peptide cation radicals were generated by intramolecular electron transfer in CuII(2,2 ':6 ',2 ″-terpyridine) complexes and shown to contain chromophores absorbing at 355 nm and undergoing photodissociation. The CID and UVPD spectra showed major differences in fragmentation for [AAAYR]+● that diminished as the Tyr residue was moved along the peptide chain. UVPD was found to be superior to CID in localizing Cα-radical positions in peptide cation radical intermediates.

Radical-induced chemistry from VUV photolysis of interstellar ice analogues containing formaldehyde

NASA Astrophysics Data System (ADS)

Butscher, Teddy; Duvernay, Fabrice; Danger, Grégoire; Chiavassa, Thierry

2016-09-01

Surface processes and radical chemistry within interstellar ices are increasingly suspected to play an important role in the formation of complex organic molecules (COMs) observed in several astrophysical regions and cometary environments. We present new laboratory experiments on the low-temperature solid state formation of complex organic molecules - glycolaldehyde, ethylene glycol, and polyoxymethylene - through radical-induced reactivity from VUV photolysis of formaldehyde in water-free and water-dominated ices. Radical reactivity and endogenous formation of COMs were monitored in situ via infrared spectroscopy in the solid state and post photolysis with temperature programmed desorption (TPD) using a quadripole mass spectrometer. We show the ability of free radicals to be stored when formed at low temperature in water-dominated ices, and to react with other radicals or on double bonds of unsaturated molecules when the temperature increases. It experimentally confirms the role of thermal diffusion in radical reactivity. We propose a new pathway for formaldehyde polymerisation induced by HCO radicals that might explain some observations made by the Ptolemy instrument on board the Rosetta lander Philae. In addition, our results seem to indicate that H-atom additions on H2CO proceed preferentially through CH2OH intermediate radicals rather than the CH3O radical.

EPR characterization of ascorbyl and sulfur dioxide anion radicals trapped during the reaction of bovine Cytochrome c Oxidase with molecular oxygen

NASA Astrophysics Data System (ADS)

Yu, Michelle A.; Egawa, Tsuyoshi; Yeh, Syun-Ru; Rousseau, Denis L.; Gerfen, Gary J.

2010-04-01

The reaction intermediates of reduced bovine Cytochrome c Oxidase (CcO) were trapped following its reaction with oxygen at 50 μs-6 ms by innovative freeze-quenching methods and studied by EPR. When the enzyme was reduced with either ascorbate or dithionite, distinct radicals were generated; X-band (9 GHz) and D-band (130 GHz) CW-EPR measurements support the assignments of these radicals to ascorbyl and sulfur dioxide anion radical (SO2-rad), respectively. The X-band spectra show a linewidth of 12 G for the ascorbyl radical and 11 G for the SO2-rad radical and an isotropic g-value of 2.005 for both species. The D-band spectra reveal clear distinctions in the g-tensors and powder patterns of the two species. The ascorbyl radical spectrum displays approximate axial symmetry with g-values of gx = 2.0068, gy = 2.0066, and gz = 2.0023. The SO2-rad>/SUP> radical has rhombic symmetry with g-values of gx = 2.0089, gy = 2.0052, and gz = 2.0017. When the contributions from the ascorbyl and SO2-rad radicals were removed, no protein-based radical on CcO could be identified in the EPR spectra.

Potent antioxidant and radical-scavenging activities of traditional Japanese cereal grains.

PubMed

Higashi-Okai, Kiyoka; Ishida, Emi; Nakamura, Yumiko; Fujiwara, Satomi; Okai, Yasuji

2008-12-01

To estimate the preventive potential of Japanese traditional cereals against oxygen radical-related chronic diseases such as cardiovascular diseases and diabetes, antioxidant and radical-scavenging activities in the extracts of five Japanese traditional cereal grains were analyzed by using an assay system of lipid peroxidation and a radical compound, 1,1-diphenyl-2-picrylhydrazyl (DPPH). DPPH radical-scavenging activities in the extracts of Japanese cereal grains were divided into two groups. One group including Japanese sorghum, black rice and red rice showed strong radical-scavenging activities, but the other group including Japanese barnyard millet and foxtail millet did not exhibit significant radical-scavenging activities. The DPPH radical-scavenging activities of these extracts were closely correlated to the contents of phenolic compound in the extracts, but not to the sugar or protein content in the extracts. In contrast, all the methanol and water extracts of the cereal grains caused significant antioxidant activities against hydroperoxide generation in the peroxidation of linoleic acid, in which the water extracts of these cereal grains caused much higher antioxidant activities than the methanol extracts of the same cereals. These results suggest that Japanese traditional cereals contain qualitatively different principles associated with antioxidant and radical-scavenging activities, and possible principles responsible for the antioxidant and radical-scavenging activities in the cereal grains are discussed.

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

PubMed Central

Nguyen, Thi Phuong; Zhang, Jie; Li, Hong; Wu, Xinchun; Cheng, Yahua

2017-01-01

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. PMID:29109694

Effect of ultraviolet irradiation on free radical scavenging activity of immunosuppressants used in lung transplantation and comparative electron paramagnetic resonance study of kinetics of their interactions with model free radicals.

PubMed

Stanjek-Cichoracka, A; Żegleń, S; Ramos, P; Pilawa, B; Wojarski, J

2018-06-01

The immunosuppressive drugs used in solid organ transplantation or autoimmunological processes were studied by electron paramagnetic resonance (EPR) spectroscopy to estimate their free radical scavenging activity. The interactions of immunosuppressants with free radicals were examined by an X-band (9.3 GHz) EPR spectroscopy and a model of DPPH free radicals. The EPR spectra of DPPH and DPPH interacting with individual drugs were compared. Kinetic studies were performed, and the effect of ultraviolet (UV) irradiation on the free radical scavenging activity of the tested drugs was determined. The free radical scavenging activity of non-irradiated drugs decreased in the order: rapamycin > mycophenolate mofetil > ciclosporin > tacrolimus. UV irradiation increased the free radical scavenging activity of all the tested immunosuppressive drugs, and the effect was highest for tacrolimus. For the non-irradiated samples, the speed of free radical interactions decreased in the order: ciclosporin > tacrolimus > mycophenolate mofetil > rapamycin. UV irradiation only slightly affected the speed of interactions of the immunosuppressive drugs with the model DPPH free radicals. Electron paramagnetic resonance spectroscopy is useful for obtaining information on interactions of immunosuppressive drugs with free radicals. We hypothesized that the long-term immunosuppressive effects of these drugs after transplantation or during autoimmune disorders may be mediated by anti-inflammatory action in addition to the known receptor/cell cycle inhibition. © 2018 John Wiley & Sons Ltd.

Development of the radical-stable Coprinus cinereus peroxidase (CiP) by blocking the radical attack.

PubMed

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

2014-11-10

Despite the potential use of peroxidases as industrial biocatalysts, their practical application is often impeded due to suicide inactivation by radicals generated in oxidative reactions. Using a peroxidase from Coprinus cinereus (CiP) as a model enzyme, we revealed a dominant factor for peroxidase inactivation during phenol oxidation, and we engineered radical-stable mutants by site-directed mutagenesis of an amino acid residue susceptible to modification by phenoxyl radical. Mass spectrometry analysis of inactivated CiP identified an adduct between F230 and a phenoxyl radical, and subsequently, the F230 residue was mutated to amino acids that resisted radical coupling. Of the F230 mutants, the F230A mutant showed the highest stability against radical inactivation, retaining 80% of its initial activity, while the wild-type protein was almost completely inactivated. The F230A mutant also exhibited a 16-fold higher turnover of the phenol substrate compared with the wild-type enzyme. Furthermore, the F230A mutant was stable during the oxidation of other phenolic compounds, including m-cresol and 3-methoxyphenol. No structural changes were observed by UV-vis and CD spectra of CiP after radical coupling, implying that the F230-phenol radical adduct inactivated CiP by blocking substrate access to the active site. Our novel strategy can be used to improve the stability of other peroxidases inactivated by radicals. Copyright © 2014 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Worster, Susannah; Kattnig, Daniel R.; Hore, P. J., E-mail: peter.hore@chem.ox.ac.uk

2016-07-21

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

IRON-PEROXYMONOSULFATE: A NOVEL SULFATE RADICAL BASED ADVANCED OXIDATION TECHNOLOGY FOR DEGRADATION OF PCBS

EPA Science Inventory

This study investigates the degradation of recalcitrant polychlorinated biphenyl (PCBs) using sulfate radical-based advanced oxidation technologies. Sulfate radicals are generated through coupling of peroxymonosulfate (PMS) with iron (Fe(II), Fe(III)). Sulfate radicals have very ...

SOMO–HOMO Level Inversion in Biologically Important Radicals

PubMed Central

2017-01-01

Conventionally, the singly occupied molecular orbital (SOMO) of a radical species is considered to be the highest occupied molecular orbital (HOMO), but this is not the case always. In this study, we considered a number of radicals from smallest diatomic anion radicals such as superoxide anion radical to one-electron oxidized DNA related base radicals that show the SOMO is energetically lower than one or more doubly occupied molecular orbitals (MOs) (SOMO–HOMO level inversion). The electronic configurations are calculated employing the B3LYP/6-31++G** method, with the inclusion of aqueous phase via the integral equation formalism of the polarized continuum model solvation model. From the extensive study of the electronic configurations of radicals produced by one-electron oxidation or reduction of natural-DNA bases, bromine-, sulfur-, selenium-, and aza-substituted DNA bases, as well as 20 diatomic molecules, we highlight the following important findings: (i) SOMO–HOMO level inversion is a common phenomenon in radical species. (ii) The more localized spin density in σ-orbital on a single atom (carbon, nitrogen, oxygen, sulfur, or selenium), the greater the gap between HOMO and SOMO. (iii) In species with SOMO–HOMO level inversion, one-electron oxidation takes place from HOMO not from the SOMO, which produces a molecule in its triplet ground state. Oxidation of aqueous superoxide anion producing triplet molecular oxygen is one example of many. (iv) These results are for conventional radicals and in contrast with those reported for distonic radical anions in which SOMO–HOMO gaps are smaller for more localized radicals and the orbital inversions vanish in water. Our findings yield new insights into the properties of free radical systems. PMID:29240424

On the complex •OH/•O--induced free radical chemistry of arylalkylamines with special emphasis on the contribution of the alkylamine side chain.

PubMed

Szabó, László; Mile, Viktória; Tóth, Tünde; Balogh, György T; Földes, Tamás; Takács, Erzsébet; Wojnárovits, László

2017-02-01

A full account of the • OH-induced free radical chemistry of an arylalkylamine is given taking all the possible reaction pathways quantitatively into consideration. Such knowledge is indispensable when the alkylamine side chain plays a crucial role in biological activity. The fundamental reactions are investigated on the model compound N-methyl-3-phenypropylamine (MPPA), and extended to its biologically active analog, to the antidepressant fluoxetine (FLX). Pulse radiolysis techniques were applied including redox titration and transient spectral analysis supplemented with DFT calculations. The contribution of the amine moiety to the free radical-induced oxidation mechanism appeared to be appreciable. • O - was used to observe hydrogen atom abstraction events at pH 14 giving rise to the strongly reducing α-aminoalkyl radicals (∼38% of the radical yield) and to benzyl (∼4%), β-aminoalkyl (∼24%), and aminyl radicals (∼31%) of MPPA. One-electron transfer was also observed yielding aminium radicals with low efficiency (∼3%). In the • OH-induced oxidation protonated α-aminoalkyl (∼49%), β-aminoalkyl (∼27%), benzyl radicals (∼4%), and aminium radicals (∼5%) are initially generated on the side chain of MPPA at pH 6, whereas hydroxycyclohexadienyl radicals (∼15%) were also produced. These initial events are followed by complex protonation-deprotonation reactions establishing acid-base equilibria; however, these processes are limited by the transient nature of the radicals and the kinetics of the ongoing reactions. The contribution of the radicals from the side chain alkylamine substituent of FLX totals up to ∼54% of the initially available oxidant yield.

Formation and implications of alpha-synuclein radical in Maneb- and paraquat-induced models of Parkinson’s disease

PubMed Central

Kumar, Ashutosh; Leinisch, Fabian; Kadiiska, Maria B.; Corbett, Jean; Mason, Ronald P.

2015-01-01

Parkinson’s disease (PD) is a debilitating, progressive, neurodegenerative disorder characterized by progressive loss of dopaminergic neurons and motor deficits. Alpha-synuclein-containing aggregates represent a feature of a variety of neurodegenerative disorders, including PD; however, the mechanism that initiates and promotes intraneuronal alpha-synuclein aggregation remains unknown. We hypothesized protein radical formation as an initiating mechanism for alpha-synuclein aggregation. Therefore, we used the highly sensitive immuno-spin trapping technique to investigate protein radical formation as a possible mechanism of alpha-synuclein aggregation as well as to investigate the source of protein radical formation in the midbrains of Maneb and paraquat coexposed mice. Coexposure to Maneb and paraquat for 6 weeks resulted in active microgliosis, NADPH oxidase activation, and inducible nitric oxide synthase (iNOS) induction, which culminated in protein radical formation in the midbrains of mice. Results obtained with immuno-spin trapping and immunoprecipitation experiments confirmed formation of alpha-synuclein radicals in dopaminergic neurons of exposed mice. Free radical formation requires NADPH oxidase and iNOS, as indicated by decreased protein radical formation in knockout mice (P47phox−/− and iNOS−/−) and in mice treated with inhibitors such as FeTPPS (a peroxynitrite decomposition catalyst), 1400W (an iNOS inhibitor), or apocynin (a NADPH oxidase inhibitor). Concurrence of protein radical formation with dopaminergic neuronal death indicated a link between protein radicals and disease progression. Taken together, these results show for the first time the formation and detection of the alpha-synuclein radical and suggest that NADPH oxidase and iNOS play roles in peroxynitrite-mediated protein radical formation and subsequent neuronal death in the midbrains of Maneb and paraquat coexposed mice. PMID:25952542

In Vivo and In Situ Detection of Macromolecular Free Radicals Using Immuno-Spin Trapping and Molecular Magnetic Resonance Imaging.

PubMed

Towner, Rheal A; Smith, Nataliya

2018-05-20

In vivo free radical imaging in preclinical models of disease has become a reality. Free radicals have traditionally been characterized by electron spin resonance (ESR) or electron paramagnetic resonance (EPR) spectroscopy coupled with spin trapping. The disadvantage of the ESR/EPR approach is that spin adducts are short-lived due to biological reductive and/or oxidative processes. Immuno-spin trapping (IST) involves the use of an antibody that recognizes macromolecular 5,5-dimethyl-pyrroline-N-oxide (DMPO) spin adducts (anti-DMPO antibody), regardless of the oxidative/reductive state of trapped radical adducts. Recent Advances: The IST approach has been extended to an in vivo application that combines IST with molecular magnetic resonance imaging (mMRI). This combined IST-mMRI approach involves the use of a spin-trapping agent, DMPO, to trap free radicals in disease models, and administration of an mMRI probe, an anti-DMPO probe, which combines an antibody against DMPO-radical adducts and an MRI contrast agent, resulting in targeted free radical adduct detection. The combined IST-mMRI approach has been used in several rodent disease models, including diabetes, amyotrophic lateral sclerosis (ALS), gliomas, and septic encephalopathy. The advantage of this approach is that heterogeneous levels of trapped free radicals can be detected directly in vivo and in situ to pin point where free radicals are formed in different tissues. The approach can also be used to assess therapeutic agents that are either free radical scavengers or generate free radicals. Smaller probe constructs and radical identification approaches are being considered. The focus of this review is on the different applications that have been studied, advantages and limitations, and future directions. Antioxid. Redox Signal. 28, 1404-1415.

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

NASA Astrophysics Data System (ADS)

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.

Strategies for generating peptide radical cations via ion/ion reactions.

PubMed

Gilbert, Joshua D; Fisher, Christine M; Bu, Jiexun; Prentice, Boone M; Redwine, James G; McLuckey, Scott A

2015-02-01

Several approaches for the generation of peptide radical cations using ion/ion reactions coupled with either collision induced dissociation (CID) or ultraviolet photo dissociation (UVPD) are described here. Ion/ion reactions are used to generate electrostatic or covalent complexes comprised of a peptide and a radical reagent. The radical site of the reagent can be generated multiple ways. Reagents containing a carbon-iodine (C-I) bond are subjected to UVPD with 266-nm photons, which selectively cleaves the C-I bond homolytically. Alternatively, reagents containing azo functionalities are collisionally activated to yield radical sites on either side of the azo group. Both of these methods generate an initial radical site on the reagent, which then abstracts a hydrogen from the peptide while the peptide and reagent are held together by either electrostatic interactions or a covalent linkage. These methods are demonstrated via ion/ion reactions between the model peptide RARARAA (doubly protonated) and various distonic anionic radical reagents. The radical site abstracts a hydrogen atom from the peptide, while the charge site abstracts a proton. The net result is the conversion of a doubly protonated peptide to a peptide radical cation. The peptide radical cations have been fragmented via CID and the resulting product ion mass spectra are compared to the control CID spectrum of the singly protonated, even-electron species. This work is then extended to bradykinin, a more broadly studied peptide, for comparison with other radical peptide generation methods. The work presented here provides novel methods for generating peptide radical cations in the gas phase through ion/ion reaction complexes that do not require modification of the peptide in solution or generation of non-covalent complexes in the electrospray process. Copyright © 2015 John Wiley & Sons, Ltd.

Structure and reactivity of the distonic and aromatic radical cations of tryptophan.

PubMed

Piatkivskyi, Andrii; Osburn, Sandra; Jaderberg, Kendall; Grzetic, Josipa; Steill, Jeffrey D; Oomens, Jos; Zhao, Junfang; Lau, Justin Kai-Chi; Verkerk, Udo H; Hopkinson, Alan C; Siu, K W Michael; Ryzhov, Victor

2013-04-01

In this work, we regiospecifically generate and compare the gas-phase properties of two isomeric forms of tryptophan radical cations-a distonic indolyl N-radical (H3N(+) - TrpN(•)) and a canonical aromatic π (Trp(•+)) radical cation. The distonic radical cation was generated by nitrosylating the indole nitrogen of tryptophan in solution followed by collision-induced dissociation (CID) of the resulting protonated N-nitroso tryptophan. The π-radical cation was produced via CID of the ternary [Cu(II)(terpy)(Trp)](•2+) complex. CID spectra of the two isomeric species were found to be very different, suggesting no interconversion between the isomers. In gas-phase ion-molecule reactions, the distonic radical cation was unreactive towards n-propylsulfide, whereas the π radical cation reacted by hydrogen atom abstraction. DFT calculations revealed that the distonic indolyl radical cation is about 82 kJ/mol higher in energy than the π radical cation of tryptophan. The low reactivity of the distonic nitrogen radical cation was explained by spin delocalization of the radical over the aromatic ring and the remote, localized charge (at the amino nitrogen). The lack of interconversion between the isomers under both trapping and CID conditions was explained by the high rearrangement barrier of ca.137 kJ/mol. Finally, the two isomers were characterized by infrared multiple-photon dissociation (IRMPD) spectroscopy in the ~1000-1800 cm(-1) region. It was found that some of the main experimental IR features overlap between the two species, making their distinction by IRMPD spectroscopy in this region problematic. In addition, DFT theoretical calculations showed that the IR spectra are strongly conformation-dependent.

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

NASA Astrophysics Data System (ADS)

Matasović, Brunislav; Bonifačić, Marija

2011-06-01

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

Radical scavenger can scavenge lipid allyl radicals complexed with lipoxygenase at lower oxygen content

PubMed Central

Koshiishi, Ichiro; Tsuchida, Kazunori; Takajo, Tokuko; Komatsu, Makiko

2006-01-01

Lipoxygenases have been proposed to be a possible factor that is responsible for the pathology of certain diseases, including ischaemic injury. In the peroxidation process of linoleic acid by lipoxygenase, the E,Z-linoleate allyl radical–lipoxygenase complex seems to be generated as an intermediate. In the present study, we evaluated whether E,Z-linoleate allyl radicals on the enzyme are scavenged by radical scavengers. Linoleic acid, the content of which was greater than the dissolved oxygen content, was treated with soya bean lipoxygenase-1 (ferric form) in the presence of radical scavenger, CmP (3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-N-oxyl). The reaction rate between oxygen and lipid allyl radical is comparatively faster than that between CmP and lipid allyl radical. Therefore a reaction between linoleate allyl radical and CmP was not observed while the dioxygenation of linoleic acid was ongoing. After the dissolved oxygen was depleted, CmP stoichiometrically trapped linoleate-allyl radicals. Accompanied by this one-electron redox reaction, the resulting ferrous lipoxygenase was re-oxidized to the ferric form by hydroperoxylinoleate. Through the adduct assay via LC (liquid chromatography)–MS/MS (tandem MS), four E,Z-linoleate allyl radical–CmP adducts corresponding to regio- and diastereo-isomers were detected in the linoleate/lipoxygenase system, whereas E,E-linoleate allyl radical–CmP adducts were not detected at all. If E,Z-linoleate allyl radical is liberated from the enzyme, the E/Z-isomer has to reach equilibrium with the thermodynamically favoured E/E-isomer. These data suggested that the E,Z-linoleate allyl radicals were not liberated from the active site of lipoxygenase before being trapped by CmP. Consequently, we concluded that the lipid allyl radicals complexed with lipoxygenase could be scavenged by radical scavengers at lower oxygen content. PMID:16396633

Lewis Structure Representation of Free Radicals Similar to ClO

ERIC Educational Resources Information Center

Hirsch, Warren; Kobrak, Mark

2007-01-01

The study describes the Lewis structure representation of various free radicals, which are quite similar to the ClO radical and its isoelectronic analogues. The analysis of the periodic trends of these radicals shows that oxygen is the most electronegative atom among them.

REACTIONS OF FREE RADICALS CONTAINING NITROGEN.

DTIC Science & Technology

deduced. The reactions of methyl and ethyl radicals with a variety of amino compounds were studied. The reactions of difluoroamino radicals in the...Hydrazines, Anilines and Cyanides were pyrolysed and the heats of formation of the resultant radicals and the strengths of the bonds formed by them

Electrophoretic analysis of quinone anion radicals in acetonitrile solutions using an on-line radical generator.

PubMed

Esaka, Yukihiro; Okumura, Noriko; Uno, Bunji; Goto, Masashi

2003-05-01

We have investigated analysis of anion radicals of phenanthrenequinone (PhQ) and anthraquinone (AQ) using acetonitrile-capillary electrophoresis (CE) under anaerobic conditions. PhQ and AQ have relatively high negative reduction potentials meaning that their anion radicals are re-oxidized quite readily by the surrounding O(2) to disappear during analysis and we failed to detect them with our previous system. In this work, we have developed an on-line system combining a unique electrolysis cell for generation of the radicals and a CE unit to keep the analysis system free from external O(2) molecules and to reduce analysis time remarkably. As a result, electrophoretic detection of the anion radicals of PhQ and AQ has been achieved. Furthermore, we have observed hydrogen-bonding interaction between the anion radicals and dimethylurea (DMU) using the present system and have indicated a characteristic interaction of the anion radical of PhQ as an ortho-quinone with DMU.

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

PubMed

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

2008-07-01

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

Superoxide Anion Radical Production in the Tardigrade Paramacrobiotus richtersi, the First Electron Paramagnetic Resonance Spin-Trapping Study.

PubMed

Savic, Aleksandar G; Guidetti, Roberto; Turi, Ana; Pavicevic, Aleksandra; Giovannini, Ilaria; Rebecchi, Lorena; Mojovic, Milos

2015-01-01

Anhydrobiosis is an adaptive strategy that allows withstanding almost complete body water loss. It has been developed independently by many organisms belonging to different evolutionary lines, including tardigrades. The loss of water during anhydrobiotic processes leads to oxidative stress. To date, the metabolism of free radicals in tardigrades remained unclear. We present a method for in vivo monitoring of free radical production in tardigrades, based on electron paramagnetic resonance and spin-trap DEPMPO, which provides simultaneous identification of various spin adducts (i.e., different types of free radicals). The spin trap can be easily absorbed in animals, and tardigrades stay alive during the measurements and during 24-h monitoring after the treatment. The results show that hydrated specimens of the tardigrade Paramacrobiotus richtersi produce the pure superoxide anion radical ((•)O2(-)). This is an unexpected result, as all previously examined animals and plants produce both superoxide anion radical and hydroxyl radical ((•)OH) or exclusively hydroxyl radical.

The role of hydrogels in the radical production of the Fricke-gel-dosimeter

NASA Astrophysics Data System (ADS)

Lazzaroni, S.; Liosi, G. M.; D'Agostino, G.; Marconi, R. P.; Mariani, M.; Buttafava, A.; Dondi, D.

2018-01-01

The radiolysis mechanism of the Fricke-gel-dosimeters has been investigated in order to evaluate the role of hydrogels in the radical production. For this purpose, electron paramagnetic resonance (EPR) spectra were acquired for samples frozen and irradiated at 77 K. The analysis was performed by increasing stepwise the temperature and acquiring the EPR spectra at 120 K in order to follow the radical reaction mechanism. The comparison between aqueous- and gel- dosimeters were performed. Both gelatin from porcine skin and PVA (polyvinyl alcohol) were investigated as gel matrix. Different radical species were identified and qualitatively compared. For gel matrix, peroxyl radicals, stemming from the hydrogel, play an important role in the survival of radicals at higher temperature. Moreover, the Fe3+ EPR signal has been studied and compared with the radicals concentration. From this comparison, it is evident the increase of Fe3+ concentration is shifted toward higher temperatures with respect to the radical decay. To explain this phenomenon, the intervention of EPR silent species like peroxides is supposed.

Polarized proton spin density images the tyrosyl radical locations in bovine liver catalase.

PubMed

Zimmer, Oliver; Jouve, Hélène M; Stuhrmann, Heinrich B

2016-09-01

A tyrosyl radical, as part of the amino acid chain of bovine liver catalase, supports dynamic proton spin polarization (DNP). Finding the position of the tyrosyl radical within the macromolecule relies on the accumulation of proton polarization close to it, which is readily observed by polarized neutron scattering. The nuclear scattering amplitude due to the polarization of protons less than 10 Å distant from the tyrosyl radical is ten times larger than the amplitude of magnetic neutron scattering from an unpaired polarized electron of the same radical. The direction of DNP was inverted every 5 s, and the initial evolution of the intensity of polarized neutron scattering after each inversion was used to identify those tyrosines which have assumed a radical state. Three radical sites, all of them close to the molecular centre and the haem, appear to be equally possible. Among these is tyr-369, the radical state of which had previously been proven by electron paramagnetic resonance.

[Research progress on free radicals in human body].

PubMed

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.

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

PubMed Central

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

2015-01-01

Lysine 2,3-aminomutase (LAM) is a radical S-adenosyl-L-methionine (SAM) enzyme and, like other members of this superfamily, LAM utilizes radical-generating machinery comprising SAM anchored to the unique Fe of a [4Fe-4S] cluster via a classical five-membered N,O chelate ring. Catalysis is initiated by reductive cleavage of the SAM S–C5′ bond, which creates the highly reactive 5′-deoxyadenosyl radical (5′-dAdo•), the same radical generated by homolytic Co–C bond cleavage in B12 radical enzymes. The SAM surrogate S-3′,4′-anhydroadenosyl-L-methionine (anSAM) can replace SAM as a cofactor in the isomerization of L-α-lysine to L-β-lysine by LAM, via the stable allylic anhydroadenosyl radical (anAdo•). Here electron nuclear double resonance (ENDOR) spectroscopy of the anAdo• radical in the presence of 13C, 2H, and 15N-labeled lysine completes the picture of how the active site of LAM from Clostridium subterminale SB4 “tames” the 5′-dAdo• radical, preventing it from carrying out harmful side reactions: this “free radical” in LAM is never free. The low steric demands of the radical-generating [4Fe-4S]/SAM construct allow the substrate target to bind adjacent to the S–C5′ bond, thereby enabling the 5′-dAdo• radical created by cleavage of this bond to react with its partners by undergoing small motions, ~0.6 Å toward the target and ~1.5 Å overall, that are controlled by tight van der Waals contact with its partners. We suggest that the accessibility to substrate and ready control of the reactive C5′ radical, with “van der Waals control” of small motions throughout the catalytic cycle, is common within the radical SAM enzyme superfamily and is a major reason why these enzymes are the preferred means of initiating radical reactions in nature. PMID:25923449

Porphyrinoids as a platform of stable radicals

PubMed Central

Shimizu, Daiki

2018-01-01

The non-innocent ligand nature of porphyrins was observed for compound I in enzymatic cycles of cytochrome P450. Such porphyrin radicals were first regarded as reactive intermediates in catabolism, but recent studies have revealed that porphyrinoids, including porphyrins, ring-contracted porphyrins, and ring-expanded porphyrins, display excellent radical-stabilizing abilities to the extent that radicals can be handled like usual closed-shell organic molecules. This review surveys four types of stable porphyrinoid radical and covers their synthetic methods and properties such as excellent redox properties, NIR absorption, and magnetic properties. The radical-stabilizing abilities of porphyrinoids stem from their unique macrocyclic conjugated systems with high electronic and structural flexibilities. PMID:29675188

Effect of hydrogen radical on decomposition of chlorosilane source gases

NASA Astrophysics Data System (ADS)

Sumiya, Masatomo; Akizuki, Tomohiro; Itaka, Kenji; Kubota, Makoto; Tsubouchi, Kenta; Ishigaki, Takamasa; Koinuma, Hideomi

2013-06-01

The effect of hydrogen radical on production of Si from chlorosilane sources has been studied. We used hydrogen radical generated from pulsed thermal plasma to decompose SiHCl3 and SiCl4. Hydrogen radical was effective for lowering the temperature to produce Si from SiHCl3. SiCl4 source, which was chemically stable and by-product in Siemens process, was decomposed effectively by hydrogen radical. The decomposition of SiCl4 was consistent with the thermo-dynamical calculation predicting that the use of hydrogen radical could drastically enhance the yield of Si production rather than case of H2 gas.

Free radicals in tetanic activity of isolated skeletal muscle.

PubMed

Koren, A; Sauber, C; Sentjurc, M; Schara, M

1983-01-01

1. The concentration of the free radicals in muscle tissue mitochondria changes with the phase of muscle contraction. 2. Potassium cyanide (KCN) influences the shape of the isotonic tetani mechanograms; the contraction is still strong and qualitatively comparable in amplitude to untreated controls. 3. On the other hand, the correlation between the free radical concentration and muscle contraction is lost. 4. The free radical concentration in isolated mitochondria is influenced by KCN and potassium ferricyanide. 5. The free radical concentration changes due to the electron flow in the respiratory chain. 6. Inhibition of the respiratory phosphorylation by KCN could affect the free radical level.

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

PubMed Central

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

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

NASA Technical Reports Server (NTRS)

Schwartz, Noah; Drucker, Nick; Campbell, Kenyth

2012-01-01

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

The influence of genistein on free radicals in normal dermal fibroblasts and keloid fibroblasts examined by EPR spectroscopy.

PubMed

Jurzak, Magdalena; Ramos, Paweł; Pilawa, Barbara

2017-01-01

Normal and keloid fibroblasts were examined using X-band (9.3 GHz) electron paramagnetic resonance spectroscopy. The effect of genistein on the concentration of free radicals in both normal dermal and keloid fibroblasts after ultraviolet irradiation was investigated. The highest concentration of free radicals was seen in keloid fibroblasts, with normal fibroblasts containing a lower concentration. The concentration of free radicals in both normal and keloid fibroblasts was altered in a concentration-dependent manner by the presence of genistein. The change in intra-cellular free radical concentration after the ultraviolet irradiation of both normal and keloid fibroblasts is also discussed. The antioxidant properties of genistein, using its 1,1-Diphenyl-2-picrylhydrazyl (DPPH) free radical-scavenging activity as a model, were tested, and the effect of ultraviolet irradiation on its interaction with free radicals was examined. The electron paramagnetic resonance spectra of DPPH showed quenching by genistein. The interaction of genistein with DPPH free radicals in the absence of ultraviolet irradiation was shown to be slow, but this interaction was much faster under ultraviolet irradiation. Ultraviolet irradiation enhanced the free radical-scavenging activity of genistein.

Electrochemical properties of new organic radical materials for lithium secondary batteries

NASA Astrophysics Data System (ADS)

Lee, Seo Hwan; Kim, Jae-Kwang; Cheruvally, Gouri; Choi, Jae-Won; Ahn, Jou-Hyeon; Chauhan, Ghanshyam S.; Song, Choong Eui

The use of ionic liquid (IL)-supported organic radicals as cathode-active materials in lithium secondary batteries is reported in this article. Two different types of IL-supported organic radicals based on the 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radical and imidazolium hexafluorophosphate IL were synthesized. The first type is a mono-radical with one unit of TEMPO and the second is a symmetrical di-radical with 2 U of TEMPO; both are viscous liquids at 25 °C. The radicals exhibit electrochemical activity at ∼3.5 V versus Li/Li + as revealed in the cyclic voltammetry tests. The organic radical batteries (ORBs) with these materials as the cathode, a lithium metal anode and 1 M LiPF 6 in EC/DMC electrolyte exhibited good performance at room temperature during the charge-discharge and cycling tests. The batteries exhibited specific capacities of 59 and 80 mAh g -1 at 1 C-rate with the mono- and di-radicals as the cathodes, respectively, resulting in 100% utilization of the materials. The performance degradation with increasing C-rate is very minimal for the ORBs, thus demonstrating good rate capability.

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

PubMed

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

2006-06-01

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

Analysis of Potential Radical Chemistry on Kuiper Belt Objects

NASA Astrophysics Data System (ADS)

Yanez, Maya Danielle; Hodyss, Robert; Cable, Morgan; Johnson, Paul

2017-10-01

Kuiper Belt Objects (KBOs) are of high interest following the New Horizons encounter with the Pluto system and the extended mission to 2014MU69. We aimed to clarify questions raised concerning the possible presence of organic radicals formed from photolysis on the surface of KBOs and other Trans-Neptunian Objects, and obtain laboratory spectra of these radicals for comparison to remote sensing data. We explored the photochemical generation of methyl radical from matrix-isolated CH3I in an attempt to create sufficient amounts of the methyl radical to obtain spectra in the near infrared. Both Ar and N2 matrices were studied, as well as varying guest:matrix ratios. Hydrogen lamp irradiation was found to be more effective than mercury lamp irradiation. The irradiation time was a significant factor when we switched matrices: methyl radical depleted rapidly in the N2 matrix with prolonged irradiation (~10 hours) whereas it survived for over 48 hours in some experiments with the Ar matrix. Reaction of the methyl radical with the N2 matrix to form HCN was observed. Future experiments will focus on alternate methods of radical generation in order to increase the yield of trapped radical.

Radiolysis of poly(acrylic acid) in aqueous solution

NASA Astrophysics Data System (ADS)

Ulanski, Piotr; Bothe, Eberhard; Hildenbrand, Knut; Rosiak, Janusz M.; von Sonntag, Clemens

1995-02-01

Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CHCH(CO 2H)- (β-radicals) and -CH 2C(CO 2H)- (α-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of α-radicals from model systems. The β-radicals convert slowly into α-radicals ( k = 0.7 s -1 at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10 -2 mol dm -3 chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 × 10 -2s -1 was observed. Oxygen reacts with PAA-radicals with k = 3.1 × 10 8 dm 3 mol -1 s -1 at pH 3.5 and k = 1.0 × 10 8 dm 3 mol -1 s -1 at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones.

Muoniated acyl and thioacyl radicals

NASA Astrophysics Data System (ADS)

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

2006-03-01

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 14N 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 14N 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.

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

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto; Kawabata, Hiroshi

2016-06-01

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

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.

PubMed

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 leaves from yacon in different free radical assays, reducing power assay, and cellular superoxide anion radical generation assay. Results support yacon tea leaves may be a good source of natural antioxidants for preventing O2(-) radical-mediated disorders. © 2015 Institute of Food Technologists®

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

PubMed

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

2013-11-13

A novel free radical reaction combined with liquid chromatography electrospray ionization tandem mass spectrometry (FRR-LC-PDA-ESI/APCI-MS/MS) screening method was developed for the detection and identification of radical-scavenging natural antioxidants. Functionalized graphene was prepared by chemical method for loading free radicals (superoxide radical, peroxyl radical and PAHs free radical). Separation was performed with and without a preliminary exposure of the sample to specific free radicals on the functionalized graphene, which can facilitate reaction kinetics (charge transfers) between free radicals and potential antioxidants. The difference in chromatographic peak areas is used to identify potential antioxidants. The structure of the antioxidants in one sample (Swertia chirayita) is identified using MS/MS and comparison with standards. Thirteen compounds were found to possess potential antioxidant activity, and their free radical-scavenging capacities were investigated. The thirteen compounds were identified as 1,3,5-trihydroxyxanthone-8-O-β-D-glucopyranoside (PD1), norswertianin (PD2), 1,3,5,8-tetrahydroxyxanthone (PD3), 3, 3', 4', 5, 8-penta hydroxyflavone-6-β-D-glucopyranosiduronic acid-6'-pentopyranose-7-O-glucopyranoside (PD4), 1,5,8-trihydroxy-3-methoxyxanthone (PD5), swertiamarin (PS1), 2-C-β-D-glucopyranosyl-1,3,7-trihydroxylxanthone (PS2), 1,3,7-trihydroxylxanthone-8-O-β-D-glucopyranoside (PL1), 1,3,8-trihydroxyl xanthone-5-O-β-D-glucopyranoside (PL2), 1,3,7-trihydroxy-8-methoxyxanthone (PL3), 1,2,3-trihydroxy-7,8-dimethoxyxanthone (PL4), 1,8-dihydroxy-2,6-dimethoxy xanthone (PL5) and 1,3,5,8-tetramethoxydecussatin (PL6). The reactivity and SC50 values of those compounds were investigated, respectively. PD4 showed the strongest capability for scavenging PAHs free radical; PL4 showed prominent scavenging capacities in the lipid peroxidation processes; it was found that all components in S. chirayita exhibited weak reactivity in the superoxide radical scavenging capacity. The use of the free radical reaction screening method based on LC-PDA-ESI/APCI-MS/MS would provide a new approach for rapid detection and identification of radical-scavenging natural antioxidants from complex matrices. Copyright © 2013 Elsevier B.V. All rights reserved.

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

PubMed

Fabbri, Claudia; Bietti, Massimo; Lanzalunga, Osvaldo

2005-04-01

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

Hybrid radical energy storage device and method of making

DOEpatents

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

2016-04-26

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

Hybrid radical energy storage device and method of making

DOEpatents

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

2015-01-27

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

Education Research Will Not Profit from Radical Constructionism.

ERIC Educational Resources Information Center

Cobern, William W.

This paper examines the historical roots of critical realism in western thought, highlights the dramatic nature of the shift in thought that the radical constructivists are seeking, and critically considers the relevance of radical constructivism in science teacher education. Radical constructivism is an epistemological philosophy that divorces…

Primary radical yields in pulse irradiated alkaline aqueous solution

NASA Technical Reports Server (NTRS)

Fielden, E. M.; Hart, E. J.

1969-01-01

Primary radical yields of hydrated electrons, H atoms, and OH radicals are determined by measuring hydrated electron formation following a 4 microsecond pulse of X rays. The pH dependence of free radical yields beyond pH 12 is determined by observation of the hydrated electrons.

Reactions of hydroxyalkyl radicals with cysteinyl peptides in a nanoESI plume.

PubMed

Stinson, Craig A; Xia, Yu

2014-07-01

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

Reactions of Hydroxyalkyl Radicals with Cysteinyl Peptides in a NanoESI Plume

NASA Astrophysics Data System (ADS)

Stinson, Craig A.; Xia, Yu

2014-07-01

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

Habitat of in vivo transformation influences the levels of free radical scavengers in Clinostomum complanatum: implications for free radical scavenger based vaccines against trematode infections.

PubMed

Zafar, Atif; Rizvi, Asim; Ahmad, Irshad; Ahmad, Masood

2014-01-01

Since free radical scavengers of parasite origin like glutathione-S-transferase and superoxide dismutase are being explored as prospective vaccine targets, availability of these molecules within the parasite infecting different hosts as well as different sites of infection is of considerable importance. Using Clinostomum complanatum, as a model helminth parasite, we analysed the effects of habitat of in vivo transformation on free radical scavengers of this trematode parasite. Using three different animal models for in vivo transformation and markedly different sites of infection, progenetic metacercaria of C. complanatum were transformed to adult ovigerous worms. Whole worm homogenates were used to estimate the levels of lipid peroxidation, a marker of oxidative stress and free radical scavengers. Site of in vivo transformation was found to drastically affect the levels of free radical scavengers in this model trematode parasite. It was observed that oxygen availability at the site of infection probably influences levels of free radical scavengers in trematode parasites. This is the first report showing that habitat of in vivo transformation affects levels of free radical scavengers in trematode parasites. Since free radical scavengers are prospective vaccine targets and parasite infection at ectopic sites is common, we propose that infections at different sites, may respond differently to free radical scavenger based vaccines.

A comparison of free radical formation by quinone antitumour agents in MCF-7 cells and the role of NAD(P)H (quinone-acceptor) oxidoreductase (DT-diaphorase).

PubMed

Fisher, G R; Patterson, L H; Gutierrez, P L

1993-09-01

Electron paramagnetic resonance (EPR/ESR) spin trapping studies with DMPO revealed that purified rat liver NAD(P)H (quinone-acceptor) oxidoreductase (QAO) mediated hydroxyl radical formation by a diverse range of quinone-based antitumour agents. However, when MCF-7 S9 cell fraction was the source of QAO, EPR studies distinguished four different interactions by these agents and QAO with respect to hydroxyl radical formation: (i) hydroxyl radical formation by diaziquone (AZQ), menadione, 1AQ; 1,5AQ and 1,8AQ was mediated entirely or partially by QAO in MCF-7 S9 fraction; (ii) hydroxyl radical formation by daunorubicin and Adriamycin was not mediated by QAO in MCF-7 S9 fraction; (iii) hydroxyl radical formation by mitomycin C was stimulated in MCF-7 S9 fraction when QAO was inhibited by dicumarol; (iv) no hydroxyl radical formation was detected for 1,4AQ or mitoxantrone in MCF-7 S9 fraction. This study shows that purified rat liver QAO can mediate hydroxyl radical formation by a variety of diverse quinone antitumour agents. However, QAO did not necessarily contribute to hydroxyl radical formation by these agents in MCF-7 S9 fraction and in the case of mitomycin C, QAO played a protective role against hydroxyl radical formation.

Environmentally persistent free radicals (EPFRs)-2. Are free hydroxyl radicals generated in aqueous solutions?

PubMed

Khachatryan, Lavrent; Dellinger, Barry

2011-11-01

A chemical spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), in conjunction with electron paramagnetic resonance (EPR) spectroscopy was employed to measure the production of hydroxyl radical (·OH) in aqueous suspensions of 5% Cu(II)O/silica (3.9% Cu) particles containing environmentally persistent free radicals (EPFRs) of 2-monochlorophenol (2-MCP). The results indicate: (1) a significant differences in accumulated DMPO-OH adducts between EPFR containing particles and non-EPFR control samples, (2) a strong correlation between the concentration of DMPO-OH adducts and EPFRs per gram of particles, and (3) a slow, constant growth of DMPO-OH concentration over a period of days in solution containing 50 μg/mL EPFRs particles + DMPO (150 mM) + reagent balanced by 200 μL phosphate buffered (pH = 7.4) saline. However, failure to form secondary radicals using standard scavengers, such as ethanol, dimethylsulfoxide, sodium formate, and sodium azide, suggests free hydroxyl radicals may not have been generated in solution. This suggests surface-bound, rather than free, hydroxyl radicals were generated by a surface catalyzed-redox cycle involving both the EPFRs and Cu(II)O. Toxicological studies clearly indicate these bound free radicals promote various types of cardiovascular and pulmonary disease normally attributed to unbound free radicals; however, the exact chemical mechanism deserves further study in light of the implication of formation of bound, rather than free, hydroxyl radicals.

Effect of Copper Oxide Concentration on the Formation and Persistency of Environmentally Persistent Free Radicals (EPFRs) in Particulates

PubMed Central

2015-01-01

Environmentally persistent free radicals (EPFRs) are formed by the chemisorption of substituted aromatics on metal oxide surfaces in both combustion sources and superfund sites. The current study reports the dependency of EPFR yields and their persistency on metal loading in particles (0.25, 0.5, 0.75, 1, 2, and 5% CuO/silica). The EPFRs were generated through exposure of particles to three adsorbate vapors at 230 °C: phenol, 2-monochlorophenol (2-MCP), and dichlorobenzene (DCBz). Adsorption resulted in the formation of surface-bound phenoxyl- and semiquinoine-type radicals with characteristic EPR spectra displaying a g value ranging from ∼2.0037 to 2.006. The highest EPFR yield was observed for CuO concentrations between 1 and 3% in relation to MCP and phenol adsorption. However, radical density, which is expressed as the number of radicals per copper atom, was highest at 0.75–1% CuO loading. For 1,2-dichlorobenzene adsorption, radical concentration increased linearly with decreasing copper content. At the same time, a qualitative change in the radicals formed was observed—from semiquinone to chlorophenoxyl radicals. The two longest lifetimes, 25 and 23 h, were observed for phenoxyl-type radicals on 0.5% CuO and chlorophenoxyl-type radicals on 0.75% CuO, respectively. PMID:24437381

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

PubMed

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.

Glycyl radical activating enzymes: Structure, mechanism, and substrate interactions☆

PubMed Central

Shisler, Krista A.; Broderick, Joan B.

2014-01-01

The glycyl radical enzyme activating enzymes (GRE–AEs) are a group of enzymes that belong to the radical S-adenosylmethionine (SAM) superfamily and utilize a [4Fe–4S] cluster and SAM to catalyze H-atom abstraction from their substrate proteins. GRE–AEs activate homodimeric proteins known as glycyl radical enzymes (GREs) through the production of a glycyl radical. After activation, these GREs catalyze diverse reactions through the production of their own substrate radicals. The GRE–AE pyruvate formate lyase activating enzyme (PFL-AE) is extensively characterized and has provided insights into the active site structure of radical SAM enzymes including GRE–AEs, illustrating the nature of the interactions with their corresponding substrate GREs and external electron donors. This review will highlight research on PFL-AE and will also discuss a few GREs and their respective activating enzymes. PMID:24486374

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

PubMed

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.

Study on the free radical scavenging activity of sea cucumber (Paracaudina chinens var.) gelatin hydrolysate

NASA Astrophysics Data System (ADS)

Zeng, Mingyong; Xiao, Feng; Zhao, Yuanhui; Liu, Zunying; Li, Bafang; Dong, Shiyuan

2007-07-01

Gelatin from the sea cucumber (Paracaudina chinens var.) was hydrolyzed by bromelain and the hydrolysate was found to have a high free radical scavenging activity. The hydrolysate was fractionated through an ultrafiltration membrane with 5 kDa molecular weight cutoff (MWCO). The portion (less than 5 kDa) was further separated by Sephadex G-25. The active peak was collected and assayed for free radical scavenging activity. The scavenging rates for superoxide anion radicals (O2·-) and hydroxyl radicals (·OH) of the fraction with the highest activity were 29.02% and 75.41%, respectively. A rabbit liver mitochondrial free radical damage model was adopted to study the free radical scavenging activity of the fraction. The results showed that the sea cucumber gelatin hydrolysate can prevent the damage of rabbit liver and mitochondria.

Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget.

PubMed

Young, Cora J; Washenfelder, Rebecca A; Roberts, James M; Mielke, Levi H; Osthoff, Hans D; Tsai, Catalina; Pikelnaya, Olga; Stutz, Jochen; Veres, Patrick R; Cochran, Anthony K; VandenBoer, Trevor C; Flynn, James; Grossberg, Nicole; Haman, Christine L; Lefer, Barry; Stark, Harald; Graus, Martin; de Gouw, Joost; Gilman, Jessica B; Kuster, William C; Brown, Steven S

2012-10-16

Photolabile nighttime radical reservoirs, such as nitrous acid (HONO) and nitryl chloride (ClNO(2)), contribute to the oxidizing potential of the atmosphere, particularly in early morning. We present the first vertically resolved measurements of ClNO(2), together with vertically resolved measurements of HONO. These measurements were acquired during the California Nexus (CalNex) campaign in the Los Angeles basin in spring 2010. Average profiles of ClNO(2) exhibited no significant dependence on height within the boundary layer and residual layer, although individual vertical profiles did show variability. By contrast, nitrous acid was strongly enhanced near the ground surface with much smaller concentrations aloft. These observations are consistent with a ClNO(2) source from aerosol uptake of N(2)O(5) throughout the boundary layer and a HONO source from dry deposition of NO(2) to the ground surface and subsequent chemical conversion. At ground level, daytime radical formation calculated from nighttime-accumulated HONO and ClNO(2) was approximately equal. Incorporating the different vertical distributions by integrating through the boundary and residual layers demonstrated that nighttime-accumulated ClNO(2) produced nine times as many radicals as nighttime-accumulated HONO. A comprehensive radical budget at ground level demonstrated that nighttime radical reservoirs accounted for 8% of total radicals formed and that they were the dominant radical source between sunrise and 09:00 Pacific daylight time (PDT). These data show that vertical gradients of radical precursors should be taken into account in radical budgets, particularly with respect to HONO.

The cost-effectiveness of active surveillance compared to watchful waiting and radical prostatectomy for low risk localised prostate cancer.

PubMed

Lao, Chunhuan; Edlin, Richard; Rouse, Paul; Brown, Charis; Holmes, Michael; Gilling, Peter; Lawrenson, Ross

2017-08-08

Radical prostatectomy is the most common treatment for localised prostate cancer in New Zealand. Active surveillance was introduced to prevent overtreatment and reduce costs while preserving the option of radical prostatectomy. This study aims to evaluate the cost-effectiveness of active surveillance compared to watchful waiting and radical prostatectomy. Markov models were constructed to estimate the life-time cost-effectiveness of active surveillance compared to watchful waiting and radical prostatectomy for low risk localised prostate cancer patients aged 45-70 years, using national datasets in New Zealand and published studies including the SPCG-4 study. This study was from the perspective of the Ministry of Health in New Zealand. Radical prostatectomy is less costly than active surveillance in men aged 45-55 years with low risk localised prostate cancer, but more costly for men aged 60-70 years. Scenario analyses demonstrated significant uncertainty as to the most cost-effective option in all age groups because of the unavailability of good quality of life data for men under active surveillance. Uncertainties around the likelihood of having radical prostatectomy when managed with active surveillance also affect the cost-effectiveness of active surveillance against radical prostatectomy. Active surveillance is less likely to be cost-effective compared to radical prostatectomy for younger men diagnosed with low risk localised prostate cancer. The cost-effectiveness of active surveillance compared to radical prostatectomy is critically dependent on the 'trigger' for radical prostatectomy and the quality of life in men on active surveillance. Research on the latter would be beneficial.

The lyocell process: Cellulose solutions in N-Methylmorpholine-N-oxide (NMMO) - degradation processes and stabilizers

Treesearch

Thomas Rosenau; Thomas Elder; Antje Potthast; Sixta Herbert; Paul Kosma

2003-01-01

Homolytic (radical) reactions in the system cellulose / N-methylmorpholine-N-oxide (NMMO, 1) involve a primary, nitrogen-centered cation radical (2), and two secondary, carbon-centered radical species (3, 4). Radical formation &om NMMO is strongly promoted by transition metal ions.

Causes of the Vietnam War: An Academic Look at Wilsoniasm and Cold War Effects

DTIC Science & Technology

1999-04-01

International Politics Makes Strange Bedfellows: Theories of the Radical Right and Radical Left,” American Political Science Review 68, no.1 (March 1874...Holsi, “The Study of International Politics Makes Strange Bedfellows: Theories of the Radical Right and Radical Left,” American Political Science

Re-Conceptualizing Adult Education's Monolithic Behaviourist Interpretation: Toward a New Understanding of Radical Behaviourism

ERIC Educational Resources Information Center

Roessger, Kevin M.

2012-01-01

The philosophy of radical behaviourism remains misunderstood within the field of adult education. Contributing to this trend is the field's homogeneous behaviourist interpretation, which attributes methodological behaviourism's principles to radical behaviourism. The guiding principles and assumptions of radical behaviourism are examined to…

Fate of the CHBrsub2O radical in air

NASA Technical Reports Server (NTRS)

Bayes, K. D.; Friedl, R. F.

2003-01-01

Trace amounts of bromoform in air have been photolyzed at 266 and 303 nm to form Br atoms and CHBr2 radicals. The Br concentration as a funtion of time is followed by resonance fluorescence. The CHBr2 radicals react with O2 in the air to form peroxy radicals.

Radical screen transversal lightlike submanifolds of indefinite Kaehler manifolds admitting a quarter-symmetric non-metric connection

NASA Astrophysics Data System (ADS)

Gupta, Garima; Kumar, Rakesh; Nagaich, Rakesh Kumar

We study radical screen transversal (ST)-lightlike submanifolds of an indefinite Kaehler manifold admitting a quarter-symmetric non-metric connection and obtain a necessary and sufficient condition for the screen distribution of a radical ST-lightlike submanifold to be integrable. We also study totally umbilical radical ST-lightlike submanifolds and obtain some characterization theorems for a radical ST-lightlike submanifold to be a lightlike product manifold. Finally, we establish some results regarding the vanishes of null sectional curvature.

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

PubMed

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

2008-10-21

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

RAIN REPELLENT

DTIC Science & Technology

COATINGS, *RAINDROPS, *SILANES, *ULTRASONIC RADIATION, ACIDS, AEROSOLS, ALKOXY RADICALS, ALKYL RADICALS, CHLORIDES, FILMS, FLUORIDES, GLASS, LIQUIDS...MATERIALS, METHYL RADICALS, MIXTURES, ORGANIC COMPOUNDS, SALTS, STABILITY, STORAGE, SURFACES

Radicals are required for thiol etching of gold particles

PubMed Central

Dreier, Timothy A.

2016-01-01

Etching of gold with excess thiol ligand is used in both synthesis and analysis of gold particles. Mechanistically, the process of etching gold with excess thiol is opaque. Previous studies have obliquely considered the role of oxygen in thiolate etching of gold. Herein, we show that oxygen or a radical initator is a necessary component for efficient etching of gold by thiolates. Attenuation of the etching process by radical scavengers in the presence of oxygen, and the restoration of activity by radical initiators under inert atmosphere, strongly implicate the oxygen radical. These data led us to propose an atomistic mechanism in which the oxygen radical initiates the etching process. PMID:26089294

Microhydration and the Enhanced Acidity of Free Radicals.

PubMed

Walton, John C

2018-02-14

Recent theoretical research employing a continuum solvent model predicted that radical centers would enhance the acidity (RED-shift) of certain proton-donor molecules. Microhydration studies employing a DFT method are reported here with the aim of establishing the effect of the solvent micro-structure on the acidity of radicals with and without RED-shifts. Microhydration cluster structures were obtained for carboxyl, carboxy-ethynyl, carboxy-methyl, and hydroperoxyl radicals. The numbers of water molecules needed to induce spontaneous ionization were determined. The hydration clusters formed primarily round the CO₂ units of the carboxylate-containing radicals. Only 4 or 5 water molecules were needed to induce ionization of carboxyl and carboxy-ethynyl radicals, thus corroborating their large RED-shifts.

Reactions of inorganic free radicals with liver protecting drugs

NASA Astrophysics Data System (ADS)

György, I.; Blázovics, A.; Fehér, J.; Földiák, G.

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

Antioxidative properties of hydroxycinnamic acid derivatives and a phenylpropanoid glycoside. A pulse radiolysis study

NASA Astrophysics Data System (ADS)

Lin, Weizhen; Navaratnam, Suppiah; Yao, Side; Lin, Nianyun

1998-10-01

Spectral and redox properties of the phenoxyl radicals from hydroxycinnamic acid derivatives and one selected component of phenylpropanoid glycosides, verbascoside, were studied using pulse radiolysis techniques. On the basis of the pH dependence of phenoxyl radical absorptions, the p Ka values for deprotonation of sinapic acid radical and ferulic acid radical are 4.9 and 5.2. The rate constants of one electron oxidation of those antioxidants by azide radical and bromide radical ion were determined at pH 7. The redox potentials of those antioxidants were determined as 0.59-0.71 V vs NHE at pH 7 with reference standard 4-methoxyphenol and resorcinol.

Effect of Heating on DPPH Radical Scavenging Activity of Meat Substitute

PubMed Central

Song, Hyeun Sung; Bae, Jun Kyu; Park, Inshik

2013-01-01

This study was conducted to evaluate the increase of DPPH radical scavenging activity of meat substitute by heating. The meat substitute showed higher DPPH radical scavenging activity than those of other foods rich in protein such as beef, pork, chicken, and soybean curd. The DPPH radical scavenging activity of meat substitute was dependent upon concentration, heating temperature and heating time of meat substitute. The DPPH radical scavenging activity of meat substitute was enhanced with increasing heating temperature and time. The increase of DPPH radical scavenging activity was only applied to meat substitute without showing any activation in other foods rich in protein such as beef, pork, chicken, and soybean curd. PMID:24471114

Effect of Heating on DPPH Radical Scavenging Activity of Meat Substitute.

PubMed

Song, Hyeun Sung; Bae, Jun Kyu; Park, Inshik

2013-03-01

This study was conducted to evaluate the increase of DPPH radical scavenging activity of meat substitute by heating. The meat substitute showed higher DPPH radical scavenging activity than those of other foods rich in protein such as beef, pork, chicken, and soybean curd. The DPPH radical scavenging activity of meat substitute was dependent upon concentration, heating temperature and heating time of meat substitute. The DPPH radical scavenging activity of meat substitute was enhanced with increasing heating temperature and time. The increase of DPPH radical scavenging activity was only applied to meat substitute without showing any activation in other foods rich in protein such as beef, pork, chicken, and soybean curd.

Radical SAM catalysis via an organometallic intermediate with an Fe-[5'-C]-deoxyadenosyl bond.

PubMed

Horitani, Masaki; Shisler, Krista; Broderick, William E; Hutcheson, Rachel U; Duschene, Kaitlin S; Marts, Amy R; Hoffman, Brian M; Broderick, Joan B

2016-05-13

Radical S-adenosylmethionine (SAM) enzymes use a [4Fe-4S] cluster to cleave SAM to initiate diverse radical reactions. These reactions are thought to involve the 5'-deoxyadenosyl radical intermediate, which has not yet been detected. We used rapid freeze-quenching to trap a catalytically competent intermediate in the reaction catalyzed by the radical SAM enzyme pyruvate formate-lyase activating enzyme. Characterization of the intermediate by electron paramagnetic resonance and (13)C, (57)Fe electron nuclear double-resonance spectroscopies reveals that it contains an organometallic center in which the 5' carbon of a SAM-derived deoxyadenosyl moiety forms a bond with the unique iron site of the [4Fe-4S] cluster. Discovery of this intermediate extends the list of enzymatic bioorganometallic centers to the radical SAM enzymes, the largest enzyme superfamily known, and reveals intriguing parallels to B12 radical enzymes. Copyright © 2016, American Association for the Advancement of Science.

Electromagnetic pulse reduces free radical generation in rat liver mitochondria in vitro.

PubMed

Wang, C; Zhou, H; Peng, R; Wang, L; Su, Z; Chen, P; Wang, S; Wang, S; Liu, Y; Cong, J; Wu, K; Hu, X; Fan, E

2013-04-01

Non-ionizing radiation electromagnetic pulse (EMP) is generally recorded to induce the generation of free radicals in vivo. Though mitochondria are the primary site to produce free radicals, a rare report is designed to directly investigate the EMP effects on free radical generation at mitochondrial level. Thus the present work was designed to study how EMP induces free radical generation in rat liver mitochondria in vitro using electron paramagnetic resonance technique. Surprisingly, our data suggest that EMP prevents free radical generation by activating antioxidant enzyme activity and reducing oxygen consumption and therefore free radical generation. Electron spin resonance measurements clearly demonstrate that disordering of mitochondrial lipid fluidity and membrane proteins mobility are the underlying contributors to this decreased oxygen consumption. Therefore, our results suggest that EMP might hold the potentiality to be developed as a non-invasive means to benefit certain diseases.

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

PubMed

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.

Highly durable organic electrode for sodium-ion batteries via a stabilized α-C radical intermediate

NASA Astrophysics Data System (ADS)

Wu, Shaofei; Wang, Wenxi; Li, Minchan; Cao, Lujie; Lyu, Fucong; Yang, Mingyang; Wang, Zhenyu; Shi, Yang; Nan, Bo; Yu, Sicen; Sun, Zhifang; Liu, Yao; Lu, Zhouguang

2016-11-01

It is a challenge to prepare organic electrodes for sodium-ion batteries with long cycle life and high capacity. The highly reactive radical intermediates generated during the sodiation/desodiation process could be a critical issue because of undesired side reactions. Here we present durable electrodes with a stabilized α-C radical intermediate. Through the resonance effect as well as steric effects, the excessive reactivity of the unpaired electron is successfully suppressed, thus developing an electrode with stable cycling for over 2,000 cycles with 96.8% capacity retention. In addition, the α-radical demonstrates reversible transformation between three states: C=C α-C.radical and α-C- anion. Such transformation provides additional Na+ storage equal to more than 0.83 Na+ insertion per α-C radical for the electrodes. The strategy of intermediate radical stabilization could be enlightening in the design of organic electrodes with enhanced cycling life and energy storage capability.

Glycyl radical activating enzymes: structure, mechanism, and substrate interactions.

PubMed

Shisler, Krista A; Broderick, Joan B

2014-03-15

The glycyl radical enzyme activating enzymes (GRE-AEs) are a group of enzymes that belong to the radical S-adenosylmethionine (SAM) superfamily and utilize a [4Fe-4S] cluster and SAM to catalyze H-atom abstraction from their substrate proteins. GRE-AEs activate homodimeric proteins known as glycyl radical enzymes (GREs) through the production of a glycyl radical. After activation, these GREs catalyze diverse reactions through the production of their own substrate radicals. The GRE-AE pyruvate formate lyase activating enzyme (PFL-AE) is extensively characterized and has provided insights into the active site structure of radical SAM enzymes including GRE-AEs, illustrating the nature of the interactions with their corresponding substrate GREs and external electron donors. This review will highlight research on PFL-AE and will also discuss a few GREs and their respective activating enzymes. Copyright © 2014. Published by Elsevier Inc.

Pulsed Corona Discharge Induced Hydroxyl Radical Transfer Through the Gas-Liquid Interface.

PubMed

Ajo, Petri; Kornev, Iakov; Preis, Sergei

2017-11-23

The highly energetic electrons in non-thermal plasma generated by gas phase pulsed corona discharge (PCD) produce hydroxyl (OH) radicals via collision reactions with water molecules. Previous work has established that OH radicals are formed at the plasma-liquid interface, making it an important location for the oxidation of aqueous pollutants. Here, by contacting water as aerosol with PCD plasma, it is shown that OH radicals are produced on the gas side of the interface, and not in the liquid phase. It is also demonstrated that the gas-liquid interfacial boundary poses a barrier for the OH radicals, one they need to cross for reactive affinity with dissolved components, and that this process requires a gaseous atomic H scavenger. For gaseous oxidation, a scavenger, oxygen in common cases, is an advantage but not a requirement. OH radical efficiency in liquid phase reactions is strongly temperature dependent as radical termination reaction rates increase with temperature.

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

PubMed

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

2016-12-01

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

Spin polarization transfer by the radical pair mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zarea, Mehdi, E-mail: m-zarea@northwestern.edu; Ratner, Mark A.; Wasielewski, Michael R.

2015-08-07

In a three-site representation, we study a spin polarization transfer from radical pair spins to a nearby electron or nuclear spin. The quantum dynamics of the radical pair spins is governed by a constant exchange interaction between the radical pair spins which have different Zeeman frequencies. Radical pair spins can recombine to the singlet ground state or to lower energy triplet states. It is then shown that the coherent dynamics of the radical pair induces spin polarization on the nearby third spin in the presence of a magnetic field. The spin polarization transfer depends on the difference between Zeeman frequencies,more » the singlet and triplet recombination rates, and on the exchange and dipole-dipole interactions between the different spins. In particular, the sign of the polarization depends on the exchange coupling between radical pair spins and also on the difference between singlet and triplet recombination rate constants.« less

Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

PubMed Central

Baker, Angela K.; Sauvage, Carina; Thorenz, Ute R.; van Velthoven, Peter; Oram, David E.; Zahn, Andreas; Brenninkmeijer, Carl A. M.; Williams, Jonathan

2016-01-01

The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry. PMID:27845366

Photoinduced reactions of dibenzoyl peroxide as studied by EPR and spin-trapping

NASA Astrophysics Data System (ADS)

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

The photochemical reactions of dibenzoyl peroxide with some organic compounds were found by EPR and spin-trapping to generate free radicals in dimethyl sulfoxide solutions at room temperature. Two reaction mechanisms occur which determine the structures of the radicals generated. The first involves a one-electron oxidation and the second a hydrogen atom transfer. The prevailing mechanism is primarily dependent on the structure of the substrate. With carboxylic acids the one-electron oxidation occurs exclusively, leading to the loss of the carboxyl group and to formation of the alkyl radical. For alcohols both alkoxy radicals and hydrogen-abstraction α-carbon radicals were spin trapped. The alkoxy radicals were generated by the electron transfer mechanism. Finally pyrimidine bases such as thymine and cytosine yielded C(5)-centered radicals which could also be explained by an electron transfer mechanism. These observations are of interest because of the recently observed skin tumor-promoting activity of dibenzoyl peroxide.

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

NASA Astrophysics Data System (ADS)

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

2012-10-01

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

Free-radical chemistry of sulfite.

PubMed Central

Neta, P; Huie, R E

1985-01-01

The free-radical chemistry of sulfite oxidation is reviewed. Chemical transformations of organic and biological molecules induced by sulfite oxidation are summarized. The kinetics of the free-radical oxidations of sulfite are discussed, as are the kinetics of the reactions of the sulfite-derived radicals SO3 and the peroxy derivative SO5 with organic compounds. PMID:3830699

"Fleshing Out Consensus": Radical Pragmatism, Civil Rights, and the Algebra Project

ERIC Educational Resources Information Center

Wahman, Jessica

2009-01-01

It has been said that pragmatism's "merely instrumental" truths fail to motivate radical change whereas absolute ideals make excellent guiding and driving forces for justice. However, in "Radical Equations: Math Literacy and Civil Rights," Robert Moses speaks of the radical success of pragmatic principles, used in the Civil Rights Movement, that…

Early Effects of Radical Position Legality in Chinese: An ERP Study

ERIC Educational Resources Information Center

Yum, Yen Na; Su, I-Fan; Law, Sam-Po

2015-01-01

This study aimed to investigate the timecourse and neural underpinnings of the coding of radical positions in Chinese character reading. To isolate effects of radical positions, four types of pseudocharacters were created in which the constituent radicals appeared in positions varying in probability of occurrence, that is, Unique, Dominant,…

Evidence of photo- and thermal-induced reversible intermolecular hydrogen-atom transfer in. gamma. -irradiated thiourea clathrates as studied by electron spin resonance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ichikawa, T.

1979-05-17

There has been a report (M. Iwasaki and Toriyama) on an electron spin resonance study of reversible intramolecular radical conversion due to photo- and thermal-induced H-atom transfer. Schlenk, Brown, White, Chatini, and Nakatani reported H-atom abstraction of a photostimulated allylic radical from its neighbor molecules and thermal recovery of the allylic radical from photoirradiation in a thiourea clathrate. Radiolysis of a thiourea clathrate containing a mixture of 10 mol% 2,3-dimethylbutadiene and 90 mol% 2,3-dimethylbutane gave a resolved room-temperature spectrum. The result seemed to suggest that the monomer radical was stabilized in the canal even at room temperature in the presencemore » of the inert DBA molecules which might block chain propagation. Results suggested that the photostimulated R/sub 1/, radicals abstract H atoms from DBA molecules to form tetramethylethylene molecules and R/sub 2/ radicals and that the R/sub 2/ radicals produced by photoirradiation abstract H atoms from TME molecules to regenerate R/sub 1/ radicals and DBA molecules. 2 figures. (DP)« less

Carbon-sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE.

PubMed

Rohac, Roman; Amara, Patricia; Benjdia, Alhosna; Martin, Lydie; Ruffié, Pauline; Favier, Adrien; Berteau, Olivier; Mouesca, Jean-Marie; Fontecilla-Camps, Juan C; Nicolet, Yvain

2016-05-01

Carbon-sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5'-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate.

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

PubMed

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

2017-01-01

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

EVALUATION OF FREEZE DRIED ALOE VERA AND NOPAL CACTUS FOR POSSIBLE HEALTH TREATMENTS BY COMPARISON OF ANTIOXIDANT PROPERTIES AND FREE RADICAL INHIBITION.

PubMed

Rodriguez, Kenneth R; Jones, Anthony E; Belmont, Barbara

2014-01-01

The goal of this project was to characterize the antioxidant powers of lyophilized Aloe Vera ( Aloe barbadensis ) and Nopal Cactus (Opuntia ficus-indica) by quantifying the phenolics content and radical scavenging abilities of preparations derived from these plants. Extracts of these lyophylized succulents were assayed for phenolic compounds by the Folin Ciocalteau method and compared for free radical scavenging capability by the DPPH method. We found that even though the Aloe lyophilizate extract contained more phenolic content, the Nopal lyophilizate exhibited better free radical scavenging ability. Aloe Vera extract contained 0.278 g/L of phenolic content and exhibited 11.1% free radical inhibition, with a free radical scavenging rate constant of 0.177±0.015 min -1 . Nopal Cactus extract contained 0.174 g/L of phenolic content and exhibited 13.2% free radical inhibition, with a free radical scavenging rate constant of 0.155±0.009 min -1 . These results showed Nopal to have greater antioxidant potency than Aloe.

Carbon-sulfur bond-forming reaction catalysed by the radical SAM enzyme HydE

NASA Astrophysics Data System (ADS)

Rohac, Roman; Amara, Patricia; Benjdia, Alhosna; Martin, Lydie; Ruffié, Pauline; Favier, Adrien; Berteau, Olivier; Mouesca, Jean-Marie; Fontecilla-Camps, Juan C.; Nicolet, Yvain

2016-05-01

Carbon-sulfur bond formation at aliphatic positions is a challenging reaction that is performed efficiently by radical S-adenosyl-L-methionine (SAM) enzymes. Here we report that 1,3-thiazolidines can act as ligands and substrates for the radical SAM enzyme HydE, which is involved in the assembly of the active site of [FeFe]-hydrogenase. Using X-ray crystallography, in vitro assays and NMR spectroscopy we identified a radical-based reaction mechanism that is best described as the formation of a C-centred radical that concomitantly attacks the sulfur atom of a thioether. To the best of our knowledge, this is the first example of a radical SAM enzyme that reacts directly on a sulfur atom instead of abstracting a hydrogen atom. Using theoretical calculations based on our high-resolution structures we followed the evolution of the electronic structure from SAM through to the formation of S-adenosyl-L-cysteine. Our results suggest that, at least in this case, the widely proposed and highly reactive 5‧-deoxyadenosyl radical species that triggers the reaction in radical SAM enzymes is not an isolable intermediate.

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

PubMed

Nakagawa, Kouichi; Maeda, Hayato

2017-02-01

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

Simultaneous and spectroscopic redox molecular imaging of multiple free radical intermediates using dynamic nuclear polarization-magnetic resonance imaging.

PubMed

Hyodo, Fuminori; Ito, Shinji; Yasukawa, Keiji; Kobayashi, Ryoma; Utsumi, Hideo

2014-08-05

Redox reactions that generate free radical intermediates are essential to metabolic processes. However, their intermediates can produce reactive oxygen species, which may promote diseases related to oxidative stress. We report here the use of dynamic nuclear polarization-magnetic resonance imaging (DNP-MRI) to conduct redox molecular imaging. Using DNP-MRI, we obtained simultaneous images of free radical intermediates generated from the coenzyme Q10 (CoQ10), flavin mononucleotide (FMN), and flavin adenine dinucleotide (FAD) involved in the mitochondrial electron transport chain as well as the radicals derived from vitamins E and K1. Each of these free radicals was imaged in real time in a phantom comprising a mixture of free radicals localized in either lipophilic or aqueous environments. Changing the frequency of electron spin resonance (ESR) irradiation also allowed each of the radical species to be distinguished in the spectroscopic images. This study is the first to report the spectroscopic DNP-MRI imaging of free radical intermediates that are derived from endogenous species involved in metabolic processes.

EVALUATION OF FREEZE DRIED ALOE VERA AND NOPAL CACTUS FOR POSSIBLE HEALTH TREATMENTS BY COMPARISON OF ANTIOXIDANT PROPERTIES AND FREE RADICAL INHIBITION

PubMed Central

Jones, Anthony E.; Belmont, Barbara

2016-01-01

The goal of this project was to characterize the antioxidant powers of lyophilized Aloe Vera (Aloe barbadensis) and Nopal Cactus (Opuntia ficus-indica) by quantifying the phenolics content and radical scavenging abilities of preparations derived from these plants. Extracts of these lyophylized succulents were assayed for phenolic compounds by the Folin Ciocalteau method and compared for free radical scavenging capability by the DPPH method. We found that even though the Aloe lyophilizate extract contained more phenolic content, the Nopal lyophilizate exhibited better free radical scavenging ability. Aloe Vera extract contained 0.278 g/L of phenolic content and exhibited 11.1% free radical inhibition, with a free radical scavenging rate constant of 0.177±0.015 min−1. Nopal Cactus extract contained 0.174 g/L of phenolic content and exhibited 13.2% free radical inhibition, with a free radical scavenging rate constant of 0.155±0.009 min−1. These results showed Nopal to have greater antioxidant potency than Aloe. PMID:27284273

Tunable, Quantitative Fenton-RAFT Polymerization via Metered Reagent Addition.

PubMed

Nothling, Mitchell D; McKenzie, Thomas G; Reyhani, Amin; Qiao, Greg G

2018-05-10

A continuous supply of radical species is a key requirement for activating chain growth and accessing quantitative monomer conversions in reversible addition-fragmentation chain transfer (RAFT) polymerization. In Fenton-RAFT, activation is provided by hydroxyl radicals, whose indiscriminate reactivity and short-lived nature poses a challenge to accessing extended polymerization times and quantitative monomer conversions. Here, an alternative Fenton-RAFT procedure is presented, whereby radical generation can be finely controlled via metered dosing of a component of the Fenton redox reaction (H 2 O 2 ) using an external pumping system. By limiting the instantaneous flux of radicals and ensuring sustained radical generation over tunable time periods, metered reagent addition reduces unwanted radical "wasting" reactions and provides access to consistent quantitative monomer conversions with high chain-end fidelity. Fine tuning of radical concentration during polymerization is achieved simply via adjustment of reagent dose rate, offering significant potential for automation. This modular strategy holds promise for extending traditional RAFT initiation toward more tightly regulated radical concentration profiles and affords excellent prospects for the automation of Fenton-RAFT polymerization. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ electrochemical-electron spin resonance investigations of multi-electron redox reaction for organic radical cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Qian; Walter, Eric D.; Cosimbescu, Lelia

2016-02-29

Organic radical batteries (ORBs) bearing robust radical polymers as energy storage species, are emerging promisingly with durable high energy and power characteristics by unique tunable redox properties. Here we report the development and application of in situ electrochemical-electron spin resonance (ESR) methodologies to identify the charge transfer mechanism of Poly(2,2,6,6- tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA) based organic radical composite cathodes in the charge-discharge process of lithium half cells. The in situ experiments allow each electrochemical state to be associated with the chemical state (or environment) of the radical species upon the cell cycling. In situ ESR spectra of the composite cathode demonstratemore » a two-electron redox reaction of PTMA. Moreover, two different local environments of radical species are found in the composite electrode that includes both concentrated and isolated radicals. These two types of radicals show similarities during the redox reaction process while behave quite differently in the non-faradic reaction of ion sorption/desorption on the electrode surface.« less

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

PubMed Central

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

2009-01-01

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

Modeling and measurement of hydrogen radical densities of in situ plasma-based Sn cleaning source

NASA Astrophysics Data System (ADS)

Elg, Daniel T.; Panici, Gianluca A.; Peck, Jason A.; Srivastava, Shailendra N.; Ruzic, David N.

2017-04-01

Extreme ultraviolet (EUV) lithography sources expel Sn debris. This debris deposits on the collector optic used to focus the EUV light, lowering its reflectivity and EUV throughput to the wafer. Consequently, the collector must be cleaned, causing source downtime. To solve this, a hydrogen plasma source was developed to clean the collector in situ by using the collector as an antenna to create a hydrogen plasma and create H radicals, which etch Sn as SnH4. This technique has been shown to remove Sn from a 300-mm-diameter stainless steel dummy collector. The H radical density is of key importance in Sn etching. The effects of power, pressure, and flow on radical density are explored. A catalytic probe has been used to measure radical density, and a zero-dimensional model is used to provide the fundamental science behind radical creation and predict radical densities. Model predictions and experimental measurements are in good agreement. The trends observed in radical density, contrasted with measured Sn removal rates, show that radical density is not the limiting factor in this etching system; other factors, such as SnH4 redeposition and energetic ion bombardment, must be more fully understood in order to predict removal rates.

Influence of Free Radicals on the Intrinsic MRI Relaxation Properties.

PubMed

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

2017-01-01

Free radicals are critical contributors in various conditions including normal aging, Alzheimer's disease, cancer, and diabetes. Currently there is no non-invasive approach to image tissue free radicals based on endogenous contrast due to their extremely short lifetimes and low in vivo concentrations. In this study we aim at characterizing the influence of free radicals on the MRI relaxation properties. Phantoms containing free radicals were created by treating egg white with various H 2 O 2 concentrations and scanned on a 9.4 T MRI scanner at room temperature. T 1 and T 2 relaxation maps were generated from data acquired with an inversion recovery sequence with varied inversion times and a multi-echo spin echo sequence with varied echo times (TEs), respectively. Results demonstrated that free radicals express a strong shortening effect on T 1 , which was proportional to the H 2 O 2 concentration, and a relatively small reduction in T 2 (<10%). Furthermore, the sensitivity of this approach in the detection of free radicals was estimated to be in the pM range that is within the physiological range of in vivo free radical expression. In conclusion, the free radicals show a strong paramagnetic effect that may be utilized as an endogenous MRI contrast for its non-invasive in vivo imaging.

Preventive and therapeutic application of molecular hydrogen in situations with excessive production of free radicals.

PubMed

Slezák, J; Kura, B; Frimmel, K; Zálešák, M; Ravingerová, T; Viczenczová, C; Okruhlicová, Ľ; Tribulová, N

2016-09-19

Excessive production of oxygen free radicals has been regarded as a causative common denominator of many pathological processes in the animal kingdom. Hydroxyl and nitrosyl radicals represent the major cause of the destruction of biomolecules either by a direct reaction or by triggering a chain reaction of free radicals. Scavenging of free radicals may act preventively or therapeutically. A number of substances that preferentially react with free radicals can serve as scavengers, thus increasing the internal capacity/activity of endogenous antioxidants and protecting cells and tissues against oxidative damage. Molecular hydrogen (H(2)) reacts with strong oxidants, such as hydroxyl and nitrosyl radicals, in the cells, that enables utilization of its potential for preventive and therapeutic applications. H(2) rapidly diffuses into tissues and cells without affecting metabolic redox reactions and signaling reactive species. H(2) reduces oxidative stress also by regulating gene expression, and functions as an anti-inflammatory and anti-apoptotic agent. There is a growing body of evidence based on the results of animal experiments and clinical observations that H(2) may represent an effective antioxidant for the prevention of oxidative stress-related diseases. Application of molecular hydrogen in situations with excessive production of free radicals, in particular, hydroxyl and nitrosyl radicals is relatively simple and effective, therefore, it deserves special attention.

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

PubMed Central

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

2017-01-01

It is well established that the formation of radical species centered on various atoms is involved in the mechanism leading to the development of several diseases or to the appearance of deleterious effects of toxic molecules. The detection of free radical is possible using Electron Paramagnetic Resonance (EPR) spectroscopy and the spin trapping technique. The classical EPR spin-trapping technique can be considered as a “hypothesis-driven” approach because it requires an a priori assumption regarding the nature of the free radical in order to select the most appropriate spin-trap. We here describe a “data-driven” approach using EPR and a cocktail of spin-traps. The rationale for using this cocktail was that it would cover a wide range of biologically relevant free radicals and have a large range of hydrophilicity and lipophilicity in order to trap free radicals produced in different cellular compartments. As a proof-of-concept, we validated the ability of the system to measure a large variety of free radicals (O-, N-, C-, or S- centered) in well characterized conditions, and we illustrated the ability of the technique to unambiguously detect free radical production in cells exposed to chemicals known to be radical-mediated toxic agents. PMID:28253308

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

PubMed

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

2008-03-01

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

Hyperoxic sheep pulmonary microvascular endothelial cells generate free radicals via mitochondrial electron transport.

PubMed Central

Sanders, S P; Zweier, J L; Kuppusamy, P; Harrison, S J; Bassett, D J; Gabrielson, E W; Sylvester, J T

1993-01-01

Free radical generation by hyperoxic endothelial cells was studied using electron paramagnetic resonance (EPR) spectroscopy and the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Studies were performed to determine the radical species produced, whether mitochondrial electron transport was involved, and the effect of the radical generation on cell mortality. Sheep pulmonary microvascular endothelial cell suspensions exposed to 100% O2 for 30 min exhibited prominent DMPO-OH and, occasionally, additional smaller DMPO-R signals thought to arise from the trapping of superoxide anion (O2-.), hydroxyl (.OH), and alkyl (.R) radicals. Superoxide dismutase (SOD) quenched both signals suggesting that the observed radicals were derived from O2-.. Studies with deferoxamine suggested that the generation of .R occurred secondary to the formation of .OH from O2-. via an iron-mediated Fenton reaction. Blocking mitochondrial electron transport with rotenone (20 microM) markedly decreased radical generation. Cell mortality increased slightly in oxygen-exposed cells. This increase was not significantly altered by SOD or deferoxamine, nor was it different from the mortality observed in air-exposed cells. These results suggest that endothelial cells exposed to hyperoxia for 30 min produce free radicals via mitochondrial electron transport, but under the conditions of these experiments, this radical generation did not appear cause cell death. PMID:8380815

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

PubMed

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

2017-12-19

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

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

PubMed

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

2017-01-01

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

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

PubMed

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

2018-04-26

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

[Study of emission spectroscopy of OH radicals in pulsed corona discharge].

PubMed

Wei, Bo; Luo, Zhong-Yang; Xu, Fei; Zhao, Lei; Gao, Xiang; Cen, Ke-Fa

2010-02-01

In the present paper, OH radicals generated by pulsed corona discharge in humidified air, N2 and Ar in a needle-plate reactor were measured by emission spectra. With the analysis of the emission spectra, the influence of pulse peak voltage and frequency on OH radical generation was investigated in the three kinds of background gases. The influence of the gas humidity on the generation and the distribution of OH radicals in the electric field was also discussed in detail. The authors studied the influence of the gas humidity on the generation of OH radicals in the electric field by the control of accurate change in humidity, and we also studied the distribution of OH radicals in the electric field in different background gases including humidified air, N2 and Ar by the accurate change in scales. The experiment shows that the output of OH radicals grows as the pulse peak voltage and frequency grow, but the influence of gas humidity on the process of generating OH radicals by pulsed corona discharge depends on the discharge background. The rules of the generation change when the background gases change. As the humidity in the background gases grows, the amount of OH radicals grows in the air, but it grows at first and decreases at last in N2, while it decreases at first and grows at last in Ar. The distribution of OH radical shows a trend of decreasing from the needle-electrode to its circumambience.

Synthesis and spectral properties of polymethine-cyanine dye-nitroxide radical hybrid compounds for use as fluorescence probes to monitor reducing species and radicals

NASA Astrophysics Data System (ADS)

Sato, Shingo; Tsunoda, Minoru; Suzuki, Minoru; Kutsuna, Masahiro; Takido-uchi, Kiyomi; Shindo, Mitsuru; Mizuguchi, Hitoshi; Obara, Heitaro; Ohya, Hiroaki

2009-01-01

Various hybrid compounds comprised of two types of nitroxide radicals and either a pentamethine (Cy5) or trimethine cyanine (Cy3) were synthesized. The nitroxide radicals were linked either via an ester-bond to one or two N-alkyl carboxyl-terminated groups of Cy5, or via two amido-bonds (aminocarbonyl or carbonylamino group) to the 5-position of the indolenine moieties of Cy5 and Cy3. Changes in fluorescence and ESR intensities of the hybrid compounds were measured before and after addition of Na ascorbate in PBS (pH 7.0) to reduce the radicals. Among the hybrid compounds synthesized, those that linked the nitroxide radicals via an aminocarbonyl residue at the 5-position of the indolenine moieties on Cy5 and Cy3 exhibited a 1.8- and 5.1-fold increase in fluorescence intensity with the reduction of the nitroxide segment by the addition of Na ascorbate, respectively. In contrast, fluorescence intensity was not enhanced in the other hybrid compounds. Thus, the hybrid compounds which exhibited an increase in fluorescent intensity with radical reduction can be used in the quantitative measurement of reducing species such as Fe 2+ and ascorbic acid, and hydroxyl radicals. Because these hybrid compounds have the advantage of fluorescing at longer wavelengths—661 (Cy5) or 568 (Cy3) nm, respectively, they can be used to measure radical-reducing species or radicals either in solution or in vivo.

The first characterization of free radicals formed from cellular COX-catalyzed peroxidation.

PubMed

Gu, Yan; Xu, Yi; Law, Benedict; Qian, Steven Y

2013-04-01

Through free radical-mediated peroxidation, cyclooxygenase (COX) can metabolize dihomo-γ-linolenic acid (DGLA) and arachidonic acid (AA) to form well-known bioactive metabolites, namely, the 1-series of prostaglandins (PGs1) and the 2-series of prostaglandins (PGs2), respectively. Unlike PGs2, which are generally viewed as proinflammatory and procarcinogenic PGs, PGs1 may possess anti-inflammatory and anti-cancer activity. Previous studies using ovine COX along with spin trapping and the LC/ESR/MS technique have shown that certain exclusive free radicals are generated from different free radical reactions in DGLA and AA peroxidation. However, it has been unclear whether the differences were associated with the contrasting bioactivity of DGLA vs AA. The aim of this study was to refine the LC/MS and spin trapping technique to make it possible for the association between free radicals and cancer cell growth to be directly tested. Using a colon cancer cell line, HCA-7 colony 29, and LC/MS along with a solid-phase extraction, we were able to characterize the reduced forms of radical adducts (hydroxylamines) as the free radicals generated from cellular COX-catalyzed peroxidation. For the first time, free radicals formed in the COX-catalyzed peroxidation of AA vs DGLA and their association with cancer cell growth were assessed (cell proliferation via MTS and cell cycle distribution via propidium iodide staining) in the same experimental setting. The exclusive free radicals formed from the COX-catalyzed peroxidation of AA and DGLA were shown to be correlated with the cell growth response. Our results indicate that free radicals generated from the distinct radical reactions in COX-catalyzed peroxidation may represent the novel metabolites of AA and DGLA that correspond to their contrasting bioactivity. Copyright © 2012 Elsevier Inc. All rights reserved.

The First Characterization of Free Radicals Formed From Cellular COX-Catalyzed Peroxidation

PubMed Central

Gu, Yan; Xu, Yi; Law, Benedict; Qian, Steven Y.

2014-01-01

Through free radical-mediated peroxidation, cyclooxygenase (COX) can metabolize dihomo-γ-linolenic acid (DGLA) and arachidonic acid(AA) to form well-known bioactive metabolites, namely, the 1-series of prostaglandins (PGs1) and 2-series of prostaglandins(PGs2), respectively. Unlike PGs2, which are generally viewed as pro-inflammatory and pro-carcinogenic PGs, PGs1 may possess anti-inflammatory and anti-cancer activity. Previous studies using ovine COX along with spin trapping and the LC/ESR/MS technique have shown that certain exclusive free radicals are generated from different free radical reactions in DGLA and AA peroxidation. However, it has been unclear whether the differences were associated with the contrasting bioactivity of DGLA vs. AA. The aim of this study was to refine the LC/MS and spin-trapping technique to make it possible for the association between free radicals and cancer cell growth to be directly tested. Using a colon cancer cell line, HCA-7 colony 29, and LC/MS along with a solid phase extraction, we were able to characterize the reduced forms of radical adducts (hydroxylamines) as the free radicals generated from cellular COX-catalyzed peroxidation. For the first time, free radicals formed in the COX-catalyzed peroxidation of AA vs. DGLA and their association with cancer cell growth was assessed (cell proliferation via MTS and cell cycle distribution via PI staining) in the same experimental setting. The exclusive free radicals formed from the COX-catalyzed peroxidation of AA and DGLA were shown to be correlated with the cell growth response. Our results indicate that free radicals generated from the distinct radical reactions in COX-catalyzed peroxidation may represent the novel metabolites of AA and DGLA that correspond to their contrasting bioactivity. PMID:23261941

Molecular weight growth in Titan's atmosphere: Branching pathways for the reaction of 1-propynyl radical (H 3CC≡C˙) with small alkenes and alkynes

DOE PAGES

Kirk, Benjamin B.; Savee, John D.; Trevitt, Adam J.; ...

2015-07-16

The reaction of small hydrocarbon radicals (i.e. ˙CN, ˙C 2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C 2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC≡C˙), a likely product frommore » the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d 4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (–H = 27%, –CH 3 = 73%) and (–H = 14%, –CH 3 = 86%), respectively. Altogether, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.« less

Molecular weight growth in Titan's atmosphere: branching pathways for the reaction of 1-propynyl radical (H3CC≡C˙) with small alkenes and alkynes.

PubMed

Kirk, Benjamin B; Savee, John D; Trevitt, Adam J; Osborn, David L; Wilson, Kevin R

2015-08-28

The reaction of small hydrocarbon radicals (i.e.˙CN, ˙C2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC[triple bond, length as m-dash]C˙), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (-H = 27%, -CH3 = 73%) and (-H = 14%, -CH3 = 86%), respectively. Together, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.

Molecular weight growth in Titan's atmosphere: Branching pathways for the reaction of 1-propynyl radical (H 3CC≡C˙) with small alkenes and alkynes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirk, Benjamin B.; Savee, John D.; Trevitt, Adam J.

The reaction of small hydrocarbon radicals (i.e. ˙CN, ˙C 2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (˙C 2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC≡C˙), a likely product frommore » the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d 4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (–H = 27%, –CH 3 = 73%) and (–H = 14%, –CH 3 = 86%), respectively. Altogether, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.« less

Health-related quality of life in the first year after laparoscopic radical prostatectomy compared with open radical prostatectomy.

PubMed

Hashine, Katsuyoshi; Nakashima, Takeshi; Iio, Hiroyuki; Ueno, Yoshiteru; Shimizu, Shinjiro; Ninomiya, Iku

2014-07-01

To assess health-related quality of life in the first year after laparoscopic radical prostatectomy compared with that after open radical prostatectomy. The subjects were 105 consecutive patients with localized prostate cancer treated with laparoscopic radical prostatectomy between January 2011 and June 2012. Health-related quality of life was evaluated using the International Prostate Symptom Score, Medical Outcome Study 8-Items Short Form Health Survey (SF-8) and Expanded Prostate Cancer Index Composite at baseline and 1, 3, 6 and 12 months after surgery. Comparisons were made with data for 107 consecutive patients treated with open radical prostatectomy between October 2005 and July 2007. The International Prostate Symptom Score change was similar in each group. The laparoscopic radical prostatectomy group had a better baseline Medical Outcome Study 8-Items Short Form Health Survey mental component summary score and a better Medical Outcome Study 8-Items Short Form Health Survey physical component summary score at 1 month after surgery. In Expanded Prostate Cancer Index Composite, obstructive/irritative symptoms did not differ between the groups, but urinary incontinence was worse until 12 months after surgery and particularly severe after 1 month in the laparoscopic radical prostatectomy group. The rate of severe urinary incontinence was much higher in the laparoscopic radical prostatectomy group in the early period. Urinary bother was worse in the laparoscopic radical prostatectomy group at 1 and 3 months, but did not differ between the groups thereafter. Urinary function and bother were good after nerve sparing procedures and did not differ between the groups. Bowel and sexual function and bother were similar in the two groups. Urinary function in the first year after laparoscopic radical prostatectomy is worse than that after open radical prostatectomy. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Absence of an effect of vitamin E on protein and lipid radical formation during lipoperoxidation of LDL by lipoxygenase

PubMed Central

Ganini, Douglas; Mason, Ronald P.

2014-01-01

LDL oxidation is the primary event in atherosclerosis, where LDL lipoperoxidation leads to modifications in the apolipoprotein B-100 (apo B-100) and lipids. Intermediate species of lipoperoxidation are known to be able to generate amino acid-centered radicals. Thus, we hypothesized that lipoperoxidation intermediates induce protein-derived free radical formation during LDL oxidation. Using DMPO and immuno spin-trapping, we detected the formation of protein free radicals on LDL incubated with Cu2+ or the soybean lipoxidase (LPOx)/phospholipase A2 (PLA2). With low concentrations of DMPO (1 mM), Cu2+ dose-dependently induced oxidation of LDL and easily detected apo B-100 radicals. Protein radical formation in LDL incubated with Cu2+ showed maximum yields after 30 minutes. In contrast, the yields of apo B-100-radicals formed by LPOx/PLA2 followed a typical enzyme-catalyzed kinetics that was unaffected by DMPO concentrations of up to 50 mM. Furthermore, when we analyzed the effect of antioxidants on protein radical formation during LDL oxidation, we found that ascorbate, urate and Trolox dose-dependently reduced apo B-100-free radical formation in LDL exposed to Cu2+. In contrast, Trolox was the only antioxidant that even partially protected LDL from LPOx/PLA2. We also examined the kinetics of lipid radical formation and protein radical formation induced by Cu2+ or LPOx/PLA2 for LDL supplemented with α-tocopherol. In contrast to the potent antioxidant effect of α-tocopherol on the delay of LDL oxidation induced by Cu2+, when we used the oxidizing system LPOx/PLA2, no significant protection was detected. The lack of protection of α-tocopherol on the apo B-100 and lipid free radical formation by LPOx may explain the failure of vitamin E as a cardiovascular protective agent for humans. PMID:25091900

Imaging free radicals in organelles, cells, tissue, and in vivo with immuno-spin trapping.

PubMed

Mason, Ronald Paul

2016-08-01

The accurate and sensitive detection of biological free radicals in a reliable manner is required to define the mechanistic roles of such species in biochemistry, medicine and toxicology. Most of the techniques currently available are either not appropriate to detect free radicals in cells and tissues due to sensitivity limitations (electron spin resonance, ESR) or subject to artifacts that make the validity of the results questionable (fluorescent probe-based analysis). The development of the immuno-spin trapping technique overcomes all these difficulties. This technique is based on the reaction of amino acid- and DNA base-derived radicals with the spin trap 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) to form protein- and DNA-DMPO nitroxide radical adducts, respectively. These adducts have limited stability and decay to produce the very stable macromolecule-DMPO-nitrone product. This stable product can be detected by mass spectrometry, NMR or immunochemistry by the use of anti-DMPO nitrone antibodies. The formation of macromolecule-DMPO-nitrone adducts is based on the selective reaction of free radical addition to the spin trap and is thus not subject to artifacts frequently encountered with other methods for free radical detection. The selectivity of spin trapping for free radicals in biological systems has been proven by ESR. Immuno-spin trapping is proving to be a potent, sensitive (a million times higher sensitivity than ESR), and easy (not quantum mechanical) method to detect low levels of macromolecule-derived radicals produced in vitro and in vivo. Anti-DMPO antibodies have been used to determine the distribution of free radicals in cells and tissues and even in living animals. In summary, the invention of the immuno-spin trapping technique has had a major impact on the ability to accurately and sensitively detect biological free radicals and, subsequently, on our understanding of the role of free radicals in biochemistry, medicine and toxicology. Published by Elsevier B.V.

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

PubMed

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

2017-08-10

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

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

DOE PAGES

Liu, Matthew J.; Wiegel, Aaron A.; Wilson, Kevin R.; ...

2017-07-14

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

Helium Nanodroplet Isolation of the Cyclobutyl, 1-Methylallyl, and Allylcarbinyl Radicals: Infrared Spectroscopy and Ab Initio Computations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Alaina R.; Franke, Peter R.; Douberly, Gary E.

Gas-phase cyclobutyl radical (*C 4H 7) is produced via pyrolysis of cyclobutylmethyl nitrite (C 4H 7(CH 2)ONO). Other (C 4H 7)-C-center dot radicals, such as 1-methylallyl and allylcarbinyl, are similarly produced from nitrite precursors. Nascent radicals are promptly solvated in liquid He droplets, allowing for the acquisition of infrared spectra in the CH stretching region. For the cyclobutyl and 1-methylallyl radicals, anharmonic frequencies are predicted by VPT2+K simulations based upon a hybrid CCSD(T) force field with quadratic (cubic and quartic) force constants computed using the ANO1 (ANO0) basis set. A density functional theoretical method is used to compute the forcemore » field for the allylcarbinyl radical. For all *C 4H 7 radicals, resonance polyads in the 2800-3000 cm -1 region appear as a result of anharmonic coupling between the CH stretching fundamentals and CH, bend overtones and combinations. Upon pyrolysis of the cyclobutylmethyl nitrite precursor to produce the cyclobutyl radical, an approximately 2-fold increase in the source temperature leads to the appearance of spectral signatures that can be assigned to 1-methylallyl and 1,3-butadiene. On the basis of a previously reported *C 4H 7 potential energy surface, this result is interpreted as evidence for the unimolecular decomposition of the cyclobutyl radical via ring opening, prior to it being captured by helium droplets. On the *C 4H 7 potential surface, 1,3-butadiene is formed from cyclobutyl ring opening and H atom loss, and the 1-methylallyl radical is the most energetically stable intermediate along the decomposition pathway. Here, the allylcarbinyl radical is a higher-energy (C 4H 7)-C-center dot intermediate along the ring-opening path, and the spectral signatures of this radical are not observed under the same conditions that produce 1-methylallyl and 1,3-butadiene from the unimolecular decomposition of cyclobutyl.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Matthew J.; Wiegel, Aaron A.; Wilson, Kevin R.

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

Helium Nanodroplet Isolation of the Cyclobutyl, 1-Methylallyl, and Allylcarbinyl Radicals: Infrared Spectroscopy and Ab Initio Computations

DOE PAGES

Brown, Alaina R.; Franke, Peter R.; Douberly, Gary E.

2017-09-22

Gas-phase cyclobutyl radical (*C 4H 7) is produced via pyrolysis of cyclobutylmethyl nitrite (C 4H 7(CH 2)ONO). Other (C 4H 7)-C-center dot radicals, such as 1-methylallyl and allylcarbinyl, are similarly produced from nitrite precursors. Nascent radicals are promptly solvated in liquid He droplets, allowing for the acquisition of infrared spectra in the CH stretching region. For the cyclobutyl and 1-methylallyl radicals, anharmonic frequencies are predicted by VPT2+K simulations based upon a hybrid CCSD(T) force field with quadratic (cubic and quartic) force constants computed using the ANO1 (ANO0) basis set. A density functional theoretical method is used to compute the forcemore » field for the allylcarbinyl radical. For all *C 4H 7 radicals, resonance polyads in the 2800-3000 cm -1 region appear as a result of anharmonic coupling between the CH stretching fundamentals and CH, bend overtones and combinations. Upon pyrolysis of the cyclobutylmethyl nitrite precursor to produce the cyclobutyl radical, an approximately 2-fold increase in the source temperature leads to the appearance of spectral signatures that can be assigned to 1-methylallyl and 1,3-butadiene. On the basis of a previously reported *C 4H 7 potential energy surface, this result is interpreted as evidence for the unimolecular decomposition of the cyclobutyl radical via ring opening, prior to it being captured by helium droplets. On the *C 4H 7 potential surface, 1,3-butadiene is formed from cyclobutyl ring opening and H atom loss, and the 1-methylallyl radical is the most energetically stable intermediate along the decomposition pathway. Here, the allylcarbinyl radical is a higher-energy (C 4H 7)-C-center dot intermediate along the ring-opening path, and the spectral signatures of this radical are not observed under the same conditions that produce 1-methylallyl and 1,3-butadiene from the unimolecular decomposition of cyclobutyl.« less

Non-linear hydroxyl radical formation rate in dispersions containing mixtures of pyrite and chalcopyrite particles

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Schoonen, Martin A.

2017-06-01

The formation of hydroxyl radicals was studied in mixed pyrite-chalcopyrite dispersions in water using the conversion rate of adenine as a proxy for hydroxyl radical formation rate. Experiments were conducted as a function of pH, presence of phosphate buffer, surface loading, and pyrite-to-chalcopyrite ratio. The results indicate that hydroxyl radical formation rate in mixed systems is non-linear with respect to the rates in the pure endmember dispersions. The only exception is a set of experiments in which phosphate buffer is used. In the presence of phosphate buffer, the hydroxyl radical formation is suppressed in mixtures and the rate is close to that predicted based on the reaction kinetics of the pure endmembers. The non-linear hydroxyl radical formation in dispersions containing mixtures of pyrite and chalcopyrite is likely the result of two complementary processes. One is the fact that pyrite and chalcopyrite form a galvanic couple. In this arrangement, chalcopyrite oxidation is accelerated, while pyrite passes electrons withdrawn from chalcopyrite to molecular oxygen, the oxidant. The incomplete reduction of molecular oxygen leads to the formation of hydrogen peroxide and hydroxyl radical. The galvanic coupling appears to be augmented by the fact that chalcopyrite generates a significant amount of hydrogen peroxide upon dispersal in water. This hydrogen peroxide is then available for conversion to hydroxyl radical, which appears to be facilitated by pyrite as chalcopyrite itself produces only minor amounts of hydroxyl radical. In essence, pyrite is a ;co-factor; that facilitates the conversion of hydrogen peroxide to hydroxyl radical. This conversion reaction is a surface-mediated reaction. Given that hydroxyl radical is one of the most reactive species in nature, the formation of hydroxyl radicals in aqueous systems containing chalcopyrite and pyrite has implications for the stability of organic molecules, biomolecules, the viability of microbes, and exposure to dust containing the two metal sulfides may present a health burden.

Biological effects of cigarette smoke, wood smoke, and the smoke from plastics: the use of electron spin resonance.

PubMed

Pryor, W A

1992-12-01

This review compares and contrasts the chemistry of cigarette smoke, wood smoke, and the smoke from plastics and building materials that is inhaled by persons trapped in fires. Cigarette smoke produces cancer, emphysema, and other diseases after a delay of years. Acute exposure to smoke in a fire can produce a loss of lung function and death after a delay of days or weeks. Tobacco smoke and the smoke inhaled in a burning building have some similarities from a chemical viewpoint. For example, both contain high concentrations of CO and other combustion products. In addition, both contain high concentrations of free radicals, and our laboratory has studied these free radicals, largely by electron spin resonance (ESR) methods, for about 15 years. This article reviews what is known about the radicals present in these different types of smokes and soots and tars and summarizes the evidence that suggests these radicals could be involved in cigarette-induced pathology and smoke-inhalation deaths. The combustion of all organic materials produces radicals, but (with the exception of the smoke from perfluoropolymers) the radicals that are detected by ESR methods (and thus the radicals that would reach the lungs) are not those that arise in the combustion process. Rather they arise from chemical reactions that occur in the smoke itself. Thus, a knowledge of the chemistry of the smoke is necessary to understand the nature of the radicals formed. Even materials as similar as cigarettes and wood (cellulose) produce smoke that contains radicals with very different lifetimes and chemical characteristics, and mechanistic rationales for this are discussed. Cigarette tar contains a semiquinone radical that is infinitely stable and can be directly observed by ESR. Aqueous extracts of cigarette tar, which contain this radical, reduce oxygen to superoxide and thus produce both hydrogen peroxide and the hydroxyl radical. These solutions both oxidize alpha-1-proteinase inhibitor (a1PI) and nick DNA. Because of the potential role of radicals in smoke-inhalation injury, we suggest that antioxidant therapy (such as use of an inhaler for persons brought out of a burning building) might prove efficacious.

Long-term penile morphometric alterations in patients treated with robot-assisted versus open radical prostatectomy.

PubMed

Capogrosso, P; Ventimiglia, E; Cazzaniga, W; Stabile, A; Pederzoli, F; Boeri, L; Gandaglia, G; Dehò, F; Briganti, A; Montorsi, F; Salonia, A

2018-01-01

Neglected side effects after radical prostatectomy have been previously reported. In this context, the prevalence of penile morphometric alterations has never been assessed in robot-assisted radical prostatectomy series. We aimed to assess prevalence of and predictors of penile morphometric alterations (i.e. penile shortening or penile morphometric deformation) at long-term follow-up in patients submitted to either robot-assisted (robot-assisted radical prostatectomy) or open radical prostatectomy. Sexually active patients after either robot-assisted radical prostatectomy or open radical prostatectomy prospectively completed a 28-item questionnaire, with sensitive issues regarding sexual function, namely orgasmic functioning, climacturia and changes in morphometric characteristics of the penis. Only patients with a post-operative follow-up ≥ 24 months were included. Patients submitted to either adjuvant or salvage therapies or those who refused to comprehensively complete the questionnaire were excluded from the analyses. A propensity-score matching analysis was implemented to control for baseline differences between groups. Logistic regression models tested potential predictors of penile morphometric alterations at long-term post-operative follow-up. Overall, 67 (50%) and 67 (50%) patients were included after open radical prostatectomy or robot-assisted radical prostatectomy, respectively. Self-rated post-operative penile shortening and penile morphometric deformation were reported by 75 (56%) and 29 (22.8%) patients, respectively. Rates of penile shortening and penile morphometric deformation were not different after open radical prostatectomy and robot-assisted radical prostatectomy [all p > 0.5]. At univariable analysis, self-reported penile morphometric alterations (either penile shortening or penile morphometric deformation) were significantly associated with baseline international index of erectile function-erectile function scores, body mass index, post-operative erectile function recovery, year of surgery and type of surgery (all p < 0.05). At multivariable analysis, robot-assisted radical prostatectomy was independently associated with a lower risk of post-operative penile morphometric alterations (OR: 0.38; 95% CI: 0.16-0.93). Self-perceived penile morphometric alterations were reported in one of two patients after radical prostatectomy at long-term follow-up, with open surgery associated with a potential higher risk of this self-perception. © 2017 American Society of Andrology and European Academy of Andrology.

Trimethyl phosphite as a trap for alkoxy radicals formed from the ring opening of oxiranylcarbinyl radicals. Conversion to alkenes. Mechanistic applications to the study of C-C versus C-O ring cleavage.

PubMed

Ding, Bangwei; Bentrude, Wesley G

2003-03-19

Trimethyl phosphite, (MeO)(3)P, is introduced as an efficient and selective trap in oxiranylcarbinyl radical (2) systems, formed from haloepoxides 8-13 under thermal AIBN/n-Bu(3)SnH conditions at about 80 degrees C. Initially, the transformations of 8-13, in the absence of phosphite, to allyl alcohol 7 and/or vinyl ether 5 were measured quantitatively (Table 1). Structural variations in the intermediate oxiranylcarbinyl (2), allyloxy (3), and vinyloxycarbinyl (4) radicals involve influences of the thermodynamics and kinetics of the C-O (2 --> 3, k(1)) and C-C (2 --> 4, k(2)) radical scission processes and readily account for the changes in the amounts of product vinyl ether (5) and allyl alcohol (7) formed. Added (MeO)(3)P is inert to vinyloxycarbinyl radical 4 and selectively and rapidly traps allyloxy radical 3, diverting it to trimethyl phosphate and allyl radical 6. Allyl radicals (6) dimerize or are trapped by n-Bu(3)SnH to give alkenes, formed from haloepoxides 8, 9, and 13 in 69-95% yields. Intermediate vinyloxycarbinyl radicals (4), in the presence or absence of (MeO)(3)P, are trapped by n-Bu(3)SnH to give vinyl ethers (5). The concentrations of (MeO)(3)P and n-Bu(3)SnH were varied independently, and the amounts of phosphate, vinyl ether (5), and/or alkene from haloepoxides 10, 11, and 13 were carefully monitored. The results reflect readily understood influences of changes in the structures of radicals 2-4, particularly as they influence the C-O (k(1)) and C-C (k(2)) cleavages of intermediate oxiranylcarbinyl radical 2 and their reverse (k(-1), k(-2)). Diversion by (MeO)(3)P of allyloxy radicals (3) from haloepoxides 11 and 12 fulfills a prior prediction that under conditions closer to kinetic control, products of C-O scission, not just those of C-C scission, may result. Thus, for oxiranylcarbinyl radicals from haloepoxides 11, 12, and 13, C-O scission (k(1), 2 --> 3) competes readily with C-C cleavage (k(2), 2 --> 4), even though C-C scission is favored thermodynamically.

Peroxy radical measurements with NCAR's chemical amplifier

NASA Technical Reports Server (NTRS)

Cantrell, Christopher; Shetter, Richard; Calvert, Jack G.

1994-01-01

The present NCAR instrument for HO2/RO2 measurements has been described previously. It is based on the reactions involving HO2, RO2, and HO radicals with CO and NO. Since (HO2) + (RO2) + (HO) is much greater than (HO) for most atmospheres, it is useful as a peroxy radical detector. Operation of the instrument depends on the creation of a chemical chain reaction which is initiated as HO2 and RO2 radicals in ambient air encounter added NO gas; this forms an NO2 molecule and an HO or RO radical: HO2(RO2) + NO yields HO(RO) + NO2. RO radicals react relatively efficiently with O2 to form an HO2 radical, and subsequently an HO-radical, by reaction with NO. CO gas added to the reaction chamber during part of the operating cycle, recycles the HO to HO2; HO + CO (+O2) yields HO2 + CO2. The reaction sequence may form several hundred NO2 molecules per HO2 (RO2) originally present, before chain termination occurs. The added CO is replaced by N2 addition periodically so that the chain reaction is suppressed, and a 'blank' signal resulting from NO2, O3 and possibly other NO2-forming species (non-chain processes) in ambient air is recorded. The difference between the signal with and without CO is proportional to the peroxy radical concentration. The NO2 produced is monitored using a sensitive luminol chemiluminescence detector system. In the NCAR instrument the length of the amplification chain is determined using a stable source of HO2 radicals (H2O2 thermal decomposition); the ratio of the signal seen with CO present to that with N2 present gives the sensitivity of the instrument to HO2 (molecules of NO2 formed/peroxy radical). The instrument is automated to carry out in hourly repeated cycles: (1) chain length determination; (2) NO2 calibration; and (3) linearity check on the response of signals. One minute averages of signals are normally recorded. The sensitivity of the instrument to detect peroxy radicals is in the pptv range. The present instrument has operated continuously (24 hr/day) in the field studies which extended over a period of several weeks. The major advantages of this instrument are as follows: (1) its relative simplicity; (2) low power requirements; and (3) its rapid response to all types of peroxy radicals--HO2, CH3O2 and the higher alkyl and acyl peroxy radicals; however not all RO2 species generate HO2 radicals with perfect efficiency and hence have somewhat lower response/molecule than HO2 radicals.

Robotic Surgical System for Radical Prostatectomy: A Health Technology Assessment

PubMed Central

Wang, Myra; Xie, Xuanqian; Wells, David; Higgins, Caroline

2017-01-01

Background Prostate cancer is the second most common type of cancer in Canadian men. Radical prostatectomy is one of the treatment options available, and involves removing the prostate gland and surrounding tissues. In recent years, surgeons have begun to use robot-assisted radical prostatectomy more frequently. We aimed to determine the clinical benefits and harms of the robotic surgical system for radical prostatectomy (robot-assisted radical prostatectomy) compared with the open and laparoscopic surgical methods. We also assessed the cost-effectiveness of robot-assisted versus open radical prostatectomy in patients with clinically localized prostate cancer in Ontario. Methods We performed a literature search and included prospective comparative studies that examined robot-assisted versus open or laparoscopic radical prostatectomy for prostate cancer. The outcomes of interest were perioperative, functional, and oncological. The quality of the body of evidence was examined according to the Grading of Recommendations, Assessment, Development, and Evaluation (GRADE) Working Group criteria. We also conducted a cost–utility analysis with a 1-year time horizon. The potential long-term benefits of robot-assisted radical prostatectomy for functional and oncological outcomes were also evaluated in a 10-year Markov model in scenario analyses. In addition, we conducted a budget impact analysis to estimate the additional costs to the provincial budget if the adoption of robot-assisted radical prostatectomy were to increase in the next 5 years. A needs assessment determined that the published literature on patient perspectives was relatively well developed, and that direct patient engagement would add relatively little new information. Results Compared with the open approach, we found robot-assisted radical prostatectomy reduced length of stay and blood loss (moderate quality evidence) but had no difference or inconclusive results for functional and oncological outcomes (low to moderate quality evidence). Compared with laparoscopic radical prostatectomy, robot-assisted radical prostatectomy had no difference in perioperative, functional, and oncological outcomes (low to moderate quality evidence). Compared with open radical prostatectomy, our best estimates suggested that robot-assisted prostatectomy was associated with higher costs ($6,234) and a small gain in quality-adjusted life-years (QALYs) (0.0012). The best estimate of the incremental cost-effectiveness ratio (ICER) was $5.2 million per QALY gained. However, if robot-assisted radical prostatectomy were assumed to have substantially better long-term functional and oncological outcomes, the ICER might be as low as $83,921 per QALY gained. We estimated the annual budget impact to be $0.8 million to $3.4 million over the next 5 years. Conclusions There is no high-quality evidence that robot-assisted radical prostatectomy improves functional and oncological outcomes compared with open and laparoscopic approaches. However, compared with open radical prostatectomy, the costs of using the robotic system are relatively large while the health benefits are relatively small. PMID:28744334

Repeated stimulation of D1 dopamine receptors enhances (-)-11-hydroxy-delta 8-tetrahydrocannabinol-dimethyl-heptyl-induced catalepsy in male rats.

PubMed

Rodríguez de Fonseca, F; Martín Calderón, J L; Mechoulam, R; Navarro, M

1994-03-21

Dopaminergic and cannabinoid receptors are localized in the outflow nuclei of the basal ganglia. We have investigated the possible interrelation of these receptors in the regulation of motor activity in male rats. To this end we have first studied the behavioural effects of the highly potent cannabinoid receptor agonist (-)11-hydroxy-delta 8-tetrahydrocannabinol-dimethylheptyl (HU-210, 20 micrograms mg) after chronic stimulation of dopamine D1 and D2 receptors. The catalepsy induced by the synthetic cannabinoid, measured as the descent latency in the bar test, was enhanced in male rats chronically treated with the dopamine D1 receptor agonist SKF38393 (8 mg kg-1, twice a day during 21 days). However, animals exposed to the dopamine D2 agonist quinpirole (1 mg kg-1 daily during 21 days) displayed the same degree of catalepsy as those exposed to HU-210 alone. Although a possible involvement of D2 receptors cannot be excluded, this finding suggests a predominant role for dopamine D1 receptors in the regulation of the cataleptic response to cannabinoids. The possible cross-talk between dopamine D1 and cannabinoid receptors is further supported by the decreased responsiveness to the acute behavioural effects of SKF38393 (8 mg kg-1) observed in animals chronically exposed to HU-210 (20 micrograms kg-1 daily during 14 days).

Bacterial dissimilatory reduction of arsenic(V) to arsenic(III) in anoxic sediments

USGS Publications Warehouse

Dowdle, P.R.; Laverman, A.M.; Oremland, R.S.

1996-01-01

Incubation of anoxic salt marsh sediment slurries with 10 mM As(V) resulted in the disappearance over time of the As(V) in conjunction with its recovery as As(III). No As(V) reduction to As(III) occurred in heat- sterilized or formalin-killed controls or in live sediments incubated in air. The rate of As(V) reduction in slurries was enhanced by addition of the electron donor lactate, H2, or glucose, whereas the respiratory inhibitor/uncoupler dinitrophenol, rotenone, or 2-heptyl-4-hydroxyquinoline N-oxide blocked As(V) reduction. As(V) reduction was also inhibited by tungstate but not by molybdate, sulfate, or phosphate. Nitrate inhibited As(V) reduction by its action as a preferred respiratory electron acceptor rather than as a structural analog of As(V). Nitrate-respiring sediments could reduce As(V) to As(III) once all the nitrate was removed. Chloramphenicol blocked the reduction of As(V) to As(III) in nitrate- respiring sediments, suggesting that nitrate and arsenate were reduced by separate enzyme systems. Oxidation of [2-14C]acetate to 14CO2 by salt marsh and freshwater sediments was coupled to As(V). Collectively, these results show that reduction of As(V) in sediments proceeds by a dissimilatory process. Bacterial sulfate reduction was completely inhibited by As(V) as well as by As(III).

The interplay between QSAR/QSPR studies and partial order ranking and formal concept analyses.

PubMed

Carlsen, Lars

2009-04-17

The often observed scarcity of physical-chemical and well as toxicological data hampers the assessment of potentially hazardous chemicals released to the environment. In such cases Quantitative Structure-Activity Relationships/Quantitative Structure-Property Relationships (QSAR/QSPR) constitute an obvious alternative for rapidly, effectively and inexpensively generatng missing experimental values. However, typically further treatment of the data appears necessary, e.g., to elucidate the possible relations between the single compounds as well as implications and associations between the various parameters used for the combined characterization of the compounds under investigation. In the present paper the application of QSAR/QSPR in combination with Partial Order Ranking (POR) methodologies will be reviewed and new aspects using Formal Concept Analysis (FCA) will be introduced. Where POR constitutes an attractive method for, e.g., prioritizing a series of chemical substances based on a simultaneous inclusion of a range of parameters, FCA gives important information on the implications associations between the parameters. The combined approach thus constitutes an attractive method to a preliminary assessment of the impact on environmental and human health by primary pollutants or possibly by a primary pollutant well as a possible suite of transformation subsequent products that may be both persistent in and bioaccumulating and toxic. The present review focus on the environmental - and human health impact by residuals of the rocket fuel 1,1-dimethylhydrazine (heptyl) and its transformation products as an illustrative example.

Bioassay-guided chemical study of the anti-inflammatory effect of Senna villosa (Miller) H.S. Irwin & Barneby (Leguminosae) in TPA-induced ear edema.

PubMed

Susunaga-Notario, Ana del Carmen; Pérez-Gutiérrez, Salud; Zavala-Sánchez, Miguel Angel; Almanza-Pérez, Julio Cesar; Gutiérrez-Carrillo, Atilano; Arrieta-Báez, Daniel; López-López, Ana Laura; Román-Ramos, Rubén; Flores-Sáenz, José Luis Eduardo; Alarcón-Aguilar, Francisco Javier

2014-07-15

Senna villosa (Miller) is a plant that grows in México. In traditional Mexican medicine, it is used topically to treat skin infections, pustules and eruptions and to heal wounds by scar formation. However, studies of its potential anti-inflammatory effects have not been performed. The aim of the present study was to determine the anti-inflammatory effect of extracts from the leaves of Senna villosa and to perform a bioassay-guided chemical study of the extract with major activity in a model of ear edema induced by 12-O-tetradecanoylphorbol 13-acetate (TPA). The results reveal that the chloroform extract from Senna villosa leaves has anti-inflammatory and anti-proliferative properties. Nine fractions were obtained from the bioassay-guided chemical study, including a white precipitate from fractions 2 and 3. Although none of the nine fractions presented anti-inflammatory activity, the white precipitate exhibited pharmacological activity. It was chemically characterized using mass spectrometry and infrared and nuclear magnetic resonance spectroscopy, resulting in a mixture of three aliphatic esters, which were identified as the principal constituents: hexyl tetradecanoate (C20H40O2), heptyl tetradecanoate (C21H42O2) and octyl tetradecanoate (C22H44O2). This research provides, for the first time, evidence of the anti-inflammatory and anti-proliferative properties of compounds isolated from Senna villosa.

Fast methodology for the reliable determination of nonylphenol in water samples by minimal labeling isotope dilution mass spectrometry.

PubMed

Fabregat-Cabello, Neus; Castillo, Ángel; Sancho, Juan V; González, Florenci V; Roig-Navarro, Antoni Francesc

2013-08-02

In this work we have developed and validated an accurate and fast methodology for the determination of 4-nonylphenol (technical mixture) in complex matrix water samples by UHPLC-ESI-MS/MS. The procedure is based on isotope dilution mass spectrometry (IDMS) in combination with isotope pattern deconvolution (IPD), which provides the concentration of the analyte directly from the spiked sample without requiring any methodological calibration graph. To avoid any possible isotopic effect during the analytical procedure the in-house synthesized (13)C1-4-(3,6-dimethyl-3-heptyl)phenol was used as labeled compound. This proposed surrogate was able to compensate the matrix effect even from wastewater samples. A SPE pre-concentration step together with exhaustive efforts to avoid contamination were included to reach the signal-to-noise ratio necessary to detect the endogenous concentrations present in environmental samples. Calculations were performed acquiring only three transitions, achieving limits of detection lower than 100ng/g for all water matrix assayed. Recoveries within 83-108% and coefficients of variation ranging from 1.5% to 9% were obtained. On the contrary a considerable overestimation was obtained with the most usual classical calibration procedure using 4-n-nonylphenol as internal standard, demonstrating the suitability of the minimal labeling approach. Copyright © 2013 Elsevier B.V. All rights reserved.

Inhibition of the sodium-translocating NADH-ubiquinone oxidoreductase [Na+-NQR] decreases cholera toxin production in Vibrio cholerae O1 at the late exponential growth phase

PubMed Central

Minato, Yusuke; Fassio, Sara R.; Reddekopp, Rylan L.; Häse, Claudia C.

2014-01-01

Two virulence factors produced by Vibrio cholerae, cholera toxin (CT) and toxin-corregulated pilus (TCP), are indispensable for cholera infection. ToxT is the central regulatory protein involved in activation of CT and TCP expression. We previously reported that lack of a respiration-linked sodium-translocating NADH–ubiquinone oxidoreductase (Na+-NQR) significantly increases toxT transcription. In this study, we further characterized this link and found that Na+-NQR affects toxT expression only at the early-log growth phase, whereas lack of Na+-NQR decreases CT production after the mid-log growth phase. Such decreased CT production was independent of toxT and ctxB transcription. Supplementing a respiratory substrate, L-lactate, into the growth media restored CT production in the nqrA-F mutant, suggesting that decreased CT production in the Na+-NQR mutant is dependent on electron transport chain (ETC) activity. This notion was supported by the observations that two chemical inhibitors, a Na+-NQR specific inhibitor 2-n-Heptyl-4-hydroxyquinoline N-oxide (HQNO) and a succinate dehydrogenase (SDH) inhibitor, thenoyltrifluoroacetone (TTFA), strongly inhibited CT production in both classical and El Tor biotype strains of V. cholerae. Accordingly, we propose the main respiratory enzyme of V. cholerae, as a potential drug target to treat cholera because human mitochondria do not contain Na+-NQR orthologs. PMID:24361395

Mechanisms of iron regulation of luminescence in Vibrio fischeri.

PubMed Central

Haygood, M G; Nealson, K H

1985-01-01

Synthesis of luciferase (an autoinducible enzyme) is repressed by iron in the symbiotic bioluminescent bacterium Vibrio fischeri. Possible mechanisms of iron regulation of luciferase synthesis were tested with V. fischeri and with Escherichia coli clones containing plasmids carrying V. fischeri luminescence genes. Experiments were conducted in complete medium with and without the synthetic iron chelator ethylenediamine-di(o-hydroxyphenyl acetic acid). Comparison of the effect of ethylenediamine-di(o-hydroxyphenyl acetic acid) and another growth inhibitor, (2-n-heptyl-4-hydroxyquinoline-N-oxide), showed that iron repression is not due to inhibition of growth. A quantitative bioassay for autoinducer was developed with E. coli HB101 containing pJE411, a plasmid carrying V. fischeri luminescence genes with a transcriptional fusion between luxI and E. coli lacZ. Bioassay experiments showed no effect of iron on either autoinducer activity or production (before induction) or transcription of the lux operon. Ethylenediamine-di(o-hydroxyphenyl acetic acid) did not affect luciferase induction in E. coli strains with wild-type iron assimilation (ED8654) or impaired iron assimilation (RW193) bearing pJE202 (a plasmid with functional V. fischeri lux genes), suggesting that the genes responsible for the iron effect are missing or substituted in these clones. Two models are consistent with the data: (i) iron represses autoinducer transport, and (ii) iron acts through an autoinduction-independent regulatory system (e.g., an iron repressor). PMID:3920202

Photocatalytic degradation properties of α-Fe2O3 nanoparticles for dibutyl phthalate in aqueous solution system

NASA Astrophysics Data System (ADS)

Liu, Yue; Sun, Nan; Hu, Jianshe; Li, Song; Qin, Gaowu

2018-04-01

The phthalate ester compounds in industrial wastewater, as kinds of environmental toxic organic pollutants, may interfere with the body's endocrine system, resulting in great harm to humans. In this work, the photocatalytic degradation properties of dibutyl phthalate (DBP) were investigated using α-Fe2O3 nanoparticles and H2O2 in aqueous solution system. The optimal parameters and mechanism of degradation were discussed by changing the morphology and usage amount of catalysts, the dosage of H2O2, pH value and the initial concentration of DBP. Hollow α-Fe2O3 nanoparticles showed the highest degradation efficiency when 30 mg of catalyst and 50 µl of H2O2 were used in the DBP solution with the initial concentration of 13 mg l-1 at pH = 6.5. When the reaction time was 90 min, DBP was degraded 93% for the above optimal parameters. The photocatalytic degradation mechanism of DBP was studied by the gas chromatography-mass spectrometry technique. The result showed that the main degradation intermediates of DBP were ortho-phthalate monobutyl ester, methyl benzoic acid, benzoic acid, benzaldehyde, and heptyl aldehyde when the reaction time was 2 h. DBP and its intermediates were almost completely degraded to CO2 and H2O in 12 h in the α-Fe2O3/ H2O2/UV system.

Computational analysis of molecular properties and spectral characteristics of cyano-containing liquid crystals: role of alkyl chains.

PubMed

Praveen, P Lakshmi; Ojha, Durga P

2011-05-01

The electronic transitions in the uv-visible range of 4'-n-alkyl-4-cyanobiphenyl (nCB) with propyl, pentyl, and heptyl groups, which are of commercial and application interests, have been studied. The uv-visible and circular dichroism spectra of nCB (n = 3,5,7) molecules have been simulated using the time dependent density functional theory Becke3-Lee-Yang-Parr hybrid functional-6-31 + G (d) method. Mulliken atomic charges for each molecule have been compared with Loewdin atomic charges to analyze the molecular charge distribution and phase stability. The highest occupied molecular orbital and lowest unoccupied molecular orbital energies corresponding to the electronic transitions in the uv-visible range have been reported. Excited states have been calculated via the configuration interaction single level with a semiempirical Hamiltonian (intermediate neglect of differential overlap method, as parametrized by Zerner and co-workers). Further, two types of calculations have been performed for model systems containing single and double molecules of nCB. Furthermore, the dimer complexes during the different modes of molecular interactions have also been studied. The interaction energies of dimer complexes have been taken into consideration in order to investigate the most energetically stable configuration. These studies are helpful for understanding the role and flexibility of end chains, in particular, phase behavior and stability.

Social Movements, Civil Society, and Radical Adult Education. Critical Studies in Education and Culture Series.

ERIC Educational Resources Information Center

Holst, John D.

This book explores the relationship between adult education and social change and argues that it is vital for all adult educators to continuously engage radical theory in their teaching, reassess radical adult education's doubting and abandonment of the Marxist tradition in favor of postmodernism and radical pluralism, and seek to reinject the…

Simultaneous laparoscopic prosthetic mesh inguinal herniorrhaphy during transperitoneal laparoscopic radical prostatectomy.

PubMed

Allaf, Mohamad E; Hsu, Thomas H; Sullivan, Wendy; Su, Li-Ming

2003-12-01

Concurrent repair of inguinal hernias during open radical retropubic prostatectomy is well described and commonly practiced. With the advent of the laparoscopic approach to radical prostatectomy, the possibility of concurrent laparoscopic hernia repair merits investigation. We present a case of simultaneous prosthetic mesh onlay hernia repair for bilateral inguinal hernias during laparoscopic transperitoneal radical prostatectomy.

Sub-Lexical Phonological and Semantic Processing of Semantic Radicals: A Primed Naming Study

ERIC Educational Resources Information Center

Zhou, Lin; Peng, Gang; Zheng, Hong-Ying; Su, I-Fan; Wang, William S.-Y.

2013-01-01

Most sinograms (i.e., Chinese characters) are phonograms (phonetic compounds). A phonogram is composed of a semantic radical and a phonetic radical, with the former usually implying the meaning of the phonogram, and the latter providing cues to its pronunciation. This study focused on the sub-lexical processing of semantic radicals which are…

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

PubMed

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

2003-12-07

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

Chain decomposition of aqueous triethanolamine. [Gamma Radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwarz, H.A.

A radiation-induced chain decomposition of aqueous triethanolamine into acetaldehyde and diethanolamine is reported. Chain lengths over 1000 have been observed, depending on pH, concentration, and radiation intensity. The chain propagation steps include OH group migration in the 2-hydroxy-1-(diethanolamino)ethyl radical and NR/sub 2/ migration in 1-hydroxy-2(diethanolamine)ethyl radical, each producing a 2-hydroxy-2-(diethanolamine)ethyl radical. Free-radical spectra and rate constants are given. Studies of diethanolamine and diethylethanolamine solutions gave similar free-radical spectra but much shorter chains.

Particle correlations in p- anti p interactions at radical s = 1800 and 630 GeV

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1990-01-01

Preliminary results on Bose-Einstein correlations and two particle pseudorapidity correlations in p{bar p} interactions at {radical}s = 1800 and 630 GeV are presented. Data were collected with a minimum- bias'' trigger with the Collider Detector at Fermilab. The size of the particle emitting source, measured via Bose-Einstein interference at {radical}s =1800 GeV, is of the order of 1 fm. The observed short-range pseudorapidity correlations, compared to lower energy data, do not show any significant energy dependence. 10 refs., 5 figs.

On the Radicalization Process.

PubMed

Leistedt, Samuel J

2016-11-01

This study aimed to provide an in-depth description of the radicalization process, which is a very important step in terrorist activities. The author proposes a translational analysis that is first based on the author's experience in the psychological evaluation of terrorist behavior and second on an exhaustive review of the current literature. The search terms "terrorism," "radicalization," "social psychology," and "psychopathology" were used to identify relevant studies in the following databases: Scopus, Medline, PubCentral, and Science Direct. Because of its importance, understanding radicalization process should be one of the priorities of behavioral scientists. International studies should be performed with a focus on several aspects, such as radicalization risk factors, brainwashing, the role of the media, and finally, in de-radicalization programs. © 2016 American Academy of Forensic Sciences.

Understanding titanium-catalysed radical-radical reactions: a DFT study unravels the complex kinetics of ketone-nitrile couplings.

PubMed

Streuff, Jan; Himmel, Daniel; Younas, Sara L

2018-04-03

The computational investigation of a titanium-catalysed reductive radical-radical coupling is reported. The results match the conclusions from an earlier experimental study and enable a further interpretation of the previously observed complex reaction kinetics. Furthermore, the interplay between neutral and cationic reaction pathways in titanium(iii)-catalysed reactions is investigated for the first time. The results show that hydrochloride additives and reaction byproducts play an important role in the respective equilibria. A full reaction profile is assembled and the computed activation barrier is found to be in reasonable agreement with the experiment. The conclusions are of fundamental importance to the field of low-valent titanium catalysis and the understanding of related catalytic radical-radical coupling reactions.

Radicals Are Required for Thiol Etching of Gold Particles.

PubMed

Dreier, Timothy A; Ackerson, Christopher J

2015-08-03

Etching of gold with an excess of thiol ligand is used in both synthesis and analysis of gold particles. Mechanistically, the process of etching gold with excess thiol is unclear. Previous studies have obliquely considered the role of oxygen in thiolate etching of gold. Herein, we show that oxygen or a radical initiator is a necessary component for efficient etching of gold by thiolates. Attenuation of the etching process by radical scavengers in the presence of oxygen, and the restoration of activity by radical initiators under inert atmosphere, strongly implicate the oxygen radical. These data led us to propose an atomistic mechanism in which the oxygen radical initiates the etching process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aluminum stress increases carbon-centered radicals in soybean roots.

PubMed

Abo, Mitsuru; Yonehara, Hiroki; Yoshimura, Etsuro

2010-10-15

The formation of radical species was examined in roots of soybean seedlings exposed to aluminum (Al). Electron spin resonance (ESR) spectra of root homogenates with the spin-trapping reagent 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) indicated the presence of carbon-centered radicals in plants not exposed to Al. Plants exposed to 50 microM Al showed a similar spectrum, with increased signal intensity. These radicals were likely produced through a H-atom abstraction reaction by hydroxyl (*OH) radicals, the synthesis of which was initiated by the formation of superoxide (O2*-) anions. The increased production of the carbon-centered radicals may be responsible for the lipid peroxidation in Al-treated roots. Copyright (c) 2010 Elsevier GmbH. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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

PubMed

Kehrer, James P; Klotz, Lars-Oliver

2015-01-01

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

DNA bases ring-expanded with a cyclopentadiene free radical: a theoretical investigation of building blocks with diradical character.

PubMed

Zhao, Peiwen; Bu, Yuxiang

2016-01-14

In this work, we computationally design radical nucleobases which possess improved electronic properties, especially diradical properties through introducing a cyclopentadiene radical. We predict that the detailed electromagnetic features of base assemblies are based on the orientation of the extra five-membered cyclopentadiene ring. Broken symmetry DFT calculations take into account the relevant structures and properties. Our results reveal that both the radicalized DNA bases and the base pairs formed when they combine with their counterparts remain stable and display larger spin delocalization. The mode of embedding the cyclopentadiene free radical in the structures has some influence on the degree of π-conjugation, which results in various diradical characteristics. Single-layered radical base pairs all have an open-shell singlet ground state, but the energy difference between singlet and triplet is not significant. For two-layered radical base pairs, the situation is more complex. All of them have an open-shell state as their ground state, including an open-shell singlet state and an open-shell triplet state. That is, the majority of radical base pairs possess anti-ferromagnetic or ferromagnetic characteristics. We present here a more in-depth discussion and analyses to study the magnetic characteristics of radical bases and base pairs. As an important factor, two-layered radical base pairs also have been carefully analyzed. We hope that all the measurements and results presented here will stimulate further detailed insights into the related mechanisms in modified DNA bases and the design of better ring-expanded DNA magnetic materials.

Exploring Applications of Covalent Organic Frameworks: Homogeneous Reticulation of Radicals for Dynamic Nuclear Polarization.

PubMed

Cao, Wei; Wang, Wei David; Xu, Hai-Sen; Sergeyev, Ivan V; Struppe, Jochem; Wang, Xiaoling; Mentink-Vigier, Frederic; Gan, Zhehong; Xiao, Ming-Xing; Wang, Lu-Yao; Chen, Guo-Peng; Ding, San-Yuan; Bai, Shi; Wang, Wei

2018-06-06

Rapid progress has been witnessed in the past decade in the fields of covalent organic frameworks (COFs) and dynamic nuclear polarization (DNP). In this contribution, we bridge these two fields by constructing radical-embedded COFs as promising DNP agents. Via polarization transfer from unpaired electrons to nuclei, DNP realizes significant enhancement of NMR signal intensities. One of the crucial issues in DNP is to screen for suitable radicals to act as efficient polarizing agents, the basic criteria for which are homogeneous distribution and fixed orientation of unpaired electrons. We therefore envisioned that the crystalline and porous structures of COFs, if evenly embedded with radicals, may work as a new "crystalline sponge" for DNP experiments. As a proof of concept, we constructed a series of proxyl-radical-embedded COFs (denoted as PR( x)-COFs) and successfully applied them to achieve substantial DNP enhancement. Benefiting from the bottom-up and multivariate synthetic strategies, proxyl radicals have been covalently reticulated, homogeneously distributed, and rigidly embedded into the crystalline and mesoporous frameworks with adjustable concentration ( x%). Excellent performance of PR( x)-COFs has been observed for DNP 1 H, 13 C, and 15 N solid-state NMR enhancements. This contribution not only realizes the direct construction of radical COFs from radical monomers, but also explores the new application of COFs as DNP polarizing agents. Given that many radical COFs can therefore be rationally designed and facilely constructed with well-defined composition, distribution, and pore size, we expect that our effort will pave the way for utilizing radical COFs as standard polarizing agents in DNP NMR experiments.

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

NASA Astrophysics Data System (ADS)

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.

Spin Polarization Transfer from a Photogenerated Radical Ion Pair to a Stable Radical Controlled by Charge Recombination.

PubMed

Horwitz, Noah E; Phelan, Brian T; Nelson, Jordan N; Mauck, Catherine M; Krzyaniak, Matthew D; Wasielewski, Michael R

2017-06-15

Photoexcitation of electron donor-acceptor molecules frequently produces radical ion pairs with well-defined initial spin-polarized states that have attracted significant interest for spintronics. Transfer of this initial spin polarization to a stable radical is predicted to depend on the rates of the radical ion pair recombination reactions, but this prediction has not been tested experimentally. In this study, a stable radical/electron donor/chromophore/electron acceptor molecule, BDPA • -mPD-ANI-NDI, where BDPA • is α,γ-bisdiphenylene-β-phenylallyl, mPD is m-phenylenediamine, ANI is 4-aminonaphthalene-1,8-dicarboximide, and NDI is naphthalene-1,4:5,8-bis(dicarboximide), was synthesized. Photoexcitation of ANI produces the triradical BDPA • -mPD +• -ANI-NDI -• in which the mPD +• -ANI-NDI -• radical ion pair is spin coupled to the BDPA • stable radical. BDPA • -mPD +• -ANI-NDI -• and its counterpart lacking the stable radical are found to exhibit spin-selective charge recombination in which the triplet radical ion pair 3 (mPD +• -ANI-NDI -• ) is in equilibrium with the 3 *NDI charge recombination product. Time-resolved EPR measurements show that this process is associated with an inversion of the sign of the polarization transferred to BDPA • over time. The polarization transfer rates are found to be strongly solvent dependent, as shifts in this equilibrium affect the spin dynamics. These results demonstrate that even small changes in electron transfer dynamics can have a large effect on the spin dynamics of photogenerated multispin systems.

C-C bond forming radical SAM enzymes involved in the construction of carbon skeletons of cofactors and natural products.

PubMed

Yokoyama, Kenichi; Lilla, Edward A

2018-04-10

Covering: up to the end of 2017C-C bond formations are frequently the key steps in cofactor and natural product biosynthesis. Historically, C-C bond formations were thought to proceed by two electron mechanisms, represented by Claisen condensation in fatty acids and polyketide biosynthesis. These types of mechanisms require activated substrates to create a nucleophile and an electrophile. More recently, increasing number of C-C bond formations catalyzed by radical SAM enzymes are being identified. These free radical mediated reactions can proceed between almost any sp3 and sp2 carbon centers, allowing introduction of C-C bonds at unconventional positions in metabolites. Therefore, free radical mediated C-C bond formations are frequently found in the construction of structurally unique and complex metabolites. This review discusses our current understanding of the functions and mechanisms of C-C bond forming radical SAM enzymes and highlights their important roles in the biosynthesis of structurally complex, naturally occurring organic molecules. Mechanistic consideration of C-C bond formation by radical SAM enzymes identifies the significance of three key mechanistic factors: radical initiation, acceptor substrate activation and radical quenching. Understanding the functions and mechanisms of these characteristic enzymes will be important not only in promoting our understanding of radical SAM enzymes, but also for understanding natural product and cofactor biosynthesis.

Role of neutrophils in radical production during ischemia and reperfusion of the rat brain: effect of neutrophil depletion on extracellular ascorbyl radical formation.

PubMed

Matsuo, Y; Kihara, T; Ikeda, M; Ninomiya, M; Onodera, H; Kogure, K

1995-11-01

A growing body of experimental data indicate that oxygen radicals may mediate the brain injury during ischemia-reperfusion. One potential source of oxygen radicals is activated neutrophils. To study the role of neutrophils in radical production during cerebral ischemia-reperfusion, we evaluated the effects of depletion of circulating neutrophils by administration of an anti-neutrophil monoclonal antibody (RP3) on radical formation in rats with 1-h middle cerebral artery (MCA) occlusion. In the present study, we employed a new electron spin resonance method coupled with brain microdialysis. The method uses the endogenous ascorbyl radical (AR) concentration as a marker of oxygen radicals and requires no spin-trapping agents. In the vehicle controls, extracellular AR decreased during MCA occlusion. After reperfusion, AR significantly increased at 30 min and 1 h, returned to near basal level until 2 h, and increased again at 24 h after reperfusion. In the rats treated with RP3, AR decreased during MCA occlusion to the same extent as in the vehicle control. However, RP3 treatment completely inhibited the increase in extracellular AR after reperfusion. RP3 treatment exerted no effect on the changes in extracellular ascorbate or tissue PO2 throughout the experimental period. In conclusion, neutrophils are a major source of oxygen radicals during reperfusion after focal cerebral ischemia.

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

PubMed

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

2014-10-01

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

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

PubMed

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

2016-12-01

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

ESR study of molecular orientation and dynamics of nitronyl nitroxide radicals in CLPOT 1D nanochannels.

PubMed

Kobayashi, Hirokazu; Morinaga, Yuka; Fujimori, Etsuko; Asaji, Tetsuo

2014-07-10

New inclusion compounds (ICs) were prepared using the organic 1D nanochannels of 2,4,6-tris(4-chlorophenoxy)-1,3,5-triazine (CLPOT) as a nanosized template and nitronyl nitroxide (NN) radicals such as phenylnitronylnitroxide (PhNN) and p-nitrophenylnitronylnitroxide (p-NPNN). ESR measurements below 255 K for the CLPOT ICs diluted with spacer molecules gave rigid limit spectra similar to that for PhNN molecules in a glassy ethanol matrix at low temperature, which suggests isolation of the radical molecules. ESR measurements for them in the range of 290-400 K gave a modulated quintet ESR signal, which suggested uniaxial rotational diffusion of NN radicals in the nanochannels approximately around the principal y-axis of the g-tensors. In the ESR measurements to 430 K for the [(CLPOT)2-(p-NPNN)0.07] IC without spacers, the broader line width than the case in dilution was observed by inter-radical dipolar interaction. In every case, the rotational diffusion activation energies of NN radicals in the CLPOT nanochannels were several times larger than those of 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical derivatives (4-X-TEMPO) in CLPOT nanochannels. This is expected due to the larger molecular size of NN radicals than 4-X-TEMPO or stronger interaction between NN radicals and the surrounding host or guest molecules.

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

PubMed

Ramos, Paweł; Pilawa, Barbara

2016-06-24

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

Interactions of short-acting, intermediate-acting and pre-mixed human insulins with free radicals--Comparative EPR examination.

PubMed

Olczyk, Paweł; Komosinska-Vassev, Katarzyna; Ramos, Paweł; Mencner, Łukasz; Olczyk, Krystyna; Pilawa, Barbara

2015-07-25

Electron paramagnetic resonance (EPR) spectroscopy was used to examine insulins interactions with free radicals. Human recombinant DNA insulins of three groups were studied: short-acting insulin (Insuman Rapid); intermediate-acting insulins (Humulin N, Insuman Basal), and pre-mixed insulins (Humulin M3, Gensulin M50, Gensulin M40, Gensulin M30). The aim of an X-band (9.3GHz) study was comparative analysis of antioxidative properties of the three groups of human insulins. DPPH was used as a stable free radical model. Amplitudes of EPR lines of DPPH as the paramagnetic free radical reference, and DPPH interacting with the individual tested insulins were compared. For all the examined insulins kinetics of their interactions with free radicals up to 60 min were obtained. The strongest interactions with free radicals were observed for the short-acting insulin - Insuman Rapid. The lowest interactions with free radicals were characteristic for intermediate-acting insulin - Insuman Basal. The pre-mixed insulins i.e. Humulin M3 and Gensulin M50 revealed the fastest interactions with free radicals. The short acting, intermediate acting and premixed insulins have been found to be effective agents in reducing free radical formation in vitro and should be further considered as potential useful tools in attenuation of oxidative stress in diabetic patients. Copyright © 2015 Elsevier B.V. All rights reserved.

Plasma Jet (V)UV-Radiation Impact on Biologically Relevant Liquids and Cell Suspension

NASA Astrophysics Data System (ADS)

Tresp, H.; Bussiahn, R.; Bundscherer, L.; Monden, A.; Hammer, M. U.; Masur, K.; Weltmann, K.-D.; Woedtke, Th. V.; Reuter, S.

2014-10-01

In this study the generation of radicals in plasma treated liquids has been investigated. To quantify the contribution of plasma vacuum ultraviolet (VUV) and ultraviolet (UV) radiation on the species investigated, three cases have been studied: UV of plasma jet only, UV and VUV of plasma jet combined, and the plasma effluent including all reactive components. The emitted VUV has been observed by optical emission spectroscopy and its effect on radical formation in liquids has been analyzed by electron spin resonance spectroscopy. Radicals have been determined in ultrapure water (dH2O), as well as in more complex, biorelevant solutions like phosphate buffered saline (PBS) solution, and two different cell culture media. Various compositions lead to different reactive species formation, e.g. in PBS superoxide anion and hydroxyl radicals have been detected, in cell suspension also glutathione thiyl radicals have been found. This study highlights that UV has no impact on radical generation, whereas VUV is relevant for producing radicals. VUV treatment of dH2O generates one third of the radical concentration produced by plasma-effluent treatment. It is relevant for plasma medicine because although plasma sources are operated in open air atmosphere, still VUV can lead to formation of biorelevant radicals. This work is funded by German Federal Ministry of Education a Research (BMBF) (Grant # 03Z2DN12+11).

Efficient, environmentally-friendly and specific valorization of lignin: promising role of non-radical lignolytic enzymes.

PubMed

Wang, Wenya; Zhang, Chao; Sun, Xinxiao; Su, Sisi; Li, Qiang; Linhardt, Robert J

2017-06-01

Lignin is the second most abundant bio-resource in nature. It is increasingly important to convert lignin into high value-added chemicals to accelerate the development of the lignocellulose biorefinery. Over the past several decades, physical and chemical methods have been widely explored to degrade lignin and convert it into valuable chemicals. Unfortunately, these developments have lagged because of several difficulties, of which high energy consumption and non-specific cleavage of chemical bonds in lignin remain the greatest challenges. A large number of enzymes have been discovered for lignin degradation and these are classified as radical lignolytic enzymes and non-radical lignolytic enzymes. Radical lignolytic enzymes, including laccases, lignin peroxidases, manganese peroxidases and versatile peroxidases, are radical-based bio-catalysts, which degrade lignins through non-specific cleavage of chemical bonds but can also catalyze the radical-based re-polymerization of lignin fragments. In contrast, non-radical lignolytic enzymes selectively cleave chemical bonds in lignin and lignin model compounds and, thus, show promise for use in the preparation of high value-added chemicals. In this mini-review, recent developments on non-radical lignolytic enzymes are discussed. These include recently discovered non-radical lignolytic enzymes, their metabolic pathways for lignin conversion, their recent application in the lignin biorefinery, and the combination of bio-catalysts with physical/chemical methods for industrial development of the lignin refinery.

Oxygen radical absorbance capacity (ORAC) of cyclodextrin-solubilized flavonoids, resveratrol and astaxanthin as measured with the ORAC-EPR method

PubMed Central

Sueishi, Yoshimi; Ishikawa, Misa; Yoshioka, Daisuke; Endoh, Nobuyuki; Oowada, Shigeru; Shimmei, Masashi; Fujii, Hirotada; Kotake, Yashige

2012-01-01

Recently, we proposed an oxygen radical absorbance capacity method that directly quantifies the antioxidant’s scavenging capacity against free radicals and evaluated the radical scavenging abilities for water soluble antioxidant compounds. In this study, we determined the radical scavenging abilities of lipophilic antioxidants which were solubilized by cyclodextrin in water. Commonly employed fluorescence-based method measures the antioxidant’s protection capability for the fluorescent probe, while we directly quantify free-radical level using electron paramagnetic resonance spin trapping technique. In addition, the spin trapping-based method adopted controlled UV-photolysis of azo-initiator for free radical generation, but in fluorescence-based method, thermal decomposition of azo-initiator was utilized. We determined the radical scavenging abilities of seven well-known lipophilic antioxidants (five flavonoids, resveratrol and astaxanthin), using methylated β-cyclodextrin as a solubilizer. The results indicated that the agreement between spin trapping-based and fluorescence-based values was only fair partly because of a large variation in the previous fluorescence-based data. Typical radical scavenging abilities in trolox equivalent unit are: catechin 0.96; epicatechin 0.94; epigallocatechin gallate 1.3; kaempferol 0.37; myricetin 3.2; resveratrol 0.64; and astaxanthin 0.28, indicating that myricetin possesses the highest antioxidant capacity among the compounds tested. We sorted out the possible causes of the deviation between the two methods. PMID:22448093

Oxygen radical absorbance capacity (ORAC) of cyclodextrin-solubilized flavonoids, resveratrol and astaxanthin as measured with the ORAC-EPR method.

PubMed

Sueishi, Yoshimi; Ishikawa, Misa; Yoshioka, Daisuke; Endoh, Nobuyuki; Oowada, Shigeru; Shimmei, Masashi; Fujii, Hirotada; Kotake, Yashige

2012-03-01

Recently, we proposed an oxygen radical absorbance capacity method that directly quantifies the antioxidant's scavenging capacity against free radicals and evaluated the radical scavenging abilities for water soluble antioxidant compounds. In this study, we determined the radical scavenging abilities of lipophilic antioxidants which were solubilized by cyclodextrin in water. Commonly employed fluorescence-based method measures the antioxidant's protection capability for the fluorescent probe, while we directly quantify free-radical level using electron paramagnetic resonance spin trapping technique. In addition, the spin trapping-based method adopted controlled UV-photolysis of azo-initiator for free radical generation, but in fluorescence-based method, thermal decomposition of azo-initiator was utilized. We determined the radical scavenging abilities of seven well-known lipophilic antioxidants (five flavonoids, resveratrol and astaxanthin), using methylated β-cyclodextrin as a solubilizer. The results indicated that the agreement between spin trapping-based and fluorescence-based values was only fair partly because of a large variation in the previous fluorescence-based data. Typical radical scavenging abilities in trolox equivalent unit are: catechin 0.96; epicatechin 0.94; epigallocatechin gallate 1.3; kaempferol 0.37; myricetin 3.2; resveratrol 0.64; and astaxanthin 0.28, indicating that myricetin possesses the highest antioxidant capacity among the compounds tested. We sorted out the possible causes of the deviation between the two methods.

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

PubMed

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

2014-01-01

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

Confirmed Assignments of Isomeric Dimethylbenzyl Radicals Generated by Corona Discharge

NASA Astrophysics Data System (ADS)

Yoon, Young Wook; Lee, Sang Kuk

2012-06-01

Polymethylbenzyl radicals, multi-methyl-substituted benzyl radicals, have been believed to be an ideal model for understanding the torsional effect of methyl group and substitution effect on electronic transition. These radicals are mainly generated from polymethylbenzenes by electric discharge for spectroscopic observation. However, the existence of several methyl groups on the benzene ring may produce several isomeric polymethylbenzyl radicals by removing one of the C-H bonds of each methyl group at different substitution position, which makes the assignment of spectrum ambiguous. In this work, the controversial vibronic assignments of isomeric dimethylbenzyl radicals were clearly resolved by using different precursors. By using corresponding dimethylbenzyl chlorides as precursors, we identified the origins of the vibronic bands of the dimethylbenzyl radicals generated by corona discharge of precursors 1,2,3- and 1,2,4-trimethylbenzenes. From the analysis of the spectra observed from the dimethylbenzyl chlorides in a corona excited supersonic expansion using a pinhole-type glass nozzle, we revised previous assignments of the 2,6- and 2,3-dimethylbenzyl radicals as well as the 3,4-, 2,4-, and 2,5-dimethylbenzyl radicals. In addition, spectroscopic data of electronic transition and vibrational mode frequencies in the ground electronic state of each isomer were accurately determined by comparing them with those obtained by an ab initio calculation and with the known vibrational data of precursors.

The Influence of Education and Socialization on Radicalization: An Exploration of Theoretical Presumptions and Empirical Research

ERIC Educational Resources Information Center

Pels, Trees; de Ruyter, Doret J.

2012-01-01

Background and Objective: Research into radicalization does not pay much attention to education. This is remarkable and possibly misses an important influence on the process of radicalization. Therefore this article sets out to explore the relation between education on the one hand and the onset or prevention of radicalization on the other hand.…

Kinetics and Product Branching Fractions of Reactions between a Cation and a Radical: Ar+ + CH3 and O2+ + CH3 (Postprint)

DTIC Science & Technology

2015-01-13

Gross group using a Chen nozzle coupled to a Fourier transform ion cyclotron reso- nance (FT-ICR) mass spectrometer for reactions of the benzyl radical...reactions: A Fourier transform ion cyclotron resonance study of allyl radical reacting with aromatic radical cations. Int. J. Mass Spectrom. 2009, 287, 8

Electron Spin Relaxation Can Enhance the Performance of a Cryptochrome-Based Magnetic Compass Sensor

DTIC Science & Technology

2016-08-19

quantumbiology,migratory birds, animal navigation, radical pairmechanism Supplementarymaterial for this article is available online Abstract The radical ...certain spin relaxationmechanisms can enhance its performance.We focus on the flavin–tryptophan radical pair in cryptochrome, currently the only...candidatemagnetoreceptor molecule. Correlation functions for fluctuations in the distance between the two radicals in Arabidopsis thaliana cryptochrome

The Role of Radical Awareness in Chinese-As-A-Second-Language Learners' Chinese Character Reading Development

ERIC Educational Resources Information Center

Wong, Yu Ka

2017-01-01

In this paper, the role of radical awareness in Chinese character reading development among young Chinese-as-a-second-language (CSL) learners is evaluated in terms of a structural property of the writing system: the distribution of elementary, one-radical (i.e. one-element) simple characters as against majority, multi-radical compound characters.…

Conflict Prediction Through Geo-Spatial Interpolation of Radicalization in Syrian Social Media

DTIC Science & Technology

2015-09-24

TRAC-M-TM-15-031 September 2015 Conflict Prediction Through Geo-Spatial Interpolation of Radicalization in Syrian Social Media ...Spatial Interpolation of Radicalization in Syrian Social Media Authors MAJ Adam Haupt Dr. Camber Warren...Spatial Interpolation of Radicalization in Syrian Social 1RAC Project Code 060114 Media 6. AUTHOR(S) MAJ Haupt, Dr. Warren 7. PERFORMING OR

The Expanding Role of Oxygen Free Radicals in Clinical Medicine

PubMed Central

Katz, Murray A.

1986-01-01

In 1969 McCord and Fridovich discovered superoxide dismutase, which converts the oxygen free radical O2- to hydrogen peroxide H2O2. In the presence of excess O2-, H2O2 may then undergo further reduction to the highly toxic hydroxyl radical, OH•. Since the description of this enzymatic process, there has been explosive growth in related biochemical research, which has now percolated through to clinical investigation. The hypoxanthine-xanthine oxidase system originally used as a radical production model has a close counterpart in the ischemia-reperfusion phenomenon purported to cause diseases of heart, brain and gastrointestinal tract, and free radicals are now known to have a critical role in postphagocytic bacterial killing. Prototypic deficiency diseases such as chronic granulomatous disease are now recognized. Some evidence indicates that excess states such as perhaps Batten's disease also occur, and environmental influences such as selenium and vitamin E deficiency may augment free radical levels. Many disorders including microvasculopathies, noncardiogenic pulmonary edema, glomerulopathies and radiation damage may owe part of their proximate pathogenesis to free radicals. Control of tissue free radical levels is now pharmacologically feasible and perhaps justified for specific diseases. PMID:3521094

Myeloperoxidase-induced Genomic DNA-centered Radicals*

PubMed Central

Gomez-Mejiba, Sandra E.; Zhai, Zili; Gimenez, Maria S.; Ashby, Michael T.; Chilakapati, Jaya; Kitchin, Kirk; Mason, Ronald P.; Ramirez, Dario C.

2010-01-01

Myeloperoxidase (MPO) released by activated neutrophils can initiate and promote carcinogenesis. MPO produces hypochlorous acid (HOCl) that oxidizes the genomic DNA in inflammatory cells as well as in surrounding epithelial cells. DNA-centered radicals are early intermediates formed during DNA oxidation. Once formed, DNA-centered radicals decay by mechanisms that are not completely understood, producing a number of oxidation products that are studied as markers of DNA oxidation. In this study we employed the 5,5-dimethyl-1-pyrroline N-oxide-based immuno-spin trapping technique to investigate the MPO-triggered formation of DNA-centered radicals in inflammatory and epithelial cells and to test whether resveratrol blocks HOCl-induced DNA-centered radical formation in these cells. We found that HOCl added exogenously or generated intracellularly by MPO that has been taken up by the cell or by MPO newly synthesized produces DNA-centered radicals inside cells. We also found that resveratrol passed across cell membranes and scavenged HOCl before it reacted with the genomic DNA, thus blocking DNA-centered radical formation. Taken together our results indicate that the formation of DNA-centered radicals by intracellular MPO may be a useful point of therapeutic intervention in inflammation-induced carcinogenesis. PMID:20406811

Microscopic progression in the free radical addition reaction: modeling, geometry, energy, and kinetics.

PubMed

Zhang, Yun; Huang, Hong; Liang, Zhiling; Liu, Houhe; Yi, Ling; Zhang, Jinhong; Zhang, Zhiqiang; Zhong, Cheng; Huang, Yugang; Ye, Guodong

2017-03-01

The free radical addition reaction is very important in UV curing. The benzoyl radical is the most commonly observed radical. In the addition process, the benzoyl radical adds to an acrylate monomer, forming a primary radical that has great value for subsequent research. In this article, a quantum chemical method was used to study the microscopic progression from the reactive complex to the saddle point. The reactions of three monomers (amylene, allyl methyl ether and methyl acrylate) with a benzoyl radical were evaluated in terms of geometry and energy. The results were also interpreted with an expanded version of the Polanyi rules and the interaction/deformation theory. The deformation energy of methyl acrylate was found to be the smallest, and the bond formation index showed that the transition state in the methyl acrylate system forms early, and can easily reach the saddle point. The activity of the monomer was ascertained by charge analysis and was further confirmed by the reaction rate. Mayer bond order curves depicted the constantly changing chemical bonds during formation and dissociation. Reduced density gradient analysis showed a weak interaction between the monomer and the benzoyl radical.

Involvement of free radicals in breast cancer.

PubMed

Ríos-Arrabal, Sandra; Artacho-Cordón, Francisco; León, Josefa; Román-Marinetto, Elisa; Del Mar Salinas-Asensio, María; Calvente, Irene; Núñez, Maria Isabel

2013-08-27

Researchers have recently shown an increased interest in free radicals and their role in the tumor microenvironment. Free radicals are molecules with high instability and reactivity due to the presence of an odd number of electrons in the outermost orbit of their atoms. Free radicals include reactive oxygen and nitrogen species, which are key players in the initiation and progression of tumor cells and enhance their metastatic potential. In fact, they are now considered a hallmark of cancer. However, both reactive species may contribute to improve the outcomes of radiotherapy in cancer patients. Besides, high levels of reactive oxygen species may be indicators of genotoxic damage in non-irradiated normal tissues. The purpose of this article is to review recent research on free radicals and carcinogenesis in order to understand the pathways that contribute to tumor malignancy. This review outlines the involvement of free radicals in relevant cellular events, including their effects on genetic instability through (growth factors and tumor suppressor genes, their enhancement of mitogenic signals, and their participation in cell remodeling, proliferation, senescence, apoptosis, and autophagy processes; the possible relationship between free radicals and inflammation is also explored. This knowledge is crucial for evaluating the relevance of free radicals as therapeutic targets in cancer.

Effects of packaging environments on free radicals in gamma-irradiated UHMWPE resin powder blend with vitamin E.

PubMed

Ridley, M D; Jahan, M S

2009-03-15

Ultra-high molecular weight polyethylene (UHMWPE) powder (GUR 1020) was blended with high concentration (20%) of vitamin E (alpha-Tocopherol (alpha-T)) for direct detection of alpha-T radicals in presence of PE radicals. Samples were gamma-irradiated in sealed packages filled with N(2), or in open air. Free radicals were measured in open air environment for 71 days using electron spin resonance (ESR) technique. When irradiated in air, both alpha-T and alpha-T-resin produced identical ESR signals characteristics of tochopheroxyl radicals (alpha-T-O(*)), suggesting that PE radicals are quenched by alpha-T. There was no indication of growth of oxygen-induced radicals (OIR) either. However, when alpha-T-resin was irradiated in N(2), presence of both PE and alpha-T radicals were evident in the ESR spectra. And, OIR were produced by the same samples when they were subsequently exposed to air (for 71 days). Oxidation data recorded 85 days after postirradiation aging in air using Fourier transform infra-red (FTIR) spectroscopy, however, did not show any measurable difference between samples irradiated in N(2) and air.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Effect of the chelation of metal cation on the antioxidant activity of chondroitin sulfates.

PubMed

Ajisaka, Katsumi; Oyanagi, Yutaka; Miyazaki, Tatsuo; Suzuki, Yasuhiro

2016-06-01

The antioxidant potencies of chondroitin sulfates (CSs) from shark cartilage, salmon cartilage, bovine trachea, and porcine intestinal mucosa were compared by three representative methods for the measurement of the antioxidant activity; DPPH radical scavenging activity, superoxide radical scavenging activity, and hydroxyl radical scavenging activity. CSs from salmon cartilage and bovine trachea showed higher potency in comparison with CSs from shark cartilage and porcine intestinal mucosa. Next, CS from salmon cartilage chelating with Ca(2+), Mg(2+), Mn(2+), or Zn(2+) were prepared, and their antioxidant potencies were compared. CS chelating with Ca(2+) or Mg(2+) ions showed rather decreased DPPH radical scavenging activity in comparison with CS of H(+) form. In contrast, CS chelating with Ca(2+) or Mg(2+) ion showed remarkably enhanced superoxide radical scavenging activity than CS of H(+) or Na(+) form. Moreover, CS chelating with divalent metal ions, Ca(2+), Mg(2+), Mn(2+), or Zn(2+), showed noticeably higher hydroxyl radical scavenging activity than CS of H(+) or Na(+) form. The present results revealed that the scavenging activities of, at least, superoxide radical and hydroxyl radical were enhanced by the chelation with divalent metal ions.

Development of a PERCA Instrument for Ambient Peroxy Radical Measurements

NASA Astrophysics Data System (ADS)

Dusanter, S.; Duncianu, M.; Lahib, A.; Tomas, A.; Stevens, P. S.

2017-12-01

Peroxy radicals (HO2 and RO2) are key species in atmospheric chemistry, which together with the hydroxyl radical (OH), lead to the oxidation of volatile organic compounds and the formation of secondary pollutants such as ozone and secondary organic aerosols. Monitoring these short-lived species during intensive field campaigns and comparing the measured concentrations to model outputs allows assessing the reliability of chemical mechanisms implemented in atmospheric models. However, ambient measurements of peroxy radicals are still considered challenging and only a few techniques have been used for field measurements. The PEroxy Radical Chemical Amplifier (PERCA) approach, whose principle is based on amplification and a conversion of ambient peroxy radicals into nitrogen dioxide (NO2), has recently seen renewed interests due to the availability of sensitive NO2 monitors. We will present (i) the construction of a PERCA instrument, (ii) experiments conducted to quantify the radical chain length for HO2 and several RO2 radicals, including those produced during the OH-oxidation of isoprene, and (iii) a comparison of the conventional CO/NO and recently proposed ethane/NO amplification chemistries. In this context, box modelling of the PERCA chemistry will be discussed.

Free Radical Scavenging Activity of Drops and Spray Containing Propolis-An EPR Examination.

PubMed

Olczyk, Pawel; Komosinska-Vassev, Katarzyna; Ramos, Pawel; Mencner, Lukasz; Olczyk, Krystyna; Pilawa, Barbara

2017-01-13

The influence of heating at a temperature of 50 °C and UV-irradiation of propolis drops and spray on their free radical scavenging activity was determined. The kinetics of interactions of the propolis samples with DPPH free radicals was analyzed. Interactions of propolis drops and propolis spray with free radicals were examined by electron paramagnetic resonance spectroscopy. A spectrometer generating microwaves of 9.3 GHz frequency was used. The EPR spectra of the model DPPH free radicals were compared with the EPR spectra of DPPH in contact with the tested propolis samples. The antioxidative activity of propolis drops and propolis spray decreased after heating at the temperature of 50 °C. A UV-irradiated sample of propolis drops more weakly scavenged free radicals than an untreated sample. The antioxidative activity of propolis spray increased after UV-irradiation. The sample of propolis drops heated at the temperature of 50 °C quenched free radicals faster than the unheated sample. UV-irradiation weakly changed the kinetics of propolis drops or spray interactions with free radicals. EPR analysis indicated that propolis drops and spray should not be stored at a temperature of 50 °C. Propolis drops should not be exposed to UV-irradiation.

Radical scavenging activity of protein from tentacles of jellyfish Rhopilema esculentum.

PubMed

Yu, Huahua; Liu, Xiguang; Xing, Ronge; Liu, Song; Li, Cuiping; Li, Pengcheng

2005-05-16

In this study, radical scavenging activity of protein from tentacles of jellyfish Rhopilema esculentum (R. esculentum) was assayed including superoxide anion radical and hydroxyl radical scavenging. The protein samples showed strong scavenging activity on superoxide anion radical and values EC50 of full protein (FP), first fraction (FF), second fraction (SF), and 30% (NH4)2 SO4 precipitate (Fr-1) were 2.65, 7.28, 1.10, and 22.51 microg/mL, respectively, while values EC50 of BHA, BHT, and alpha-tocopherol were 31, 61, and 88 microg/mL, respectively. Also, the protein samples had strong scavenging effect on hydroxyl radical and the values EC50 of FP, FF, SF, Fr-1, and Fr-2 were 48.91, 27.72, 1.82, 16.36, and 160.93 microg/mL, but values EC50 of Vc and mannitol were 1907 and 4536 microg/mL, respectively. Of the five protein samples, SF had the strongest radical scavenging activity and may have a use as a possible supplement in the food and pharmaceutical industries. The radical scavenging activity was stable at high temperature so that R. esculentum may be used as a kind of natural functional food.

Light-dependent magnetoreception in birds: the crucial step occurs in the dark.

PubMed

Wiltschko, Roswitha; Ahmad, Margaret; Nießner, Christine; Gehring, Dennis; Wiltschko, Wolfgang

2016-05-01

The Radical Pair Model proposes that the avian magnetic compass is based on spin-chemical processes: since the ratio between the two spin states singlet and triplet of radical pairs depends on their alignment in the magnetic field, it can provide information on magnetic directions. Cryptochromes, blue light-absorbing flavoproteins, with flavin adenine dinucleotide as chromophore, are suggested as molecules forming the radical pairs underlying magnetoreception. When activated by light, cryptochromes undergo a redox cycle, in the course of which radical pairs are generated during photo-reduction as well as during light-independent re-oxidation. This raised the question as to which radical pair is crucial for mediating magnetic directions. Here, we present the results from behavioural experiments with intermittent light and magnetic field pulses that clearly show that magnetoreception is possible in the dark interval, pointing to the radical pair formed during flavin re-oxidation. This differs from the mechanism considered for cryptochrome signalling the presence of light and rules out most current models of an avian magnetic compass based on the radical pair generated during photo-reduction. Using the radical pair formed during re-oxidation may represent a specific adaptation of the avian magnetic compass. © 2016 The Authors.

Growing up Radical: Investigation of Benzyl-Like Radicals with Increasing Chain Lengths

NASA Astrophysics Data System (ADS)

Korn, Joseph A.; Jawad, Khadija M.; Hewett, Daniel M.; Zwier, Timothy S.

2015-06-01

Combustion processes involve complex chemistry including pathways leading to polyaromatic hydrocarbons (PAHs) from small molecule precursors. Resonance stabilized radicals (RSRs) likely play an important role in the pathways to PAHs due to their unusual stability. Benzyl radical is a prototypical RSR that is stabilized by conjugation with the phenyl ring. Earlier work on α-methyl benzyl radical showed perturbations to the spectroscopy due to a hindered methyl rotor. If the alkyl chain is lengthened then multiple conformations become possible. This talk will discuss the jet-cooled spectroscopy of α-ethyl benzyl radical and α-propyl benzyl radical produced from the discharge of 1-phenyl propanol and 1-phenyl butanol respectively. Electronic spectra were obtained via resonant two-photon ionization, and IR spectra were obtained by resonant ion-dip infrared spectroscopy. Kidwell, N. M.; Reilly, N. J.; Nebgen, B.; Mehta-Hurt, D. N.; Hoehn, R. D.; Kokkin, D. L.; McCarthy, M. C.; Slipchenko, L. V.; Zwier, T. S. The Journal of Physical Chemistry A 2013, 117, 13465.

Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines.

PubMed

Sersen, Frantisek; Gregan, Fridrich; Kotora, Peter; Kmetova, Jarmila; Filo, Juraj; Loos, Dusan; Gregan, Juraj

2017-05-29

Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene)-N'-[2,6-dinitro-4-(trifluoromethyl)]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), galvinoxyl radical (GOR), and 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

New tricks for the glycyl radical enzyme family

PubMed Central

Backman, Lindsey R.F.; Funk, Michael A.; Dawson, Christopher D.; Drennan, Catherine. L.

2018-01-01

Glycyl radical enzymes (GREs) are important biological catalysts in both strict and facultative anaerobes, playing key roles both in the human microbiota and in the environment. GREs contain a backbone glycyl radical that is post-translationally installed, enabling radical-based mechanisms. GREs function in several metabolic pathways including mixed acid fermentation, ribonucleotide reduction, and the anaerobic breakdown of the nutrient choline and the pollutant toluene. By generating a substrate-based radical species within the active site, GREs enable C-C, C-O, and C-N bond breaking and formation steps that are otherwise challenging for non-radical enzymes. Identification of previously unknown family members from genomic data and the determination of structures of well-characterized GREs have expanded the scope of GRE-catalyzed reactions as well as defined key features that enable radical catalysis. Here we review the structures and mechanisms of characterized GREs, classifying members into five categories. We consider the open questions about each of the five GRE classes and evaluate the tools available to interrogate uncharacterized GREs. PMID:28901199

Metal-free carbon materials-catalyzed sulfate radical-based advanced oxidation processes: A review on heterogeneous catalysts and applications.

PubMed

Zhao, Qingxia; Mao, Qiming; Zhou, Yaoyu; Wei, Jianhong; Liu, Xiaocheng; Yang, Junying; Luo, Lin; Zhang, Jiachao; Chen, Hong; Chen, Hongbo; Tang, Lin

2017-12-01

In recent years, advanced oxidation processes (AOPs), especially sulfate radical based AOPs have been widely used in various fields of wastewater treatment due to their capability and adaptability in decontamination. Recently, metal-free carbon materials catalysts in sulfate radical production has been more and more concerned because these materials have been demonstrated to be promising alternatives to conventional metal-based catalysts, but the review of metal-free catalysts is rare. The present review outlines the current state of knowledge on the generation of sulfate radical using metal-free catalysts including carbon nanotubes, graphene, mesoporous carbon, activated carbon, activated carbon fiber, nanodiamond. The mechanism such as the radical pathway and non-radical pathway, and factors influencing of the activation of sulfate radical was also be revealed. Knowledge gaps and research needs have been identified, which include the perspectives on challenges related to metal-free catalyst, heterogeneous metal-free catalyst/persulfate systems and their potential in practical environmental remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hydrogen abstraction from deoxyribose by a neighboring 3'-uracil peroxyl radical.

PubMed

Schyman, Patric; Eriksson, Leif A; Laaksonen, Aatto

2009-05-07

Theoretical examination of the reactivity of the uracil-5-peroxyl radical when abstracting a hydrogen atom from a neighboring 5'-deoxyribose in 5'-ApU-5-peroxyl-3' has been performed using density functional theory with the MPWB1K functional. Halogenated uracils are often used as radiosensitizers in DNA since the reactive uracil-5-yl radical is formed upon radiation and is known to create strand break and alkali-labile sites. Under aerobic conditions, such as in the cell, it has been proposed that the uracil-5-peroxyl radical is formed and would be the damaging agent. Our results show low reactivity for the uracil-5-peroxyl radical, determined by calculating the activation and reaction energies for the plausible hydrogen abstraction sites C1', C2', and C3' of the neighboring 5'-deoxyribose. These findings support the hypothesis that hydrogen abstraction primarily occurs by the uracil-5-yl radical, also under aerobic conditions, prior to formation of the peroxyl radical.

Radical formation in the coma from photodissociation of ice grains

NASA Technical Reports Server (NTRS)

Jackson, William M.; Gerth, Christopher

1990-01-01

Long ago visual observations of comets suggested that there are jets in comets but it has only been recently that A'Hearn et al. have proven that some of these jets are due to emission from the CN radical. Recent studies in the lab have shown that CN radicals can be ejected directly into the gas phase from the photolysis of frozen vapors if the parent molecular has been excited to repulsive excited state. This later observation suggests that the jets that have been observed may be due to photodissociation of icy grains in the coma. A theory of radical formation from icy grains is presented. It is shown that direct formation of free radicals in the coma is an effective way to produce radicals from icy grains in the coma. The model predicts that icy grains could produce from 6 to 800,000 OH radicals/s per grain depending upon whether the radius of the grain is 0.3 to 100 micron.

Gamma and Ion-Beam Irradiation of DNA: Free Radical Mechanisms, Electron Effects, and Radiation Chemical Track Structure

PubMed Central

Sevilla, Michael D.; Becker, David; Kumar, Anil; Adhikary, Amitava

2016-01-01

The focus of our laboratory’s investigation is to study the direct-type DNA damage mechanisms resulting from γ-ray and ion-beam radiation-induced free radical processes in DNA which lead to molecular damage important to cellular survival. This work compares the results of low LET (γ−) and high LET (ion-beam) radiation to develop a chemical track structure model for ion-beam radiation damage to DNA. Recent studies on protonation states of cytosine cation radicals in the N1-substituted cytosine derivatives in their ground state and 5-methylcytosine cation radicals in ground as well as in excited state are described. Our results exhibit a radical signature of excitations in 5-methylcytosine cation radical. Moreover, our recent theoretical studies elucidate the role of electron-induced reactions (low energy electrons (LEE), presolvated electrons (epre−), and aqueous (or, solvated) electrons (eaq−)). Finally DFT calculations of the ionization potentials of various sugar radicals show the relative reactivity of these species. PMID:27695205

Gamma and ion-beam irradiation of DNA: Free radical mechanisms, electron effects, and radiation chemical track structure

NASA Astrophysics Data System (ADS)

Sevilla, Michael D.; Becker, David; Kumar, Anil; Adhikary, Amitava

2016-11-01

The focus of our laboratory's investigation is to study the direct-type DNA damage mechanisms resulting from γ-ray and ion-beam radiation-induced free radical processes in DNA which lead to molecular damage important to cellular survival. This work compares the results of low LET (γ-) and high LET (ion-beam) radiation to develop a chemical track structure model for ion-beam radiation damage to DNA. Recent studies on protonation states of cytosine cation radicals in the N1-substituted cytosine derivatives in their ground state and 5-methylcytosine cation radicals in ground as well as in excited state are described. Our results exhibit a radical signature of excitations in 5-methylcytosine cation radical. Moreover, our recent theoretical studies elucidate the role of electron-induced reactions (low energy electrons (LEE), presolvated electrons (epre-), and aqueous (or, solvated) electrons (eaq-)). Finally DFT calculations of the ionization potentials of various sugar radicals show the relative reactivity of these species.

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

NASA Astrophysics Data System (ADS)

Maimon, Eric; Samuni, Uri; Goldstein, Sara

2018-02-01

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

Inactivation of Bacillus atrophaeus by OH radicals

NASA Astrophysics Data System (ADS)

Ono, Ryo; Yonetamari, Kenta; Tokumitsu, Yusuke; Yonemori, Seiya; Yasuda, Hachiro; Mizuno, Akira

2016-08-01

The inactivation of Bacillus atrophaeus by OH radicals is measured. This study aims to evaluate the bactericidal effects of OH radicals produced by atmospheric-pressure nonthermal plasma widely used for plasma medicine; however, in this study, OH radicals are produced by vacuum ultraviolet (VUV) photolysis of water vapor instead of plasma to allow the production of OH radicals with almost no other reactive species. A 172 nm VUV light from a Xe2 excimer lamp irradiates a He-H2O mixture flowing in a quartz tube to photodissociate H2O to produce OH, H, O, HO2, H2O2, and O3. The produced reactive oxygen species (ROS) flow out of the quartz tube nozzle to the bacteria on an agar plate and cause inactivation. The inactivation by OH radicals among the six ROS is observed by properly setting the experimental conditions with the help of simulations calculating the ROS densities. A 30 s treatment with approximately 0.1 ppm OH radicals causes visible inactivation.

Radiolysis of carbohydrates as studied by ESR and spin-trapping—II. Glycerol- d8 xylitol, dulcitol, d-sorbitol and d-mannitol

NASA Astrophysics Data System (ADS)

Kuwabara, M.; Zhang, Z.-Y.; Inanami, O.; Yoshii, G.

Studies concerning the radicals produced in glycerol by reactions with OH radicals have been carried out by investigating deuterated glycerol (glycerol-d 8) by spin-trapping with 2-methyl-2-nitrosopropane. Free radicals produced in linear carbohydrates such as xylitol, dulcitol, D-sorbitol and D-mannitol by reactions with OH radicals as well as by direct γ-radiolysis have been also investigated by spin-trapping. The ESR spectra of the spin-trapped radicals were analysed on the basis of the results from ESR and spin-trapping experiments on glycerol and deuterated glycerol, and the formation of three radical species, CHO-CH-, CH 2-CO- and HO-CH-, due to both OH reactions and direct γ-radiolysis was confirmed for all compounds. The presence of a radical, -CO-CH-, was detected for xylitol, D-sorbitol and D-mannitol. General reactions processes induced by OH reactions or γ-radiolysis in the solid state are discussed.

Investigation of the antioxidant and radical scavenging activities of some phenolic Schiff bases with different free radicals.

PubMed

Marković, Zoran; Đorović, Jelena; Petrović, Zorica D; Petrović, Vladimir P; Simijonović, Dušica

2015-11-01

The antioxidant properties of some phenolic Schiff bases in the presence of different reactive particles such as (•)OH, (•)OOH, (CH2=CH-O-O(•)), and (-•)O2 were investigated. The thermodynamic values, ΔH BDE, ΔH IP, and ΔH PA, were used for this purpose. Three possible mechanisms for transfer of hydrogen atom, concerted proton-electron transfer (CPET), single electron transfer followed by proton transfer (SET-PT), and sequential proton loss electron transfer (SPLET) were considered. These mechanisms were tested in solvents of different polarity. On the basis of the obtained results it was shown that SET-PT antioxidant mechanism can be the dominant mechanism when Schiff bases react with radical cation, while SPLET and CPET are competitive mechanisms for radical scavenging of hydroxy radical in all solvents under investigation. Examined Schiff bases react with the peroxy radicals via SPLET mechanism in polar and nonpolar solvents. The superoxide radical anion reacts with these Schiff bases very slowly.

Comparison of scavenging capacities of vegetables by ORAC and EPR.

PubMed

Kameya, Hiromi; Watanabe, Jun; Takano-Ishikawa, Yuko; Todoriki, Setsuko

2014-02-15

Reactive oxygen species (ROS) are considered to be causative agents of many health problems. In spite of this, the radical-specific scavenging capacities of food samples have not been well studied. In the present work, we have developed an electron paramagnetic resonance (EPR) spin trapping method for analysis of the scavenging capacities of food samples for multiple ROS, utilising the same photolysis procedure for generating each type of radical. The optimal conditions for effective evaluation of hydroxyl, superoxide, and alkoxyl radical scavenging capacity were determined. Quantification of radical adducts was found to be highly reproducible, with variations of less than 4%. The optimised EPR spin trapping method was used to analyse the scavenging capacities of 54 different vegetable extracts for multiple radicals, and the results were compared with oxygen radical absorption capacity values. Good correlations between the two methods were observed for superoxide and alkoxyl radicals, but not for hydroxyl. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

PubMed

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

2017-06-28

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

Toluene nitration in irradiated nitric acid and nitrite solutions

NASA Astrophysics Data System (ADS)

Elias, Gracy; Mincher, Bruce J.; Mezyk, Stephen P.; Muller, Jim; Martin, Leigh R.

2011-04-01

The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using γ and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0 M HNO3, ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the rad NO2 radical.

Understanding the stability of pyrolysis tars from biomass in a view point of free radicals.

PubMed

He, Wenjing; Liu, Qingya; Shi, Lei; Liu, Zhenyu; Ci, Donghui; Lievens, Caroline; Guo, Xiaofen; Liu, Muxin

2014-03-01

Fast pyrolysis of biomass has attracted increasing attention worldwide to produce bio-tars that can be upgraded into liquid fuels and chemicals. However, the bio-tars are usually poor in quality and stability and are difficult to be upgraded. To better understand the nature of the bio-tars, this work reveals radical concentration of tars derived from pyrolysis of two kinds of biomass. The tars were obtained by condensing the pyrolysis volatiles in 3s. It shows that the tars contain large amounts of radicals, at a level of 10(16)spins/g, and are able to generate more radicals at temperatures of 573K or higher, reaching a level of 10(19)spins/g at 673K in less than 30min. The radical generation in the tar samples is attributed to the formation of THF insoluble matters (coke), which also contain radicals. The radical concentrations of the aqueous liquids obtained in pyrolysis are also studied. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of various vitamins and coenzymes Q on reactions involving alpha-hydroxyl-containing radicals.

PubMed

Shadyro, Oleg I; Sosnovskaya, Anna A; Edimecheva, Irina P; Grintsevich, Ivan B; Lagutin, Petr Yu; Alekseev, Aleksei V; Kazem, Kamel

2005-07-01

Effects of vitamins B, C, E, K and P, as well as coenzymes Q, on formation of final products of radiation-induced free-radical transformations of ethanol, ethylene glycol, alpha-methylglycoside and glucose in aqueous solutions were studied. Based on the obtained results, it can be concluded that there are substances among vitamins and coenzymes that effectively interact with alpha-hydroxyl-containing radicals. In the presence of these substances, recombination reactions of alpha-hydroxyalkyl radicals and fragmentation of alpha-hydroxy-beta-substituted organic radicals are suppressed. It has been established that the observed effects are due to the ability of the vitamins and coenzymes under study to either oxidize alpha-hydroxyl-containing radicals yielding the respective carbonyl compounds or reduce them into the initial molecules.

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

PubMed

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

2006-01-01

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

Mechanism of Air Oxidation of the Fragrance Terpene Geraniol.

PubMed

Bäcktorp, Carina; Hagvall, Lina; Börje, Anna; Karlberg, Ann-Therese; Norrby, Per-Ola; Nyman, Gunnar

2008-01-01

The fragrance terpene geraniol autoxidizes upon air exposure and forms a mixture of oxidation products, some of which are skin sensitizers. Reactions of geraniol with O2 have been studied with DFT (B3LYP) and the computational results compared to experimentally observed product ratios. The oxidation is initiated by hydrogen abstraction, forming an allylic radical which combines with an O2 molecule to yield an intermediate peroxyl radical. In the subsequent step, geraniol differs from previously studied cases, in which the radical chain reaction is propagated through intermolecular hydrogen abstraction. The hydroxy-substituted allylic peroxyl radical prefers an intramolecular rearrangement, producing observable aldehydes and the hydroperoxyl radical, which in turn can propagate the radical reaction. Secondary oxidation products like epoxides and formates were also considered, and plausible reaction pathways for formation are proposed.

Iodine(III) Reagents in Radical Chemistry

PubMed Central

2017-01-01

Conspectus The chemistry of hypervalent iodine(III) compounds has gained great interest over the past 30 years. Hypervalent iodine(III) compounds show valuable ionic reactivity due to their high electrophilicity but also express radical reactivity as single electron oxidants for carbon and heteroatom radical generation. Looking at ionic chemistry, these iodine(III) reagents can act as electrophiles to efficiently construct C–CF3, X–CF3 (X = heteroatom), C–Rf (Rf = perfluoroalkyl), X–Rf, C–N3, C–CN, S–CN, and C–X bonds. In some cases, a Lewis or a Bronsted acid is necessary to increase their electrophilicity. In these transformations, the iodine(III) compounds react as formal “CF3+”, “Rf+”, “N3+”, “Ar+”, “CN+”, and “X+” equivalents. On the other hand, one electron reduction of the I(III) reagents opens the door to the radical world, which is the topic of this Account that focuses on radical reactivity of hypervalent iodine(III) compounds such as the Togni reagent, Zhdankin reagent, diaryliodonium salts, aryliodonium ylides, aryl(cyano)iodonium triflates, and aryl(perfluoroalkyl)iodonium triflates. Radical generation starting with I(III) reagents can also occur via thermal or light mediated homolysis of the weak hypervalent bond in such reagents. This reactivity can be used for alkane C–H functionalization. We will address important pioneering work in the area but will mainly focus on studies that have been conducted by our group over the last 5 years. We entered the field by investigating transition metal free single electron reduction of Togni type reagents using the readily available sodium 2,2,6,6-tetramethylpiperidine-1-oxyl salt (TEMPONa) as an organic one electron reductant for clean generation of the trifluoromethyl radical and perfluoroalkyl radicals. That valuable approach was later successfully also applied to the generation of azidyl and aryl radicals starting with the corresponding benziodoxole (Zhdankin reagent) and iodonium salts. In the presence of alkenes as radical acceptors, vicinal trifluoromethyl-, azido-, and arylaminoxylation products result via a sequence comprising radical addition to the alkene and subsequent TEMPO trapping. Electron-rich arenes also react with I(III) reagents via single electron transfer (SET) to give arene radical cations, which can then engage in arylation reactions. We also recognized that the isonitrile functionality in aryl isonitriles is a highly efficient perfluoroalkyl radical acceptor, and reaction of Rf-benziodoxoles (Togni type reagents) in the presence of a radical initiator provides various perfluoroalkylated N-heterocycles (indoles, phenanthridines, quinolines, etc.). We further found that aryliodonium ylides, previously used as carbene precursors in metal-mediated cyclopropanation reactions, react via SET reduction with TEMPONa to the corresponding aryl radicals. As a drawback of all these transformations, we realized that only one ligand of the iodine(III) reagent gets transferred to the substrate. To further increase atom-economy of such conversions, we identified cyano or perfluoroalkyl iodonium triflate salts as valuable reagents for stereoselective vicinal alkyne difunctionalization, where two ligands from the I(III) reagent are sequentially transferred to an alkyne acceptor. Finally, we will discuss alkynyl-benziodoxoles as radical acceptors for alkynylation reactions. Similar reactivity was found for the Zhdankin reagent that has been successfully applied to azidation of C-radicals, and also cyanation is possible with a cyano I(III) reagent. To summarize, this Account focuses on the design, development, mechanistic understanding, and synthetic application of hypervalent iodine(III) reagents in radical chemistry. PMID:28636313

Formation of a Criegee intermediate in the low-temperature oxidation of dimethyl sulfoxide.

PubMed

Asatryan, Rubik; Bozzelli, Joseph W

2008-04-07

Dimethyl sulfoxide (DMSO) is the major sulfur-containing constituent of the Marine Boundary Layer. It is a significant source of H2SO4 aerosol/particles and methane sulfonic acid via atmospheric oxidation processes, where the mechanism is not established. In this study, several new, low-temperature pathways are revealed in the oxidation of DMSO using CBS-QB3 and G3MP2 multilevel and B3LYP hybrid density functional quantum chemical methods. Unlike analogous hydrocarbon peroxy radicals the chemically activated DMSO peroxy radical, [CH3S(=O)CH2OO*]*, predominantly undergoes simple dissociation to a methylsulfinyl radical CH3S*(=O) and a Criegee intermediate, CH2OO, with the barrier to dissociation 11.3 kcal mol(-1) below the energy of the CH3S(=O)CH2* + O2 reactants. The well depth for addition of O2 to the CH3S(=O)CH2 precursor radical is 29.6 kcal mol(-1) at the CBS-QB3 level of theory. We believe that this reaction may serve an important role in atmospheric photochemical and irradiated biological (oxygen-rich) media where formation of initial radicals is facilitated even at lower temperatures. The Criegee intermediate (carbonyl oxide, peroxymethylene) and sulfinyl radical can further decompose, resulting in additional chain branching. A second reaction channel important for oxidation processes includes formation (via intramolecular H atom transfer) and further decomposition of hydroperoxide methylsulfoxide radical, *CH2S(=O)CH2OOH over a low barrier of activation. The initial H-transfer reaction is similar and common in analogous hydrocarbon radical + O2 reactions; but the subsequent very low (3-6 kcal mol(-1)) barrier (14 kcal mol(-1) below the initial reagents) to beta-scission products is not common in HC systems. The low energy reaction of the hydroperoxide radical is a beta-scission elimination of *CH2S(=O)CH2OOH into the CH2=S=O + CH2O + *OH product set. This beta-scission barrier is low, because of the delocalization of the *CH2 radical center through the -S(=O) group, to the -CH2OOH fragment in the transition state structure. The hydroperoxide methylsulfoxide radical can also decompose via a second reaction channel of intramolecular OH migration, yielding formaldehyde and a sulfur-centered hydroxymethylsulfinyl radical HOCH2S*(=O). The barrier of activation relative to initial reagents is 4.2 kcal mol(-1). Heats of formation for DMSO, DMSO carbon-centered radical and Criegee intermediate are evaluated at 298 K as -35.97 +/- 0.05, 13.0 +/- 0.2 and 25.3 +/- 0.7 kcal mol(-1) respectively using isodesmic reaction analysis. The [CH3S*(=O) + CH2OO] product set is shown to form a van der Waals complex that results in O-atom transfer reaction and the formation of new products CH3SO2* radical and CH2O. Proper orientation of the Criegee intermediate and methylsulfinyl radical, as a pre-stabilized pre-reaction complex, assist the process. The DMSO radical reaction is also compared to that of acetonyl radical.

Complex Biotransformations Catalyzed by Radical S-Adenosylmethionine Enzymes*

PubMed Central

Zhang, Qi; Liu, Wen

2011-01-01

The radical S-adenosylmethionine (AdoMet) superfamily currently comprises thousands of proteins that participate in numerous biochemical processes across all kingdoms of life. These proteins share a common mechanism to generate a powerful 5′-deoxyadenosyl radical, which initiates a highly diverse array of biotransformations. Recent studies are beginning to reveal the role of radical AdoMet proteins in the catalysis of highly complex and chemically unusual transformations, e.g. the ThiC-catalyzed complex rearrangement reaction. The unique features and intriguing chemistries of these proteins thus demonstrate the remarkable versatility and sophistication of radical enzymology. PMID:21771780

Free Radical Oxidation in Rat Myocardium after Maximum Permissible Hepatic Resection.

PubMed

Ermolaev, P A; Khramykh, T P; Barskaya, L O

2016-03-01

Free radical oxidation in rat myocardial homogenate was studied by chemiluminescent assay during the early terms after maximum permissible liver resection. During this period, activation of free radical oxidation was biphasic. The critical terms characterized by dramatic intensification of free radical oxidation in the myocardium are the first hour and the first day after surgery. The period from 3 to 12 h after surgery, in which the indices of chemiluminescence decrease, can be tentatively termed as the period of "putative wellbeing". Normalization of the free radical oxidation processes in the myocardium occurred by day 7 after surgery.

The laser versus the lamp: Reactivity of the diphenyl ketyl radical in the ground and excited states

NASA Astrophysics Data System (ADS)

Baumann, H.; Merckel, C.; Timpe, H.-J.; Graness, A.; Kleinschmidt, J.; Gould, I. R.; Turro, N. J.

1984-01-01

The diphenyl ketyl radical which is formed upon photolysis of α-phenyl benzoin is produced in its excited state upon intense pulsed laser irradiation. Using the techniques of time-resolved absorption and emission spectroscopy, reaction rate constants for the ground and excited states of this radical were obtained. For the radical quenchers employed, the excited state reactivity is found to be typically several orders of magnitude greater than that of the ground state. It is concluded that the excited state of diphenyl ketyl radical reacts predominantly by electron transfer processes.

Lipid oxidation in bilayer liposomes induced by radicals from the surrounding water phases

NASA Astrophysics Data System (ADS)

Sprinz, H.; Brede, O.

1996-03-01

Some features of the radiation chemistry of organized assemblies were studied in aqueous dispersions of small unilamellar vesicles of egg yolk lecithin. The kinetics for the reaction of OH radicals with the bilayer was determined by pulse radiolysis. The conversion of OH radicals into N 3 radicals results in a remarkable reduction of the radiolysis of the hydrophylic part of the phospholipid and in an enhanced degradation of the most radiosensitive group of polyunsaturated fatty acid residues. The transverse proton relaxation of the choline head group is very sensitive to the radical attack on the bilayer.

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

NASA Astrophysics Data System (ADS)

Volkamer, R.; Sheehy, P. M.; Molina, L. T.; Molina, M. J.

2007-04-01

A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10-25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: HCHO and O3 photolysis, each about 20%; O3/alkene reactions and HONO photolysis, each about 15%; unmeasured sources about 30%. While the direct contribution of O3/alkene reactions appears to be moderately small, source-apportionment of ambient HCHO and HONO identifies O3/alkene reactions as being largely responsible for jump-starting photochemistry about one hour after sunrise. The peak radical production is found to be higher than in any other urban influenced environment studied to date; further, differences exist in the timing of radical production. Our measurements and analysis comprise a database that enables testing of the representation of radical sources in photochemical models. Since the photochemical processing of pollutants is radical-limited in the MCMA, our analysis identifies the drivers for such processing. Three pathways are identified by which reductions in VOC emissions induce reductions in peak concentrations of secondary pollutants, such as O3 and secondary organic aerosol (SOA).

Quantitative determination of atmospheric hydroperoxyl radical

DOEpatents

Springston, Stephen R.; Lloyd, Judith; Zheng, Jun

2007-10-23

A method for the quantitative determination of atmospheric hydroperoxyl radical comprising: (a) contacting a liquid phase atmospheric sample with a chemiluminescent compound which luminesces on contact with hydroperoxyl radical; (b) determining luminescence intensity from the liquid phase atmospheric sample; and (c) comparing said luminescence intensity from the liquid phase atmospheric sample to a standard luminescence intensity for hydroperoxyl radical. An apparatus for automating the method is also included.

Visual Field Differences in Visual Word Recognition Can Emerge Purely from Perceptual Learning: Evidence from Modeling Chinese Character Pronunciation

ERIC Educational Resources Information Center

Hsiao, Janet Hui-wen

2011-01-01

In Chinese orthography, a dominant character structure exists in which a semantic radical appears on the left and a phonetic radical on the right (SP characters); a minority opposite arrangement also exists (PS characters). As the number of phonetic radical types is much greater than semantic radical types, in SP characters the information is…

π to σ Radical Tautomerization in One-Electron Oxidized 1-Methylcytosine and its Analogs

PubMed Central

Adhikary, Amitava; Kumar, Anil; Bishop, Casandra T.; Wiegand, Tyler J.; Hindi, Ragda M.; Adhikary, Ananya; Sevilla, Michael D.

2015-01-01

In this work iminyl σ-radical formation in several one-electron oxidized cytosine analogs including 1-MeC, cidofovir, 2′-deoxycytidine (dCyd), and 2′-deoxycytidine 5′-monophosphate (5′-dCMP) were investigated in homogeneous aqueous (D2O or H2O) glassy solutions at low temperatures employing electron spin resonance (ESR) spectroscopy. Employing density functional theory (DFT) (DFT/B3LYP/6-31G* method), the calculated hyperfine coupling constant (HFCC) values of iminyl σ-radical agree quite well with the experimentally observed ones thus confirming its assignment. ESR and DFT studies show that the cytosine-iminyl σ-radical is a tautomer of the deprotonated cytosine π-cation radical (cytosine π-aminyl radical, C(N4-H)•). Employing 1-MeC samples at various pHs ranging ca. 8 to ca. 11, ESR studies show that the tautomeric equilibrium between C(N4-H)• and the iminyl σ-radical at low temperature is too slow to be established without added base. ESR and DFT studies agree that in the iminyl-σ radical, the unpaired spin is localized to the exocyclic nitrogen (N4) in an in-plane pure p-orbital. This gives rise to an anisotropic nitrogen hyperfine coupling (Azz = 40 G) from N4 and a near isotropic β-nitrogen coupling of 9.7 G from the cytosine ring nitrogen at N3. Iminyl σ-radical should exist in its N3-protonated form as the N3-protonated iminyl σ-radical is stabilized in solution by over 30 kcal/mol (ΔG= −32 kcal/mol) over its conjugate base, the N3-deprotonated form. This is the first observation of an isotropic β-hyperfine ring nitrogen coupling in an N-centered DNA-radical. Our theoretical calculations predict that the cytosine iminyl σ-radical can be formed in dsDNA by a radiation-induced ionization–deprotonation process that is only 10 kcal/mol above the lowest energy path. PMID:26237072

Reversible Hydrogen Transfer Reactions in Thiyl Radicals From Cysteine and Related Molecules: Absolute Kinetics and Equilibrium Constants Determined by Pulse Radiolysis

PubMed Central

Koppenol, Willem H.

2013-01-01

The mercapto group of cysteine (Cys) is a predominant target for oxidative modification, where one-electron oxidation leads to the formation of Cys thiyl radicals, CysS•. These Cys thiyl radicals enter 1,2- and 1,3-hydrogen transfer reactions, for which rate constants are reported in this paper. The products of these 1,2- and 1,3-hydrogen transfer reactions are carbon-centered radicals at position C3 (α-mercaptoalkyl radicals) and C2 (•Cα radicals) of Cys, respectively. Both processes can be monitored separately in Cys analogues such as cysteamine (CyaSH) and penicillamine (PenSH). At acidic pH, thiyl radicals from CyaSH permit only the 1,2-hydrogen transfer according to equilibrium 12, +H3NCH2CH2S• ⇌ +H3NCH2 •CH–SH, where rate constants for forward and reverse reaction are k12 ≈ 105 s−1 and k−12 ≈ 1.5 × 105s−1, respectively. In contrast, only the 1,3-hydrogen transfer is possible for thiyl radicals from PenSH according to equilibrium 14, (+H3N/CO2H)Cα–C(CH3)2–S• ⇌ (+H3N/CO2H)•Cα–C(CH3)2–SH, where rate constants for the forward and the reverse reaction are k14 = 8 × 104 s−1 and k−14 = 1.4 × 106 s−1. The •Cα radicals from PenSH and Cys have the additional opportunity for β-elimination of HS•/S•−, which proceeds with k39 ≈ (3 ± 1) × 104 s−1 from •Cα radicals from PenSH and k−34 ≈ 5 × 103 s−1 from •Cα radicals from Cys. The rate constants quantified for the 1,2- and 1,3-hydrogen transfer reactions can be used as a basis to calculate similar processes for Cys thiyl radicals in proteins, where hydrogen transfer reactions, followed by the addition of oxygen, may lead to the irreversible modification of target proteins. PMID:22483034

Sources, Sinks and Cycling of Acetyl Radicals in Tobacco Smoke: A Model for Biomass Burning Chemistry

NASA Astrophysics Data System (ADS)

Hu, N.; Green, S. A.

2012-12-01

Smoke near the source of biomass burning contains high concentrations of reactive compounds, with NO and CH3CHO concentrations four to six orders of magnitude higher than those in the ambient atmosphere. Tobacco smoke represents a special case of biomass burning that is quite reproducible in the lab and may elucidate early processes in smoke from other sources. The origins, identities, and reactions of radical species in tobacco smoke are not well understood, despite decades of study on the concentrations and toxicities of the relatively stable compounds in smoke. We propose that reactions of NO2 and aldehydes are a primary source for transient free radicals in tobacco smoke, which contrasts with the long-surmised mechanism of reaction between NO2 and dienes. The objective of this study was to investigate the sources, sinks and cycling of acetyl radical in tobacco smoke. Experimentally, the production of acetyl radical was demonstrated both in tobacco smoke and in a simplified mixture of air combined with NO and acetaldehyde, both of which are significant components of smoke. Acetyl radicals were trapped from the gas phase using 3-amino-2, 2, 5, 5-tetramethyl-proxyl (3AP) on solid support to form stable 3AP adducts for later analysis by high performance liquid chromatography (HPLC), mass spectrometry/tandem mass spectrometry (MS-MS/MS) and liquid chromatography-mass spectrometry (LC-MS). The dynamic nature of radical cycling in smoke makes it impossible to define a fixed concentration of radical species; 2.15×e13-3.18×e14 molecules/cm3 of acetyl radicals were measured from different cigarette samples and smoking conditions. Matlab was employed to simulate reactions of NO, NO2, O2, and a simplified set of organic compounds known to be present in smoke, with a special emphasis on acetaldehyde and the acetyl radical. The NO2/acetaldehyde mechanism initiates a cascade of chain reactions, which accounts for the most prevalent known carbon-centered radicals found in tobacco smoke, and pathways for formation of OH and peroxyl species. Tobacco smoke provides a new perspective of radical generation in a relatively well-defined biomass burning process.

Characterization of the product radical structure in the Co(II)-product radical pair state of coenzyme B12-dependent ethanolamine deaminase by using three-pulse 2H ESEEM spectroscopy.

PubMed

Warncke, Kurt

2005-03-08

Molecular structural features of the product radical in the Co(II)-product radical pair catalytic intermediate state in coenzyme B(12)- (adenosylcobalamin-) dependent ethanolamine deaminase from Salmonella typhimurium have been characterized by using X-band three-pulse electron spin-echo envelope modulation (ESEEM) spectroscopy in the disordered solid state. The Co(II)-product radical pair state was prepared by cryotrapping holoenzyme during steady-state turnover on excess 1,1,2,2-(2)H(4)-aminoethanol or natural abundance, (1)H(4)-aminoethanol. Simulation of the (2)H/(1)H quotient ESEEM (obtained at two microwave frequencies, 8.9 and 10.9 GHz) from the interaction of the unpaired electron localized at C2 of the product radical with nearby (2)H nuclei requires four types of coupled (2)H, which are assigned as follows: (a) a single strongly coupled (effective dipole distance, r(eff) = 2.3 A) (2)H in the C5' methyl group of 5'-deoxyadenosine, (b) two weakly coupled (r(eff) = 4.2 A) (2)H in the C5' methyl group, (c) one (2)H coupling from a beta-(2)H bonded to C1 of the product radical (isotropic hyperfine coupling, A(iso) = 4.7 MHz), and (d) a second type of C1 beta-(2)H coupling (A(iso) = 7.7 MHz). The two beta-(2)H couplings are proposed to arise from two C1-C2 rotamer states of the product radical that are present in approximately equal proportion. A model is presented, in which C5' is positioned at a distance of 3.3 A from C2, which is comparable with the C1-C5' distance in the Co(II)-substrate radical pair intermediate. Therefore, the C5'methyl group remains in close (van der Waals) contact with the substrate and product radical species during the radical rearrangement step of the catalytic cycle, and the C5' center is the sole mediator of radical pair recombination in ethanolamine deaminase.

Quality of life and satisfaction with information after radical prostatectomy, radical external beam radiotherapy and postoperative radiotherapy: a long-term follow-up study.

PubMed

Nicolaisen, Marianne; Müller, Stig; Patel, Hitendra R H; Hanssen, Tove Aminda

2014-12-01

To assess patients' symptoms, quality of life and satisfaction with information three to four years after radical prostatectomy, radical external beam radiotherapy and postoperative radiotherapy and to analyse differences between treatment groups and the relationship between disease-specific, health-related and overall quality of life and satisfaction with information. Radical prostate cancer treatments are associated with changes in quality of life. Differences between patients undergoing different treatments in symptoms and quality of life have been reported, but there are limited long-term data comparing radical prostatectomy with radical external beam radiotherapy and postoperative radiotherapy. A cross-sectional survey design was used. The study sample included 143 men treated with radical prostatectomy and/or radical external beam radiotherapy. Quality of life was measured using the 12-item Short Form Health Survey and the 50-item Expanded Prostate Cancer Index Composite Instrument. Questions assessing overall Quality of life and satisfaction with information were included. Descriptive statistics and interference statistical methods were applied to analyse the data. Radical external beam radiotherapy was associated with less urinary incontinence and better urinary function. There were no differences between the groups for disease-specific quality of life sum scores. Sexual quality of life was reported very low in all groups. Disease-specific quality of life and health-related quality of life were associated with overall quality of life. Patients having undergone surgery were more satisfied with information, and there was a positive correlation between quality of life and patient satisfaction. Pretreatment information and patient education lead to better quality of life and satisfaction. This study indicates a need for structured, pretreatment information and follow-up for all men going through radical prostate cancer treatment. Long-term quality of life effects should be considered when planning follow-up and information for men after radical prostate cancer treatment. Structured and organised information/education may increase preparedness for symptoms and bother after the treatment, improve symptom management strategies and result in improved quality of life. © 2014 John Wiley & Sons Ltd.

Extended Venous Thromboembolism Prophylaxis after Radical Cystectomy: A Call for Adherence to Current Guidelines.

PubMed

Klaassen, Zachary; Arora, Karan; Goldberg, Hanan; Chandrasekar, Thenappan; Wallis, Christopher J D; Sayyid, Rashid K; Fleshner, Neil E; Finelli, Antonio; Kutikov, Alexander; Violette, Philippe D; Kulkarni, Girish S

2018-04-01

Radical cystectomy is inherently associated with morbidity. We assess the timing and incidence of venous thromboembolism, review current guideline recommendations and provide evidence for considering extended venous thromboembolism prophylaxis in all patients undergoing radical cystectomy. We searched PubMed® for available literature on radical cystectomy and venous thromboembolism, focusing on incidence and timing, evidence supporting extended venous thromboembolism prophylaxis in patients undergoing radical cystectomy or abdominal oncologic surgery, current guideline recommendations, safety considerations and direct oral anticoagulants. Search terms included "radical cystectomy," "venous thromboembolism," "prophylaxis," and "extended oral anticoagulants" and "direct oral anticoagulants" alone and in combination. Relevant articles were reviewed, including original research, reviews and clinical guidelines. References from review articles and guidelines were also assessed to develop a narrative review. The incidence of symptomatic venous thromboembolism in short-term followup after radical cystectomy is 3% to 11.6%, of which more than 50% of cases will occur after hospital discharge. Meta-analyses of clinical trials in patients undergoing major abdominal oncologic operations suggest a decreased risk of venous thromboembolisms for patients receiving extended (4 weeks) venous thromboembolism prophylaxis. Extended prophylaxis should be considered in all radical cystectomy cases. Although the relative risk of bleeding also increases, the overall net benefit of extended prophylaxis clearly favors use for at least 28 days postoperatively. Extrarenal eliminated prophylaxis agents are preferred given the risk of renal insufficiency in radical cystectomy cases, with newer oral anticoagulants providing an alternative route of administration. Patients undergoing radical cystectomy are at high risk for venous thromboembolism after hospital discharge. There is strong evidence that extended prophylaxis significantly decreases the risk of venous thromboembolism in oncologic surgery cases. Use of extended prophylaxis after radical cystectomy has been poorly adopted, emphasizing the need for better adherence to current urology procedure specific guidelines as extended prophylaxis for radical cystectomy is the standard of care. Specific and rare circumstances may require case by case assessment. Copyright © 2018 American Urological Association Education and Research, Inc. Published by Elsevier Inc. All rights reserved.

Gas-Phase Ozonolysis of Cycloalkenes: Formation of Highly Oxidized RO2 Radicals and Their Reactions with NO, NO2, SO2, and Other RO2 Radicals.

PubMed

Berndt, Torsten; Richters, Stefanie; Kaethner, Ralf; Voigtländer, Jens; Stratmann, Frank; Sipilä, Mikko; Kulmala, Markku; Herrmann, Hartmut

2015-10-15

The gas-phase reaction of ozone with C5-C8 cycloalkenes has been investigated in a free-jet flow system at atmospheric pressure and a temperature of 297 ± 1 K. Highly oxidized RO2 radicals bearing at least 5 O atoms in the molecule and their subsequent reaction products were detected in most cases by means of nitrate-CI-APi-TOF mass spectrometry. Starting from a Criegee intermediate after splitting-off an OH-radical, the formation of these RO2 radicals can be explained via an autoxidation mechanism, meaning RO2 isomerization (ROO → QOOH) and subsequently O2 addition (QOOH + O2 → R'OO). Time-dependent RO2 radical measurements concerning the ozonolysis of cyclohexene indicate rate coefficients of the intramolecular H-shifts, ROO → QOOH, higher than 1 s(-1). The total molar yield of highly oxidized products (predominantly RO2 radicals) from C5-C8 cycloalkenes in air is 4.8-6.0% affected with a calibration uncertainty by a factor of about two. For the most abundant RO2 radical from cyclohexene ozonolysis, O,O-C6H7(OOH)2O2 ("O,O" stands for two O atoms arising from the ozone attack), the determination of the rate coefficients of the reaction with NO2, NO, and SO2 yielded (1.6 ± 0.5) × 10(-12), (3.4 ± 0.9) × 10(-11), and <10(-14) cm(3) molecule(-1) s(-1), respectively. The reaction of highly oxidized RO2 radicals with other peroxy radicals (R'O2) leads to detectable accretion products, RO2 + R'O2 → ROOR' + O2, which allows to acquire information on peroxy radicals not directly measurable with the nitrate ionization technique applied here. Additional experiments using acetate as the charger ion confirm conclusively the existence of highly oxidized RO2 radicals and closed-shell products. Other reaction products, detectable with this ionization technique, give a deeper insight in the reaction mechanism of cyclohexene ozonolysis.

Multicomponent kinetic analysis and theoretical studies on the phenolic intermediates in the oxidation of eugenol and isoeugenol catalyzed by laccase.

PubMed

Qi, Yan-Bing; Wang, Xiao-Lei; Shi, Ting; Liu, Shuchang; Xu, Zhen-Hao; Li, Xiqing; Shi, Xuling; Xu, Ping; Zhao, Yi-Lei

2015-11-28

Laccase catalyzes the oxidation of natural phenols and thereby is believed to initialize reactions in lignification and delignification. Numerous phenolic mediators have also been applied in laccase-mediator systems. However, reaction details after the primary O-H rupture of phenols remain obscure. In this work two types of isomeric phenols, EUG (eugenol) and ISO (trans-/cis-isoeugenol), were used as chemical probes to explore the enzymatic reaction pathways, with the combined methods of time-resolved UV-Vis absorption spectra, MCR-ALS, HPLC-MS, and quantum mechanical (QM) calculations. It has been found that the EUG-consuming rate is linear to its concentration, while the ISO not. Besides, an o-methoxy quinone methide intermediate, (E/Z)-4-allylidene-2-methoxycyclohexa-2,5-dienone, was evidenced in the case of EUG with the UV-Vis measurement, mass spectra and TD-DFT calculations; in contrast, an ISO-generating phenoxyl radical, a (E/Z)-2-methoxy-4-(prop-1-en-1-yl) phenoxyl radical, was identified in the case of ISO. Furthermore, QM calculations indicated that the EUG-generating phenoxyl radical (an O-centered radical) can easily transform into an allylic radical (a C-centered radical) by hydrogen atom transfer (HAT) with a calculated activation enthalpy of 5.3 kcal mol(-1) and then be fast oxidized to the observed eugenol quinone methide, rather than an O-radical alkene addition with barriers above 12.8 kcal mol(-1). In contrast, the ISO-generating phenoxyl radical directly undergoes a radical coupling (RC) process, with a barrier of 4.8 kcal mol(-1), while the HAT isomerization between O- and C-centered radicals has a higher reaction barrier of 8.0 kcal mol(-1). The electronic conjugation of the benzyl-type radical and the aromatic allylic radical leads to differentiation of the two pathways. These results imply that competitive reaction pathways exist for the nascent reactive intermediates generated in the laccase-catalyzed oxidation of natural phenols, which is important for understanding the lignin polymerization and may shed some light on the development of efficient laccase-mediator systems.

Effects of Solvent and Temperature on Free Radical Formation in Electronic Cigarette Aerosols.

PubMed

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

2018-01-16

The ever-evolving market of electronic cigarettes (e-cigarettes) presents a challenge for analyzing and characterizing the harmful products they can produce. Earlier we reported that e-cigarette aerosols can deliver high levels of reactive free radicals; however, there are few data characterizing the production of these potentially harmful oxidants. Thus, we have performed a detailed analysis of the different parameters affecting the production of free radical by e-cigarettes. Using a temperature-controlled e-cigarette device and a novel mechanism for reliably simulating e-cigarette usage conditions, including coil activation and puff flow, we analyzed the effects of temperature, wattage, and e-liquid solvent composition of propylene glycol (PG) and glycerol (GLY) on radical production. Free radicals in e-cigarette aerosols were spin-trapped and analyzed using electron paramagnetic resonance. Free radical production increased in a temperature-dependent manner, showing a nearly 2-fold increase between 100 and 300 °C under constant-temperature conditions. Free radical production under constant wattage showed an even greater increase when going from 10 to 50 W due, in part, to higher coil temperatures compared to constant-temperature conditions. The e-liquid PG content also heavily influenced free radical production, showing a nearly 3-fold increase upon comparison of ratios of 0:100 (PG:GLY) and 100:0 (PG:GLY). Increases in PG content were also associated with increases in aerosol-induced oxidation of biologically relevant lipids. These results demonstrate that the production of reactive free radicals in e-cigarette aerosols is highly solvent dependent and increases with an increase in temperature. Radical production was somewhat dependent on aerosol production at higher temperatures; however, disproportionately high levels of free radicals were observed at ≥100 °C despite limited aerosol production. Overall, these findings suggest that e-cigarettes can be designed to minimize exposure to these potentially harmful products.

Combining the Power of Irmpd with Ion-Molecule Reactions: the Structure and Reactivity of Radical Ions of Cysteine and its Derivatives

NASA Astrophysics Data System (ADS)

Lesslie, Michael; Osburn, Sandra; Berden, Giel; Oomens, J.; Ryzhov, Victor

2015-06-01

Most of the work on peptide radical cations has involved protons as the source of charge. Nonetheless, using metal ions as charge sources often offers advantages like stabilization of the structure via multidentate coordination and the elimination of the "mobile proton". Moreover, characterization of metal-bound amino acids is of general interest as the interaction of peptide side chains with metal ions in biological systems is known to occur extensively. In the current study, we generate thiyl radicals of cysteine and homocysteine in the gas phase complexed to alkali metal ions. Subsequently, we utilize infrared multiple-photon dissociation (IRMPD) and ion-molecule reactions (IMR) to characterize the structure and reactivity of these radical ions. Our group has worked extensively with the cysteine-based radical cations and anions, characterizing the gas-phase reactivity and rearrangement of the amino acid and several of its derivatives. In a continuation of this work, we are perusing the effects of metal ions as the charge bearing species on the reactivity of the sulfur radical. Our S-nitroso chemistry can easily be used in conjunction with metal ion coordination to produce initial S-based radicals in peptide radical-metal ion complexes. In all cases we have been able to achieve radical formation with significant yield to study reactivity. Ion-molecule reactions of metallated radicals with allyl iodide, dimethyl disulfide, and allyl bromide have all shown decreasing reactivity going down group 1A. Recently, we determined the experimental IR spectra for the homocysteine radical cation with Li+, Na+, and K+ as the charge bearing species at the FELIX facility. For comparison, the protonated IR spectrum of homocysteine has previously been obtained by our group. A preliminary match of the IR spectra has been confirmed. Finally, calculations are underway to determine the bond distances of all the metal adduct structures.

Ultraviolet-B radiation applied to detached peach fruit: A study of free radical generation by EPR spin trapping.

PubMed

Sgherri, C; Scattino, C; Pinzino, C; Tonutti, P; Ranieri, A M

2015-11-01

In peaches, phenolic compounds are the major sources of antioxidants, and cyanidin-3-O-glucoside is the main anthocyanin present, above all in the skin. Anthocyanin content has been shown to increase after UV-B irradiation, which may be very harmful for all biological organisms due to the induction of the generation of reactive oxygen species (ROS). Peach fruits (cv. 'Suncrest') were exposed during post-harvest to supplemental ultraviolet-B radiation. A spin-trapping technique was used to monitor the generation of free radicals under UV-B, and 5-(diethoxy-phosphoryl)-5-methyl-1-pyrroline-N-oxide (DEPMPO) was used as the spin trap. The flesh of peaches was essentially unaffected by the treatment, whereas the skin was responsive at the end of the treatment, accumulating ascorbate, flavonoids, cyanidin-3-O-glucoside, and showing a higher antioxidant activity. The levels of stable free radicals were also lower at the end of treatment. Carbon-centred radicals contributed the most to the total amounts of free radicals, whereas hydroxyl radicals and oxygen-centred free radicals contributed minimally. The carbon-centred free radical identified was the same as the one obtained after irradiation of authentic cyanidin-3-O-glucoside. During UV-B treatment cyanidin-3-O-glucoside increased and was capable of radicalization protecting the other organic molecules of the cell from oxidation. ROS, among which hydroxyl radicals, were thus maintained to minimal levels. This ability of cyanidin-3-O-glucoside displayed the mechanism underlined the tolerance to UV-B irradiation indicating that shelf life can be prolonged by the presence of anthocyanins. Thus, UV-B technique results a good approach to induce antioxidant production in peach fruits increasing their nutraceutical properties. Copyright © 2015. Published by Elsevier Masson SAS.

Catalase Expression Is Modulated by Vancomycin and Ciprofloxacin and Influences the Formation of Free Radicals in Staphylococcus aureus Cultures

PubMed Central

Wang, Ying; Hougaard, Anni B.; Paulander, Wilhelm; Skibsted, Leif H.

2015-01-01

Detection of free radicals in biological systems is challenging due to their short half-lives. We have applied electron spin resonance (ESR) spectroscopy combined with spin traps using the probes PBN (N-tert-butyl-α-phenylnitrone) and DMPO (5,5-dimethyl-1-pyrroline N-oxide) to assess free radical formation in the human pathogen Staphylococcus aureus treated with a bactericidal antibiotic, vancomycin or ciprofloxacin. While we were unable to detect ESR signals in bacterial cells, hydroxyl radicals were observed in the supernatant of bacterial cell cultures. Surprisingly, the strongest signal was detected in broth medium without bacterial cells present and it was mitigated by iron chelation or by addition of catalase, which catalyzes the decomposition of hydrogen peroxide to water and oxygen. This suggests that the signal originates from hydroxyl radicals formed by the Fenton reaction, in which iron is oxidized by hydrogen peroxide. Previously, hydroxyl radicals have been proposed to be generated within bacterial cells in response to bactericidal antibiotics. We found that when S. aureus was exposed to vancomycin or ciprofloxacin, hydroxyl radical formation in the broth was indeed increased compared to the level seen with untreated bacterial cells. However, S. aureus cells express catalase, and the antibiotic-mediated increase in hydroxyl radical formation was correlated with reduced katA expression and catalase activity in the presence of either antibiotic. Therefore, our results show that in S. aureus, bactericidal antibiotics modulate catalase expression, which in turn influences the formation of free radicals in the surrounding broth medium. If similar regulation is found in other bacterial species, it might explain why bactericidal antibiotics are perceived as inducing formation of free radicals. PMID:26150471

Catalase Expression Is Modulated by Vancomycin and Ciprofloxacin and Influences the Formation of Free Radicals in Staphylococcus aureus Cultures.

PubMed

Wang, Ying; Hougaard, Anni B; Paulander, Wilhelm; Skibsted, Leif H; Ingmer, Hanne; Andersen, Mogens L

2015-09-01

Detection of free radicals in biological systems is challenging due to their short half-lives. We have applied electron spin resonance (ESR) spectroscopy combined with spin traps using the probes PBN (N-tert-butyl-α-phenylnitrone) and DMPO (5,5-dimethyl-1-pyrroline N-oxide) to assess free radical formation in the human pathogen Staphylococcus aureus treated with a bactericidal antibiotic, vancomycin or ciprofloxacin. While we were unable to detect ESR signals in bacterial cells, hydroxyl radicals were observed in the supernatant of bacterial cell cultures. Surprisingly, the strongest signal was detected in broth medium without bacterial cells present and it was mitigated by iron chelation or by addition of catalase, which catalyzes the decomposition of hydrogen peroxide to water and oxygen. This suggests that the signal originates from hydroxyl radicals formed by the Fenton reaction, in which iron is oxidized by hydrogen peroxide. Previously, hydroxyl radicals have been proposed to be generated within bacterial cells in response to bactericidal antibiotics. We found that when S. aureus was exposed to vancomycin or ciprofloxacin, hydroxyl radical formation in the broth was indeed increased compared to the level seen with untreated bacterial cells. However, S. aureus cells express catalase, and the antibiotic-mediated increase in hydroxyl radical formation was correlated with reduced katA expression and catalase activity in the presence of either antibiotic. Therefore, our results show that in S. aureus, bactericidal antibiotics modulate catalase expression, which in turn influences the formation of free radicals in the surrounding broth medium. If similar regulation is found in other bacterial species, it might explain why bactericidal antibiotics are perceived as inducing formation of free radicals. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

The effect of laparotomy on hydroxyl radicals, singlet oxygen and antioxidants measured by EPR method in the tails of rats.

PubMed

Fricova, Jitka; Stopka, Pavel; Krizova, Jana; Yamamotova, Anna; Rokyta, Richard

2009-01-01

The aim of the study was to demonstrate that direct measurement of hydroxyl radicals and singlet oxygen in the tail of living rats is possible. The basic level of hydroxyl radicals and singlet oxygen were measured and the effects of antioxidants on their levels were studied in the tail of living anaesthetized rats after acute postoperative pain. Laparotomy was performed as the source of acute abdominal pain. After closure of the abdominal cavity, the animals began to awaken within 30-60 minutes. They were left to recover for 2-3 hours; then they were reanesthetized and the effect of antioxidants was measured on the numbers of hydroxyl radicals and singlet oxygen via blood in the tail. The laparotomy was preformed under general anesthesia (Xylazin and Ketamin) using Wistar rats. After recovery and several hours of consciousness they were reanaesthetized and free radicals and singlet oxygen were measured. An antioxidant mixture (vitamins A, C, D and Selenium) was administered intramuscularly prior to the laparotomy. All measurements were done on the tail of anaesthetized animals. In this particular article, the effect of antioxidants is only reported for hydroxyl radicals. After laparotomy, which represented both somatic and visceral pain, hydroxyl radicals and singlet oxygen were increased. Antioxidant application prior to laparotomy decreased the numbers of hydroxyl radicals. Results are in agreement with our previous finding regarding the increase in hydroxyl free radicals and singlet oxygen following nociceptive stimulation, in this case a combination of both somatic and visceral pain. The administered antioxidants mitigated the increase. This is further confirmation that direct measurement of free radicals and singlet oxygen represents a very useful method for the biochemical evaluation of pain and nociception.

Improvement of catalytic performance of lignin peroxidase for the enhanced degradation of lignocellulose biomass based on the imbedded electron-relay in long-range electron transfer route.

PubMed

Pham, Le Thanh Mai; Kim, Su Jin; Kim, Yong Hwan

2016-01-01

Although lignin peroxidase is claimed as a key enzyme in enzyme-catalyzed lignin degradation, in vitro enzymatic degradation of lignin was not easily observed in lab-scale experiments. It implies that other factors may hinder the enzymatic degradation of lignin. Irreversible interaction between phenolic compound and lignin peroxidase was hypothesized when active enzyme could not be recovered after the reaction with degradation product (guaiacol) of lignin phenolic dimer. In the study of lignin peroxidase isozyme H8 from white-rot fungi Phanerochaete chrysosporium (LiPH8), W251 site was revealed to make the covalent coupling with one moiety of monolignolic radical (guaiacol radical) by LC-MS/MS analysis. Hypothetical electron-relay containing W251 residue was newly suggested based on the observation of repressed radical coupling and remarkably lower electron transfer rate for W215A mutant. Furthermore, the retardation of the suicidal radical coupling between the W251 residue and the monolignolic radical was attempted by supplementing the acidic microenvironment around the W251 residue to engineer radical-robust LiPH8. Among many mutants, mutant A242D showed exceptional catalytic performances by yielding 21.1- and 4.9-fold higher increases of k cat and k cat /K M values, respectively, in the oxidation of non-phenolic model lignin dimer. A mechanism-based suicide inhibition of LiPH8 by phenolic compounds was firstly revealed and investigated in this work. Radical-robust LiPH8 was also successfully engineered by manipulating the transient radical state of radical-susceptible electron-relay. Radical-robust LiPH8 will play an essential role in degradation of lignin, which will be consequently linked with improved production of sugars from lignocellulose biomass.

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

PubMed Central

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

2008-01-01

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

The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buckingham, Grant T.; Ormond, Thomas K.; National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401

2015-01-28

The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C{sub 6}H{sub 5}CH{sub 2}, as well as a set of isotopically labeled radicals: C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C{sub 5}H{submore » 4}=C=CH{sub 2}, H atom, C{sub 5}H{sub 4}—C ≡ CH, C{sub 5}H{sub 5}, HCCCH{sub 2}, and HC ≡ CH. Pyrolysis of the C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2} benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C{sub 6}H{sub 5}CH{sub 2}⇋C{sub 7}H{sub 7}. These labeling studies suggest that there must be other thermal decomposition routes for the C{sub 6}H{sub 5}CH{sub 2} radical that differ from the fulvenallene pathway.« less

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

PubMed

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

2018-01-01

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

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

PubMed

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

2011-04-07

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

Contemporary Radical Economics.

ERIC Educational Resources Information Center

Sherman, Howard J.

1984-01-01

The origins of contemporary radical economics are examined. Applications of radical economics to price and value theory, labor segmentation theory, business cycles, industrial organization, government and business, imperialism and development, and comparative systems are reviewed. (Author/RM)

Monolignol radical-radical coupling networks in western red cedar and Arabidopsis and their evolutionary implications

NASA Technical Reports Server (NTRS)

Kim, Myoung K.; Jeon, Jae-Heung; Davin, Laurence B.; Lewis, Norman G.

2002-01-01

The discovery of a nine-member multigene dirigent family involved in control of monolignol radical-radical coupling in the ancient gymnosperm, western red cedar, suggested that a complex multidimensional network had evolved to regulate such processes in vascular plants. Accordingly, in this study, the corresponding promoter regions for each dirigent multigene member were obtained by genome-walking, with Arabidopsis being subsequently transformed to express each promoter fused to the beta-glucuronidase (GUS) reporter gene. It was found that each component gene of the proposed network is apparently differentially expressed in individual tissues, organs and cells at all stages of plant growth and development. The data so obtained thus further support the hypothesis that a sophisticated monolignol radical-radical coupling network exists in plants which has been highly conserved throughout vascular plant evolution.

EPR spin trapping of oxygen radicals in plants: a methodological overview.

PubMed

Bacić, Goran; Mojović, Milos

2005-06-01

We present a brief account of the difficulties involved in detection of oxygen free radicals in plants and give a rationale for using the EPR spin trapping technique in such studies. Comparative analysis of characteristics of different spin traps is given, having in mind their suitability in trapping oxygen-centered free radicals. Certain technical aspects of EPR experiments related to successful trapping of free radicals are discussed. Previous studies of trapping of oxygen radicals in plants are reviewed in terms of how efficient the experimental approach employed has been in their detection and how this influences conclusions about the mechanisms of their production. In addition, we analyze the potential of spin labels in the analysis of free radical production in plants and demonstrate that the combination of EPR spin traps and spin labels is extremely efficient for this purpose.

Free Radical Scavenging and Cellular Antioxidant Properties of Astaxanthin.

PubMed

Dose, Janina; Matsugo, Seiichi; Yokokawa, Haruka; Koshida, Yutaro; Okazaki, Shigetoshi; Seidel, Ulrike; Eggersdorfer, Manfred; Rimbach, Gerald; Esatbeyoglu, Tuba

2016-01-14

Astaxanthin is a coloring agent which is used as a feed additive in aquaculture nutrition. Recently, potential health benefits of astaxanthin have been discussed which may be partly related to its free radical scavenging and antioxidant properties. Our electron spin resonance (ESR) and spin trapping data suggest that synthetic astaxanthin is a potent free radical scavenger in terms of diphenylpicryl-hydrazyl (DPPH) and galvinoxyl free radicals. Furthermore, astaxanthin dose-dependently quenched singlet oxygen as determined by photon counting. In addition to free radical scavenging and singlet oxygen quenching properties, astaxanthin induced the antioxidant enzyme paroxoanase-1, enhanced glutathione concentrations and prevented lipid peroxidation in cultured hepatocytes. Present results suggest that, beyond its coloring properties, synthetic astaxanthin exhibits free radical scavenging, singlet oxygen quenching, and antioxidant activities which could probably positively affect animal and human health.

Free Radical Scavenging and Cellular Antioxidant Properties of Astaxanthin

PubMed Central

Dose, Janina; Matsugo, Seiichi; Yokokawa, Haruka; Koshida, Yutaro; Okazaki, Shigetoshi; Seidel, Ulrike; Eggersdorfer, Manfred; Rimbach, Gerald; Esatbeyoglu, Tuba

2016-01-01

Astaxanthin is a coloring agent which is used as a feed additive in aquaculture nutrition. Recently, potential health benefits of astaxanthin have been discussed which may be partly related to its free radical scavenging and antioxidant properties. Our electron spin resonance (ESR) and spin trapping data suggest that synthetic astaxanthin is a potent free radical scavenger in terms of diphenylpicryl-hydrazyl (DPPH) and galvinoxyl free radicals. Furthermore, astaxanthin dose-dependently quenched singlet oxygen as determined by photon counting. In addition to free radical scavenging and singlet oxygen quenching properties, astaxanthin induced the antioxidant enzyme paroxoanase-1, enhanced glutathione concentrations and prevented lipid peroxidation in cultured hepatocytes. Present results suggest that, beyond its coloring properties, synthetic astaxanthin exhibits free radical scavenging, singlet oxygen quenching, and antioxidant activities which could probably positively affect animal and human health. PMID:26784174

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Tropospheric reactions of the haloalkyl radicals formed from hydroxyl radical reaction with a series of alternative fluorocarbons

NASA Technical Reports Server (NTRS)

Atkinson, Roger

1990-01-01

In the present assessment, the hydrogen containing halocarbons being considered as alternatives to the the presently used chlorofluorocarbons are the hydrochlorofluorocarbons (HCFCs) 123 (CF3CHCl2), 141b (CFCl2CH3), 142b (CF2ClCH3), 22 (CHF2Cl) and 124 (CF3CHFCl) and the hydrofluorocarbons (HFCs) 134a (CF3CH2F), 152a (CHF2CH3) and 125 (CF3CHF2). All of these HCFCs and HFCs will react with the hydroxyl (OH) radical in the troposphere, giving rise to haloalkyl radicals which then undergo a complex series of reactions in the troposphere. These reactions of the haloalkyl radicals formed from the initial OH radical reactions with the HCFCs and HFCs under tropospheric conditions are the focus here.

Study of Wastewater Treatment by OH Radicals Using DC and Pulsed Corona Discharge over Water

NASA Astrophysics Data System (ADS)

Tochikubo, Fumiyoshi; Furuta, Yasutomo; Uchida, Satoshi; Watanabe, Tsuneo

2006-04-01

Water treatment by OH radicals is studied using dc and pulsed corona discharge over water at atmospheric pressure and reduced pressure. In particular, we pay attention to the influence of discharge configuration on the efficiency of wastewater treatment. Experiment is carried out in N2 to clarify the contribution of OH radicals. Needle-cylinder electrodes are designed expecting the efficient generation of OH radicals close to the water surface. N,N-dimethyl- p-nitrosoaniline (RNO) solution is used as a persistent test pollutant. The results strongly suggest that OH radical production close to the water surface is a key factor for efficient wastewater treatment. The use of pulsed discharge at reduced pressure is effective in improving RNO reduction efficiency because of the rapid diffusion of OH radicals to the water surface.

Photochemical Kinetics of a Phosphine Oxide Free Radical Initiator from Femtosecond UV-Pump/Mid-IR-Probe Spectroscopy.

PubMed

Straub, Steffen; Lindner, Jörg; Vöhringer, Peter

2017-07-06

Femtosecond UV-pump/mid-infrared-probe spectroscopy was used to explore in detail the primary photochemical events of the free radical initiator, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, in liquid dichloromethane solution at room temperature. Following electronic excitation of its lowest excited singlet state, S 1 , the radical initiator undergoes an intersystem crossing to the triplet ground state, T 1 , with a time constant of 135 ps. A subsequent α-cleavage occurs from the triplet state with a time constant of 15 ps and yields a trimethylbenzoyl radical together with a diphenylphosphinoyl radical. Transient absorptions from the S 1 and T 1 states are observed that can be assigned to the P═O stretching mode and the symmetric in-plane deformation mode of the trimethylphenyl moiety of the radical initiator.

IRON AND FREE RADICAL OXIDATIONS IN CELL MEMBRANES

PubMed Central

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

Oxidative stress induces protein and DNA radical formation in follicular dendritic cells (FDCs) of the germinal center and modulates its cell death patterns in late sepsis

PubMed Central

Chatterjee, Saurabh; Lardinois, Olivier; Bhattacharjee, Suchandra; Tucker, Jeff; Corbett, Jean; Deterding, Leesa; Ehrenshaft, Marilyn; Bonini, Marcelo; Mason, Ronald P.

2011-01-01

Profound depletion of follicular dendritic cells (FDCs) is a hallmark of sepsis-like syndrome, but the exact causes for the ensuing cell death are unknown. The cell death-driven depletion contributes to immunoparalysis and is responsible for most of the morbidity and mortality in sepsis. Here we have utilized immuno-spin trapping, a method for detection of free radical formation, to detect oxidative stress-induced protein and DNA radical adducts in FDCs isolated from the spleen of septic mice and human tonsil-derived HK cells, a subtype of germinal center FDCs, to study their role in FDC depletion. At 24 h post-LPS administration, protein radical formation and oxidation was significantly elevated in vivo and in HK cells as shown by ELISA and confocal microscopy. The xanthine oxidase inhibitor allopurinol and the iron chelator desferrioxamine significantly decreased the formation of protein radicals, suggesting the role of xanthine oxidase and Fenton-like chemistry in radical formation. Protein and DNA radical formation correlated mostly with apoptotic features at 24 h and necrotic morphology of all the cell types studied at 48 h with concomitant inhibition of caspase-3. The cytotoxity of FDCs resulted in decreased CD45R/CD138+ve plasma cell numbers, indicating a possible defect in B cell differentiation. In one such mechanism, radical formation initiated by xanthine oxidase formed protein and DNA radicals which may lead to cell death of germinal center FDCs. PMID:21215311

Vibrational Excitation of Both Products of the Reaction of CN Radicals with Acetone in Solution

PubMed Central

2015-01-01

Transient electronic and vibrational absorption spectroscopy unravel the mechanisms and dynamics of bimolecular reactions of CN radicals with acetone in deuterated chloroform solutions. The CN radicals are produced by ultrafast ultraviolet photolysis of dissolved ICN. Two reactive forms of CN radicals are distinguished by their electronic absorption bands: “free” (uncomplexed) CN radicals, and “solvated” CN radicals that are complexed with solvent molecules. The lifetimes of the free CN radicals are limited to a few picoseconds following their photolytic production because of geminate recombination to ICN and INC, complexation with CDCl3 molecules, and reaction with acetone. The acetone reaction occurs with a rate coefficient of (8.0 ± 0.5) × 1010 M–1 s–1 and transient vibrational spectra in the C=N and C=O stretching regions reveal that both the nascent HCN and 2-oxopropyl (CH3C(O)CH2) radical products are vibrationally excited. The rate coefficient for the reaction of solvated CN with acetone is 40 times slower than for free CN, with a rate coefficient of (2.0 ± 0.9) × 109 M–1 s–1 obtained from the rise in the HCN product v1(C=N stretch) IR absorption band. Evidence is also presented for CN complexes with acetone that are more strongly bound than the CN–CDCl3 complexes because of CN interactions with the carbonyl group. The rates of reactions of these more strongly associated radicals are slower still. PMID:26192334

[Effects of vitamin E and selenium on the metabolism of free radicals in broilers].

PubMed

Xu, Jian-Xiong; Wang, Jing; Wang, Tian

2007-08-01

Taking 200 healthy broilers at 14 d of age as test materials, the free radicals in their blood and tissues were detected by electron spin resonance (ESR) and biochemical methods, aimed to investigate the effects of vitamin E (V(E)) and selenium (Se) on the metabolism of different free radicals and their dynamic changes in the broilers. The results showed that the content of NO free radicals in broilers tissues decreased with increasing supplementing level of V(E), while high supplementation of Se tended to induce the production of NO free radicals. High supplementation of V(E) and Se in feeds improved the GSH-Px and SOD activities in broilers serum and liver significantly. With the extension of experimental period, the SOD activity in tissues decreased, while GSH-PX activity increased gradually, implying that the deficiency of V(E) and/or Se might induce the overproduction of O2*- and H2O2 free radicals. H2O2 free radicals might be produced largely at early stage of V(E) and Se deficiency and declined then, while the over-production of O2*- free radicals could maintain for a long time. The deficiency of V(E) and/or Se could improve the MDA content significantly, and Se deficiency had higher effects than V(E) deficiency. There were synergic effects in the metabolism of NO, O2 and H2O2 free radicals.

Inhibitory activities of soluble and bound millet seed phenolics on free radicals and reactive oxygen species.

PubMed

Chandrasekara, Anoma; Shahidi, Fereidoon

2011-01-12

Oxidative stress, caused by reactive oxygen species (ROS), is responsible for modulating several pathological conditions and aging. Soluble and bound phenolic extracts of commonly consumed millets, namely, kodo, finger (Ravi), finger (local), foxtail, proso, little, and pearl, were investigated for their phenolic content and inhibition of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and ROS, namely, hydroxyl radical, peroxyl radical, hydrogen peroxide (H(2)O(2)), hypochlorous acid (HOCl), and singlet oxygen ((1)O(2)). Inhibition of DPPH and hydroxyl radicals was detrmined using electron paramagnetic resonance (EPR) spectroscopy. The peroxyl radical inhibitory activity was measured using the oxygen radical absorbance capacity (ORAC) assay. The scavenging of H(2)O(2), HOCl, and (1)O(2) was evaluated using colorimetric methods. The results were expressed as micromoles of ferulic acid equivalents (FAE) per gram of grain on a dry weight basis. In addition, major hydroxycinnamic acids were identified and quantified using high-performance liquid chromatography (HPLC) and HPLC-mass spectrometry (MS). All millet varieties displayed effective radical and ROS inhibition activities, which generally positively correlated with phenolic contents, except for hydroxyl radical. HPLC analysis revealed the presence of ferulic and p-coumaric acids as major hydroxycinnamic acids in phenolic extract and responsible for the observed effects. Bound extracts of millet contributed 38-99% to ROS scavenging, depending on the variety and the test system employed. Hence, bound phenolics must be included in the evaluation of the antioxidant activity of millets and other cereals.

The Inversion Effect for Chinese Characters is Modulated by Radical Organization.

PubMed

Luo, Canhuang; Chen, Wei; Zhang, Ye

2017-06-01

In studies of visual object recognition, strong inversion effects accompany the acquisition of expertise and imply the involvement of configural processing. Chinese literacy results in sensitivity to the orthography of Chinese characters. While there is some evidence that this orthographic sensitivity results in an inversion effect, and thus involves configural processing, that processing might depend on exact orthographic properties. Chinese character recognition is believed to involve a hierarchical process, involving at least two lower levels of representation: strokes and radicals. Radicals are grouped into characters according to certain types of structure, i.e. left-right structure, top-bottom structure, or simple characters with only one radical by itself. These types of radical structures vary in both familiarity, and in hierarchical level (compound versus simple characters). In this study, we investigate whether the hierarchical-level or familiarity of radical-structure has an impact on the magnitude of the inversion effect. Participants were asked to do a matching task on pairs of either upright or inverted characters with all the types of structure. Inversion effects were measured based on both reaction time and response sensitivity. While an inversion effect was observed in all 3 conditions, the magnitude of the inversion effect varied with radical structure, being significantly larger for the most familiar type of structure: characters consisting of 2 radicals organized from left to right. These findings indicate that character recognition involves extraction of configural structure as well as radical processing which play different roles in the processing of compound characters and simple characters.

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

PubMed

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

2010-09-01

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

Radical scavenging activity of lipophilized products from lipase-catalyzed transesterification of triolein with cinnamic and ferulic acids.

PubMed

Choo, Wee-Sim; Birch, Edward John

2009-02-01

Lipase-catalyzed transesterification of triolein with cinnamic and ferulic acids using an immobilized lipase from Candida antarctica (E.C. 3.1.1.3) was conducted to evaluate the antioxidant activity of the lipophilized products as model systems for enhanced protection of unsaturated oil. The lipophilized products were identified using ESI-MS. Free radical scavenging activity was determined using the DPPH radical method. The polarity of the solvents proved important in determining the radical scavenging activity of the substrates. Ferulic acid showed much higher radical scavenging activity than cinnamic acid, which has limited activity. The esterification of cinnamic acid and ferulic acid with triolein resulted in significant increase and decrease in the radical scavenging activity, respectively. These opposite effects were due to the effect of addition of electron-donating alkyl groups on the predominant mechanism of reaction (hydrogen atom transfer or electron transfer) of a species with DPPH. The effect of esterification of cinnamic acid was confirmed using ethyl cinnamate which greatly enhances the radical scavenging activity. Although, compared to the lipophilized cinnamic acid product, the activity was lower. The radical scavenging activity of the main component isolated from lipophilized cinnamic acid product using solid phase extraction, monocinnamoyl dioleoyl glycerol, was as good as the unseparated mixture of lipophilized product. Based on the ratio of a substrate to DPPH concentration, lipophilized ferulic acid was a much more efficient radical scavenger than lipophilized cinnamic acid.

The formation of DNA sugar radicals from photoexcitation of guanine cation radicals.

PubMed

Shukla, Lata I; Pazdro, Robert; Huang, James; DeVreugd, Christopher; Becker, David; Sevilla, Michael D

2004-05-01

In this investigation of radical formation and reaction in gamma- irradiated DNA and model compounds, we report the conversion of the guanine cation radical (one-electron oxidized guanine, G(.+)) to the C1' sugar radical and another sugar radical at the C3' or C4' position (designated C3'(.)/C4'(.)) by visible and UV photolysis. Electron spin resonance (ESR) spectroscopic investigations were performed on salmon testes DNA as well as 5'-dGMP, 3'-dGMP, 2'-deoxyguanosine and other nucleosides/nucleotides as model systems. DNA samples (25- 150 mg/ml D(2)O) were prepared with Tl(3+) or Fe(CN)(3-)(6) as electron scavengers. Upon gamma irradiation of such samples at 77 K, the electron-gain path in the DNA is strongly suppressed and predominantly G(.+) is found; after UV or visible photolysis, the fraction of the C1' sugar radical increases with a concomitant reduction in the fraction of G(.+). In model systems, 3'- dGMP(+.) and 5'-dGMP(+.) were produced by attack of Cl(.-)(2) on the parent nucleotide in 7 M LiCl glass. Subsequent visible photolysis of the 3'-dGMP(+.) (77 K) results predominantly in formation of C1'(.) whereas photolysis of 5'-dGMP(+.) results predominantly in formation of C3'(.)/C4'(.). We propose that sugar radical formation is a result of delocalization of the hole in the electronically excited base cation radical into the sugar ring, followed by deprotonation at specific sites on the sugar.

Observation and modelling of the OH, HO_{2} and RO_{2} radicals at a suburban site of Beijing (Huairou) in winter 2016

NASA Astrophysics Data System (ADS)

Tan, Zhaofeng; Lu, Keding; Ma, Xuefei; Birger, Bohn; Broch, Sebastian; Fuchs, Hendrik; Hofzumahaus, Andreas; Holland, Frank; Li, Xin; Liu, Yuhan; Novelli, Anna; Rohrer, Franz; Shao, Min; Wang, Haichao; Wu, Yusheng; Zeng, Limin; Kiendler-Scharr, Astrid; Wahner, Andreas; Zhang, Yuanhang

2017-04-01

A comprehensive field campaign was carried out in winter 2016 in Huairou, a small town located 60 km northeast of Beijing downtown. Concentrations of OH, HO2and RO2 radicals were measured by a laser induced fluorescence instrument. Radical concentrations were smaller than during summer because of reduced solar radiation. 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. Chemical modulation measurements were applied on a few days showing no significant OH interference for different chemical conditions. HONO and HCHO photolysis were found to be the most important primary source of ROx radicals. OH reactivity, the inverse of the OH radical lifetime, was also measured by a laser-photolysis and laser induced fluorescence instrument. In general, CO and NOx were the dominated 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 products. The observed radical concentrations were compared with the results from a chemical box model. The model is capable of reproducing radical concentrations in the moderate NOx conditions but has difficulty in both the low and high NOx regimes. The underestimation of RO2 radical concentrations in the high NOx conditions indicate a missing RO2 source.

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling.

PubMed

Dubnikova, Faina; Tamburu, Carmen; Lifshitz, Assa

2016-09-29

The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates.

PubMed

Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir

2018-03-01

A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser induced photoluminescence spectroscopy of cometary radicals

NASA Technical Reports Server (NTRS)

Jackson, W. M.; Cody, R. J.; Sabety-Dzvonik, M.

1976-01-01

Flash photolysis together with laser excitation of the product fragments was used in laboratory studies of cometary radicals. The LIPS method has been applied to the CN radical to determine: (1) Radiative lifetimes of individual rotational levels in the zeroth vibrational level of the B state; (2) energy partitioning during photodissociation of C2N2; and (3) vibrational and rotational excitation during formation of CN radicals in the photodissociation of dicyanoacetylene.

Metabolic Activation of Sulfur Mustard Leads to Oxygen Free Radical Formation

DTIC Science & Technology

2012-01-01

spin trapping results that demonstrated the enzymatic reduction of sulfur mustard sulfonium ions to carbon-based free radicals using an in vitro system ...BMPO EPR signals were reduced or eliminated when mustard carbon radical production was impeded by systematically removing system components, indicating...referred to as complete incubation mixture. EPR spectrometry Mustard-related carbon or oxygen free radical production was recorded using a Bruker EMX Plus

Hypochlorite-induced damage to proteins: formation of nitrogen-centred radicals from lysine residues and their role in protein fragmentation.

PubMed Central

Hawkins, C L; Davies, M J

1998-01-01

Stimulated monocytes and neutrophils generate hypochlorite (HOCl) via the release of the enzyme myeloperoxidase and hydrogen peroxide. HOCl damages proteins by reaction with amino acid side-chains or backbone cleavage. Little information is available about the mechanisms and intermediates involved in these reactions. EPR spin trapping has been employed to identify radicals on proteins, peptides and amino acids after treatment with HOCl. Reaction with HOCl gives both high- and low-molecular-mass nitrogen-centred, protein-derived radicals; the yield of the latter increases with both higher HOCl:protein ratios and enzymic digestion. These radicals, which arise from lysine side-chain amino groups, react with ascorbate, glutathione and Trolox. Reaction of HOCl-treated proteins with excess methionine eliminates radical formation, which is consistent with lysine-derived chloramines (via homolysis of N-Cl bonds) being the radical source. Incubation of HOCl-treated proteins, after removal of excess oxidant, gives rise to both nitrogen-centred radicals, over a period of hours, and time-dependent fragmentation of the protein. Treatment with excess methionine or antioxidants (Trolox, ascorbate, glutathione) protects against fragmentation; urate and bilirubin do not. Chloramine formation and nitrogen-centred radicals are therefore key species in HOCl-induced protein fragmentation. PMID:9620862

Expanding the Chemistry of the Class C Radical SAM Methyltransferase NosN by Using an Allyl Analogue of SAM.

PubMed

Ji, Xinjian; Mandalapu, Dhanaraju; Cheng, Jinduo; Ding, Wei; Zhang, Qi

2018-03-30

The radical S-adenosylmethionine (SAM) superfamily enzymes cleave SAM reductively to generate a highly reactive 5'-deoxyadenosyl (dAdo) radical, which initiates remarkably diverse reactions. Unlike most radical SAM enzymes, the class C radical SAM methyltransferase NosN binds two SAMs in the active site, using one SAM to produce a dAdo radical and the second as a methyl donor. Here, we report a mechanistic investigation of NosN in which an allyl analogue of SAM (allyl-SAM) was used. We show that NosN cleaves allyl-SAM efficiently and the resulting dAdo radical can be captured by the olefin moieties of allyl-SAM or 5'-allylthioadenosine (ATA), the latter being a derivative of allyl-SAM. Remarkably, we found that NosN produced two distinct sets of products in the presence and absence of the methyl acceptor substrate, thus suggesting substrate-triggered production of ATA from allyl-SAM. We also show that NosN produces S-adenosylhomocysteine from 5'-thioadenosine and homoserine lactone. These results support the idea that 5'-methylthioadenosine is the direct methyl donor in NosN reactions, and demonstrate great potential to modulate radical SAM enzymes for novel catalytic activities. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

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

2017-06-01

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

Photochemical synthesis of simple organic free radicals on simulated planetary surfaces - An ESR study

NASA Technical Reports Server (NTRS)

Tseng, S.-S.; Chang, S.

1975-01-01

Electron spin resonance (ESR) spectroscopy provided evidence for formation of hydroxyl radicals during ultraviolet photolysis (254 nm) at -170 C of H2O adsorbed on silica gel or of silica gel alone. The carboxyl radical was observed when CO or CO2 or a mixture of CO and CO2 adsorbed on silica gel at -170 C was irradiated. The ESR signals of these radicals slowly disappeared when the irradiated samples were warmed to room temperature. However, reirradiation of CO or CO2, or the mixture CO and CO2 on silica gel at room temperature then produced a new species, the carbon dioxide anion radical, which slowly decayed and was identical with that produced by direct photolysis of formic acid adsorbed on silica gel. The primary photochemical process may involve formation of hydrogen and hydroxyl radicals. Subsequent reactions of these radicals with adsorbed CO or CO2 or both yield carboxyl radicals, CO2H, the precursors of formic acid. These results confirm the formation of formic acid under simulated Martian conditions and provide a mechanistic basis for gauging the potential importance of gas-solid photochemistry for chemical evolution on other extraterrestrial bodies, on the primitive earth, and on dust grains in the interstellar medium.

Kinetic studies of retinol addition radicals.

PubMed

El-Agamey, Ali; Fukuzumi, Shunichi; Naqvi, K Razi; McGarvey, David J

2011-03-07

Retinol neutral radicals (RS-retinol˙), generated from the reaction of retinol with 4-pyridylthiyl and 2-pyridylthiyl radicals in argon-saturated methanol, undergo β-elimination, which can be monitored via the slow secondary absorption rise at 380 nm attributed to the rearrangement of the unstable retinol neutral addition radicals to the more stable addition radicals. Rate constants for the β-elimination reactions (k(β)) of 4-PyrS-retinol˙ were measured at different temperatures and the Arrhenius equation for the reaction is described by log (k(β)/s(-1)) = (12.7 ± 0.2) - (54.3 ± 1.3)/θ, where θ = 2.3RT kJ mol(-1). The reactivities of retinol addition radicals (RS-retinol˙), generated from the reaction of retinol with various thiyl radicals, towards oxygen have also been investigated in methanol. In the presence of oxygen, the decay of RS-retinol˙ fits to biexponential kinetics and both observed rate constants for the RS-retinol˙ decay are oxygen-concentration dependent. This suggests that at least two thiyl addition radicals, formed from the reaction of RS˙ with retinol, undergo oxygen addition reactions. In light of the estimated rate constants for oxygen addition to RS-retinol˙ and RS-CAR˙ (CAR: carotenoid), the antioxidant-prooxidant properties of retinol are discussed.

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

PubMed

Masood, Nusrat; Fatima, Kaneez; Luqman, Suaib

2014-01-01

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

Combined chemical and mechanical effects on free radicals in UHMWPE joints during implantation.

PubMed

Jahan, M S; Wang, C; Schwartz, G; Davidson, J A

1991-08-01

An electron spin resonance (ESR) technique is employed to determine the free radical distribution in the articulating surfaces of retrieved acetabular cups and knee-joint plateaus (retrieved after more than 6 years of implantation). Similar measurements made on samples prepared from cyclically stressed and unstressed cups, and on samples following oxidations in nitric acid and intralipid solutions provided sufficient data to gain more knowledge about the combined chemical and mechanical effects on PE free radicals during implantation. In UHMWPE free radicals are primarily initiated by gamma-ray sterilization; however, during implantation, peroxy (scission type) free radicals are formed and reach a maximum concentration level (equilibrium state) due to oxidation by chemical (hemoglobin and/or synovial fluids) environment of the joints. Subsequently, due to frictional heating and stress in the loading zones, free radical reaction is accelerated and their number is reduced only in those areas. This is consistent with the observations of a temperature rise in acetabular cups during in vitro frictional wear stress tests and in vivo telemetry observations, as reported by others. Compared with the previously reported SEM micrographs the low-free-radical regions are correlated with high-wear areas and the high-free-radical regions with the low-wear areas.

Spectroscopic Identification of Isomeric Trimethylbenzyl Radicals Generated in Corona Discharge of Tetramethylbenzene

NASA Astrophysics Data System (ADS)

Yoon, Young Wook; Lee, Sang Kuk; Lee, Gi Woo

2011-06-01

The visible vibronic emission spectra were recorded from the corona discharge of precursor tetramethylbenzene with a large amount of inert carrier gas helium using a pinhole-type glass nozzle coupled with corona excited supersonic expansion (CESE) well developed in this laboratory. The spectra showed a series of vibronic bands in the D_1 → D_0 electronic transition of jet-cooled benzyl-type radicals formed from the precursor in a corona excitation. The analysis confirmed that two isomeric radicals, 2,3,4- and 2,3,6-trimethylbenzyl radicals and three isomeric radicals, 3,4,5-, 2,3,5- and 2,4,6-trimethylbenzyl radicals were produced, respectively, from 1,2,3,4- and 1,2,3,5-tetramethylbenzenes as a result of removal of a hydrogen atom from the methyl group at different substitution position. For each isomeric trimethylbenzyl radical generated in the corona discharge of precursor, the electronic transition and a few vibrational mode frequencies were determined in the ground electronic state by comparing with those from both ab initio calculations and the known vibrational data of the precursor. The substitution effect that states the shift of electronic transition depends on the nature, the number, and the position of substituents on the ring has been qualitatively proved for the case of benzyl-type radicals.

The Interaction between Central and Peripheral Processing in Chinese Handwritten Production: Evidence from the Effect of Lexicality and Radical Complexity

PubMed Central

Zhang, Qingfang; Feng, Chen

2017-01-01

The interaction between central and peripheral processing in written word production remains controversial. This study aims to investigate whether the effects of radical complexity and lexicality in central processing cascade into peripheral processing in Chinese written word production. The participants were asked to write characters and non-characters (lexicality) with different radical complexity (few- and many-strokes). The findings indicated that regardless of the lexicality, the writing latencies were longer for characters with higher complexity (the many-strokes condition) than for characters with lower complexity (the few-strokes condition). The participants slowed down their writing execution at the radicals' boundary strokes, which indicated a radical boundary effect in peripheral processing. Interestingly, the lexicality and the radical complexity affected the pattern of shift velocity and writing velocity during the execution of writing. Lexical processing cascades into peripheral processing but only at the beginning of Chinese characters. In contrast, the radical complexity influenced the execution of handwriting movement throughout the entire character, and the pattern of the effect interacted with the character frequency. These results suggest that the processes of the lexicality and the radical complexity function during the execution of handwritten word production, which suggests that central processing cascades over peripheral processing during Chinese characters handwriting. PMID:28348536

Are free radicals involved in thiol-based redox signaling?

PubMed

Winterbourn, Christine C

2015-03-01

Cells respond to many stimuli by transmitting signals through redox-regulated pathways. It is generally accepted that in many instances signal transduction is via reversible oxidation of thiol proteins, although there is uncertainty about the specific redox transformations involved. The prevailing view is that thiol oxidation occurs by a two electron mechanism, most commonly involving hydrogen peroxide. Free radicals, on the other hand, are considered as damaging species and not generally regarded as important in cell signaling. This paper examines whether it is justified to dismiss radicals or whether they could have a signaling role. Although there is no direct evidence that radicals are involved in transmitting thiol-based redox signals, evidence is presented that they are generated in cells when these signaling pathways are activated. Radicals produce the same thiol oxidation products as two electron oxidants, although by a different mechanism, and at this point radical-mediated pathways should not be dismissed. There are unresolved issues about how radical mechanisms could achieve sufficient selectivity, but this could be possible through colocalization of radical-generating and signal-transducing proteins. Colocalization is also likely to be important for nonradical signaling mechanisms and identification of such associations should be a priority for advancing the field. Copyright © 2014 Elsevier Inc. All rights reserved.

Pulse radiolytic study of the oxidation reactions of uric acid in presence of bovine serum albumin. Evidence of possible complex formation in the transient state

NASA Astrophysics Data System (ADS)

Adhikari, S.; Joshi, R.; Gopinathan, C.

1997-01-01

The pulse radiolytic and spectrophotometric study of uric acid in presence of bovine serum albumin (BSA) has been carried out. In the spectrophotometric study there is no evidence for ground state interaction between BSA and uric acid. The oxidation reactions of uric acid in presence and absence of BSA employing CCl 3OO and Br radicals have been carried out. In a composition of equal concentration of uric acid and BSA, the CCl 3OO and Br radicals produce a transient absorption spectrum which show two peaks at 330 and 360 nm. The peak at 360 nm is ascribed due to weak complex formation between semioxidised BSA and uric acid radicals. The rate constant of CCl 3OO . radical with uric acid increases with the increase in BSA concentration which is explained as protection of BSA by uric acid from radical attack. The Br radical attacks uric acid and BSA in a manner similar to CCl 3OO radical. The bimolecular rate constants for the reaction of Br radical with BSA and uric acid have been found as 2.9 × 10 10 dm 3 mol -1 s -1 and 6.33 × 10 9 dm 3 mol -1 s -, respectively.

The reactions of cytidine and 2'-deoxycytidine with SO4.- revisited. Pulse radiolysis and product studies.

PubMed

Aravindakumar, Charuvila T; Schuchmann, Man Nien; Rao, Balijepalli S; von Sonntag, Justus; von Sonntag, Clemens

2003-01-21

The reactions of SO4.- with 2'-deoxycytidine 1a and cytidine 1b lead to very different intermediates (base radicals with 1a, sugar radicals with 1b). The present study provides spectral and kinetic data for the various intermediates by pulse radiolysis as well as information on final product yields (free cytosine). Taking these and literature data into account allows us to substantiate but also modify in essential aspects the current mechanistic concept (H. Catterall, M. J. Davies and B. C. Gilbert, J. Chem. Soc., Perkin Trans. 2, 1992, 1379). SO4.- radicals have been generated radiolytically in the reaction of peroxodisulfate with the hydrated electron (and the H. atom). In the reaction of SO4.- with 1a (k = 1.6 x 10(9) dm3 mol-1 s-1), a transient (lambda max = 400 nm, shifted to 450 nm at pH 3) is observed. This absorption is due to two intermediates. The major component (lambda max approximately 385 nm) does not react with O2 and has been attributed to an N-centered radical 4a formed upon sulfate release and deprotonation at nitrogen. The minor component, rapidly wiped out by O2, must be due to C-centered OH-adduct radical(s) 6a and/or 7a suggested to be formed by a water-induced nucleophilic replacement. These radicals decay by second-order kinetics. Free cytosine is only formed in low yields (G = 0.14 x 10(-7) mol J-1 upon electron-beam irradiation). In contrast, 1b gives rise to an intermediate absorbing at lambda max = 530 nm (shifted to 600 nm in acid solution) which rapidly decays (k = 6 x 10(4) s-1). In the presence of O2, the decay is much faster (k approximately 1.3 x 10(9) dm3 mol-1 s-1) indicating that this species must be a C-centered radical. This has been attributed to the C(5)-yl radical 8 formed upon the reaction of the C(2')-OH group with the cytidine SO4(.-)-adduct radical 2b. This reaction competes very effectively with the corresponding reaction of water and the release of sulfate and a proton generating the N-centered radical. Upon the decay of 8, sugar radical 11 is formed with the release of cytosine. The latter is formed with a G value of 2.8 x 10(-7) mol J-1 (85% of primary SO4.-) at high dose rates (electron beam irradiation). At low dose rates (gamma-radiolysis) its yield is increased to 7 x 10(-7) mol J-1 due to a chain reaction involving peroxodisulfate and reducing free radicals. Phosphate buffer prevents the formation of the sugar radical at the SO4(.-)-adduct stage by enhancing the rate of sulfate release by deprotonation of 2b and also by speeding up the decay of the C(5)-yl radical into another (base) radical. Cytosine release in cytidine is mechanistically related to strand breakage in poly(C). Literature data on the effect of dioxygen on strand breakage yields in poly(C) induced by SO4.- (suppressed) and upon photoionisation (unaltered) lead us to conclude that in poly(C) and also in the present system free radical cations are not involved to a major extent. This conclusion modifies an essential aspect of the current mechanistic concept.

Textbook Forum: Who is Anti-Markovnikov?

ERIC Educational Resources Information Center

Tedder, J. M.

1984-01-01

Discusses factors which control rate and orientation of free radical addition to alkenes. Although based primarily on results involving behavior of alkyl radicals, arguments developed apply to addition of atoms and hetero-radicals to olefins. (JN)

Chain Reaction Polymerization.

ERIC Educational Resources Information Center

McGrath, James E.

1981-01-01

The salient features and importance of chain-reaction polymerization are discussed, including such topics as the thermodynamics of polymerization, free-radical polymerization kinetics, radical polymerization processes, copolymers, and free-radical chain, anionic, cationic, coordination, and ring-opening polymerizations. (JN)

40 CFR 268.40 - Applicability of treatment standards.

Code of Federal Regulations, 2011 CFR

2011-07-01

... chlorinated aliphatic hydrocarbons by free radical catalyzed processes. These chlorinated aliphatic... chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic... production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These...

40 CFR 268.40 - Applicability of treatment standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... chlorinated aliphatic hydrocarbons by free radical catalyzed processes. These chlorinated aliphatic... chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These chlorinated aliphatic... production of certain chlorinated aliphatic hydrocarbons, by free radical catalyzed processes. These...

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

PubMed

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.

Noncanonical Radical SAM Enzyme Chemistry Learned from Diphthamide Biosynthesis.

PubMed

Dong, Min; Zhang, Yugang; Lin, Hening

2018-05-10

Radical S-adenosylmethionine (SAM) enzymes are a superfamily of enzymes that use SAM and reduced [4Fe-4S] cluster to generate a 5'-deoxyadenosyl radical to catalyze numerous challenging reactions. We have reported a type of noncanonical radical SAM enzymes in the diphthamide biosynthesis pathway. These enzymes also use SAM and reduced [4Fe-4S] clusters, but generate a 3-amino-3-carboxypropyl (ACP) radical to modify the substrate protein, translation elongation factor 2. The regioselective cleavage of a different C-S bond of the sulfonium center of SAM in these enzymes comparing to canonical radical SAM enzymes is intriguing. Here, we highlight some recent findings in the mechanism of these types of enzymes, showing that the diphthamide biosynthetic radial SAM enzymes bound SAM with a distinct geometry. In this way, the unique iron of the [4Fe-4S] cluster in the enzyme can only attack the carbon on the ACP group to form an organometallic intermediate. The homolysis of the organometallic intermediate releases the ACP radical and generates the EF2 radial.

Potential for free radical-induced lipid peroxidation as a cause of endothelial cell injury in Rocky Mountain spotted fever.

PubMed Central

Silverman, D J; Santucci, L A

1988-01-01

Cells infected by Rickettsia rickettsii, the causative agent of Rocky Mountain spotted fever, display unusual intracellular morphological changes characterized by dilatation of the membranes of the endoplasmic reticulum and outer nuclear envelope. These changes are consistent with those that might be expected to occur following peroxidation of membrane lipids initiated by oxygen radical species, such as the hydroxyl radical or a variety of organic radicals. Using a fluorescent probe, we have found significantly increased levels of peroxides in human endothelial cells infected by R. rickettsii. Studies with desferrioxamine, an iron chelator effective in preventing formation of the hydroxyl radical from hydrogen peroxide and the superoxide free radical, reduced peroxide levels in infected cells to those found in uninfected cells. This observation suggests that the increased peroxides in infected cells may be lipid peroxides, degradation products of free radical attack on polyenoic fatty acids. The potential for lipid peroxidation as an important mechanism in endothelial cell injury caused by R. rickettsii is discussed. Images PMID:3141280

New free radicals to measure antiradical capacity: a theoretical study.

PubMed

León-Carmona, Jorge Rafael; Martínez, Ana; Galano, Annia

2014-08-28

A new family of free radicals, that are soluble in water and stable at all pH values, were recently synthesized and used to assess the antiradical capacity of several polyphenols. In the present work, density functional calculations were used to investigate the single electron transfer reactions between these new free radicals and polyphenols in aqueous solution. The quantification of the antiradical capacity is a challenge, particularly for polyphenols, since they become unstable under experimental conditions. It was found that the electron transfer from polyphenols to the newly developed free radicals can be used to assess the efficiency of this kind of compound for preventing oxidative stress. Since one of the free radicals can be deprotonated under experimental conditions, this newly synthesized radical can help distinguish more clearly between different antiradical compounds with similar antioxidant capacity by modifying the pH in the experiments. The results reported here are in good agreement with the available experimental data and allowed making recommendations about possible experimental conditions in the design of antioxidant assays using the investigated radicals.

Detection and Quantification of Free Radicals in Peroxisomal Disorders: A Comparative Study with Oxidative Stress Parameters.

PubMed

Abd-Elmaksoud, Sohair Abd-El Mawgood; El-Bassyouni, Hala; Afifi, Hanan; Thomas, Manal Micheal; Ibrahim, Alshaymaa Ahmed; Shalaby, Aliaa; Hamid, Tamer Ahmed Abdel; Hamid, Nehal Abdel; El-Ghobary, Hany

2015-11-01

Free radicals have been thought to participate in pathogenesis of peroxisomal disorders. The aim of the work is to detect free oxide radicals in blood of patients with peroxisomal disorders and to study their relation with various oxidative stress parameters. Twenty patients with peroxisomal disorders and 14 age and sex matched healthy subjects were included in the study. Patients with peroxisomal disorders were subdivided according to diagnosis into peroxisomal biogenesis disorders and single enzyme deficiency. Oxidative stress was evaluated in both patients and control subjects by assessment of free radicals, malondialdehyde, nitric oxide metabolites and superoxide dismutase. There was increase in free radicals, malondialdehyde, nitric oxide metabolites in patients compared with control subjects. However, there was decrease in superoxide dismutase levels in patients compared with control subjects. We concluded that there is excess free radicals production accompanied with decrease in antioxidant defenses in patients with peroxisomal disorders. These results strongly support a role of free radicals in the pathophysiology of peroxisomal disorders and strengthen the importance of oxidative stress phenomenon in peroxisomal disorders pathogenesis.

Site-specific detection of radicals on α-lactalbumin after a riboflavin-sensitized reaction, detected by immuno-spin trapping, ESR, and MS.

PubMed

Dalsgaard, Trine K; Triquigneaux, Mathilde; Deterding, Leesa; Summers, Fiona; Ranguelova, Kalina; Mortensen, Grith; Mason, Ronald P

2013-01-16

Free radicals and other oxidation products were characterized on α-lactalbumin with electron spin resonance (ESR), immuno-spin trapping, and mass spectrometry (MS) after riboflavin-mediated oxidation. Radicals were detected using the spin trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in immuno-spin trapping with both enzyme-linked immunosorbent assay (ELISA) and Western blotting and further characterized with mass spectrometry. A DMPO-trapped radical was identified at His68 and another at one of the tyrosine residues, Tyr50 or Tyr36, respectively, generated by a type II or I mechanism. Not all tyrosyl radicals were trapped, as the secondary oxidation product, 3,4-dihydroxyphenylalanine (DOPA), was detected by mass spectrometry at Tyr18 and Tyr50. A further oxidation of DOPA resulted in the DOPA o-semiquinone radical, which was characterized by ESR. Both surface exposure and the neighboring residues in the local environment of the tertiary structure of α-lactalbumin seem to play a role in the generation of DMPO trapped radicals and secondary oxidation products.

Biosynthetic versatility and coordinated action of 5'-deoxyadenosyl radicals in deazaflavin biosynthesis.

PubMed

Philmus, Benjamin; Decamps, Laure; Berteau, Olivier; Begley, Tadhg P

2015-04-29

Coenzyme F420 is a redox cofactor found in methanogens and in various actinobacteria. Despite the major biological importance of this cofactor, the biosynthesis of its deazaflavin core (8-hydroxy-5-deazaflavin, F(o)) is still poorly understood. F(o) synthase, the enzyme involved, is an unusual multidomain radical SAM enzyme that uses two separate 5'-deoxyadenosyl radicals to catalyze F(o) formation. In this paper, we report a detailed mechanistic study on this complex enzyme that led us to identify (1) the hydrogen atoms abstracted from the substrate by the two radical SAM domains, (2) the second tyrosine-derived product, (3) the reaction product of the CofH-catalyzed reaction, (4) the demonstration that this product is a substrate for CofG, and (5) a stereochemical study that is consistent with the formation of a p-hydroxybenzyl radical at the CofH active site. These results enable us to propose a mechanism for F(o) synthase and uncover a new catalytic motif in radical SAM enzymology involving the use of two 5'-deoxyadenosyl radicals to mediate the formation of a complex heterocycle.

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

PubMed Central

Jin, Hang; Sun, Xin; Huang, Shuo; Zhang, Fu-Liang; Guo, Zhen-Ni

2018-01-01

Acute ischemic stroke is a common cause of morbidity and mortality worldwide. Thrombolysis with recombinant tissue plasminogen activator and endovascular thrombectomy are the main revascularization therapies for acute ischemic stroke. However, ischemia-reperfusion injury after revascularization therapy can result in worsening outcomes. Among all possible pathological mechanisms of ischemia-reperfusion injury, free radical damage (mainly oxidative/nitrosative stress injury) has been found to play a key role in the process. Free radicals lead to protein dysfunction, DNA damage, and lipid peroxidation, resulting in cell death. Additionally, free radical damage has a strong connection with inducing hemorrhagic transformation and cerebral edema, which are the major complications of revascularization therapy, and mainly influencing neurological outcomes due to the disruption of the blood-brain barrier. In order to get a better clinical prognosis, more and more studies focus on the pharmaceutical and nonpharmaceutical neuroprotective therapies against free radical damage. This review discusses the pathological mechanisms of free radicals in ischemia-reperfusion injury and adjunctive neuroprotective therapies combined with revascularization therapy against free radical damage. PMID:29770166