Exploring the limitations of the Hantzsch method used for quantification of hydroxyl radicals in systems of relevance for interfacial radiation chemistry

NASA Astrophysics Data System (ADS)

Yang, Miao; Soroka, Inna; Jonsson, Mats

2017-01-01

In the presence of Tris or methanol, hydroxyl radicals in systems of relevance for interfacial radiation chemistry can be quantified indirectly via the Hantzsch method by determining the amount of the scavenging product formaldehyde formed. In this work, the influence of the presence of H2O2 on the Hantzsch method using acetoacetanilide (AAA) as derivatization reagent is studied. The experiments show that the measured CH2O concentration deviates from the actual concentration in the presence of H2O2 and the deviation increases with increasing [H2O2]0/[CH2O]0. The deviation is negative, i.e., the measured formaldehyde concentration is lower than the actual concentration. This leads to an underestimation of the hydroxyl radical production in systems containing significant amount of H2O2. The main reason for the deviation is found to be three coupled equilibria involving H2O2, CH2O and the derivative produced in the Hantzsch method.

The Tropospheric Lifetimes of Halocarbons and Their Reactions with OH Radicals: an Assessment Based on the Concentration of CO-14

NASA Technical Reports Server (NTRS)

Derwent, Richard G.; Volz-Thomas, Andreas

1990-01-01

Chemical reaction with hydroxyl radicals formed in the troposphere from ozone photolysis in the presence of methane, carbon monoxide and nitrogen oxides provides an important removal mechanism for halocarbons containing C-H and C = C double bonds. The isotropic distribution in atmospheric carbon monoxide was used to quantify the tropospheric hydroxyl radical distribution. Here, this methodology is reevaluated in the light of recent chemical kinetic data evaluations and new understandings gained in the life cycles of methane and carbon monoxide. None of these changes has forced a significant revision in the CO-14 approach. However, it is somewhat more clearly apparent how important basic chemical kinetic data are to the accurate establishment of the tropospheric hydroxyl radical distribution.

The role of surface generated radicals in catalytic combustion

NASA Technical Reports Server (NTRS)

Santavicca, D. A.; Stein, Y.; Royce, B. S. H.

1985-01-01

Experiments were conducted to better understand the role of catalytic surface reactions in determining the ignition characteristics of practical catalytic combustors. Hydrocarbon concentrations, carbon monoxide and carbon dioxide concentrations, hydroxyl radical concentrations, and gas temperature were measured at the exit of a platinum coated, stacked plate, catalytic combustor during the ignition of lean propane-air mixtures. The substrate temperature profile was also measured during the ignition transient. Ignition was initiated by suddenly turning on the fuel and the time to reach steady state was of the order of 10 minutes. The gas phase reaction, showed no pronounced effect due to the catalytic surface reactions, except the absence of a hydroxyl radical overshoot. It is found that the transient ignition measurements are valuable in understanding the steady state performance characteristics.

Alleviation effect of arbutin on oxidative stress generated through tyrosinase reaction with l-tyrosine and l-DOPA

PubMed Central

2014-01-01

Background Hydroxyl radical that has the highest reactivity among reactive oxygen species (ROS) is generated through l-tyrosine-tyrosinase reaction. Thus, the melanogenesis might induce oxidative stress in the skin. Arbutin (p-hydroxyphenyl-β-d-glucopyranoside), a well-known tyrosinase inhibitor has been widely used for the purpose of skin whitening. The aim of the present study was to examine if arbutin could suppress the hydroxyl radical generation via tyrosinase reaction with its substrates, l-tyrosine and l-DOPA. Results The hydroxyl radical, which was determined by an electron spin resonance-spin trapping technique, was generated by the addition of not only l-tyrosine but l-DOPA to tyrosinase in a concentration dependent manner. Arbutin could inhibit the hydroxyl radical generation in the both reactions. Conclusion It is presumed that arbutin could alleviate oxidative stress derived from the melanogenic pathway in the skin in addition to its function as a whitening agent in cosmetics. PMID:25297374

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.

Laser-induced oxidation of cholesterol observed during MALDI-TOF mass spectrometry.

PubMed

McAvey, Kevin M; Guan, Bing; Fortier, Chanel A; Tarr, Matthew A; Cole, Richard B

2011-04-01

Conditions for the detection of three odd-electron cholesterol oxidation peaks were determined and these peaks were shown to be artifacts of the matrix-assisted laser desorption time of flight (MALDI-TOF) process. Matrix choice, solvent, laser intensity and cholesterol concentration were systematically varied to characterize the conditions leading to the highest signals of the radical cation peaks, and it was found that initial cholesterol solution concentration and resultant density of solid cholesterol on the MALDI target were important parameters in determining signal intensities. It is proposed that hydroxyl radicals, generated as a result of laser irradiation of the employed 2,5-dihydroxybenzoic acid (DHB) matrix, initiate cholesterol oxidation on the MALDI target. An attempt to induce the odd-electron oxidation peaks by means of adding an oxidizing agent succeeded using an acetonitrile solution of DHB, cholesterol, and cumene hydroperoxide. Moreover, addition of free radical scavengers reduced the abundances of some oxidation products under certain conditions. These results are consistent with the mechanism of oxidation proposed herein involving laser-induced hydroxyl radical production followed by attack on neutral cholesterol. Hydroxyl radical production upon irradiation of dithranol matrix may also be responsible for generation of the same radical peaks observed from cholesterol in dithranol by an analogous mechanism. © American Society for Mass Spectrometry, 2011

Novel denture-cleaning system based on hydroxyl radical disinfection.

PubMed

Kanno, Taro; Nakamura, Keisuke; Ikai, Hiroyo; Hayashi, Eisei; Shirato, Midori; Mokudai, Takayuki; Iwasawa, Atsuo; Niwano, Yoshimi; Kohno, Masahiro; Sasaki, Keiichi

2012-01-01

The purpose of this study was to evaluate a new denture-cleaning device using hydroxyl radicals generated from photolysis of hydrogen peroxide (H2O2). Electron spin resonance analysis demonstrated that the yield of hydroxyl radicals increased with the concentration of H2O2 and light irradiation time. Staphylococcus aureus, Pseudomonas aeruginosa, and methicillin-resistant S aureus were killed within 10 minutes with a > 5-log reduction when treated with photolysis of 500 mM H2O2; Candida albicans was killed within 30 minutes with a > 4-log reduction with photolysis of 1,000 mM H2O2. The clinical test demonstrated that the device could effectively reduce microorganisms in denture plaque by approximately 7-log order within 20 minutes.

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

Degradation and intermediates of diclofenac as instructive example for decomposition of recalcitrant pharmaceuticals by hydroxyl radicals generated with pulsed corona plasma in water.

PubMed

Banaschik, Robert; Jablonowski, Helena; Bednarski, Patrick J; Kolb, Juergen F

2018-01-15

Seven recalcitrant pharmaceutical residues (diclofenac, 17α-ethinylestradiol, carbamazepine, ibuprofen, trimethoprim, diazepam, diatrizoate) were decomposed by pulsed corona plasma generated directly in water. The detailed degradation pathway was investigated for diclofenac and 21 intermediates could be identified in the degradation cascade. Hydroxyl radicals have been found primarily responsible for decomposition steps. By spin trap enhanced electron paramagnetic resonance spectroscopy (EPR), OH-adducts and superoxide anion radical adducts were detected and could be distinguished applying BMPO as a spin trap. The increase of concentrations of adducts follows qualitatively the increase of hydrogen peroxide concentrations. Hydrogen peroxide is eventually consumed in Fenton-like processes but the concentration is continuously increasing to about 2mM for a plasma treatment of 70min. Degradation of diclofenac is inversely following hydrogen peroxide concentrations. No qualitative differences between byproducts formed during plasma treatment or due to degradation via Fenton-induced processes were observed. Findings on degradation kinetics of diclofenac provide an instructive understanding of decomposition rates for recalcitrant pharmaceuticals with respect to their chemical structure. Accordingly, conclusions can be drawn for further development and a first risk assessment of the method which can also be applied towards other AOPs that rely on the generation of hydroxyl radicals. Copyright © 2017 Elsevier B.V. All rights reserved.

Indirect Estimation of Tropospheric and Stratospheric Hydroxyl Radical Concentration

NASA Astrophysics Data System (ADS)

Li, M.; Williams, J.

2017-12-01

Hydroxyl radical (OH) react with many gasous compounds in the atmosphere and is regarded as the cleanser of our atmosphere and affect human health, air quality and climate. Mean age of air, which means the average transit time since an air parcel is emitted from earth surface until sampled, is derived from SF6 based on aircraft observations in mid-latitude UTLS region. The domain loss of methyl chloride and methane is the removal by OH, thus using pseudo first order reaction the OH concentration is calculated against mean age. A tropospheric mean OH concentration is calculated in the range of (4 8)*10^5 molecules cm-3 and a stratospheric mean OH concentration is around (3 5)*10^5 molecules cm-3.

Role of ascorbic acid in stratum corneum lipid models exposed to UV irradiation.

PubMed

Trommer, Hagen; Böttcher, Roif; Pöppl, Andreas; Hoentsch, Joachim; Wartewig, Siegfried; Neubert, Reinhard H H

2002-07-01

The effects of ascorbic acid on Stratum corneum lipid models following ultraviolet irradiation were studied adding iron ions as transition metal catalysts. Lipid peroxidation was quantified by the thiobarbituric acid assay. The qualitative changes were studied on a molecular level by mass spectrometry. To elucidate the nature of free radical involvement we carried out electron paramagnetic resonance studies. The influence of ascorbic acid on the concentration of hydroxyl radicals was examined using the spin trapping technique. Moreover, we checked the vitamin's ability to react with stable radicals. Ascorbic acid was found to have prooxidative effects in all lipid systems in a concentration dependent manner. The degradation products of ascorbic acid after its prooxidative action were detected. The concentration of the hydroxyl radicals in the Fenton assay was decreased by ascorbic acid. The quantification assay of 2,2-diphenyl-1-picrylhydrazyl hydrate showed reduced concentration levels of the stable radical caused by ascorbic acid. Considering human skin and its constant exposure to UV light and oxygen, an increased pool of iron ions in irradiated skin and the depletion of co-antioxidants, the administration of ascorbic acid in cosmetic formulations or in sunscreens could unfold adverse effects among the Stratum corneum lipids.

Laser-saturated fluorescence measurements in laminar sooting diffusion flames

NASA Technical Reports Server (NTRS)

Wey, Changlie

1993-01-01

The hydroxyl radical is known to be one of the most important intermediate species in the combustion processes. The hydroxyl radical has also been considered a dominant oxidizer of soot particles in flames. In this investigation the hydroxyl concentration profiles in sooting diffusion flames were measured by the laser-saturated fluorescence (LSF) method. The temperature distributions in the flames were measured by the two-line LSF technique and by thermocouple. In the sooting region the OH fluorescence was too weak to make accurate temperature measurements. The hydroxyl fluorescence profiles for all four flames presented herein show that the OH fluorescence intensities peaked near the flame front. The OH fluorescence intensity dropped sharply toward the dark region of the flame and continued declining to the sooting region. The OH fluorescence profiles also indicate that the OH fluorescence decreased with increasing height in the flames for all flames investigated. Varying the oxidizer composition resulted in a corresponding variation in the maximum OH concentration and the flame temperature. Furthermore, it appears that the maximum OH concentration for each flame increased with increasing flame temperature.

Protective effect of Pterostilbene against free radical mediated oxidative damage

PubMed Central

2013-01-01

Background Pterostilbene, a methoxylated analog of Resveratrol, is gradually gaining more importance as a therapeutic drug owing to its higher lipophilicity, bioavailability and biological activity than Resveratrol. This study was undertaken to characterize its ability to scavenge free radicals such as superoxide, hydroxyl and hydrogen peroxide and to protect bio-molecules within a cell against oxidative insult. Methods Anti-oxidant activity of Pterostilbene was evaluated extensively by employing several in vitro radical scavenging/inhibiting assays and pulse radiolysis study. In addition, its ability to protect rat liver mitochondria against tertiary-butyl hydroperoxide (TBHP) and hydroxyl radical generated oxidative damage was determined by measuring the damage markers such as protein carbonyls, protein sulphydryls, lipid hydroperoxides, lipid peroxides and 8-hydroxy-2'-deoxyguanosine. Pterostilbene was also evaluated for its ability to inhibit •OH radical induced single strand breaks in pBR322 DNA. Result Pterostilbene exhibited strong anti-oxidant activity against various free radicals such as DPPH, ABTS, hydroxyl, superoxide and hydrogen peroxide in a concentration dependent manner. Pterostilbene conferred protection to proteins, lipids and DNA in isolated mitochondrial fractions against TBHP and hydroxyl radical induced oxidative damage. It also protected pBR322 DNA against oxidative assault. Conclusions Thus, present study provides an evidence for the strong anti-oxidant property of Pterostilbene, methoxylated analog of Resveratrol, thereby potentiating its role as an anti-oxidant. PMID:24070177

Antioxidant potential of Aesculus hippocastanum extract and escin against reactive oxygen and nitrogen species.

PubMed

Vašková, J; Fejerčáková, A; Mojžišová, G; Vaško, L; Patlevič, P

2015-01-01

Antioxidant, anti-inflammatory and venoconstrictor properties have been attributed to extracts from Aesculus hippocastanum. These unusual and diverse properties may be possibly basically linked with ability to scavenge free radicals. The scavenging capacity of dry horse chestnut extract of and escin have been investigated in vitro against superoxide anion radicals, hydroxyl radicals, nitrites and peroxynitrite. In general, the activity of the whole extract against superoxide radicals did not exceed 15% at pH 7.4, but the highest inhibition (46.11%) was recorded against hydroxyl radicals at a concentration of 100 µg.ml-1; however, the activity against other radicals was lower. Escin demonstrated a better ability to counteract nitric oxide oxidation products, nitrites. However, the efficiency of the whole extract completely disappeared as the concentration increased. Both extracts showed very low activity towards peroxynitrite. Escin was even able to induce peroxynitrite formation at the lower concentrations used. Whole extract showed better antiradical properties compared to its main active ingredient, escin, probably due to potential synergistic interaction with a mixture of compounds present in the plant extract. These findings can be the basis of both the presentation of side-effects and the persistence of disease in spite of ongoing treatment.

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.

Comparison of salicylate and D-phenylalanine for detection of hydroxyl radicals in chemical and biological reactions.

PubMed

Bailey, S M; Fauconnet, A L; Reinke, L A

1997-02-01

Hydroxylation of salicylate and D-phenylalanine was measured to test the usefulness of these compounds for hydroxyl radical (HO(•)) detection in chemical and biological systems. When HO(•) were produced by the photolytic decomposition of hydrogen peroxide, nearly equal amounts of 2,5- and 2,3-dihydroxybenzoic acid (DHBA) were produced from salicylate, with catechol as a minor product. In the photolytic reaction, nearly equal concentrations of p-,m-, and o-tyrosine were formed from D-phenylalanine. When salicylate or D-phenylalanine was present with Fenton reagents or in iron(II) autoxidation systems, the relative proportions of hydroxylated products were similar to those observed after photolysis, although less total products were usually detected. In contrast, when similar experiments were conducted with isolated hepatic microsomes and perfused livers, 2,5-DHBA was the primary product from salicylate, and p-tyrosine was the major product from D-phenylalanine. Cytochrome P-450 enzymes can hydroxylate salicylate to produce 2,5-DHBA, and it is likely that phenylalanine hydroxylase produces most of the p-tyrosine detected in hepatic tissues. Thus, although both salicylate and D-phenylalanine are useful probes for hydroxyl radical formation in chemical systems, hydroxylated products formed from enzymatic reactions complicate interpretation of data from both compounds in vivo.

Hippophae leaf extract concentration regulates antioxidant and prooxidant effects on DNA.

PubMed

Saini, Manu; Tiwari, Sandhya; Prasad, Jagdish; Singh, Surender; Kumar, M S Yogendra; Bala, Madhu

2010-03-01

Extracts from Hippophae leaves constitute some commonly consumed beverages such as tea and wine. We had developed an extract of Hippophae leaves (SBL-1), which was rich in quercetin, had antimutagenic effects, radioprotective effects, and countered radiation-induced gene conversion in Saccharomyces cerevisiae. This study was designed to investigate the action of SBL-1 on guanine cytosine (GC)-rich nascent and mouse genomic DNA in vitro. The human and mouse liver DNA have about 43% GC content. Our results showed that at small concentration SBL-1 protected nascent as well as genomic DNA, while at large concentration SBL-1 damaged both types of DNA. The concentration of SBL-1 that protected DNA also demonstrated higher free radical scavenging activity. The reducing power of SBL-1 was greater than its free radical scavenging activity. The greater reducing power may have reduced the trace metals present in the SBL-1, leading to generation of hydroxyl radicals via Fenton reaction. The increased proportion of unscavenged hydroxyl radicals with increase in SBL-1 concentration may have been responsible for DNA damage or prooxidant effect of SBL-1 in vitro. This study suggests that the dietary supplements prepared from Hippophae should have low metal content.

Inhibition of peroxynitrite-mediated DNA strand cleavage and hydroxyl radical formation by aspirin at pharmacologically relevant concentrations: implications for cancer intervention

PubMed Central

Chen, Wei; Zhu, Hong; Jia, Zhenquan; Li, Jianrong; Misra, Hara P.; Zhou, Kequan; Li, Yunbo

2009-01-01

Epidemiological studies have suggested that the long-term use of aspirin is associated with a decreased incidence of human malignancies, especially colorectal cancer. Since accumulating evidence indicates that peroxynitrite is critically involved in multistage carcinogenesis, this study was undertaken to investigate the ability of aspirin to inhibit peroxynitrite-mediated DNA damage. Peroxynitrite and its generator 3-morpholinosydnonimine (SIN-1) were used to cause DNA strand breaks in φX-174 plasmid DNA. We demonstrated that the presence of aspirin at concentrations (0.25 -2 mM) compatible with amounts in plasma during chronic anti-inflammatory therapy resulted in a significant inhibition of DNA cleavage induced by both peroxynitrite and SIN-1. Moreover, the consumption of oxygen caused by 250 µM SIN-1 was found to be decreased in the presence of aspirin, indicating that aspirin might affect the auto-oxidation of SIN-1. Furthermore, EPR spectroscopy using 5,5-dimethylpyrroline-N-oxide (DMPO) as a spin trap demonstrated the formation of DMPO-hydroxyl radical adduct (DMPO-OH) from authentic peroxynitrite, and that aspirin at 0.25 - 2 mM potently diminished the radical adduct formation in a concentration-dependent manner. Taken together, these results demonstrate for the first time that aspirin at pharmacologically relevant concentrations can inhibit peroxynitrite-mediated DNA strand breakage and hydroxyl radical formation. These results may have implications for cancer intervention by aspirin. PMID:19785994

Inhibition of peroxynitrite-mediated DNA strand cleavage and hydroxyl radical formation by aspirin at pharmacologically relevant concentrations: Implications for cancer intervention

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

Chen, Wei; College of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310035; Department of Food Science and Technology, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061

Epidemiological studies have suggested that the long-term use of aspirin is associated with a decreased incidence of human malignancies, especially colorectal cancer. Since accumulating evidence indicates that peroxynitrite is critically involved in multistage carcinogenesis, this study was undertaken to investigate the ability of aspirin to inhibit peroxynitrite-mediated DNA damage. Peroxynitrite and its generator 3-morpholinosydnonimine (SIN-1) were used to cause DNA strand breaks in {phi}X-174 plasmid DNA. We demonstrated that the presence of aspirin at concentrations (0.25-2 mM) compatible with amounts in plasma during chronic anti-inflammatory therapy resulted in a significant inhibition of DNA cleavage induced by both peroxynitrite and SIN-1.more » Moreover, the consumption of oxygen caused by 250 {mu}M SIN-1 was found to be decreased in the presence of aspirin, indicating that aspirin might affect the auto-oxidation of SIN-1. Furthermore, EPR spectroscopy using 5,5-dimethylpyrroline-N-oxide (DMPO) as a spin trap demonstrated the formation of DMPO-hydroxyl radical adduct (DMPO-OH) from authentic peroxynitrite, and that aspirin at 0.25-2 mM potently diminished the radical adduct formation in a concentration-dependent manner. Taken together, these results demonstrate for the first time that aspirin at pharmacologically relevant concentrations can inhibit peroxynitrite-mediated DNA strand breakage and hydroxyl radical formation. These results may have implications for cancer intervention by aspirin.« less

Fluorescence-Based Sensor for Monitoring Activation of Lunar Dust

NASA Technical Reports Server (NTRS)

Wallace, William T.; Jeevarajan, Antony S.

2012-01-01

This sensor unit is designed to determine the level of activation of lunar dust or simulant particles using a fluorescent technique. Activation of the surface of a lunar soil sample (for instance, through grinding) should produce a freshly fractured surface. When these reactive surfaces interact with oxygen and water, they produce hydroxyl radicals. These radicals will react with a terephthalate diluted in the aqueous medium to form 2-hydroxyterephthalate. The fluorescence produced by 2-hydroxyterephthalate provides qualitative proof of the activation of the sample. Using a calibration curve produced by synthesized 2-hydroxyterephthalate, the amount of hydroxyl radicals produced as a function of sample concentration can also be determined.

Kinetic and mechanistic study of microcystin-LR degradation by nitrous acid under ultraviolet irradiation.

PubMed

Ma, Qingwei; Ren, Jing; Huang, Honghui; Wang, Shoubing; Wang, Xiangrong; Fan, Zhengqiu

2012-05-15

Degradation of microcystin-LR (MC-LR) in the presence of nitrous acid (HNO(2)) under irradiation of 365nm ultraviolet (UV) was studied for the first time. The influence of initial conditions including pH value, NaNO(2) concentration, MC-LR concentration and UV intensity were studied. MC-LR was degraded in the presence of HNO(2); enhanced degradation of MC-LR was observed with 365nm UV irradiation, caused by the generation of hydroxyl radicals through the photolysis of HNO(2). The degradation processes of MC-LR could well fit the pseudo-first-order kinetics. Mass spectrometry was applied for identification of the byproducts and the analysis of degradation mechanisms. Major degradation pathways were proposed according to the results of LC-MS analysis. The degradation of MC-LR was initiated via three major pathways: attack of hydroxyl radicals on the conjugated carbon double bonds of Adda, attack of hydroxyl radicals on the benzene ring of Adda, and attack of nitrosonium ion on the benzene ring of Adda. Copyright © 2012 Elsevier B.V. All rights reserved.

Determining the local origin of hydroxyl radical generation during phacoemulsification.

PubMed

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

2011-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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.

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.

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

PubMed

Gołembiowska, Krystyna; Dziubina, Anna

2012-08-01

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

Novel hydroxyl radical scavenging antioxidant activity assay for water-soluble antioxidants using a modified CUPRAC method.

PubMed

Bektaşoğlu, Burcu; Esin Celik, Saliha; Ozyürek, Mustafa; Güçlü, Kubilay; Apak, Reşat

2006-07-07

Reactive oxygen species (ROS) such as superoxide anion, hydroxyl ((*)OH), peroxyl, and alkoxyl radicals may attack biological macromolecules giving rise to oxidative stress-originated diseases. Since (*)OH is very short-lived, secondary products resulting from (*)OH attack to various probes are measured. Although the measurement of aromatic hydroxylation with HPLC/electrochemical detection is more specific than the low-yield TBARS test, it requires sophisticated instrumentation. As a more convenient and less costly alternative, we used p-aminobenzoate, 2,4- and 3,5-dimethoxybenzoate probes for detecting hydroxyl radicals generated from an equivalent mixture of Fe(II)+EDTA with hydrogen peroxide. The produced hydroxyl radicals attacked both the probe and the water-soluble antioxidants in 37 degrees C-incubated solutions for 2h. The CUPRAC (i.e., our original method for total antioxidant capacity assay) absorbance of the ethylacetate extract due to the reduction of Cu(II)-neocuproine reagent by the hydroxylated probe decreased in the presence of (*)OH scavengers, the difference being proportional to the scavenging ability of the tested compound. A rate constant for the reaction of the scavenger with hydroxyl radical can be deduced from the inhibition of color formation. The second-order rate constants of the scavengers were determined with competition kinetics by means of a linear plot of A(0)/A as a function of C(scavenger)/C(probe), where A(0) and A are the CUPRAC absorbances of the system in the absence and presence of scavenger, respectively, and C is the molar concentration of relevant species. The 2,4- and 3,5-dimethoxybenzoates were the best probes in terms of linearity and sensitivity. Iodide, metabisulfite, hexacyanoferrate(II), thiourea, formate, and dimethyl sulfoxide were shown by the modified CUPRAC assay to be more effective scavengers than mannitol, glucose, lysine, and simple alcohols, as in the TBARS assay. The developed method is less lengthy, more specific, and of a higher yield than the classical TBARS assay. The hydroxyl radical scavenging rate constants of ascorbic acid, formate, and hexacyanoferrate(II) that caused interference in other assays could be easily found with the proposed procedure.

Photocatalytic activity of Pt-TiO2 films supported on hydroxylated fly ash cenospheres under visible light

NASA Astrophysics Data System (ADS)

Wang, Bing; Yang, Zewei; An, Hao; Zhai, Jianping; Li, Qin; Cui, Hao

2015-01-01

TiO2 was coated on the surface of hydroxylated fly ash cenospheres (FACs) by the sol-gel method. Platinum (Pt) was then deposited on these TiO2/FAC particles by a photoreduction method to form PTF photocatalyst. The photocatalytic activity of PTF for the degradation of methylene blue (MB) under visible-light irradiation was determined. The PTF sample that was calcined at 450 °C and had a Pt/TiO2 mass ratio of 1.5% exhibited the optimal photocatalytic activity for degradation of MB with a catalyst concentration of 3 g L-1. MB was photodecomposed by PTF in aqueous solution more effectively at alkali pH than at acidic pH, because more MB molecules were adsorbed on the surface of PTF under alkaline conditions than that under acidic. The effect of various inorganic anions (HCO3-, F-, SO42-, NO3-, and Cl-) on the photodegradation of MB by PTF was also investigated. Addition of anions with a concentration of 5 mM enhanced the photocatalytic efficiency of PTF because of the improved adsorption of MB. This effect weakened as the anion concentration was increased, which was attributed to the ability of the anions to scavenge hydroxyl radicals and holes. Our results indicated that the photodegradation of MB took place mainly on the catalyst surface. The generation of hydroxyl radicals in the photocatalytic reaction was measured by the fluorescence method. KI was used to determine the participation of holes in the photocatalytic reaction. Both hydroxyl radicals and valence-band holes were detected in the PTF system. Recycling tests revealed that calcination of the used PTF helped to regain its photocatalytic activity.

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.

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.

SU-F-T-676: Measurement of Hydroxyl Radicals in Radiolized Water Systems

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

Ouyang, Z; Ngwa, W; Brigham and Women’s Hospital, Dana-Farber Cancer Institute and Harvard Medical School, Boston, MA

2016-06-15

Purpose: Hydroxyl radicals can be produced within tissue by radiation therapy, and they are largely responsible for DNA damage and cell killing. Coumarin-3-carboxylic acid (3-CCA) and crystal violet are reported to react with hydroxyl radicals and can be used for fluorescence and absorbance measurements, respectively. This study assesses the ability of hydroxyl measurement for both 3-CCA and crystal violet in radiolized water systems in order to provide dosimetric information in radiation chemistry and radiation biology experiments. Methods: 3-CCA and crystal violet were both dissolved in phosphate buffered saline (PBS, pH 7.4) with final concentrations 0.5 mg/mL and 0.05 mg/mL. 3-CCAmore » and control solutions (PBS only) were loaded in black bottom 96-well plates. Crystal violet and control solutions were loaded in clear bottom 96-well plates. The prepared solutions were irradiated at 2 Gy using a small animal radiation research platform. Fluorescence reading with 360 nm excitation wavelength and 485 nm emission wavelength was done for 3-CCA, and absorbance reading at wavelength 580 nm was done for crystal violet before and after radiation. Results: 3-CCA showed clear difference in fluorescence before and after radiation, which suggested hydroxyl production during radiation. However, crystal violet absorbance at 580 nm was not changed significantly by radiation. Conclusion: The overall conclusion is that 3-CCA can be used for hydroxyl measurement in radiolized water systems, while crystal violet cannot, although crystal violet is reported widely to react with hydroxyl radicals produced in Fenton reactions. Possible reasons could relate to reaction pH.« less

[Study on antioxidative activities of Psidium guajava Linn leaves extracts].

PubMed

Wang, Bo; Jiao, Shirong; Liu, Hengchuan; Hong, Junrong

2007-05-01

To study the antioxidative activities of the extracts from Psidium guajava Linn leaves (PGL). The PGL was submersed with distilled water, 65% ethanol and 95% ethanol respectively. The 3 extracts were obtained after the solutions were filtered, concentrated and dried. The scavenging rate to hydroxyl radicals and inhibiting rate to lipid peroxidation were analyzed for the 3 extracts. Their contents of total flavonoids were determined by ultraviolet spectrophotometry, and the components of total flavonoids were primarily identified by high performance liquid chromatography (HPLC) and ultraviolet-visible absorption spectrometry (UV). The extracts from distilled water, 65% ethanol and 95% ethanol respectively showed effects on scavenging hydroxyl radicals and inhibiting lipid peroxidation in the dose-dependent manner, had 50% effective concentration (EC50) on scavenging hydroxyl radicals of 0.63, 0.47 and 0.58g/L, had EC50 on inhibiting lipid peroxidation of 0.20, 0.035, 0.18g/L and had total flavonoids contents of 3.28, 30.71 and 55.98g/kg respectively. The aquatic and the ethanol extracts from PGL possess the potential antioxidative activities in the study. The flavonoids may be one of their antioxidative components.

Molecular detection and in vitro antioxidant activity of S-allyl-L-cysteine (SAC) extracted from Allium sativum.

PubMed

Sun, Y-E; Wang, W-D

2016-06-30

It is well known that Allium sativum has potential applications to clinical treatment of various cancers due to its remarkable ability in eliminating free radicals and increasing metabolism. An allyl-substituted cysteine derivative - S-allyl-L-cysteine (SAC) was separated and identified from Allium sativum. The extracted SAC was reacted with 1-pyrenemethanol to obtain pyrene-labelled SAC (Py-SAC) to give SAC fluorescence properties. Molecular detection of Py-SAC was conducted by steady-state fluorescence spectroscopy and time-resolved fluorescence method to quantitatively measure concentrations of Py-SAC solutions. The ability of removing 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroxyl radical using Py-SAC was determined through oxygen radical absorbance capacity (ORAC). Results showed the activity of Py-SAC and Vitamin C (VC) with ORAC as index, the concentrations of Py-SAC and VC were 58.43 mg/L and 5.72 mg/L respectively to scavenge DPPH, and 8.16 mg/L and 1.67 mg/L to scavenge •OH respectively. Compared with VC, the clearance rates of Py-SAC to scavenge DPPH were much higher, Py-SAC could inhibit hydroxyl radical. The ability of removing radical showed a dose-dependent relationship within the scope of the drug concentration.

Preliminary study on the photoproduction of hydroxyl radicals in aqueous solution with Aldrich humic acid, algae and Fe(III) under high-pressure mercury lamp irradiation.

PubMed

Liu, Xianli; Xu, Dong; Wu, Feng; Liao, Zhenhuan; Liu, Jiantong; Deng, Nansheng

2004-03-01

Under a high-pressure mercury lamp (HPML) and using an exposure time of 4 h, the photoproduction of hydroxyl radicals (*OH) could be induced in an aqueous solution containing humic acid (HA). Hydroxyl radicals were determined by high-performance liquid chromatography using benzene as a probe. The results showed that *OH photoproduction increased from 1.80 to 2.74 microM by increasing the HA concentration from 10 to 40 mg L(-1) at an exposure time of 4 h (pH 6.5). Hydroxyl radical photoproduction in aqueous solutions of HA containing algae was greater than that in the aqueous solutions of HA without algae. The photoproduction of *OH in the HA solution with Fe(III) was greater than that of the solution without Fe(III) at pH ranging from 4.0 to 8.0. The photoproduction of *OH in HA solution with algae with or without Fe(III) under a 250 W HPML was greater than that under a 125 W HPML. The photoproduction of *OH in irradiated samples was influenced by the pH. The results showed that HPML exposure for 4 h in the 4-8 pH range led to the highest *OH photoproduction at pH 4.0.

Pulsed Electron Beam Water Radiolysis for Sub-Microsecond Hydroxyl Radical Protein Footprinting

PubMed Central

Watson, Caroline; Janik, Ireneusz; Zhuang, Tiandi; Charvátová, Olga; Woods, Robert J.; Sharp, Joshua S.

2009-01-01

Hydroxyl radical footprinting is a valuable technique for studying protein structure, but care must be taken to ensure that the protein does not unfold during the labeling process due to oxidative damage. Footprinting methods based on sub-microsecond laser photolysis of peroxide that complete the labeling process faster than the protein can unfold have been recently described; however, the mere presence of large amounts of hydrogen peroxide can also cause uncontrolled oxidation and minor conformational changes. We have developed a novel method for sub-microsecond hydroxyl radical protein footprinting using a pulsed electron beam from a 2 MeV Van de Graaff electron accelerator to generate a high concentration of hydroxyl radicals by radiolysis of water. The amount of oxidation can be controlled by buffer composition, pulsewidth, dose, and dissolved nitrous oxide gas in the sample. Our results with ubiquitin and β-lactoglobulin A demonstrate that one sub-microsecond electron beam pulse produces extensive protein surface modifications. Highly reactive residues that are buried within the protein structure are not oxidized, indicating that the protein retains its folded structure during the labeling process. Time-resolved spectroscopy indicates that the major part of protein oxidation is complete in a timescale shorter than that of large scale protein motions. PMID:19265387

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.

Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid

PubMed Central

Gómez Alvarez, Elena; Amedro, Damien; Afif, Charbel; Gligorovski, Sasho; Schoemaecker, Coralie; Fittschen, Christa; Doussin, Jean-Francois; Wortham, Henri

2013-01-01

The hydroxyl (OH) radical is the most important oxidant in the atmosphere since it controls its self-oxidizing capacity. The main sources of OH radicals are the photolysis of ozone and the photolysis of nitrous acid (HONO). Due to the attenuation of solar radiation in the indoor environment, the possibility of OH formation through photolytic pathways indoors has been ignored up to now. In the indoor air, the ozonolysis of alkenes has been suggested as an alternative route of OH formation. Models and indirect measurements performed up to now according to this hypothesis suggest concentrations of OH radicals on the order of 104–105 molecules per cubic centimeter. Here, we present direct measurements of significant amounts of OH radicals of up to 1.8⋅106 molecules per cubic centimeter during an experimental campaign carried out in a school classroom in Marseille. This concentration is on the same order of magnitude of outdoor OH levels in the urban scenario. We also show that photolysis of HONO is an important source of OH radicals indoors under certain conditions (i.e., direct solar irradiation inside the room). Additionally, the OH concentrations were found to follow a linear dependence with the product J(HONO)⋅[HONO]. This was also supported by using a simple quasiphotostationary state model on the OH radical budget. These findings force a change in our understanding of indoor air quality because the reactivity linked to OH would involve formation of secondary species through chemical reactions that are potentially more hazardous than the primary pollutants in the indoor air. PMID:23898188

Reaction kinetics and efficiencies for the hydroxyl and sulfate radical based oxidation of artificial sweeteners in water.

PubMed

Toth, Janie E; Rickman, Kimberly A; Venter, Andre R; Kiddle, James J; Mezyk, Stephen P

2012-10-11

Over the past several decades, the increased use of artificial sweeteners as dietary supplements has resulted in rising concentrations of these contaminants being detected in influent waters entering treatment facilities. As conventional treatments may not quantitatively remove these sweeteners, radical-based advanced oxidation and reduction (AO/RP) treatments could be a viable alternative. In this study, we have established the reaction kinetics for both hydroxyl ((•)OH) and sulfate (SO(4)(•-)) radical reaction with five common artificial sweeteners, as well as their associated reaction efficiencies. Rate constants for acesulfame K, aspartame, rebaudioside A, saccharin, and sucralose were <2 × 10(7), (2.28 ± 0.02) × 10(9), (2.1 ± 0.1) × 10(8), <2 × 10(7), and (1.7 ± 0.1) × 10(8) M(-1) s(-1) for the sulfate radical, and (3.80 ± 0.27) × 10(9), (6.06 ± 0.05) × 10(9), (9.97 ± 0.12) × 10(9), (1.85 ± 0.01) × 10(9), and (1.50 ± 0.01) × 10(9) M(-1) s(-1) for the hydroxyl radical, respectively. These latter values have to be combined with their corresponding reaction efficiencies of 67.9 ± 0.9, 52.2 ± 0.7, 43.0 ± 2.5, 52.7 ± 2.9, and 98.3 ± 3.5% to give effective rate constants for the hydroxyl radical reaction that can be used in the modeling of the AOP based removal of these contaminants.

Hydroxyl and Hydroperoxy Radical Chemistry during the MCMA-2006 Field Campaign: Measurement and Model Comparison

NASA Astrophysics Data System (ADS)

Dusanter, S.; Vimal, D.; Stevens, P. S.; Volkamer, R.; Molina, L. T.

2007-12-01

The Mexico City Metropolitan Area (MCMA) field campaign, held in March 2006, was a unique opportunity to collect data in one of the most polluted megacities in the world. Such environments exhibit a complex oxidation chemistry involving a strong coupling between odd hydrogen radicals (HOX=OH+HO2) and nitrogen oxides species (NOX=NO+NO2). High levels of volatile organic compounds (VOCs) and NOX control the HOX budget and lead to elevated tropospheric ozone formation. The HOX-NOX coupling can be investigated by comparing measured and model-predicted HOx concentrations. Atmospheric HOX concentrations were measured by the Indiana University laser-induced fluorescence instrument and data were collected at the Instituto Mexicano del Petroleo between 14 and 31 March. Measured hydroxyl radical (OH) concentrations are comparable to that measured in less polluted urban environments and suggest that the OH concentrations are highly buffered under high NOX conditions. In contrast, hydroperoxy radical (HO2) concentrations are more sensitive to the NOX levels and are highly variable between different urban sites. Enhanced levels of OH and HO2 radicals were observed on several days between 9h30-11h00 AM and suggest an additional HOX source for the morning hours and/or a fast HOX cycling under the high NOX conditions of the MCMA. A preliminary investigation of the HOX chemistry occurring in the MCMA urban atmosphere was performed using a photochemical box model based on the Regional Atmospheric Chemistry Mechanism (RACM). Model comparisons will be presented and the agreement between measured and predicted HOX concentrations will be discussed.

Hydroxyl radical-modified fibrinogen as a marker of thrombosis: the role of iron.

PubMed

Lipinski, B; Pretorius, E

2012-07-01

Excessive free iron in blood and in organ tissues (so called iron overload) has been observed in degenerative diseases such as atherosclerosis, cancer, neurological, and certain autoimmune diseases, in which fibrin-like deposits are also found. Although most of the body iron is bound to hemoglobin and myoglobin in a divalent ferrous form, a certain amount of iron exists in blood as a trivalent (ferric) ion. This particular chemical state of iron has been shown to be toxic to the human body when not controlled by endogenous and/or dietary chelating agents. Experiments described in this paper show for the first time that ferric ions (Fe(3+)) can generate hydroxyl radicals without participation of any redox agent, thus making it a special case of the Fenton reaction. Ferric chloride was also demonstrated to induce aggregation of purified fibrinogen at the same molar concentrations that were used for the generation of hydroxyl radicals. Iron-aggregated fibrinogen, by contrast to native molecule, could not be dissociated into polypeptide subunit chains as shown in a polyacrylamide gel electrophoresis. The mechanism of this phenomenon is very likely based on hydroxyl radical-induced modification of fibrinogen tertiary structure with the formation of insoluble aggregates resistant to enzymatic and chemical degradations. Soluble modified fibrinogen species can be determined in blood of thrombotic patients by the reaction with protamine sulfate and/or by scanning electron microscopy. In view of these findings, it is postulated that iron-induced alterations in fibrinogen structure is involved in pathogenesis of certain degenerative diseases associated with iron overload and persistent thrombosis. It is concluded that the detection of hydroxyl radical-modified fibrinogen may be utilized as a marker of a thrombotic condition in human subjects.

Differential Mechanism of Escherichia coli Inactivation by (+)-Limonene as a Function of Cell Physiological State and Drug's Concentration

PubMed Central

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

2014-01-01

(+)-limonene is a lipophilic antimicrobial compound, extracted from citrus fruits' essential oils, that is used as a flavouring agent and organic solvent by the food industry. A recent study has proposed a common and controversial mechanism of cell death for bactericidal antibiotics, in which hydroxyl radicals ultimately inactivated cells. Our objective was to determine whether the mechanism of Escherichia coli MG1655 inactivation by (+)-limonene follows that of bactericidal antibiotics. A treatment with 2,000 μL/L (+)-limonene inactivated 4 log10 cycles of exponentially growing E. coli cells in 3 hours. On one hand, an increase of cell survival in the ΔacnB mutant (deficient in a TCA cycle enzyme), or in the presence of 2,2′-dipyridyl (inhibitor of Fenton reaction by iron chelation), thiourea, or cysteamine (hydroxyl radical scavengers) was observed. Moreover, the ΔrecA mutant (deficient in an enzyme involved in SOS response to DNA damage) was more sensitive to (+)-limonene. Thus, this indirect evidence indicates that the mechanism of exponentially growing E. coli cells inactivation by 2,000 μL/L (+)-limonene is due to the TCA cycle and Fenton-mediated hydroxyl radical formation that caused oxidative DNA damage, as observed for bactericidal drugs. However, several differences have been observed between the proposed mechanism for bactericidal drugs and for (+)-limonene. In this regard, our results demonstrated that E. coli inactivation was influenced by its physiological state and the drug's concentration: experiments with stationary-phase cells or 4,000 μL/L (+)-limonene uncovered a different mechanism of cell death, likely unrelated to hydroxyl radicals. Our research has also shown that drug's concentration is an important factor influencing the mechanism of bacterial inactivation by antibiotics, such as kanamycin. These results might help in improving and spreading the use of (+)-limonene as an antimicrobial compound, and in clarifying the controversy about the mechanism of inactivation by bactericidal antibiotics. PMID:24705541

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

PubMed

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

2014-01-01

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

Levofloxacin oxidation by ozone and hydroxyl radicals: kinetic study, transformation products and toxicity.

PubMed

Hamdi El Najjar, Nasma; Touffet, Arnaud; Deborde, Marie; Journel, Romain; Leitner, Nathalie Karpel Vel

2013-10-01

This work was carried out to investigate the fate of the antibiotic levofloxacin upon oxidation with ozone and hydroxyl radicals. A kinetic study was conducted at 20 °C for each oxidant. Ozonation experiments were performed using a competitive kinetic method with carbamazepin as competitor. Significant levofloxacin removal was observed during ozonation and a rate constant value of 6.0×10(4) M(-1) s(-1) was obtained at pH 7.2. An H2O2/UV system was used for the formation of hydroxyl radicals HO. The rate constant of HO was determined in the presence of a high H2O2 concentration. The kinetic expressions yielded a [Formula: see text] value of 4.5×10(9) M(-1) s(-1) at pH 6.0 and 5.2×10(9) M(-1) s(-1) at pH 7.2. These results were used to develop a model to predict the efficacy of the ozonation process and pharmaceutical removal was estimated under different ozonation conditions (i.e. oxidant concentrations and contact times). The results showed that levofloxacin was completely degraded by molecular ozone during ozonation of water and that hydroxyl radicals had no effect in real waters conditions. Moreover, LC/MS/MS and toxicity assays using Lumistox test were performed to identify ozonation transformation products. Under these conditions, four transformation products were observed and their chemical structures were proposed. The results showed an increase in toxicity during ozonation, even after degradation of all of the observed transformation products. The formation of other transformation products not identified under our experimental conditions could be responsible for the observed toxicity. These products might be ozone-resistant and more toxic to Vibrio fisheri than levofloxacin. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

PubMed

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

2014-03-01

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

Sensitive determination of endogenous hydroxyl radical in live cell by a BODIPY based fluorescent probe.

PubMed

Lei, Kepeng; Sun, Mingtai; Du, Libo; Zhang, Xiaojie; Yu, Huan; Wang, Suhua; Hayat, Tasawar; Alsaedi, Ahmed

2017-08-01

The sensitive and selective fluorescence probe for hydroxyl radical analysis is of significance because hydroxyl radical plays key roles in many physiological and pathological processes. In this work, a novel organic fluorescence molecular probe OHP for hydroxyl radical is synthesized by a two-step route. The probe employs 4-bora-3a,4a-diaza-s-indacene (difluoroboron dipyrromethene, BODIPY) as the fluorophore and possesses relatively high fluorescence quantum yields (77.14%). Hydroxyl radical can rapidly react with the probe and quench the fluorescence in a good linear relationship (R 2 =0.9967). The limit of detection is determined to be as low as 11nM. In addition, it has been demonstrated that the probe has a good stability against pH and light illumination, low cytotoxicity and high biocompatibility. Cell culture experimental results show that the probe OHP is sensitive and selective for imaging and tracking endogenous hydroxyl radical in live cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Sono-activated persulfate oxidation of diclofenac: Degradation, kinetics, pathway and contribution of the different radicals involved.

PubMed

Monteagudo, J M; El-Taliawy, H; Durán, A; Caro, G; Bester, K

2018-06-20

Degradation of a diclofenac aqueous solution was performed using persulfate anions activated by ultrasound. The objective of this study was to analyze different parameters affecting the diclofenac (DCF) removal reaction by the ultrasonic persulfate (US/PS) process and to evaluate the role played by various intermediate oxidative species such as hydroxyl- and sulfate radicals, superoxide radical anion or singlet oxygen in the removal process as well as to determine a possible reaction pathway. The effects of pH, initial persulfate anion concentration, ultrasonic amplitude and temperature on DCF degradation were examined. Sulfate and hydroxyl radicals were involved in the main reaction pathway of diclofenac. Diclofenac amide and three hydroxy-diclofenac isomers (3´-hydroxy diclofenac, 4´-hydroxy diclofenac and 5-hydroxy diclofenac) were identified as reaction intermediates. Copyright © 2018 Elsevier B.V. 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.

Free radical scavenging injectable hydrogels for regenerative therapy.

PubMed

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

2017-02-01

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

Chemistry of neutral species in the effluent of the micro atmospheric pressure plasma jet in water-helium admixture

NASA Astrophysics Data System (ADS)

Willems, Gert; Benedikt, Jan; von Keudell, Achim

2016-09-01

A thorough understanding and good control of produced neutral and charged species by cold atmospheric plasmas is essential for potential environmental and/or bio-medical applications. In this study we use the COST reference micro plasma jet (µ-APPJ), which is a radio-frequency capacitive coupled plasma source with 1 mm electrode distance, which has been operated in helium-water vapour mixture and has been studied as a potential source of hydroxyl radicals and hydrogen peroxide molecules. The water vapour concentration was up to 1.2%. Molecular Beam mass spectrometry is used as diagnostic tool. An absolute calibration of hydrogen peroxide was conducted using a double bubbler concept, because the ionization cross section for hydrogen peroxide is not available. Additionally the effluent chemistry was investigated by use of a 0D and 2D model. Absolute densities of hydrogen peroxide and hydroxyl radicals from atmospheric plasma will be presented. Their dependency on water vapour concentration in the carrier gas as well as distance to target have been investigated. The measured density is between 5E-13 cm-3 (2.4ppm) and 1.5E-14 cm-3 (7.2ppm) for both hydrogen peroxide molecules and hydroxyl radicals. The achieved results are in good agreement with other experiments.

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.

Antioxidant and antigenotoxic activities in Acacia salicina extracts and its protective role against DNA strand scission induced by hydroxyl radical.

PubMed

Chatti, Ines Bouhlel; Boubaker, Jihed; Skandrani, Ines; Bhouri, Wissem; Ghedira, Kamel; Chekir Ghedira, Leila

2011-08-01

The antioxidant potency of Acacia salicina extracts was investigated. Total antioxidant capacity was determined using an ABTS(+) assay. Superoxide radical scavenging was measured using riboflavin-light-nitro blue tetrazolium (NBT) assay. In addition, the content of phenols, total flavonoids and sterols were measured in the tested extracts. The petroleum ether exhibited a potent scavenging activity toward ABTS radical cations. Whereas, chloroform extract showed the highest activity against superoxides radicals and was also able to protect pKS plasmid DNA against hydroxyl radicals induced DNA damages. The antimutagenicity of these extracts was assayed using the Ames assay against Salmonella typhimurium TA98 and S. typhimurium TA 1535 tester strains at different concentrations. These extracts decreased significantly the mutagenecity induced by sodium azide (SA) and 4-nitro-o-phenylenediamine (NOP). The antioxidant and antimutagenecity activities exhibited by A. salicina depended on the chemical composition of the tested extracts. Copyright © 2011 Elsevier Ltd. All rights reserved.

Hydroxyl radical mediated DNA base modification by manmade mineral fibres.

PubMed Central

Leanderson, P; Söderkvist, P; Tagesson, C

1989-01-01

Manmade mineral fibres (MMMFs) were examined for their ability to hydroxylate 2-deoxyguanosine (dG) to 8-hydroxydeoxyguanosine (8-OH-dG), a reaction that is mediated by hydroxyl radicals. It appeared that (1) catalase and the hydroxyl radical scavengers, dimethylsulphoxide and sodium benzoate, inhibited the hydroxylation, whereas Fe2+ and H2O2 potentiated it; (2) pretreatment of MMMFs with the iron chelator, deferoxamine, or with extensive heat (200-400 degrees C), attenuated the hydroxylation; (3) the hydroxylation obtained by various MMMFs varied considerably; (4) there was no apparent correlation between the hydroxylation and the surface area of different MMMFs, although increasing the surface area of a fibre by crushing it increased its hydroxylating capacity; and (5) there was good correlation between the hydroxylation of dG residues in DNA and the hydroxylation of pure dG in solution for the 16 different MMMFs investigated. These findings indicate that MMMFs cause a hydroxyl radical mediated DNA base modification in vitro and that there is considerable variation in the reactivity of different fibre species. The DNA modifying ability seems to depend on physical or chemical characteristics, or both, of the fibre. PMID:2765416

Time-Resolved Hydroxyl Radical Footprinting of RNA with X-Rays.

PubMed

Hao, Yumeng; Bohon, Jen; Hulscher, Ryan; Rappé, Mollie C; Gupta, Sayan; Adilakshmi, Tadepalli; Woodson, Sarah A

2018-06-01

RNA footprinting by hydroxyl radical cleavage provides 'snapshots' of RNA tertiary structure or protein interactions that bury the RNA backbone. Generation of hydroxyl radicals with a high-flux synchrotron X-ray beam provides analysis on a short timescale (5-100 msec), which enables the structures of folding intermediates or other transient conformational states to be determined in biochemical solutions or cells. This article provides protocols for using synchrotron beamlines for hydroxyl radical footprinting. © 2018 by John Wiley & Sons, Inc. © 2018 John Wiley & Sons, Inc.

A kinetic study of 3-chlorophenol enhanced hydroxyl radical generation during ozonation.

PubMed

Utsumi, Hideo; Han, Youn-Hee; Ichikawa, Kazuhiro

2003-12-01

Hydroxyl (OH) radical is proposed as an important factor in the ozonation of water. In the present study, the enhancing effect of 3-chlorophenol on OH radical generation was mathematically evaluated using electron spin resonance (ESR)/spin-trapping technique. OH radical was trapped with a 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a stable adduct, DMPO-OH. The initial velocity of DMPO-OH generation in ozonated water containing 3-chlorophenol was quantitatively measured using a combined system of ESR spectroscopy with stopped-flow apparatus which was controlled by home-made software. The initial velocity of DMPO-OH generation increased as a function of the concentration of ozone and the more effectively of 3-chlorophenol concentration. The relation among ozone concentration, amount of 3-chlorophenol and the initial velocity (nu(0)) of DMPO-OH generation was mathematically analyzed and the following equation was obtained, nu(0) (10(-6)M/s)=[9.7 x [3-chlorophenol (10(-9)M)] + 0.0005]exp(57 x [ozone (10(-9)M)]). The equation fitted very well with the experimental results, and the correlation coefficient was larger than 0.99. The equation for the enhancing effect by 3-chlorophenol should provide useful information to optimize the condition in ozone treatment process of water containing phenolic pollutants.

Iodide oxidation and iodine reduction mediated by horseradish peroxidase in the presence of ethylenediaminetetraacetic acid (EDTA): the superoxide effect.

PubMed

Chang, H C; Bumpus, J A

2001-04-01

Ethylenediaminetetraacetic acid (EDTA) is an inhibitor of iodide (I-) oxidation that is catalyzed by horseradish peroxidase (HRP). HRP-mediated iodine (I2) reduction and triiodide (I3+) disappearance occur in the presence of this inhibitor. It is interesting that in the presence of EDTA, HRP produces superoxide radical, a reactive oxygen species that is required for iodine reduction. Substitution of potassium superoxide (KO2) or a biochemical superoxide generating system (xanthine/xanthine oxidase) for HRP and H2O2 in the reaction mixture also can reduce iodine to iodide. Thus, iodine reduction mediated by HRP occurs because HRP is able to mediate the formation of superoxide in the presence of EDTA and H2O2. Although superoxide is able to mediate iodine reduction directly, other competing reactions appear to be more important. For example, high concentrations (mM range) of EDTA are required for efficient iodine reduction in this system. Under such conditions, the concentration (microM range) of contaminating EDTA-Fe(III) becomes catalytically important. In the presence of superoxide, EDTA-Fe(III) is reduced to EDTA-Fe(II), which is able to reduce iodine and form triiodide rapidly. Also of importance is the fact that EDTA-Fe(II) reacts with hydrogen peroxide to form hydroxyl radical. Hydroxyl radical involvement is supported by the fact that a wide variety of hydroxyl radical (OH) scavengers can inhibit HRP dependent iodine reduction in the presence of EDTA and hydrogen peroxide.

Degradation of fifteen emerging contaminants at microg L(-1) initial concentrations by mild solar photo-Fenton in MWTP effluents.

PubMed

Klamerth, N; Rizzo, L; Malato, S; Maldonado, Manuel I; Agüera, A; Fernández-Alba, A R

2010-01-01

The degradation of 15 emerging contaminants (ECs) at low concentrations in simulated and real effluent of municipal wastewater treatment plant with photo-Fenton at unchanged pH and Fe=5 mg L(-1) in a pilot-scale solar CPC reactor was studied. The degradation of those 15 compounds (Acetaminophen, Antipyrine, Atrazine, Caffeine, Carbamazepine, Diclofenac, Flumequine, Hydroxybiphenyl, Ibuprofen, Isoproturon, Ketorolac, Ofloxacin, Progesterone, Sulfamethoxazole and Triclosan), each with an initial concentration of 100 microg L(-1), was found to depend on the presence of CO(3)(2-) and HCO(3)(-) (hydroxyl radicals scavengers) and on the type of water (simulated water, simulated effluent wastewater and real effluent wastewater), but is relatively independent of pH, the type of acid used for release of hydroxyl radicals scavengers and the initial H(2)O(2) concentration used. Toxicity tests with Vibrio fisheri showed that degradation of the compounds in real effluent wastewater led to toxicity increase. (c) 2009 Elsevier Ltd. All rights reserved.

The impact of the hydroxyl radical photochemical sources on the rivastigmine drug transformation in mimic and natural waters.

PubMed

Passananti, Monica; Temussi, Fabio; Iesce, Maria Rosaria; Mailhot, Gilles; Brigante, Marcello

2013-09-15

In this paper we investigated the degradation of the rivastigmine drug induced by hydroxyl radical in synthetic and natural waters focusing on both reactivity and photoproducts identification. The hydroxyl radical formation rate was quantified by using terephthalic acid as trapping molecule and it was related with the rivastigmine degradation rate. The second order rate constant between hydroxyl radical and rivastigmine was estimated to be ≈ 5.8 × 10(9) M(-1) s(-1). Irradiation of rivastigmine in three natural waters (rain, lake and river) and comparison with degradation rates observed in synthetic solutions using nitrite, nitrate and hydrogen peroxide suggest that, in addition to hydroxyl radical, also nitroderived radicals (NO/NO2) are responsible for the pollutant degradation in natural media. In fact, the evaluated degradation rates in three natural waters are greatly higher than those estimated considering only the reactivity with photogenerated hydroxyl radical. Using nitrites and nitrates as photochemical OH source, the rivastigmine degradation cannot be described considering only the hydroxyl radical reactivity suggesting that NO and NO2 radicals could play a key role during indirect degradation. Moreover main degradation products have been identified by means of HPLC-MS. Hydroxylation of the aromatic ring as well as carbamate and amino chain oxidation were suggested as main reaction mechanisms, but also nitroderived compounds were characterized. Finally polychromatic irradiations of three rivastigmine doped natural waters (rain, river and lake) underlined the role of the indirect degradation that needs to be considered when direct degradation of selected pollutants is negligible under environmental-like conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Generation of hydroxyl radicals and singlet oxygen during oxidation of rhododendrol and rhododendrol-catechol.

PubMed

Miyaji, Akimitsu; Gabe, Yu; Kohno, Masahiro; Baba, Toshihide

2017-03-01

The generation of hydroxyl radicals and singlet oxygen during the oxidation of 4-(4-hydroxyphenyl)-2-butanol (rhododendrol) and 4-(3,4-dihydroxyphenyl)-2-butanol (rhododendrol-catechol) with mushroom tyrosinase in a phosphate buffer (pH 7.4) was examined as the model for the reactive oxygen species generation via the two rhododendrol compounds in melanocytes. The reaction was performed in the presence of 5,5-dimethyl-1-pyrroline- N -oxide (DMPO) spin trap reagents for hydroxyl radical or 2,2,6,6-tetramethyl-4-piperidone (4-oxo-TEMP), an acceptor of singlet oxygen, and their electron spin resonances were measured. An increase in the electron spin resonances signal attributable to the adduct of DMPO reacting with the hydroxyl radical and that of 4-oxo-TEMP reacting with singlet oxygen was observed during the tyrosinase-catalyzed oxidation of rhododendrol and rhododendrol-catechol, indicating the generation of hydroxyl radical and singlet oxygen. Moreover, hydroxyl radical generation was also observed in the autoxidation of rhododendrol-catechol. We show that generation of intermediates during tyrosinase-catalyzed oxidation of rhododendrol enhances oxidative stress in melanocytes.

Radical-scavenging activity, protective effect against lipid peroxidation and mineral contents of monofloral Cuban honeys.

PubMed

Alvarez-Suarez, José M; Giampieri, Francesca; Damiani, Elisabetta; Astolfi, Paola; Fattorini, Daniele; Regoli, Francesco; Quiles, José L; Battino, Maurizio

2012-03-01

Several monofloral Cuban honeys were analyzed to determine their free radical-scavenging activity and from this the total antioxidant content was estimated. The protective effect against lipid peroxidation in an in vitro model of rat liver homogenates was evaluated and, lastly, the mineral content of the honeys, which can be related to the maintenance of intracellular oxidative balance, was determined. The scavenging capacities against hydroxyl and superoxide radicals were determined using the spin-trapping technique and the hypoxanthine/xanthine oxidase assay, respectively. Lipid peroxidation was evaluated through the production of TBARS and hydroperoxides. All honeys tested showed potential antioxidant activity with Linen vine displaying the highest scavenging capacity towards the DPPH, hydroxyl and superoxide radicals, while the least efficient was Christmas vine honey. Honeys also inhibited, in a concentration-dependent mode, lipid peroxidation in rat liver homogenates, with Linen vine resulting the best while the least effective was Christmas vine honey. The ability to scavenge free radicals and protect against lipid peroxidation may contribute to the ability of certain Cuban honeys to help in preventing/reducing some inflammatory diseases in which oxidative stress is involved. A total of eight minerals were identified and quantified as follows: cadmium, chromium, copper, nickel, iron, manganese, lead, and zinc. Minerals found in higher concentrations were iron, zinc and manganese.

Efficacy of puffer fish (Takifugu rubripes) sauce in reducing hydroxyl radical damage to DNA assessed using the apurinic/apyrimidinic site method.

PubMed

Harada, Kazuki; Makino, Yoshio; Yamauchi, Tomio; Fukuda, Nami; Tamaru, Miki; Okubo, Yasue; Maeda, Toshimichi; Fukuda, Yutaka; Shiba, Tsuneo

2007-09-01

Apurinic/apyrimidinic (AP) sites are frequently observed DNA lesions when cells are exposed to hydroxyl radicals. We developed a new method for measurement of the antioxidative activity of foods using the occurrence frequency of AP sites on DNA. Combined with the electron spin resonance (ESR) method as a standard method, we examined whether fish and soy sauces including puffer fish [Takifugu rubripes (Temminck et Schlegel)] sauce could protect DNA from damage caused by hydroxyl radicals. The results showed that the ratios of DNA protection by puffer fish sauce, salmon fish sauce, sandfish fish sauce (Shottsuru), colorless soy sauce, squid fish sauce (Ishiru), dark color soy sauce and light color soy sauce were 68.9, 67.0, 60.1, 49.7, 34.1, 28.2 and -4.4%, respectively. Puffer, salmon, and sandfish fish sauces showed high ratios of DNA protection against hydroxyl radicals. On the other hand, IC(50) values of hydroxyl radical scavenging of the puffer, salmon, sandfish, squid fish sauces and colorless, dark and light color soy sauces were 0.20, 0.09, 4.16, 0.26% and 0.28, 0.14 and 0.18%, respectively. Though the puffer fish sauce exhibited the highest level of DNA protection among the examined samples and a high hydroxyl radical scavenging capability, a correlation between the radical scavenging capability and DNA protection against hydroxyl radicals among the examined fish and soy sauces was not found.

Recent Advances and Applications in Synchrotron X-Ray Protein Footprinting for Protein Structure and Dynamics Elucidation.

PubMed

Gupta, Sayan; Feng, Jun; Chance, Mark; Ralston, Corie

2016-01-01

Synchrotron X-ray Footprinting is a powerful in situ hydroxyl radical labeling method for analysis of protein structure, interactions, folding and conformation change in solution. In this method, water is ionized by high flux density broad band synchrotron X-rays to produce a steady-state concentration of hydroxyl radicals, which then react with solvent accessible side-chains. The resulting stable modification products are analyzed by liquid chromatography coupled to mass spectrometry. A comparative reactivity rate between known and unknown states of a protein provides local as well as global information on structural changes, which is then used to develop structural models for protein function and dynamics. In this review we describe the XF-MS method, its unique capabilities and its recent technical advances at the Advanced Light Source. We provide a comparison of other hydroxyl radical and mass spectrometry based methods with XFMS. We also discuss some of the latest developments in its usage for studying bound water, transmembrane proteins and photosynthetic protein components, and the synergy of the method with other synchrotron based structural biology methods.

Mechanism and kinetics of the atmospheric degradation of 2-formylcinnamaldehyde with O3 and hydroxyl OH radicals - a theoretical study

NASA Astrophysics Data System (ADS)

Thangamani, D.; Shankar, R.; Vijayakumar, S.; Kolandaivel, P.

2016-10-01

In the present investigation, the reaction mechanism and kinetics of 2-formylcinnamaldehyde (2-FC) with O3 and hydroxyl OH radicals were studied. The reaction of 2-FC with O3 radical are initiated by the formation of primary ozonide, whereas the reaction of 2-FC with the hydroxyl OH radical are initiated by two different ways: (1). H-atom abstraction by hydroxyl OH radical from the -CHO and -CH = CHCHO group of 2-FC (2). Hydroxyl OH addition to the -CH = CHCHO group to the ring-opened 2-FC. These reactions lead to the formation of an alkyl radical. The reaction pathways corresponding to the reactions between 2-FC with O3 and hydroxyl OH radicals have been analysed using density functionals of B3LYP and M06-2X level of methods with the 6-31+G(d,p) basis set. Single-point energy calculations for the most favourable reactive species are determined by B3LYP/6-311++G(d,p) and CCSD(T)/6-31+G(d,p) levels of theory. From the obtained results, the hydroxyl OH addition at C8 position of 2-FC are most favourable than the C9 position of 2-FC. The subsequent reactions of the alkyl radicals, formed from the hydroxyl OH addition at C8 position, are analysed in detail. The individual and overall rate constant for the most favourable reactions are calculated by canonical variational transition theory with small-curvature tunnelling corrections over the temperature range of 278-350 K. The calculated theoretical rate constants are in good agreement with the available experimental data. The Arrhenius plot of the rate constants with the temperature are fitted and the atmospheric lifetimes of the 2-FC with hydroxyl OH radical reaction in the troposphere calculate for the first time, which can be applied to the study on the atmospheric implications. The condensed Fukui function has been verified for the most favourable reaction sites. This study can be regarded as an attempt to investigate the O3-initiated and hydroxyl OH-initiated reaction mechanisms of 2-FC in the atmosphere.

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

PubMed

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

2015-11-01

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

Re-engineering an artificial sweetener: transforming sucralose residuals in water via advanced oxidation.

PubMed

Keen, Olya S; Linden, Karl G

2013-07-02

Sucralose is an artificial sweetener persistently present in wastewater treatment plant effluents and aquatic environments impacted by human activity. It has a potential to accumulate in the water cycle due to its resistance to common water and wastewater treatment processes. This study examined UV/H2O2 advanced oxidation and found that hydroxyl substitution of the chlorine atoms on the sucralose molecule can form a carbohydrate consisting of fructose and sugar alcohol, very similar to environmentally benign sucrose. The second-order reaction rate constant for loss of parent molecule via reaction with hydroxyl radical was determined to be (1.56 ± 0.03)·10(9) M(-1)s(-1). The degradation pathway involves substitution of a single chlorine by a hydroxyl group, with cyclic moiety being a preferential site for initial dechlorination. Further reaction leads to full dechlorination of the molecule, presumably via hydroxyl group substitution as well. No direct photolysis by UV wavelengths above 200 nm was observed. Because of its photostability when exposed to UV wavelengths ≥200 nm, known stability with ozone, limits of quantification by mass spectrometry close to or below environmental concentrations (<5 μg/L) without preconcentration, and otherwise stable nature, sucralose can be used as an in situ hydroxyl radical probe for UV-based and ozone-based AOP processes. As a compound safe for human consumption, sucralose makes a suitable full scale hydroxyl radical probe fit even for drinking water treatment plant applications. Its main drawback as a probe is lack of UV detection and as a result a need for mass spectrometry analysis.

Tailoring charge density and hydrogen bonding of imidazolium copolymers for efficient gene delivery.

PubMed

Allen, Michael H; Green, Matthew D; Getaneh, Hiwote K; Miller, Kevin M; Long, Timothy E

2011-06-13

Conventional free radical polymerization with subsequent postpolymerization modification afforded imidazolium copolymers with controlled charge density and side chain hydroxyl number. Novel imidazolium-containing copolymers where each permanent cation contained one or two adjacent hydroxyls allowed precise structure-transfection efficiency studies. The degree of polymerization was identical for all copolymers to eliminate the influence of molecular weight on transfection efficiency. DNA binding, cytotoxicity, and in vitro gene transfection in African green monkey COS-7 cells revealed structure-property-transfection relationships for the copolymers. DNA gel shift assays indicated that higher charge densities and hydroxyl concentrations increased DNA binding. As the charge density of the copolymers increased, toxicity of the copolymers also increased; however, as hydroxyl concentration increased, cytotoxicity remained constant. Changing both charge density and hydroxyl levels in a systematic fashion revealed a dramatic influence on transfection efficiency. Dynamic light scattering of the polyplexes, which were composed of copolymer concentrations required for the highest luciferase expression, showed an intermediate DNA-copolymer binding affinity. Our studies supported the conclusion that cationic copolymer binding affinity significantly impacts overall transfection efficiency of DNA delivery vehicles, and the incorporation of hydroxyl sites offers a less toxic and effective alternative to more conventional highly charged copolymers.

Pulsed corona discharge: the role of ozone and hydroxyl radical in aqueous pollutants oxidation.

PubMed

Preis, S; Panorel, I C; Kornev, I; Hatakka, H; Kallas, J

2013-01-01

Ozone and hydroxyl radical are the most active oxidizing species in water treated with gas-phase pulsed corona discharge (PCD). The ratio of the species dependent on the gas phase composition and treated water contact surface was the objective for the experimental research undertaken for aqueous phenol (fast reaction) and oxalic acid (slow reaction) solutions. The experiments were carried out in the reactor, where aqueous solutions showered between electrodes were treated with 100-ns pulses of 20 kV voltage and 400 A current amplitude. The role of ozone increased with increasing oxygen concentration and the oxidation reaction rate. The PCD treatment showed energy efficiency surpassing that of conventional ozonation.

Aliphatic peptidyl hydroperoxides as a source of secondary oxidation in hydroxyl radical protein footprinting

PubMed Central

Saladino, Jessica; Liu, Mian; Live, David; Sharp, Joshua S.

2009-01-01

Hydroxyl radical footprinting is a technique for studying protein structure and binding that entails oxidizing a protein system of interest with diffusing hydroxyl radicals, and then measuring the amount of oxidation of each amino acid. One important issue in hydroxyl radical footprinting is limiting amino acid oxidation by secondary oxidants to prevent uncontrolled oxidation which can cause amino acids to appear more solvent accessible than they really are. Previous work suggested that hydrogen peroxide was the major secondary oxidant of concern in hydroxyl radical footprinting experiments; however, even after elimination of all hydrogen peroxide, some secondary oxidation was still detected. Evidence is presented for the formation of peptidyl hydroperoxides as the most abundant product upon oxidation of aliphatic amino acids. Both reverse phase liquid chromatography and catalase treatment were shown to be ineffective at eliminating peptidyl hydroperoxides. The ability of these peptidyl hydroperoxides to directly oxidize methionine is demonstrated, suggesting the value of methionine amide as an in situ protectant. Hydroxyl radical footprinting protocols require the use of an organic sulfide or similar peroxide scavenger in addition to removal of hydrogen peroxide in order to successfully eradicate all secondary oxidizing species and prevent uncontrolled oxidation of sulfur-containing residues. PMID:19278868

ENHANCED CHEMICAL CLEANING: EFFECTIVENESS OF THE UV LAMP TO DECOMPOSE OXALATES

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

Ketusky, E.; Huff, T.; Sudduth, C.

2010-01-19

Enhanced Chemical Cleaning is a new process scheduled to begin cleaning Savannah River Site High Level Waste Tanks in 2012. It is an improvement over the current chemical cleaning method, in that it minimizes downstream impacts on the High Level Waste System. It is based on a state of the art scale removal process used on the secondary side of nuclear power plants, with modifications to accommodate the unique constraints created by the tanks. Both Enhanced Chemical Cleaning and the scale removal process are founded on dissolving metal oxides/hydroxides using oxalic acid, with subsequent oxalate decomposition via hydroxylation using ozonemore » or peroxide, and UV light as a catalyst. A divergence Enhanced Chemical Cleaning has from nuclear power scale removal is the significantly increased solids concentration during oxalate decomposition. These solids can limit the ability of the UV light to create hydroxyl radicals, either by limiting the ability of the light to penetrate through the solution, or by increasing the fouling rate on the UV light. Both will decrease the overall catalytic effectiveness, thereby decreasing the concentration of formed hydroxyl radicals. The hydroxyl radicals are the driving force behind the oxalate decomposition. To understand the impact of increased solids, testing was performed using a medium pressure UV light inside an ozone supplied Oxalate Decomposition Reactor. Using a dissolved metal sludge simulant with an initial oxalate concentration greater than 12,000 ppm, and an initial pH of about 2.0, the spent acid solution was recirculated through the reactor, while the UV light was allowed to foul. For the first few hours, the oxalate decomposition rate was about 1,300 ppm/hour. After about 3 hours, enough time for the UV lamp to foul, the oxalate decomposition rate decreased to about 500 ppm/hour. The decomposition rate then remained roughly constant for the next 16 hours. Overall, testing showed that the oxalate destruction rate decreased by about 2.8. Results from very similartests with similar chemistry suggest that the impact should be about 10. Based on the limited reaction pathwayfor the creation of hydroxyl radicals with iron, ozone, and no UV, the discrepancy suggests that initially, at 'time zero' the UV light failed to perform up to expectations. It is therefore concluded that regardless of the fouling rate, either the increased solids concentration is impacting the initial penetrability (i.e. to many solids), or the light is not adequately sized/configured to have the appropriate flux.« less

Numerical analysis of quantitative measurement of hydroxyl radical concentration using laser-induced fluorescence in flame

NASA Astrophysics Data System (ADS)

Shuang, Chen; Tie, Su; Yao-Bang, Zheng; Li, Chen; Ting-Xu, Liu; Ren-Bing, Li; Fu-Rong, Yang

2016-06-01

The aim of the present work is to quantitatively measure the hydroxyl radical concentration by using LIF (laser-induced fluorescence) in flame. The detailed physical models of spectral absorption lineshape broadening, collisional transition and quenching at elevated pressure are built. The fine energy level structure of the OH molecule is illustrated to understand the process with laser-induced fluorescence emission and others in the case without radiation, which include collisional quenching, rotational energy transfer (RET), and vibrational energy transfer (VET). Based on these, some numerical results are achieved by simulations in order to evaluate the fluorescence yield at elevated pressure. These results are useful for understanding the real physical processes in OH-LIF technique and finding a way to calibrate the signal for quantitative measurement of OH concentration in a practical combustor. Project supported by the National Natural Science Foundation of China (Grant No. 11272338) and the Fund from the Science and Technology on Scramjet Key Laboratory, China (Grant No. STSKFKT2013004).

Inhibition of platelet aggregation and in vitro free radical scavenging activity of dried fruiting bodies of Pleurotus eous.

PubMed

Suseem, S R; Saral, Mary

2015-07-01

To evaluate the ethyl acetate, methanol and aqueous extracts of dried fruiting bodies of Pleurotus eous for its anti-platelet activity on human volunteer's blood. And also to analyze the free radical scavenging property of the extracts of P.eous by using various in vitro models. Anti-platelet activity of dried fruiting bodies of P.eous was evaluated by in vitro model using blood platelets. Inhibition of platelet aggregation was monitored after pre-incubation of platelets with the crude extracts of mushroom P.eous. Antioxidant activities of extracts of P.eous were evaluated by different in vitro experiments, namely, 1, 1-diphenyl-2-picryl hydrazyl (DPPH), superoxide, hydroxyl radical and lipid peroxide radical models. Crude extracts of mushroom P.eous inhibited platelet aggregation dose-dependently which was induced by adenosine diphosphate (ADP). At a maximum concentration of 10 mg/mL, methanol extract effected 64.02% inhibition of lipid per-oxidation and 50.12% scavenging effect on superoxide anion radical. Aqueous extract of P.eous have shown 69.43% chelating ability on ferrous ions, 24.27% scavenging effect on hydroxyl radical and 49.57% scavenging effect on DPPH radical at 10 mg/mL. Increasing concentrations of the extract were found to cause progressively decreasing of the intensity of absorbance. Anti-platelet effects could be related in part to the polyphenolic compounds present in the extracts. Antioxidant activity results indicated the free radical scavenging property of the extracts of P.eous which might be due to the high content of phenolic compounds and flavonoids.

Evaluation of In Vitro Antioxidant Potential of Cordia retusa.

PubMed

Amudha, Murugesan; Rani, Shanmugam

2016-01-01

The present study was carried out to investigate the antioxidant potential, total flavonoid and phenolic content in extracts of aerial parts of Cordia retua (Vahl.) Masam. The samples such as ethyl acetate and ethanol extracts were tested using six in vitro models such as 2,2-diphenyl-1-picrylhydrazyl, nitric oxide radical, iron chelating, hydroxyl radical, superoxide radical scavenging activity and total antioxidant activity to evaluate the in vitro antioxidant potential of C. retusa by spectrophotometrically. Total flavonoid and phenolic content in samples were estimated using aluminum chloride colorimetric and Folin-Ciocalteu method. The results were analyzed statistically by the regression method. Half maximal inhibitory concentration (IC50) of the ethanol extract was found to be 596 μg/ml for DPPH, 597 μg/ml for nitric oxide radical, 554 μg/ml for iron chelating, 580 μg/ml for hydroxyl radical, 562 μg/ml for superoxide radical and 566 μg/ml for total antioxidant capacity. Furthermore, the total flavonoid content and total phenolic content of the ethanol extract were found to be 2.71 mg gallic acid equivalent per gram of extract and 1.86 mg quercetin equivalent per gram of extract, respectively. In all the testing, a significant correlation existed between concentrations of the extract and percentage inhibition of free radicals. The results of the present comprehensive analysis demonstrated that C. retusa possess potent antioxidant activity, high flavonoid and phenolic content. The antioxidant property may be related to the polyphenols and flavonoids present in the extract. These results clearly indicated that C. retusa is effective against free radical mediated diseases as a natural antioxidant.

Optimization of the NO photooxidation and the role of relative humidity.

PubMed

Ângelo, Joana; Magalhães, Pedro; Andrade, Luísa; Madeira, Luís M; Mendes, Adélio

2018-05-11

Photocatalysis was recognised as a suitable process for the photoabatement of atmospheric pollutants. The photooxidation mechanism on TiO 2 has been widely studied. However, recent studies demonstrated that the very often-assumed photooxidation intermediated by the hydroxyl radical cannot explain all the experimental observations. Indeed, this study contributes for a new understanding of NO photooxidation. First, the adsorption equilibrium isotherms of NO, NO 2 and H 2 O on the photocatalyst, Aeroxide ® P25 from Evonik Industries, were obtained. Also, the concentration of hydroxyl radicals was determined by photoluminescence. A comprehensive design of experiments was then followed; NO conversion and selectivity were obtained as a function of the relative humidity, irradiance, NO inlet concentration and residence time, following a response surface methodology (RSM). These results were then used to discuss the photooxidation mechanism of NO. Copyright © 2018 Elsevier Ltd. All rights reserved.

Vacuum ultraviolet photoionization cross section of the hydroxyl radical.

PubMed

Dodson, Leah G; Savee, John D; Gozem, Samer; Shen, Linhan; Krylov, Anna I; Taatjes, Craig A; Osborn, David L; Okumura, Mitchio

2018-05-14

The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O( 1 D) + H 2 O in a flow reactor in He at 8 Torr. The initial O( 1 D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O( 3 P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O( 3 P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O( 3 P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra.

Vacuum ultraviolet photoionization cross section of the hydroxyl radical

NASA Astrophysics Data System (ADS)

Dodson, Leah G.; Savee, John D.; Gozem, Samer; Shen, Linhan; Krylov, Anna I.; Taatjes, Craig A.; Osborn, David L.; Okumura, Mitchio

2018-05-01

The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O(1D) + H2O in a flow reactor in He at 8 Torr. The initial O(1D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O(3P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O(3P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O(3P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra.

The preparation and antioxidant activity of glucosamine sulfate

NASA Astrophysics Data System (ADS)

Xing, Ronge; Liu, Song; Wang, Lin; Cai, Shengbao; Yu, Huahua; Feng, Jinhua; Li, Pengcheng

2009-05-01

Glucosamine sulfate was prepared from glucosamine hydrochloride that was produced by acidic hydrolysis of chitin by ion-exchange method. Optical rotation and elemental analysis characterized the degree of its purity. In addition, the antioxidant potency of chitosan derivative-glucosamine sulfate was investigated in various established in vitro systems, such as superoxide (O{2/-})/hydroxyl (·OH) radicals scavenging, reducing power, iron ion chelating. The following results are obtained: first, glucosamine sulfate had pronounced scavenging effect on superoxide radical. For example the O{2/-} scavenging activity of glucosamine sulfate was 92.11% at 0.8 mg/mL. Second, the ·OH scavenging activity of glucosamine sulfate was also strong, and was about 50% at 3.2 mg/mL. Third, the reducing power of glucosamine sulfate was more pronounced. The reducing power of glucosamine sulfate was 0.643 at 0.75 mg/mL. However, its potency for ferrous ion chelating was weak. Furthermore, except for ferrous ion chelating potency, the scavenging rate of radical and reducing power of glucosamine sulfate were concentration-dependent and increased with their increasing concentrations, but its ferrous ion chelating potency decreased with the increasing concentration. The multiple antioxidant activities of glucosamine sulfate were evidents of reducing power and superoxide/hydroxyl radicals scavenging ability. These in vitro results suggest the possibility that glucosamine sulfate could be used effectively as an ingredient in health or functional food, to alleviate oxidative stress.

Kinetic Study of Hydroxyl and Sulfate Radical-Mediated Oxidation of Pharmaceuticals in Wastewater Effluents.

PubMed

Lian, Lushi; Yao, Bo; Hou, Shaodong; Fang, Jingyun; Yan, Shuwen; Song, Weihua

2017-03-07

Advanced oxidation processes (AOPs), such as hydroxyl radical (HO • )- and sulfate radical (SO 4 •- )-mediated oxidation, are alternatives for the attenuation of pharmaceuticals and personal care products (PPCPs) in wastewater effluents. However, the kinetics of these reactions needs to be investigated. In this study, kinetic models for 15 PPCPs were built to predict the degradation of PPCPs in both HO • - and SO 4 •- -mediated oxidation. In the UV/H 2 O 2 process, a simplified kinetic model involving only steady state concentrations of HO • and its biomolecular reaction rate constants is suitable for predicting the removal of PPCPs, indicating the dominant role of HO • in the removal of PPCPs. In the UV/K 2 S 2 O 8 process, the calculated steady state concentrations of CO 3 •- and bromine radicals (Br • , Br 2 •- and BrCl •- ) were 600-fold and 1-2 orders of magnitude higher than the concentrations of SO 4 •- , respectively. The kinetic model, involving both SO 4 •- and CO 3 •- as reactive species, was more accurate for predicting the removal of the 9 PPCPs, except for salbutamol and nitroimidazoles. The steric and ionic effects of organic matter toward SO 4 •- could lead to overestimations of the removal efficiencies of the SO 4 •- -mediated oxidation of nitroimidazoles in wastewater effluents.

Effects of various chemical compounds on spontaneous and hydrogen peroxide-induced reversion in strain TA104 of Salmonella typhimurium.

PubMed

Han, J S

1992-04-01

In experiments designed to determine which active oxygen species contribute to hydrogen peroxide (HP)-induced reversion in strain TA104 of Salmonella typhimurium, 1,10-phenanthroline (an iron chelator, which prevents the formation of hydroxyl radicals from HP and DNA-bound iron by the Fenton reaction), sodium azide (a singlet oxygen scavenger), and potassium iodide (an hydroxyl radical scavenger) inhibited HP-induced reversion. These results indicate that hydroxyl radicals generated from HP by the Fenton reaction, and perhaps singlet oxygen, contribute to HP-induced reversion in TA104. However, reduced glutathione (reduces Fe3+ to Fe2+ and/or HP to water), diethyldithiocarbamic acid (an inhibitor of superoxide dismutase), diethyl maleate (a glutathione scavenger), and 3-amino-1,2,4-triazole (an inhibitor of catalase) did not inhibit HP-induced reversion in TA104. Thus, superoxide radical anions and HP itself do not appear to be the cause of HP-induced reversion in this strain. In experiments on the effect of 5 common dietary compounds (beta-carotene, retinoic acid, and vitamins A, C and E), chlorophyllin (CHL), and ergothioneine, the frequency of revertants in TA104 increased above the spontaneous frequency in the presence of beta-carotene or vitamin C (about 2-fold) or vitamin A (about 3-fold). The 5 dietary antimutagens and CHL did not inhibit HP-induced reversion in TA104. However, L-ergothioneine inhibited HP-induced reversion in this strain. Therefore, it is likely that L-ergothioneine is a scavenger of hydroxyl radicals or an inhibitor of their formation, and perhaps of singlet oxygen, at the concentrations tested in TA104.

Dosimetry determines the initial OH radical concentration in fast photochemical oxidation of proteins (FPOP).

PubMed

Niu, Ben; Zhang, Hao; Giblin, Daryl; Rempel, Don L; Gross, Michael L

2015-05-01

Fast photochemical oxidation of proteins (FPOP) employs laser photolysis of hydrogen peroxide to give OH radicals that label amino acid side-chains of proteins on the microsecond time scale. A method for quantitation of hydroxyl radicals after laser photolysis is of importance to FPOP because it establishes a means to adjust the yield of •OH, offers the opportunity of tunable modifications, and provides a basis for kinetic measurements. The initial concentration of OH radicals has yet to be measured experimentally. We report here an approach using isotope dilution gas chromatography/mass spectrometry (GC/MS) to determine quantitatively the initial •OH concentration (we found ~0.95 mM from 15 mM H2O2) from laser photolysis and to investigate the quenching efficiencies for various •OH scavengers.

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

PubMed

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

2011-07-01

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

Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia.

PubMed

Liu, Yingjun; Seco, Roger; Kim, Saewung; Guenther, Alex B; Goldstein, Allen H; Keutsch, Frank N; Springston, Stephen R; Watson, Thomas B; Artaxo, Paulo; Souza, Rodrigo A F; McKinney, Karena A; Martin, Scot T

2018-04-01

Nitrogen oxides (NO x ) emitted from human activities are believed to regulate the atmospheric oxidation capacity of the troposphere. However, observational evidence is limited for the low-to-median NO x concentrations prevalent outside of polluted regions. Directly measuring oxidation capacity, represented primarily by hydroxyl radicals (OH), is challenging, and the span in NO x concentrations at a single observation site is often not wide. Concentrations of isoprene and its photo-oxidation products were used to infer the equivalent noontime OH concentrations. The fetch at an observation site in central Amazonia experienced varied contributions from background regional air, urban pollution, and biomass burning. The afternoon concentrations of reactive nitrogen oxides (NO y ), indicative of NO x exposure during the preceding few hours, spanned from 0.3 to 3.5 parts per billion. Accompanying the increase of NO y concentration, the inferred equivalent noontime OH concentrations increased by at least 250% from 0.6 × 10 6 to 1.6 × 10 6 cm -3 . The conclusion is that, compared to background conditions of low NO x concentrations over the Amazon forest, pollution increased NO x concentrations and amplified OH concentrations, indicating the susceptibility of the atmospheric oxidation capacity over the forest to anthropogenic influence and reinforcing the important role of NO x in sustaining OH concentrations.

Effects of extraction methods on the antioxidant activities of polysaccharides from Agaricus blazei Murrill.

PubMed

Jia, Shaoyi; Li, Feng; Liu, Yong; Ren, Haitao; Gong, Guili; Wang, Yanyan; Wu, Songhai

2013-11-01

Five polysaccharides were obtained from Agaricus blazei Murrill (ABM) through different extraction methods including hot water extraction, single enzyme extraction (pectinase, cellulase or papain) and compound enzymes extraction (cellulase:pectinase:papain). Their characteristics such as the polysaccharide yield, polysaccharide content, protein content, infrared spectra were determined, and antioxidant activities were investigated on the basis of hydroxyl radical, DPPH free radical, ABTS free radical and reducing power. The results showed that five extracts exhibited antioxidant activities in a concentration-dependent manner. Compared with other methods, the compound enzymes extraction method was found to present the highest polysaccharides yield (17.44%). Moreover, compound enzymes extracts exhibited the strongest reducing power and highest scavenging rates on hydroxyl radicals, DPPH radicals and ABTS radicals. On the contrary, hot water extraction method had the lowest polysaccharides yield of 11.95%, whose extracts also exhibited the lowest antioxidant activities. Overall, the available data obtained in vitro models suggested that ABM extracts were natural antioxidants and compound enzymes extraction was an appropriate, mild and effective extracting method for obtaining the polysaccharide extracts from Agaricus blazei Murrill (ABM). Copyright © 2013 Elsevier B.V. All rights reserved.

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

Atmospheric Hydroxyl Radical Production from Electronically Excited NO2 and H2O

NASA Astrophysics Data System (ADS)

Li, Shuping; Matthews, Jamie; Sinha, Amitabha

2008-03-01

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

Atmospheric hydroxyl radical production from electronically excited NO2 and H2O.

PubMed

Li, Shuping; Matthews, Jamie; Sinha, Amitabha

2008-03-21

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

In vitro antioxidant activity of pet ether extract of black pepper

PubMed Central

Singh, Ramnik; Singh, Narinder; Saini, B.S.; Rao, Harwinder Singh

2008-01-01

Objective: To investigate the in vitro antioxidant activity of different fractions (R1, R2 and R3) obtained from pet ether extract of black pepper fruits (Piper nigrum Linn.) Materials and Methods: The fractions R1, R2 and R3 were eluted from pet ether and ethyl acetate in the ratio of 6:4, 5:5 and 4:6, respectively. 1,1-Diphenyl-2-picryl-hydrazyl (DPPH) radical, superoxide anion radical, nitric oxide radical, and hydroxyl radical scavenging assays were carried out to evaluate the antioxidant potential of the extract. Results: The free radical scavenging activity of the different fractions of pet ether extract of P. nigrum (PEPN) increased in a concentration dependent manner. The R3 and R2 fraction of PEPN in 500 µg/ml inhibited the peroxidation of a linoleic acid emulsion by 60.48±3.33% and 58.89±2.51%, respectively. In DPPH free radical scavenging assay, the activity of R3 and R2 were found to be almost similar. The R3 (100µg/ml) fraction of PEPN inhibited 55.68±4.48% nitric oxide radicals generated from sodium nitroprusside, whereas curcumin in the same concentration inhibited 84.27±4.12%. Moreover, PEPN scavenged the superoxide radical generated by the Xanthine/Xanthine oxidase system. The fraction R2 and R3 in the doses of 1000µg/ml inhibited 61.04±5.11% and 63.56±4.17%, respectively. The hydroxyl radical was generated by Fenton's reaction. The amounts of total phenolic compounds were determined and 56.98 µg pyrocatechol phenol equivalents were detected in one mg of R3. Conclusions: P. nigrum could be considered as a potential source of natural antioxidant. PMID:20040947

Antioxidant, lipid peroxidation inhibition and free radical scavenging efficacy of a diterpenoid compound sugiol isolated from Metasequoia glyptostroboides.

PubMed

Bajpai, Vivek K; Sharma, Ajay; Kang, Sun Chul; Baek, Kwang-Hyun

2014-01-01

To investigate the antioxidant efficacy of a biologically active diterpenoid compound sugiol isolated from Metasequoia glyptostroboides (M. glyptostroboides) in various antioxidant models. An abietane type diterpenoid sugiol, isolated from ethyl acetate extract of M. glyptostroboides cones, was analyzed for its antioxidant efficacy as reducing power ability and lipid peroxidation inhibition as well as its ability to scavenge free radicals such as 1,1-diphenyl-2-picryl hydrazyl, nitric oxide, superoxide and hydroxyl radicals. The sugiol showed significant and concentration-dependent antioxidant and free radical scavenging activities. Consequently, the sugiol exerted lipid peroxidation inhibitory effect by 76.5% as compared to α-tocopherol (80.13%) and butylated hydroxyanisole (76.59%). In addition, the sugiol had significant scavenging activities of 1,1-diphenyl-2-picryl hydrazyl, nitric oxide, superoxide and hydroxyl free radicals in a concentration-dependent manner by 78.83%, 72.42%, 72.99% and 85.04%, when compared to the standard compound ascorbic acid (81.69%, 74.62%, 73.00% and 73.79%) and α-tocopherol/butylated hydroxyanisole (84.09%, 78.61%, 74.45% and 70.02%), respectively. These findings justify the biological and traditional uses of M. glyptostroboides or its secondary metabolites as confirmed by its promising antioxidant efficacy. Copyright © 2014 Hainan Medical College. Published by Elsevier B.V. All rights reserved.

Phenols removal using ozonation-adsorption with granular activated carbon (GAC) in rotating packed bed reactor

NASA Astrophysics Data System (ADS)

Karamah, E. F.; Leonita, S.; Bismo, S.

2018-01-01

Synthetic wastewater containing phenols was treated using combination method of ozonation-adsorption with GAC (Granular Activated Carbon) in a packed bed rotating reactor. Ozone reacts quickly with phenol and activated carbon increases the oxidation process by producing hydroxyl radicals. Performance parameters evaluated are phenol removal percentage, the quantity of hydroxyl radical formed, changes in pH and ozone utilization, dissolved ozone concentration and ozone concentration in off gas. The performance of the combination method was compared with single ozonation and single adsorption. The influence of GAC dose and initial pH of phenols were evaluated in ozonation-adsorption method. The results show that ozonation-adsorption method generates more OH radicals than a single ozonation. Quantity of OH radical formation increases with increasing pH and quantity of the GAC. The combination method prove better performance in removing phenols. At the same operation condition, ozonation-adsorption method is capable of removing of 78.62% phenols as compared with single ozonation (53.15%) and single adsorption (36.67%). The increasing percentage of phenol removal in ozonation-adsorption method is proportional to the addition of GAC dose, solution pH, and packed bed rotator speed. Maximum percentage of phenol removal is obtained under alkaline conditions (pH 10) and 125 g of GAC

In vitro evaluation of the antioxidant potential, phenolic and flavonoid contents of the stem bark ethanol extract of Anogeissus leiocarpus.

PubMed

Olugbami, J O; Gbadegesin, M A; Odunola, O A

2014-09-01

Plant-derived antioxidants with free radical scavenging activities can be relevant as chemopreventive agents against the numerous diseases associated with free radicals and reactive oxygen species. Some phytoconstituents possess antioxidant activities in biological systems. On this basis, we evaluated the antioxidant potential, and determined the total phenolic and flavonoid contents of the e thanol e xtract of the s tem bark of A nogeissus l eiocarpus [ EESAL ]. Antioxidant assays carried out include: 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging, phosphomolybdate, β-carotene bleaching, ferric reducing, and hydroxyl radical scavenging activities. Results of DPPH assay showed no significant difference ( p < 0.001) between EESAL and butylated hydroxyanisole [BHA], while EESAL exhibited a significantly ( p < 0.001) higher activity than BHT [butylated hydroxytoluene]. Phosphomolybdate method recorded a total antioxidant capacity of 190.00 ± 70.53 µg butylated hydroxytoluene equivalents [BHTE]/mg dry extract, while β-carotene bleaching assay gave percent antioxidant activities of both EESAL and BHT as 81.46±1.62 and 80.90±1.39 respectively. Ferric reducing abilities of both EESAL and ascorbic acid increased in a concentration-dependent manner with EESAL displaying a significantly ( p < 0.001) higher reductive activity than vitamin C. EESAL displayed a significantly higher hydroxyl radical scavenging activity as compared with BHT at the lowest concentration with no significant difference at the highest concentration. Total phenolic and flavonoid contents of EESAL were obtained as 608.10 ± 2.12 µg GAE/mg and 78.96 ± 3.37 µg QE/mg respectively. Taken together, the free radical scavenging and antioxidant activity of EESAL is likely due to its high phenolic content with complementary effects of the flavonoid components.

Production of Hydroxyl Radical via the Activation of Hydrogen Peroxide by Hydroxylamine.

PubMed

Chen, Liwei; Li, Xuchun; Zhang, Jing; Fang, Jingyun; Huang, Yanmin; Wang, Ping; Ma, Jun

2015-09-01

The production of the hydroxyl radical (HO·) is important in environmental chemistry. This study reports a new source of HO· generated solely from hydrogen peroxide (H2O2) activated by hydroxylamine (HA). Electron paramagnetic resonance analysis and the oxidation of a HO· probe, benzoic acid, were used to confirm the production of HO·. The production of HO· increased with increasing concentrations of either HA or H2O2 as well as decreasing pH. The second-order rate constant for the reaction was (2.2 ± 0.2) × 10(-4) M(-1) s(-1). HO· was probably produced in two steps: the activation of H2O2 by protonated HA and then reaction between the H2O2 and the intermediate protonated aminoxyl radical generated in the first step. Such a two-step oxidation can possibly be ascribed to the ionizable hydroxyl moiety in the molecular structure of HA, as is suggested by comparing the reactivity of a series of HA derivatives in HO· production. The results shed light on a previously unknown source of HO· formation, which broadens the understanding of its role in environmental processes.

Hepatoprotective Effect of Houttuynia cordata Thunb Extract against Carbon Tetrachloride-induced Hepatic Damage in Mice

PubMed Central

Kang, H.; Koppula, S.

2014-01-01

Houttuynia cordata Thunb (Saururaceae) is a traditional medicinal herb used to treat several disease symptoms. The present study was focused on the hepatoprotective effects of H. cordata ethyl acetate extract in experimental mice. Further the antioxidant potential of the extract was also evaluated to substantiate its hepatoprotective properties. Carbon tetrachloride-induced hepatic damage in mice was used to measure the serum biochemical parameters. Morphological changes in hepatocyte architecture were studied by haematoxylin and eosin staining. In vitro alkyl and hydroxyl free radical scavenging assays were performed to evaluate the antioxidant effect. Administration of H. cordata extract significantly reduced the elevated serum levels and regulated the altered levels of serum cholesterol in carbon tetrachloride-treated mice (P<0.05). The morphological changes in hepatocyte architecture were also reversed by H. cordata treatment. Further, the extract showed significant antioxidant actions by scavenging the alkyl and hydroxyl free radicals. The concentration of the extract necessary for 50% scavenging of alkyl and hydroxyl radicals was 15.5 and 410 μg/ml, respectively. H. cordata extract exhibited significant hepatoprotective property in carbon tetrachloride-induced hepatotoxicity in mice. The strong antioxidant activities possessed by the extract might be responsible for such actions. PMID:25284923

Hepatoprotective Effect of Houttuynia cordata Thunb Extract against Carbon Tetrachloride-induced Hepatic Damage in Mice.

PubMed

Kang, H; Koppula, S

2014-07-01

Houttuynia cordata Thunb (Saururaceae) is a traditional medicinal herb used to treat several disease symptoms. The present study was focused on the hepatoprotective effects of H. cordata ethyl acetate extract in experimental mice. Further the antioxidant potential of the extract was also evaluated to substantiate its hepatoprotective properties. Carbon tetrachloride-induced hepatic damage in mice was used to measure the serum biochemical parameters. Morphological changes in hepatocyte architecture were studied by haematoxylin and eosin staining. In vitro alkyl and hydroxyl free radical scavenging assays were performed to evaluate the antioxidant effect. Administration of H. cordata extract significantly reduced the elevated serum levels and regulated the altered levels of serum cholesterol in carbon tetrachloride-treated mice (P<0.05). The morphological changes in hepatocyte architecture were also reversed by H. cordata treatment. Further, the extract showed significant antioxidant actions by scavenging the alkyl and hydroxyl free radicals. The concentration of the extract necessary for 50% scavenging of alkyl and hydroxyl radicals was 15.5 and 410 μg/ml, respectively. H. cordata extract exhibited significant hepatoprotective property in carbon tetrachloride-induced hepatotoxicity in mice. The strong antioxidant activities possessed by the extract might be responsible for such actions.

Enhanced degradation of p-chlorophenol in a novel pulsed high voltage discharge reactor.

PubMed

Bian, Wenjuan; Ying, Xiangli; Shi, Junwen

2009-03-15

The yields of active specie such as ozone, hydrogen peroxide and hydroxyl radical were all enhanced in a novel discharge reactor. In the reactor, the original formation rate of hydroxyl radical was 2.27 x 10(-7) mol L(-1)s(-1), which was about three times than that in the contrast reactor. Ozone was formed in gas-phase and was transferred into the liquid. The characteristic of mass transfer was better in the novel reactor than that in the contrast reactor, which caused much higher ozone concentration in liquid. The dissociation of hydrogen peroxide was more evident in the former, which promoted the formations of hydroxyl radical. The p-chlorophenol (4-CP) degradation was also enhanced. Most of the ozone transferred into the liquid and hydrogen peroxide generated by discharge could be utilized by the degradation process of 4-CP. About 97% 4-CP was removed in 36 min discharge in the novel reactor. Organic acids such as formic, acetic, oxalic, propanoic and maleic acid were generated and free chloride ions were released in the degradation process. With the formation of organic acid, the pH was decreased and the conductivity was increased.

Photo degradation of methyl orange an azo dye by advanced Fenton process using zero valent metallic iron: influence of various reaction parameters and its degradation mechanism.

PubMed

Gomathi Devi, L; Girish Kumar, S; Mohan Reddy, K; Munikrishnappa, C

2009-05-30

Advanced Fenton process (AFP) using zero valent metallic iron (ZVMI) is studied as a potential technique to degrade the azo dye in the aqueous medium. The influence of various reaction parameters like effect of iron dosage, concentration of H(2)O(2)/ammonium per sulfate (APS), initial dye concentration, effect of pH and the influence of radical scavenger are studied and optimum conditions are reported. The degradation rate decreased at higher iron dosages and also at higher oxidant concentrations due to the surface precipitation which deactivates the iron surface. The rate constant for the processes Fe(0)/UV and Fe(0)/APS/UV is twice compared to their respective Fe(0)/dark and Fe(0)/APS/dark processes. The rate constant for Fe(0)/H(2)O(2)/UV process is four times higher than Fe(0)/H(2)O(2)/dark process. The increase in the efficiency of Fe(0)/UV process is attributed to the cleavage of stable iron complexes which produces Fe(2+) ions that participates in cyclic Fenton mechanism for the generation of hydroxyl radicals. The increase in the efficiency of Fe(0)/APS/UV or H(2)O(2) compared to dark process is due to continuous generation of hydroxyl radicals and also due to the frequent photo reduction of Fe(3+) ions to Fe(2+) ions. Though H(2)O(2) is a better oxidant than APS in all respects, but it is more susceptible to deactivation by hydroxyl radical scavengers. The decrease in the rate constant in the presence of hydroxyl radical scavenger is more for H(2)O(2) than APS. Iron powder retains its recycling efficiency better in the presence of H(2)O(2) than APS. The decrease in the degradation rate in the presence of APS as an oxidant is due to the fact that generation of free radicals on iron surface is slower compared to H(2)O(2). Also, the excess acidity provided by APS retards the degradation rate as excess H(+) ions acts as hydroxyl radical scavenger. The degradation of Methyl Orange (MO) using Fe(0) is an acid driven process shows higher efficiency at pH 3. The efficiency of various processes for the de colorization of MO dye is of the following order: Fe(0)/H(2)O(2)/UV>Fe(0)/H(2)O(2)/dark>Fe(0)/APS/UV>Fe(0)/UV>Fe(0)/APS/dark>H(2)O(2)/UV approximately Fe(0)/dark>APS/UV. Dye resisted to degradation in the presence of oxidizing agent in dark. The degradation process was followed by UV-vis and GC-MS spectroscopic techniques. Based on the intermediates obtained probable degradation mechanism has been proposed. The result suggests that complete degradation of the dye was achieved in the presence of oxidizing agent when the system was amended with iron powder under UV light illumination. The concentration of Fe(2+) ions leached at the end of the optimized degradation experiment is found to be 2.78 x 10(-3)M. With optimization, the degradation using Fe(0) can be effective way to treat azo dyes in aqueous solution.

Evaluation of In Vitro Antioxidant Potential of Cordia retusa

PubMed Central

Amudha, Murugesan; Rani, Shanmugam

2016-01-01

The present study was carried out to investigate the antioxidant potential, total flavonoid and phenolic content in extracts of aerial parts of Cordia retua (Vahl.) Masam. The samples such as ethyl acetate and ethanol extracts were tested using six in vitro models such as 2,2-diphenyl-1-picrylhydrazyl, nitric oxide radical, iron chelating, hydroxyl radical, superoxide radical scavenging activity and total antioxidant activity to evaluate the in vitro antioxidant potential of C. retusa by spectrophotometrically. Total flavonoid and phenolic content in samples were estimated using aluminum chloride colorimetric and Folin-Ciocalteu method. The results were analyzed statistically by the regression method. Half maximal inhibitory concentration (IC50) of the ethanol extract was found to be 596 μg/ml for DPPH, 597 μg/ml for nitric oxide radical, 554 μg/ml for iron chelating, 580 μg/ml for hydroxyl radical, 562 μg/ml for superoxide radical and 566 μg/ml for total antioxidant capacity. Furthermore, the total flavonoid content and total phenolic content of the ethanol extract were found to be 2.71 mg gallic acid equivalent per gram of extract and 1.86 mg quercetin equivalent per gram of extract, respectively. In all the testing, a significant correlation existed between concentrations of the extract and percentage inhibition of free radicals. The results of the present comprehensive analysis demonstrated that C. retusa possess potent antioxidant activity, high flavonoid and phenolic content. The antioxidant property may be related to the polyphenols and flavonoids present in the extract. These results clearly indicated that C. retusa is effective against free radical mediated diseases as a natural antioxidant. PMID:27168685

Metal Oxide Nanoparticles in Electrospun Polymers and Their Fate in Aqueous Waste Streams

NASA Astrophysics Data System (ADS)

Hoogesteijn von Reitzenstein, Natalia

Nanotechnology is becoming increasingly present in our environment. Engineered nanoparticles (ENPs), defined as objects that measure less than 100 nanometers in at least one dimension, are being integrated into commercial products because of their small size, increased surface area, and quantum effects. These special properties have made ENPs antimicrobial agents in clothing and plastics, among other applications in industries such as pharmaceuticals, renewable energy, and prosthetics. This thesis incorporates investigations into both application of nanoparticles into polymers as well as implications of nanoparticle release into the environment. First, the integration of ENPs into polymer fibers via electrospinning was explored. Electrospinning uses an external electric field applied to a polymer solution to produce continuous fibers with large surface area and small volume, a quality which makes the fibers ideal for water and air purification purposes. Indium oxide and titanium dioxide nanoparticles were embedded in polyvinylpyrrolidone and polystyrene. Viscosity, critical voltage, and diameter of electrospun fibers were analyzed in order to determine the effects of nanoparticle integration into the polymers. Critical voltage and viscosity of solution increased at 5 wt% ENP concentration. Fiber morphology was not found to change significantly as a direct effect of ENP addition, but as an effect of increased viscosity and surface tension. These results indicate the possibility for seamless integration of ENPs into electrospun polymers. Implications of ENP release were investigated using phase distribution functional assays of nanoscale silver and silver sulfide, as well as photolysis experiments of nanoscale titanium dioxide to quantify hydroxyl radical production. Functional assays are a means of screening the relevant importance of multiple processes in the environmental fate and transport of ENPs. Four functional assays---water-soil, water-octanol, water-wastewater sludge and water-surfactant---were used to compare concentrations of silver sulfide ENPs (Ag2S-NP) and silver ENPs (AgNP) capped by four different coatings. The functional assays resulted in reproducible experiments which clearly showed variations between nanoparticle phase distributions; the findings may be a product of the effects of the different coatings of the ENPs used. In addition to phase distribution experiments, the production of hydroxyl radical (HO˙) by nanoscale titanium dioxide (TiO2) under simulated solar irradiation was investigated. Hydroxyl radical are a short-lived, highly reactive species produced by solar radiation in aquatic environments that affect ecosystem function and degrades pollutants. HO˙ is produced by photolysis of TiO2 and nitrate (NO3-); these two species were used in photolysis experiments to compare the relative loads of hydroxyl radical which nanoscale TiO2 may add upon release to natural waters. Para-chlorobenzoic acid (pCBA) was used as a probe. Measured rates of pCBA oxidation in the presence of various concentrations of TiO2 nanoparticles and NO3 - were utilized to calculate pseudo first order rate constants. Results indicate that, on a mass concentration basis in water, TiO2 produces hydroxyl radical steady state concentrations at 1.3 times more than the equivalent amount of NO3-; however, TiO 2 concentrations are generally less than one order of magnitude lower than concentrations of NO3-. This has implications for natural waterways as the amount of nanoscale TiO2 released from consumer products into natural waterways increases in proportion to its use.

Comparative study of radical scavenger activities of crude extract and fractions from Cuphea carthagenensis leaves.

PubMed

Schuldt, E Z; Farias, M R; Ribeiro-do-Valle, R M; Ckless, K

2004-09-01

This study investigated the superoxide anion and hydroxyl radical scavenger properties, as well as the inhibition of lipid peroxidation by the crude hydroalcoholic extract (CE) and the butanolic (BF) and ethyl acetate (EAF) fractions of Cuphea carthagenensis leaves. In a enzymatic system of O2- production (xanthine/xanthine oxidase system) the CE, EAF and BF (0.1-100 microg ml(-1)) were effective at inhibiting both uric acid formation and NBT reduction by O2(-1). In the non-enzymatic system of O2- generation, the CE and fractions were effective only at the concentration of 100 microg ml(-1). The CE, EAF and BF were also evaluated for their ability to scavenge hydroxyl radicals and/or to chelate iron. The results showed that CE, BF and EAF from C. carthagenensis (0.1-100 microg ml(-1)) were able to inhibit deoxyribose degradation in a concentration-dependent manner. CE was more potent than the fractions. In a hydrophobic system, increasing concentrations of CE, EAF and BF (0.1-100 microg ml(-1)) caused graded inhibition of lipid peroxidation of rat liver homogenate. The EAF displayed the lowest median inhibitory concentration. The present study suggests that an extract (CE) and fractions (EAF and BF) from C. carthagenensis leaves are significant sources of phenolic compounds with antioxidant activity in vitro and may have important health effects, for example, in cardiovascular disease.

THE EFFECT OF DNOM PROPERTIES ON THE KINETICS OF OZONE DECOMPOSITION AND HYDROXYL RADICAL SCAVENGING

EPA Science Inventory

The influence of temperature, pH, alkalinity, and type and concentration of the dissolved organic matter (DOM) on the rate of ozone (O3) decomposition, O3-exposure, *OH-exposure and the ratio R ct of the concentrations of *OH and O3 has been studied. For a standardized single oz...

HYDROXYL RADICAL/OZONE RATIOS DURING OZONATION PROCESSES. II. THE EFFECT OF TEMPERATURE, PH, ALKALINITY, AND DOM PROPERTIES

EPA Science Inventory

The influence of temperature, pH, alkalinity, and type and concentration of the dissolved organic matter (DOM) on the rate of ozone (O3) decomposition, O3-exposure, .OH-exposure and the ratio Rct of the concentrations of .OH and O3 has been studied. For a standardized single ozon...

Chemical repair activity of free radical scavenger edaravone: reduction reactions with dGMP hydroxyl radical adducts and suppression of base lesions and AP sites on irradiated plasmid DNA

PubMed Central

Hata, Kuniki; Urushibara, Ayumi; Yamashita, Shinichi; Lin, Mingzhang; Muroya, Yusa; Shikazono, Naoya; Yokoya, Akinari; Fu, Haiying; Katsumura, Yosuke

2015-01-01

Reactions of edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) with deoxyguanosine monophosphate (dGMP) hydroxyl radical adducts were investigated by pulse radiolysis technique. Edaravone was found to reduce the dGMP hydroxyl radical adducts through electron transfer reactions. The rate constants of the reactions were greater than 4 × 108 dm3 mol−1 s−1 and similar to those of the reactions of ascorbic acid, which is a representative antioxidant. Yields of single-strand breaks, base lesions, and abasic sites produced in pUC18 plasmid DNA by gamma ray irradiation in the presence of low concentrations (10–1000 μmol dm−3) of edaravone were also quantified, and the chemical repair activity of edaravone was estimated by a method recently developed by the authors. By comparing suppression efficiencies to the induction of each DNA lesion, it was found that base lesions and abasic sites were suppressed by the chemical repair activity of edaravone, although the suppression of single-strand breaks was not very effective. This phenomenon was attributed to the chemical repair activity of edaravone toward base lesions and abasic sites. However, the chemical repair activity of edaravone for base lesions was lower than that of ascorbic acid. PMID:25212600

Treatability of phenol-production wastewater: Rate constant and pathway of dimethyl phenyl carbinol oxidation by hydroxyl radicals.

PubMed

Boonrattanakij, Nonglak; Joysampao, Atsawin; Pobsuktanasub, Tuksinaiya; Anotai, Jin; Ruangchainikom, Chalermchai

2017-12-15

Phenol-production wastewater is difficult to treat biologically by aerobic processes to meet the effluent standard COD of 120 mg L -1 because it contains several highly refractory aromatic pollutants, particularly dimethyl phenyl carbinol. Pretreatment revealed that dimethyl phenyl carbinol was slowly oxidized by molecular ozone; however, it readily reacted with hydroxyl radicals to yield acetophenone as a primary product. Acetophenone was further oxidized, first through five different pathways to form benzoic acid, phenyl glyoxalic acid, 4-4'-diacetyl biphenyl, and several hydroxylated aromatic compounds, and later to aliphatic carboxylic acids via ring cleavage. Regardless of system configuration (homogeneous vs heterogeneous), operating mode (batch vs continuous), and chemical concentration, the average intrinsic rate constants were 1.05 × 10 10 and 9.29 × 10 9  M -1  s -1 for dimethyl phenyl carbinol and acetophenone, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Ethylene formation from methionine as a method to evaluate oxygen free radical scavenging and metal inactivation by cosmetics.

PubMed

Galey, J B; Millecamps, F; Nguyen, Q L

1991-04-01

Synopsis It has been proposed that oxygen free radicals are involved in skin aging. This paper describes a new method for the evaluation of oxygen free radical scavenging by cosmetic products. It is based on the measurement, by gas chromatography, of ethylene produced during the oxidation of methionine by the hydroxyl radical. OH. is produced by an iron catalyzed superoxide-driven Fenton reaction in which superoxide is obtained by photochemical oxygen reduction. The cosmetic is applied, together with methionine, riboflavine, NADH, FeCl(3) and EDTA, on a glass microfibre filter and submitted to UVA exposure through a quartz cell. Ethylene is then measured from aliquots of the atmosphere inside the cell. Catalase or Desferal completely inhibits ethylene production. SOD or high concentrations of hydroxyl radical scavengers (Mannitol, DMSO etc.) afford a partial protection. Thus the efficiency of O(2) (-)., H(2)O(2) and OH. scavengers and iron chelators can be measured. The main advantage of this test is that it is performed in conditions which simulate skin during UV exposure (e.g. air and UV exposed thin layer). Furthermore, as it is non-invasive, it can also be applied to human skin in vivo.

Ab initio molecular dynamics of the reaction of quercetin with superoxide radical

NASA Astrophysics Data System (ADS)

Lespade, Laure

2016-08-01

Superoxide plays an important role in biology but in unregulated concentrations it is implicated in a lot of diseases such as cancer or atherosclerosis. Antioxidants like flavonoids are abundant in plant and are good scavengers of superoxide radical. The modeling of superoxide scavenging by flavonoids from the diet still remains a challenge. In this study, ab initio molecular dynamics of the reaction of the flavonoid quercetin toward superoxide radical has been carried out using Car-Parrinello density functional theory. The study has proven different reactant solvation by modifying the number of water molecules surrounding superoxide. The reaction consists in the gift of a hydrogen atom of one of the hydroxyl groups of quercetin to the radical. When it occurs, it is relatively fast, lower than 100 fs. Calculations show that it depends largely on the environment of the hydroxyl group giving its hydrogen atom, the geometry of the first water layer and the presence of a certain number of water molecules in the second layer, indicating a great influence of the solvent on the reactivity.

Punicalagin and catechins contain polyphenolic substructures that influence cell viability and can be monitored by radical chemosensors sensitive to electron transfer.

PubMed

Carreras, Anna; Mateos-Martín, María Luisa; Velázquez-Palenzuela, Amado; Brillas, Enric; Sánchez-Tena, Susana; Cascante, Marta; Juliá, Luis; Torres, Josep Lluís

2012-02-22

Plant polyphenols may be free radical scavengers or generators, depending on their nature and concentration. This dual effect, mediated by electron transfer reactions, may contribute to their influence on cell viability. This study used two stable radicals (tris(2,3,5,6-tetrachloro-4-nitrophenyl)methyl (TNPTM) and tris(2,4,6-trichloro-3,5-dinitrophenyl)methyl (HNTTM)) sensitive only to electron transfer reduction reactions to monitor the redox properties of polyphenols (punicalagin and catechins) that contain phenolic hydroxyls with different reducing capacities. The use of the two radicals reveals that punicalagin's substructures consisting of gallate esters linked together by carbon-carbon (C-C) bonds are more reactive than simple gallates and less reactive than the pyrogallol moiety of green tea catechins. The most reactive hydroxyls, detected by TNPTM, are present in the compounds that affect HT-29 cell viability the most. TNPTM reacts with C-C-linked gallates and pyrogallol and provides a convenient way to detect potentially beneficial polyphenols from natural sources.

Antioxidant Activity and Total Phenolic and Flavonoid Contents of Hieracium pilosella L. Extracts

PubMed Central

Stanojević, Ljiljana; Stanković, Mihajlo; Nikolić, Vesna; Nikolić, Ljubiša; Ristić, Dušica; Čanadanovic-Brunet, Jasna; Tumbas, Vesna

2009-01-01

The antioxidant activity of water, ethanol and methanol Hieracium pilosella L. extracts is reported. The antioxidative activity was tested by spectrophotometrically measuring their ability to scavenge a stable DPPH• free radical and a reactive hydroxyl radical trapped by DMPO during the Fenton reaction, using the ESR spectroscopy. Total phenolic content and total flavonoid content were evaluated according to the Folin-Ciocalteu procedure, and a colorimetric method, respectively. A HPLC method was used for identification of some phenolic compounds (chlorogenic acid, apigenin-7-O-glucoside and umbelliferone). The antioxidant activity of the investigated extracts slightly differs depending on the solvent used. The concentration of 0.30 mg/mL of water, ethanol and methanol extract is less effective in scavenging hydroxyl radicals (56.35, 58.73 and 54.35%, respectively) in comparison with the DPPH• radical scavenging activity (around 95% for all extracts). The high contents of total phenolic compounds (239.59–244.16 mg GAE/g of dry extract) and total flavonoids (79.13–82.18 mg RE/g of dry extract) indicated that these compounds contribute to the antioxidative activity. PMID:22346723

Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

NASA Astrophysics Data System (ADS)

Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

2011-08-01

The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H2O2) as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10-10-10-11 M s-1). The chemical composition (marine or continental origin) had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5. In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH) radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10-12 M) led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10-14 M), microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach. Combining these two approaches (experimental and theoretical), our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more efficient than its biodegradation; the biodegradation of acetate and succinate seemed to exceed their photodegradation.

Measurement of trace stratospheric constituents with a balloon borne laser radar

NASA Technical Reports Server (NTRS)

Heaps, William S.; Mcgee, Thomas J.

1990-01-01

The objective of this research was to measure the concentration of the stratospheric hydroxyl radical and related chemical species as a function of altitude, season, and time of day. Although hydroxyl plays a very important role in the chemistry controlling stratospheric ozone, little is known about its behavior because it has been a difficult species to measure. The instrument employed in this program was a laser radar, employing the technique of remote laser induced fluorescence. This instrument offers a number of attractive features including extreme specificity and sensitivity, a straightforward relationship between observed quantity and the desired concentration, and immunity to self-contamination.

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 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.

Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia

DOE PAGES

Liu, Yingjun; Seco, Roger; Kim, Saewung; ...

2018-04-11

Nitrogen oxides (NO x) emitted from human activities are believed to regulate the atmospheric oxidation capacity of the troposphere. However, observational evidence is limited for the low-to-median NO x concentrations prevalent outside of polluted regions. Directly measuring oxidation capacity, represented primarily by hydroxyl radicals (OH), is challenging, and the span in NO x concentrations at a single observation site is often not wide. Concentrations of isoprene and its photo-oxidation products were used to infer the equivalent noontime OH concentrations. The fetch at an observation site in central Amazonia experienced varied contributions from background regional air, urban pollution, and biomass burning.more » The afternoon concentrations of reactive nitrogen oxides (NO y), indicative of NO x exposure during the preceding few hours, spanned from 0.3 to 3.5 parts per billion. Accompanying the increase of NO y concentration, the inferred equivalent noontime OH concentrations increased by at least 250% from 0.6 × 10 6 to 1.6 × 10 6 cm -3. The conclusion is that, compared to background conditions of low NO x concentrations over the Amazon forest, pollution increased NO x concentrations and amplified OH concentrations, indicating the susceptibility of the atmospheric oxidation capacity over the forest to anthropogenic influence and reinforcing the important role of NO x in sustaining OH concentrations.« less

Isoprene photo-oxidation products quantify the effect of pollution on hydroxyl radicals over Amazonia

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

Liu, Yingjun; Seco, Roger; Kim, Saewung

Nitrogen oxides (NO x) emitted from human activities are believed to regulate the atmospheric oxidation capacity of the troposphere. However, observational evidence is limited for the low-to-median NO x concentrations prevalent outside of polluted regions. Directly measuring oxidation capacity, represented primarily by hydroxyl radicals (OH), is challenging, and the span in NO x concentrations at a single observation site is often not wide. Concentrations of isoprene and its photo-oxidation products were used to infer the equivalent noontime OH concentrations. The fetch at an observation site in central Amazonia experienced varied contributions from background regional air, urban pollution, and biomass burning.more » The afternoon concentrations of reactive nitrogen oxides (NO y), indicative of NO x exposure during the preceding few hours, spanned from 0.3 to 3.5 parts per billion. Accompanying the increase of NO y concentration, the inferred equivalent noontime OH concentrations increased by at least 250% from 0.6 × 10 6 to 1.6 × 10 6 cm -3. The conclusion is that, compared to background conditions of low NO x concentrations over the Amazon forest, pollution increased NO x concentrations and amplified OH concentrations, indicating the susceptibility of the atmospheric oxidation capacity over the forest to anthropogenic influence and reinforcing the important role of NO x in sustaining OH concentrations.« less

Evaluation of antibacterial, antioxidant and GC-MS analysis of ethanolic seed extract of Myristica dactyloides

NASA Astrophysics Data System (ADS)

Bhavani, R.; Vijayalakshmi, R.; Venkat Kumar, S.; Rajeshkumar, S.

2017-11-01

In this present investigation we analysed the antimicrobial and antioxidant activities of ethanol extract of Myristica dactyloides. The antimicrobial activity of the ethanol extract was evaluated by the agar well diffusion method against of E. coli, Klebsiella pneumonia, Streptococcus sp, and Staphylococcus aureus at different concentrations. The antibacterial activity showed the result in a dose-dependent manner. The free radical scavenging was evaluated against DPPH, hydroxyl, and nitric oxide radicals. In DPPH, hydroxyl and nitric oxide scavenging assay showed the IC 50 value of the extract was found to be 20 μg/ml, 48.25 and 30 μg/ml, respectively. The plant can be considered as promising antioxidant properties with high potential value for drug development for various diseases.

Distribution of electrical energy consumption for the efficient degradation control of THMs mixture in sonophotolytic process.

PubMed

Park, Beomguk; Cho, Eunju; Son, Younggyu; Khim, Jeehyeong

2014-11-01

Sonophotolytic degradation of THMs mixture with different electrical energy ratio was carried out for efficient design of process. The total consumed electrical energy was fixed around 50W, and five different energy conditions were applied. The maximum degradation rate showed in conditions of US:UV=1:3 and US:UV=0:4. This is because the photolytic degradation of bromate compounds is dominant degradation mechanism for THMs removal. However, the fastest degradation of total organic carbon was observed in a condition of US:UV=1:3. Because hydrogen peroxide generated by sonication was effectively dissociated to hydroxyl radicals by ultraviolet, the concentration of hydroxyl radical was maintained high. This mechanism provided additional degradation of organics. This result was supported by comparison between the concentration of hydrogen peroxide sole and combined process. Consequently, the optimal energy ratio was US:UV=1:3 for degradation of THMs in sonophotolytic process. Copyright © 2014 Elsevier Ltd. All rights reserved.

N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds.

PubMed

Marti, Erica J; Pisarenko, Aleksey N; Peller, Julie R; Dickenson, Eric R V

2015-04-01

Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61-78% for 3 precursors, 12-23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging. Copyright © 2014 Elsevier Ltd. All rights reserved.

Degradation of cellulose at the wet-dry interface. II. Study of oxidation reactions and effect of antioxidants.

PubMed

Jeong, Myung-Joon; Dupont, Anne-Laurence; de la Rie, E René

2014-01-30

To better understand the degradation of cellulose upon the formation of a tideline at the wet-dry interface when paper is suspended in water, the production of chemical species involved in oxidation reactions was studied. The quantitation of hydroperoxides and hydroxyl radicals was carried out in reverse phase chromatography using triphenylphosphine and terephthalic acid, respectively, as chemical probes. Both reactive oxygen species were found in the tideline immediately after its formation, in the range of micromoles and nanomoles per gram of paper, respectively. The results indicate that hydroxyl radicals form for the most part in paper before the tideline experiment, whereas hydroperoxides appear to be produced primarily during tideline formation. Iron sulfate impregnation of the paper raised the production of hydroperoxides. After hygrothermal aging in sealed vials the hydroxyl radical content in paper increased significantly. When aged together in the same vial, tideline samples strongly influenced the degradation of samples from other areas of the paper (multi-sample aging). Different types of antioxidants were added to the paper before the tideline experiment to investigate their effect on the oxidation reactions taking place. In samples treated with iron sulfate or artificially aged, the addition of Irgafos 168 (tris(2,4-ditert-butylphenyl) phosphate) and Tinuvin 292 (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate) reduced the concentration of hydroperoxides and hydroxyl radicals, respectively. Tinuvin 292 was also found to considerably lower the rate of cellulose chain scission reactions during hygrothermal aging of the paper. Copyright © 2013 Elsevier Ltd. All rights reserved.

Degradation and mineralization of Bisphenol A (BPA) in aqueous solution using advanced oxidation processes: UV/H2O2 and UV/S2O8(2-) oxidation systems.

PubMed

Sharma, Jyoti; Mishra, I M; Kumar, Vineet

2015-06-01

This work reports on the removal and mineralization of an endocrine disrupting chemical, Bisphenol A (BPA) at a concentration of 0.22 mM in aqueous solution using inorganic oxidants (hydrogen peroxide, H2O2 and sodium persulfate, Na2S2O8;S2O8(2-)) under UV irradiation at a wavelength of 254 nm and 40 W power (Io = 1.26 × 10(-6) E s(-1)) at its natural pH and a temperature of 29 ± 3 °C. With an optimum persulfate concentration of 1.26 mM, the UV/S2O8(2-) process resulted in ∼95% BPA removal after 240 min of irradiation. The optimum BPA removal was found to be ∼85% with a H2O2 concentration of 11.76 mM. At higher concentrations, either of the oxidants showed an adverse effect because of the quenching of the hydroxyl or sulfate radicals in the BPA solution. The sulfate-based oxidation process could be used over a wider initial pH range of 3-12, but the hydroxyl radical-based oxidation of BPA should be carried out in the acidic pH range only. The water matrix components (bicarbonate, chloride and humic acid) showed higher scavenging effect in hydroxyl radical-based oxidation than that in the sulfate radical-based oxidation of BPA. UV/S2O8(2-) oxidation system utilized less energy (307 kWh/m(3)) EE/O in comparison to UV/H2O2 system (509 kWh/m(3)) under optimum operating conditions. The cost of UV irradiation far outweighed the cost of the oxidants in the process. However, the total cost of treatment of persulfate-based system was much lower than that of H2O2-based oxidation system. Copyright © 2015 Elsevier Ltd. All rights reserved.

In Vitro Evaluation of Antioxidant and Antimicrobial Activities of Melaleuca alternifolia Essential Oil

PubMed Central

Zhang, Xiaofeng; Guo, Yanjun; Guo, Liying; Jiang, Hui

2018-01-01

The in vitro antioxidant and antimicrobial activity of the essential oil from Melaleuca alternifolia (M. alternifolia) was evaluated in this report. The antioxidant potential of the essential oil from M. alternifolia was evaluated by the DPPH (2,2-diphenyl-1-picrylhydrazyl) method, thiobarbituric acid reactive species (TBARS) assay, and the hydroxyl radical scavenging activity method. The essential oil from M. alternifolia was able to reduce DPPH with an EC50 (concentration for 50% of maximal effect) of 48.35 μg/ml, inhibit the lipid peroxidation with an IC50 (50% inhibitory concentration) of 135.9 μg/ml, and eliminate hydroxyl radicals with an EC50 of 43.71 μg/ml. Antimicrobial screening, minimum inhibitory concentration, and minimum bactericidal concentration assays showed that the essential oil from M. alternifolia inhibited strongly the growth of different types of microorganisms, including Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Penicillium italicum Wehmer, and Penicillium digitatum Sacc. Thus, the essential oil of M. alternifolia possesses antioxidant and antimicrobial activity and could be suitable for use as a natural preservative ingredient in food, agriculture, and pharmaceutical industries. PMID:29854733

Degradation of diethyl phthalate (DEP) by UV/persulfate: An experiment and simulation study of contributions by hydroxyl and sulfate radicals.

PubMed

Wang, Ziying; Shao, Yisheng; Gao, Naiyun; Lu, Xian; An, Na

2018-02-01

Degradation of diethyl phthalate (DEP) by ultraviolet/persulfate (UV/PS) process at different reaction conditions was evaluated. DEP can be degraded effectively via this process. Both tert-butyl (TBA) and methanol (MeOH) inhibited the degradation of DEP with MeOH having a stronger impact than TBA, suggesting sulfate radical () and hydroxyl radical (HO) both existed in the reaction systems studied. The second-order rate constants of DEP reacting with and HO were calculated to be (6.4±0.3)×10 7 M -1 s -1 and (3.7±0.1)×10 9 M -1 s -1 , respectively. To further access the potential degradation mechanism in this system, the pseudo-first-order rate constants (k o ) and the radical contributions were modeled using a simple steady-state kinetic model involving and HO. Generally, HO had a greater contribution to DEP degradation than . The k o of DEP increased as PS dosages increased when PS dosages were below 1.9 mM. However, it decreased with increasing initial DEP concentrations, which might be due to the radical scavenging effect of DEP. The k o values in acidic conditions were higher than those in alkaline solutions, which was probably caused by the increasing concentration of hydrogen phosphate (with higher scavenging effects than dihydrogen phosphate) from the phosphate buffer as pH values rose. Natural organic matter and bicarbonate dramatically suppressed the degradation of DEP by scavenging and HO. Additionally, the presence of chloride ion (Cl - ) promoted the degradation of DEP at low Cl - concentrations (0.25-1 mM). Finally, the proposed degradation pathways were illustrated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Hepatoprotective and antioxidant capacity of Melochia corchorifolia extracts.

PubMed

Rao, B Ganga; Rao, Y Venkateswara; Rao, T Mallikarjuna

2013-07-01

To evaluate hepato protective and antioxidant capacity of Melochia corchorifolia (M. corchorifolia) aerial part extracts. Antioxidant activity was evaluated by using three free radicals (Superoxide, Hydroxyl and DPPH) and hepatoprotective activity was assessed against CCl4 induced liver intoxication in rats. The extracts produced concentration dependent percentage protection in decrease of serum enzymes and percentage inhibition on free radicals. Among all extracts methanol extract showed better activity with percentage protection of SGOT (78.98%), SGPT (79.65%), ALP (82.48%) and total bilirubin (80.0%) levels against CCl4 liver intoxication and also methanolic extract showed better activity with IC50 values on superoxide, hydroxyl and DPPH radicals were 127 μ g, 240 μ g and 179 μ g. From the results obtained during the study it could be concluded that M. corchorifolia aerial part extracts have antioxidant and hepatoprotective components. Further study is necessary for isolation and characterization of bioactive molecules which are responsible for hepatoprotective and antioxidant activity. Copyright © 2013 Hainan Medical College. Published by Elsevier B.V. All rights reserved.

Aircraft-borne, laser-induced fluorescence instrument for the in situ detection of hydroxyl and hydroperoxyl radicals

NASA Technical Reports Server (NTRS)

Wennberg, P. O.; Cohen, R. C.; Hazen, N. L.; Lapson, L. B.; Allen, N. T.; Hanisco, T. F.; Oliver, J. F.; Lanham, N. W.; Demusz, J. N.; Anderson, J. G.

1994-01-01

The odd-hydrogen radicals OH and HO2 are central to most of the gas-phase chemical transformations that occur in the atmosphere. Of particular interest is the role that these species play in controlling the concentration of stratospheric ozone. This paper describes an instrument that measures both of these species at volume mixing ratios below one part in 10(exp 14) in the upper troposphere and lower stratosphere. The hydroxyl radical (OH) is measured by laser induced fluorescence at 309 nm. Tunable UV light is used to pump OH to the first electric state near 282 nm. the laser light is produced by a high-repetition rate pulsed dye-laser powered with all solid-state pump lasers. HO2 is measured as OH after gas-phase titration with nitric oxide. Measurements aboard a NASA ER-2 aircraft demonstrate the capability of this instrument to perform reliably with very high signal-to-noise ratios (greater than 30) achieved in short integration times (less than 20 sec).

Enhanced hydroxyl radical production by dihydroxybenzene-driven Fenton reactions: implications for wood biodegradation.

PubMed

Contreras, David; Rodríguez, Jaime; Freer, Juanita; Schwederski, Brigitte; Kaim, Wolfgang

2007-09-01

Brown rot fungi degrade wood, in initial stages, mainly through hydroxyl radicals (.OH) produced by Fenton reactions. These Fenton reactions can be promoted by dihydroxybenzenes (DHBs), which can chelate and reduce Fe(III), increasing the reactivity for different substrates. This mechanism allows the extensive degradation of carbohydrates and the oxidation of lignin during wood biodegradation by brown rot fungi. To understand the enhanced reactivity in these systems, kinetics experiments were carried out, measuring .OH formation by the spin-trapping technique of electron paramagnetic resonance spectroscopy. As models of the fungal DHBs, 1,2-dihydroxybenzene (catechol), 2,3-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid were utilized as well as 1,2-dihydroxy-3,5-benzenedisulfonate as a non-Fe(III)-reducing substance for comparison. Higher amounts and maintained concentrations of .OH were observed in the driven Fenton reactions versus the unmodified Fenton process. A linear correlation between the logarithms of complex stability constants and the .OH production was observed, suggesting participation of such complexes in the radical production.

Respiratory Health Effects of Volcanic Ash - a new Approach

NASA Astrophysics Data System (ADS)

Horwell, C. J.; Fenoglio, I.; Sparks, R. J.; Ragnarsdottir, K. V.; Fubini, B.

2003-12-01

Attempts to characterise the toxicity of volcanic ash have focused on the presence of the crystalline silica polymorph cristobalite, which is known to cause silicosis and lung cancer in industrial settings. Within the lung, it is the surface of the particles which will react with endogenous molecules. Free radicals, produced on particle surfaces, can react with DNA and other cellular components, instigating a chain of toxic events. For the first time, the ability of volcanic ash to form free radicals has been assessed using Electron Paramagnetic Resonance techniques specific to the hydroxyl radical. Respirable (< 4 microns) crystalline silica, separated from volcanic ash from the Soufriere Hills volcano, Montserrat, West Indies, did not produce hydroxyl free radicals or surface radicals. However, the ash, itself, generated up to 3 times more hydroxyl radicals than a quartz of known toxicity. The cause of the reactivity is reduced iron on the surface of iron-rich minerals such as amphiboles and pyroxenes. Fresh volcanic ash generates more free radicals than weathered volcanic ash which will have oxidised (and leached away) surface iron. These results have implications for volcanic health hazard research as it was previously assumed that volcanoes which did not produce respirable crystalline silica presented a lesser respiratory health hazard. The International Volcanic Health Hazard Network (IVHHN) promotes research into the health effects of volcanic emissions. Under the auspices of IVHHN, volcanic ash samples from volcanoes world-wide are being analysed for surface reactivity, grain-size distribution and composition to form a comprehensive database for use by volcano observatories, emergency managers, medical practitioners and researchers. The results will highlight volcanoes which have the potential to cause a respiratory health hazard through generation of iron-catalysed free radicals, as well as more conventional markers such as concentration of respirable particles. At the onset of new eruptions, the database will be used to aid the rapid assessment of health hazard from volcanic ash.

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.

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.

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.

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.

Concentration-dependent photodegradation kinetics and hydroxyl-radical oxidation of phenicol antibiotics.

PubMed

Li, Kai; Zhang, Peng; Ge, Linke; Ren, Honglei; Yu, Chunyan; Chen, Xiaoyang; Zhao, Yuanfeng

2014-09-01

Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

QSPR prediction of the hydroxyl radical rate constant of water contaminants.

PubMed

Borhani, Tohid Nejad Ghaffar; Saniedanesh, Mohammadhossein; Bagheri, Mehdi; Lim, Jeng Shiun

2016-07-01

In advanced oxidation processes (AOPs), the aqueous hydroxyl radical (HO) acts as a strong oxidant to react with organic contaminants. The hydroxyl radical rate constant (kHO) is important for evaluating and modelling of the AOPs. In this study, quantitative structure-property relationship (QSPR) method is applied to model the hydroxyl radical rate constant for a diverse dataset of 457 water contaminants from 27 various chemical classes. The constricted binary particle swarm optimization and multiple-linear regression (BPSO-MLR) are used to obtain the best model with eight theoretical descriptors. An optimized feed forward neural network (FFNN) is developed to investigate the complex performance of the selected molecular parameters with kHO. Although the FFNN prediction results are more accurate than those obtained using BPSO-MLR, the application of the latter is much more convenient. Various internal and external validation techniques indicate that the obtained models could predict the logarithmic hydroxyl radical rate constants of a large number of water contaminants with less than 4% absolute relative error. Finally, the above-mentioned proposed models are compared to those reported earlier and the structural factors contributing to the AOP degradation efficiency are discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Desulfurization of phosphorothioate oligonucleotides via the sulfur-by-oxygen replacement induced by the hydroxyl radical during negative electrospray ionization mass spectrometry.

PubMed

Wu, Lianming; White, David E; Ye, Connie; Vogt, Frederick G; Terfloth, Gerald J; Matsuhashi, Hayao

2012-07-01

While the occurrence of desulfurization of phosphorothioate oligonucleotides in solution is well established, this study represents the first attempt to investigate the basis of the unexpected desulfurization via the net sulfur-by-oxygen (S-O) replacement during negative electrospray ionization (ESI). The current work, facilitated by quantitative mass deconvolution, demonstrates that considerable desulfurization can take place even under common negative ESI operating conditions. The extent of desulfurization is dependent on the molar phosphorothioate oligonucleotide-to-hydroxyl radical ratio, which is consistent with the corona discharge-induced origin of the hydroxyl radical leading to the S-O replacement. This hypothesis is supported by the fact that an increase of the high-performance liquid chromatography (HPLC) flow rate and the on-column concentration of a phosphorothioate oligonucleotide, as well as a decrease of the electrospray voltage reduce the degree of desulfurization. Comparative LC-tandem mass spectrometry (MS/MS) sequencing of a phosphorothioate oligonucleotide and its corresponding desulfurization product revealed evidence that the S-O replacement occurs at multiple phosphorothioate internucleotide linkage sites. In practice, the most convenient and effective strategy for minimizing this P = O artifact is to increase the LC flow rate and the on-column concentration of phosphorothioate oligonucleotides. Another approach to mitigate possible detrimental effects of the undesired desulfurization is to operate the ESI source at a very low electrospray voltage to diminish the corona discharge; however this will significantly compromise sensitivity when analyzing the low-level P = O impurities in phosphorothioate oligonucleotides. Copyright © 2012 John Wiley & Sons, Ltd.

Chemical repair activity of free radical scavenger edaravone: reduction reactions with dGMP hydroxyl radical adducts and suppression of base lesions and AP sites on irradiated plasmid DNA.

PubMed

Hata, Kuniki; Urushibara, Ayumi; Yamashita, Shinichi; Lin, Mingzhang; Muroya, Yusa; Shikazono, Naoya; Yokoya, Akinari; Fu, Haiying; Katsumura, Yosuke

2015-01-01

Reactions of edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one) with deoxyguanosine monophosphate (dGMP) hydroxyl radical adducts were investigated by pulse radiolysis technique. Edaravone was found to reduce the dGMP hydroxyl radical adducts through electron transfer reactions. The rate constants of the reactions were greater than 4 × 10(8) dm(3) mol(-1) s(-1) and similar to those of the reactions of ascorbic acid, which is a representative antioxidant. Yields of single-strand breaks, base lesions, and abasic sites produced in pUC18 plasmid DNA by gamma ray irradiation in the presence of low concentrations (10-1000 μmol dm(-3)) of edaravone were also quantified, and the chemical repair activity of edaravone was estimated by a method recently developed by the authors. By comparing suppression efficiencies to the induction of each DNA lesion, it was found that base lesions and abasic sites were suppressed by the chemical repair activity of edaravone, although the suppression of single-strand breaks was not very effective. This phenomenon was attributed to the chemical repair activity of edaravone toward base lesions and abasic sites. However, the chemical repair activity of edaravone for base lesions was lower than that of ascorbic acid. © The Author 2014. Published by Oxford University Press on behalf of The Japan Radiation Research Society and Japanese Society for Radiation Oncology.

Sugars as hydroxyl radical scavengers: proof-of-concept by studying the fate of sucralose in Arabidopsis.

PubMed

Matros, Andrea; Peshev, Darin; Peukert, Manuela; Mock, Hans-Peter; Van den Ende, Wim

2015-06-01

Substantial formation of reactive oxygen species (ROS) is inevitable in aerobic life forms. Due to their extremely high reactivity and short lifetime, hydroxyl radicals are a special case, because cells have not developed enzymes to detoxify these most dangerous ROS. Thus, scavenging of hydroxyl radicals may only occur by accumulation of higher levels of simple organic compounds. Previous studies have demonstrated that plant-derived sugars show hydroxyl radical scavenging capabilities during Fenton reactions with Fe(2+) and hydrogen peroxide in vitro, leading to formation of less detrimental sugar radicals that may be subject of regeneration to non-radical carbohydrates in vivo. Here, we provide further evidence for the occurrence of such radical reactions with sugars in planta, by following the fate of sucralose, an artificial analog of sucrose, in Arabidopsis tissues. The expected sucralose recombination and degradation products were detected in both normal and stressed plant tissues. Oxidation products of endogenous sugars were also assessed in planta for Arabidopsis and barley, and were shown to increase in abundance relative to the non-oxidized precursor during oxidative stress conditions. We concluded that such non-enzymatic reactions with hydroxyl radicals form an integral part of plant antioxidant mechanisms contributing to cellular ROS homeostasis, and may be more important than generally assumed. This is discussed in relation to the recently proposed roles for Fe(2+) and hydrogen peroxide in processes leading to the origin of metabolism and the origin of life. © 2015 The Authors The Plant Journal © 2015 John Wiley & Sons Ltd.

HETEROGENOUS PHOTOREACTION OF FORMALDEHYDE WITH HYDROXYL RADICALS

EPA Science Inventory

Atmospheric heterogeneous photoreactions occur between formaldehyde and hydroxyl radicals to produce formic acid. hese photoreactions not only occur in clouds, but also in other tropospheric hydrometeors such as precipitation and dew droplets. xperiments were performed by irradia...

Protective effects of buckwheat honey on DNA damage induced by hydroxyl radicals.

PubMed

Zhou, Juan; Li, Peng; Cheng, Ni; Gao, Hui; Wang, Bini; Wei, Yahui; Cao, Wei

2012-08-01

To understand the antioxidant properties of buckwheat honeys, we investigated their antioxidant effects on hydroxyl radical-induced DNA breaks in the non-site-specific and site-specific systems, the physicochemical properties, antioxidant activities (1,1-diphenyl-2-picrylhydrazyl (DPPH), hydroxyl radical scavenging activity, chelating, and reducing power assays), total phenolic content and individual phenolic acids were also determined. Total phenolic content of buckwheat honeys ranged from 774 to 1694 mg PA/kg, and p-hydroxybenzoic and p-coumaric acids proved to be the main components in buckwheat honeys. All the buckwheat honey samples possess stronger capability to protect DNA in the non-site-specific systems than in the site-specific systems from being damaged by hydroxyl radicals. In the non-site-specific and site-specific system, buckwheat honeys samples prevented ()OH-induced DNA breaks by 21-78% and 5-31% over control value, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

CHEMICAL DESTRUCTION OF MTBE USING FENTON'S REAGENT: EFFECT OF FERROUS IRON/HYDROGEN PEROXIDE RATIO

EPA Science Inventory

In previous laboratory experiments Fenton's Reagent (FR) was successfully used as the source of hydroxyl radicals (OH*) for chemical treatment of low concentrations of methyl tert-butyl ether (MTBE) in water. Although under certain conditions MTBE degradation levels as high as 99...

Hydroxylation of D-phenylalanine as a novel approach to detect hydroxyl radicals: application to cardiac pathophysiology.

PubMed

Biondi, Roberto; Ambrosio, Giuseppe; Liebgott, Tibaud; Cardounel, Arturo J; Bettini, Marco; Tritto, Isabella; Zweier, Jay L

2006-07-15

Research in the pathophysiology of ischemia/reperfusion or redox signaling is hindered by lack of simple methodology to measure short-lived oxygen radicals. In the presence of hydroxyl radical ((*)OH), d-phenylalanine (d-Phe) yields para-, meta- and ortho-tyrosine. We have previously demonstrated that d-Phe can accurately detect (*)OH formation in chemical, enzymatic and cellular systems by simple HPLC methodology [Anal Biochem 290:138;2001]. In the present study, we tested whether d-Phe hydroxylation can be used to detect (*)OH formation in intact organs. Rat hearts were perfused with buffer containing 5 mM d-Phe and subjected to 30 min of total global ischemia at 37 degrees C followed by 45 min of reperfusion. Quantitative analysis of the three hydroxytyrosine isomers was achieved by HPLC-based electrochemical detection of cardiac venous effluent, with the analytical cells operating in the oxidative mode. The detection limit of this assay was <10 fmol. Under baseline conditions, hydroxytyrosine release from the heart was very low ( congruent with0.8 nmol/min/g). However, a prominent tyrosine burst occurred immediately upon post-ischemic reflow. In cardiac effluent collected 40 s into reperfusion, the hydroxytyrosine concentration was more than 40 times greater than at baseline; hydroxytyrosine concentration then progressively declined, to return to pre-ischemic values by 5 min of reperfusion. In parallel experiments, formation of hydroxytyrosines was markedly reduced in hearts reperfused in the presence of the (*)OH scavenger mannitol. Inclusion of 5 mm d-Phe in the perfusion medium altered neither basal cardiac function nor coronary vascular tone, but it enhanced recovery of myocardial function during post-ischemic reperfusion, consistent with direct reaction with (*)OH. Our results demonstrate that d-Phe is a sensitive method for detection of (*)OH generation in the heart. Since d-Phe is not a substrate for endogenous enzymes, it can be exploited as a reliable method to measure (*)OH formation under a variety of pathophysiological conditions.

Degradation of selected organophosphate pesticides in wastewater by dielectric barrier discharge plasma.

PubMed

Hu, Yingmei; Bai, Yanhong; Yu, Hu; Zhang, Chunhong; Chen, Jierong

2013-09-01

In this paper, degradation of selected organophosphate pesticides (dichlorvos and dimethoate) in wastewater by dielectric barrier discharge plasma (DBD) was studied. DBD parameters, i.e. discharge powers and air-gap distances, differently affect their degradation efficiency. The results show that better degradation efficiency is obtained with a higher discharge power and a shorter air-gap distance. The effect of radical intervention degradation was also investigated by adding radical scavenger (tert-butyl alcohol) to the pesticide solution during the experiments. The result shows that the degradation efficiency is restrained in the presence of radical scavenger. It clearly demonstrates that hydroxyl radicals are most likely the main driver for degradation process. Moreover, the kinetics indicate that the disappearance rate of pesticides follows the first-order rate law when the initial concentration of the solution is low, but shifts to zero-order at a higher initial concentration.

Enhanced degradation of benzene by percarbonate activated with Fe(II)-glutamate complex.

PubMed

Fu, Xiaori; Gu, Xiaogang; Lu, Shuguang; Miao, Zhouwei; Xu, Minhui; Zhang, Xiang; Danish, Muhammad; Cui, Hang; Farooq, Usman; Qiu, Zhaofu; Sui, Qian

2016-04-01

Effective degradation of benzene was achieved in sodium percarbonate (SPC)/Fe(II)-Glu system. The presence of glutamate (Glu) could enhance the regeneration of Fe(III) to Fe(II), which ensures the benzene degradation efficiency at wider pH range and eliminate the influence of HCO3 (-) in low concentration. Meanwhile, the significant scavenging effects of high HCO3 (-) concentration could also be overcome by increasing the Glu/SPC/Fe(II)/benzene molar ratio. Free radical probe compound tests, free radical scavenger tests, and electron paramagnetic resonance (EPR) analysis were conducted to explore the reaction mechanism for benzene degradation, in which hydroxyl radical (HO•) and superoxide anion radical (O2 (•-)) were confirmed as the predominant species responsible for benzene degradation. In addition, the results obtained in actual groundwater test strongly indicated that SPC/Fe(II)-Glu system is applicable for the remediation of benzene-contaminated groundwater in practice.

Hydroxyl and Hydroperoxy Chemistry at the CalNex-LA 2010 Site: Measurements and Modeling

NASA Astrophysics Data System (ADS)

Griffith, S. M.; Hansen, R. F.; Dusanter, S.; Stevens, P. S.; Gilman, J. B.; Kuster, W. C.; Veres, P. R.; Graus, M.; Warneke, C.; De Gouw, J. A.; Young, C. J.; Washenfelder, R. A.; Brown, S. S.; Flynn, J. H.; Alvarez, S. L.; Grossberg, N.; Lefer, B. L.; Rappenglueck, B.; Mielke, L. H.; Osthoff, H. D.

2011-12-01

Hydroxyl (OH) and hydroperoxy (HO2) radicals are key species in the atmosphere driving the oxidation of organic trace gases leading to the production of ozone and secondary organic aerosols. Previous measurements of these radicals in urban environments have shown similarities and differences across sites due to differing levels of nitrogen oxides (NOx) and volatile organic compounds (VOCs), and the control strategies for dealing with these chemical species. Understanding the free radical chemistry is essential for effectively regulating NOx and VOC emissions and controlling ozone and other secondary pollutants. Measurements of OH and HO2 radicals were made using a laser-induced fluorescence technique as part of the CalNex LA campaign during May-June, 2010. Median HOx (OH + HO2) concentrations, as well as HO2-to-OH ratios, were similar to previous measurements in other urban areas. An extensive suite of supporting measurements including photolysis rates, NOx, and other inorganic species, biogenic, aromatic, and other anthropogenic VOCs are used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism. Model comparisons provide details about the ability of commonly used chemical mechanisms to reproduce HOx production and loss rates, the radical cycling, and instantaneous O3 production rates in the Los Angeles area.

Hydroxyl free radical production during torsional phacoemulsification.

PubMed

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

2010-12-01

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

A unique dosing system for the production of OH under high vacuum for the study of environmental heterogeneous reactions.

PubMed

Brown, Matthew A; Johánek, Viktor; Hemminger, John C

2008-02-01

A unique dosing system for the production of hydroxyl radicals under high vacuum for the study of environmental heterogeneous reactions is described. Hydroxyl radicals are produced by the photodissociation of a hydrogen peroxide aqueous gas mixture with 254 nm radiation according to the reaction H2O2+hnu (254 nm)-->OH+OH. Under the conditions of the current design, 0.6% conversion of hydrogen peroxide is expected yielding a hydroxyl number density on the order of 10(10) molecules/cm3. The flux distribution of the dosing system is calculated using a Monte Carlo simulation method and compared with the experimentally determined results. The performance of this unique hydroxyl dosing system is demonstrated for the heterogeneous reaction with a solid surface of potassium iodide. Coupling of the hydroxyl radical dosing system to a quantitative surface analysis system should help provide molecular level insight into detailed reaction mechanisms.

Protective effects of polysaccharides from Psidium guajava leaves against oxidative stresses.

PubMed

Kim, Seo-Young; Kim, Eun-A; Kim, Young-Sun; Yu, Seok-Kyu; Choi, Changyong; Lee, Jung-Suk; Kim, Yong-Tae; Nah, Jae-Woon; Jeon, You-Jin

2016-10-01

The aim of this study was to analyze antioxidant properties of a polysaccharide isolated from Psidium guajava leaves (PS-PGL) in vitro including its radical scavenging activities and protective effects against damage to cells as well as in vivo in zebrafish. The water extract of P. guajava leaves (WE-PGL) and PS-PGL showed strong radical scavenging effects in terms of 2,2-diphenyl-1-picrylhydrazyl (DPPH), hydroxyl, and alkyl radical. Compared to WE-PGL, PS-PGL enhanced all scavenging activities and in particular strongly scavenged the hydroxyl radical (50% inhibitory concentration [IC50], 0.02mg/mL). In addition, PS-PGL exerted a protective effect against hydrogen peroxide-induced oxidative stress and against toxicity to Vero cells. Furthermore, in vivo experiments using zebrafish embryos indicated that treatment with hydrogen peroxide decreased the survival rate and heart-beating rate of zebrafish embryos, whereas these problems were reduced by PS-PGL treatment. Moreover, PS-PGL inhibited hydrogen peroxide-induced reactive oxygen species (ROS) production, lipid peroxidation, and cell death. Taken together, these results suggest that PS-PGL may be useful as a beneficial antioxidant material in the food and cosmetic industries. Copyright © 2016 Elsevier B.V. All rights reserved.

Formation of hydroxyl radicals and Co3+ in the reaction of Co(2+)-EDTA with hydrogen peroxide. Catalytic effect of Fe3+.

PubMed

Eberhardt, M K; Santos, C; Soto, M A

1993-05-07

Co2+ ions (Co(NO3)2.6H2O) react with H2O2 only in presence of EDTA to yield OH radicals and Co3+. This reaction was carried out in unbuffered aqueous solutions (pH = 2.6). The formation of Co3+ was confirmed by spectroscopy. The Co(3+)-EDTA complex shows two typical absorptions at 382 nm and 532 nm. The Co(3+)-EDTA complex can be prepared by a number of oxidizing agents, like Fe3+, Fe(3+)-EDTA, Ag+, Ag2+, Ce4+, and hydroxyl radicals. Since Fe3+ oxidizes Co(2+)-EDTA to Co(3+)-EDTA and Fe2+ we initiate a chain reaction for .OH formation. Our results show that there are two modes for H2O2 decomposition: (1) One electron transfer to give OH radicals and (2) Decomposition of H2O2 to H2O and O2 without intermediate .OH formation. This reaction depends strongly on the pH of the buffer. The H2O2 decomposition increases with increasing pH and increasing Co2+ concentration.

Antioxidant activities of Vaccinium uliginosum L. extract and its active components.

PubMed

Kim, Young-Hee; Bang, Chae-Young; Won, Eun-Kyung; Kim, Jong-Pyung; Choung, Se-Young

2009-08-01

Vaccinium uliginosum L. (also known as bog bilberry) is a low-growing deciduous shrub classified in the Ericaceae family of plants, which includes numerous Vaccinium berries, blueberries, and cranberries. Berries of the Ericaceae family are known to contain organic acids, vitamins, glycosides, and anthocyanins and have been reported to have antioxidant activity. In order to identify the antioxidative principles of V. uliginosum, we separated water extracts into polyphenol, anthocyanin-rich (pigment), and sugar/acid fractions by using ethyl acetate, acidic methanol (MeOH), and 0.01 N HCl. Antioxidant activities were assessed by 2,2-diphenyl-1-picrylhydrazyl (DPPH), superoxide radical, and hydroxyl radical assays. The crude extract and fractions containing polyphenol and pigment exhibited the greatest antioxidant activities with 50% inhibitory concentration (IC(50)) values of 85.8 microg/mL, 33.2 microg/mL, and 16.7 microg/mL, respectively, for the DPPH assay and 48.1 microg/mL, 83.8 microg/mL, and 51.9 microg/mL for the nonenzymatic superoxide radical assay. The fractions containing polyphenol, pigment, and sugar/acid significantly inhibited xanthine oxidase. To investigate the functional compounds from the active fractions, we purified the polyphenol fraction and separated the compounds by using chromatographic techniques. The crude extract was dissolved in MeOH and further purified by reversed-phase high-performance liquid chromatography (HPLC) using MeOH-water (35:65 vol/vol) (with 0.04% trifluoroacetic acid) to obtain VU-EA-1 (16.6 mg), VU-EA-2 (8.5 mg), VU-EA-3 (19.8 mg), VU-EA-4 (12.8 mg), VU-EA-5 (6.5 mg), and VU-EA-6 (23.5 mg). The MeOH-washed fraction from the HPLC was concentrated and purified by reversed-phase HPLC using MeOH-water (50:50 vol/vol) to give VU-EA-10 (12.4 mg). Antioxidant activity was assessed by DPPH, superoxide radical, and hydroxyl radical assays. The isolated compounds exhibited dose-dependent antioxidant activity with IC(50) values of 7.6 microg/mL (VU-EA-10) for the DPPH assay, 67.8 microg/mL (VU-EA-4) for the nonenzymatic superoxide radical assay, and 3.7 microg/mL (VU-EA-10) and 7.6 microg/ml (VU-EA-6) for the enzymatic superoxide radical assay and 30% inhibitory concentration values of 0.58 microg/mL (VU-EA-1), 0.57 microg/mL (VU-EA-5), and 0.70 microg/mL (VU-EA-6) for the hydroxyl radical assay. In conclusion, V. uliginosum had potent antioxidative activity, and flavonoids were isolated as the main active principles.

Radical Polymerization of Diene Hydrocarbons in a Presence of Peroxide of Hydrogen and Solvent. 1. Effectiveness of Initiation and Rate of Expansion H2O2 during Oligomerization in Metallic Equipment

DTIC Science & Technology

1990-04-10

the hydroxyl groups. These are liquid oligobutadienes of brand R-15M and R-45M (firm "Sinclair Retgochemical Suc."/OSA) [5, 6, 10] and hydroxyl... ionic mechanism. Most promising, in view of simplicity and cheapness, is considered the I DOC - 90010000 PAGE - method of the radical polymerization of...Initiators of polimerization in this method are the hydroxyl radicals, which are generated during the homolytic decomposition of peroxide of hydrogen PDO

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.

Nitric oxide induces hypoxia ischemic injury in the neonatal brain via the disruption of neuronal iron metabolism.

PubMed

Lu, Qing; Harris, Valerie A; Rafikov, Ruslan; Sun, Xutong; Kumar, Sanjiv; Black, Stephen M

2015-12-01

We have recently shown that increased hydrogen peroxide (H2O2) generation is involved in hypoxia-ischemia (HI)-mediated neonatal brain injury. H2O2 can react with free iron to form the hydroxyl radical, through Fenton Chemistry. Thus, the objective of this study was to determine if there was a role for the hydroxyl radical in neonatal HI brain injury and to elucidate the underlying mechanisms. Our data demonstrate that HI increases the deposition of free iron and hydroxyl radical formation, in both P7 hippocampal slice cultures exposed to oxygen-glucose deprivation (OGD), and the neonatal rat exposed to HI. Both these processes were found to be nitric oxide (NO) dependent. Further analysis demonstrated that the NO-dependent increase in iron deposition was mediated through increased transferrin receptor expression and a decrease in ferritin expression. This was correlated with a reduction in aconitase activity. Both NO inhibition and iron scavenging, using deferoxamine administration, reduced hydroxyl radical levels and neuronal cell death. In conclusion, our results suggest that increased NO generation leads to neuronal cell death during neonatal HI, at least in part, by altering iron homeostasis and hydroxyl radical generation. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Antioxidant properties of Aller-7, a novel polyherbal formulation for allergic rhinitis.

PubMed

D'Souza, P; Amit, A; Saxena, V S; Bagchi, D; Bagchi, M; Stohs, S J

2004-01-01

Allergic rhinitis, a frequently occurring immunological disorder affecting men, women and children worldwide, is a state of hypersensitivity that occurs when the body overreacts to a substance such as pollen, mold, mites or dust. Allergic rhinitis exerts inflammatory response and irritation of the nasal mucosal membranes leading to sneezing; stuffy/runny nose; nasal congestion; and itchy, watery and swollen eyes. A novel, safe polyherbal formulation (Aller-7/NR-A2) has been developed for the treatment of allergic rhinitis using a unique combination of extracts from seven medicinal plants including Phyllanthus emblica, Terminalia chebula, Terminalia bellerica, Albizia lebbeck, Piper nigrum, Zingiber officinale and Piper longum. In this study, the antioxidant efficacy of Aller-7 was investigated by various assays including hydroxyl radical scavenging assay, superoxide anion scavenging assay, 1,1-diphenyl-2-picryl hydrazyl (DPPH) and 2,2-azinobis-ethyl-benzothiozoline-sulphonic acid diammonium salt (ABTS) radical scavenging assays. The protective effect of Aller-7 on free radical-induced lysis of red blood cells and inhibition of nitric oxide release by Aller-7 in lipopolysaccharide-stimulated murine macrophages were determined. Aller-7 exhibited concentration-dependent scavenging activities toward biochemically generated hydroxyl radicals (IC50 741.73 microg/ml); superoxide anion (IC50 24.65 microg/ml by phenazine methosulfate-nicotinamide adenine dinucleotide [PMS-NADH] assay and IC50 4.27 microg/ml by riboflavin/nitroblue tetrazolium [NBT] light assay), nitric oxide (IC50 16.34 microg/ml); 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical (IC50 5.62 microg/ml); and 2,2-azinobis-ethyl-benzothiozoline-sulphonic acid diammonium salt (ABTS) radical (IC50 7.35 microg/ml). Aller-7 inhibited free radical-induced hemolysis in the concentration range of 20-80 microg/ml. Aller-7 also significantly inhibited nitric oxide release from lipopolysaccharide-stimulated murine macrophages. These results demonstrate that Aller-7 is a potent scavenger of free radicals and that it may serve.

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

PubMed

Karthikeyan, S; Sekaran, G

2014-03-07

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

Impact of induced levels of specific free radicals and malondialdehyde on chicken semen quality and fertility.

PubMed

Rui, Bruno R; Shibuya, Fábio Y; Kawaoku, Allison J T; Losano, João D A; Angrimani, Daniel S R; Dalmazzo, Andressa; Nichi, Marcilio; Pereira, Ricardo J G

2017-03-01

Over the past decades, scientists endeavored to comprehend oxidative stress in poultry spermatozoa and its relationship with fertilizing ability, lipid peroxidation (LPO), free-radical scavenging systems, and antioxidant therapy. Although considerable progress has been made, further improvement is needed in understanding how specific reactive oxygen species (ROS) and malondialdehyde (MDA, a toxic byproduct of LPO) disrupt organelles in avian spermatozoon. Hence, this study examined functional changes in chicken spermatozoa after incubation with different ROS, and their implications for the fertility. First, semen samples from 14 roosters were individually diluted and aliquoted into five equal parts: control, superoxide anion, hydrogen peroxide (H 2 O 2 ), hydroxyl radicals, and MDA. After incubation with these molecules, aliquots were analyzed for motility, plasma membrane and acrosome integrity, mitochondrial activity, and LPO and DNA damage. Hydrogen peroxide was more detrimental for sperm motility than hydroxyl radicals, whereas the superoxide anion and MDA exhibited no differences compared with controls. In turn, plasma membrane and acrosome integrity, mitochondrial activity, LPO and DNA integrity rates were only affected by hydroxyl radicals. Thereafter, semen aliquots were incubated under the same conditions and used for artificial insemination. In accordance to our in vitro observations, H 2 O 2 and hydroxyl radicals sharply reduced egg fertility, whereas superoxide anion and MDA only induced slight declines. Thus, chicken sperm function was severely impaired by H 2 O 2 and hydroxyl radicals, but their mechanisms of action seemingly comprise different pathways. Further analysis regarding susceptibility of spermatozoon organelles to specific radicals in other poultry will help us to understand the development of interspecific differences in scavenging systems and to outline more oriented antioxidant approaches. Copyright © 2016 Elsevier Inc. All rights reserved.

Interconnection of reactive oxygen species chemistry across the interfaces of atmospheric, environmental, and biological processes.

PubMed

Anglada, Josep M; Martins-Costa, Marilia; Francisco, Joseph S; Ruiz-López, Manuel F

2015-03-17

Oxidation reactions are ubiquitous and play key roles in the chemistry of the atmosphere, in water treatment processes, and in aerobic organisms. Ozone (O3), hydrogen peroxide (H2O2), hydrogen polyoxides (H2Ox, x > 2), associated hydroxyl and hydroperoxyl radicals (HOx = OH and HO2), and superoxide and ozonide anions (O2(-) and O3(-), respectively) are the primary oxidants in these systems. They are commonly classified as reactive oxygen species (ROS). Atmospheric chemistry is driven by a complex system of chain reactions of species, including nitrogen oxides, hydroxyl and hydroperoxide radicals, alkoxy and peroxy radicals, and ozone. HOx radicals contribute to keeping air clean, but in polluted areas, the ozone concentration increases and creates a negative impact on plants and animals. Indeed, ozone concentration is used to assess air quality worldwide. Clouds have a direct effect on the chemical composition of the atmosphere. On one hand, cloud droplets absorb many trace atmospheric gases, which can be scavenged by rain and fog. On the other hand, ionic species can form in this medium, which makes the chemistry of the atmosphere richer and more complex. Furthermore, recent studies have suggested that air-cloud interfaces might have a significant impact on the overall chemistry of the troposphere. Despite the large differences in molecular composition, concentration, and thermodynamic conditions among atmospheric, environmental, and biological systems, the underlying chemistry involving ROS has many similarities. In this Account, we examine ROS and discuss the chemical characteristics common to all of these systems. In water treatment, ROS are key components of an important subset of advanced oxidation processes. Ozonation, peroxone chemistry, and Fenton reactions play important roles in generating sufficient amounts of hydroxyl radicals to purify wastewater. Biochemical processes within living organisms also involve ROS. These species can come from pollutants in the environment, but they can also originate endogenously, initiated by electron reduction of molecular oxygen. These molecules have important biological signaling activities, but they cause oxidative stress when dysfunction within the antioxidant system occurs. Excess ROS in living organisms can lead to problems, such as protein oxidation-through either cleavage of the polypeptide chain or modification of amino acid side chains-and lipid oxidation.

Atmospheric production of oxalic acid/oxalate and nitric acid/nitrate in the Tampa Bay airshed: Parallel pathways

NASA Astrophysics Data System (ADS)

Martinelango, P. Kalyani; Dasgupta, Purnendu K.; Al-Horr, Rida S.

Oxalic acid is the dominant dicarboxylic acid (DCA), and it constitutes up to 50% of total atmospheric DCAs, especially in non-urban and marine atmospheres. A significant amount of particulate H 2Ox/oxalate (Ox) occurred in the coarse particle fraction of a dichotomous sampler, the ratio of oxalate concentrations in the PM 10 to PM 2.5 fractions ranged from 1 to 2, with mean±sd being 1.4±0.2. These results suggest that oxalate does not solely originate in the gas phase and condense into particles. Gaseous H 2Ox concentrations are much lower than particulate Ox concentrations and are well correlated with HNO 3, HCHO, and O 3, supporting a photochemical origin. Of special relevance to the Bay Region Atmospheric Chemistry Experiment (BRACE) is the extent of nitrogen deposition in the Tampa Bay estuary. Hydroxyl radical is primarily responsible for the conversion of NO 2 to HNO 3, the latter being much more easily deposited. Hydroxyl radical is also responsible for the aqueous phase formation of oxalic acid from alkenes. Hence, we propose that an estimate of rad OH can be obtained from H 2Ox/Ox production rate and we accordingly show that the product of total oxalate concentration and NO 2 concentration approximately predicts the total nitrate concentration during the same period.

Ortho- and meta-tyrosine formation from phenylalanine in human saliva as a marker of hydroxyl radical generation during betel quid chewing.

PubMed

Nair, U J; Nair, J; Friesen, M D; Bartsch, H; Ohshima, H

1995-05-01

The habit of betel quid chewing, common in South-East Asia and the South Pacific islands, is causally associated with an increased risk of oral cancer. Reactive oxygen species formed from polyphenolic betel quid ingredients and lime at alkaline pH have been implicated as the agents responsible for DNA and tissue damage. To determine whether hydroxyl radical (HO.) is generated in the human oral cavity during chewing of betel quid, the formation of o- and m-tyrosine from L-phenylalanine was measured. Both o- and m-tyrosine were formed in vitro in the presence of extracts of areca nut and/or catechu, transition metal ions such as Cu2+ and Fe2+ and lime or sodium carbonate (alkaline pH). Omission of any of these ingredients from the reaction mixture significantly reduced the yield of tyrosines. Hydroxyl radical scavengers such as ethanol, D-mannitol and dimethylsulfoxide inhibited the phenylalanine oxidation in a dose-dependent fashion. Five volunteers chewed betel quid consisting of betel leaf, areca nut, catechu and slaked lime (without tobacco). Their saliva, collected after chewing betel quid, contained high concentrations of p-tyrosine, but no appreciable amounts of o- or m-tyrosine. Saliva samples from the same subjects after chewing betel quid to which 20 mg phenylalanine had been added contained o- and m-tyrosine at concentrations ranging from 1010 to 3000 nM and from 1110 to 3140 nM respectively. These levels were significantly higher (P < 0.005) than those of subjects who kept phenylalanine in the oral cavity without betel quid, which ranged from 14 to 70 nM for o-tyrosine and from 10 to 35 nM for m-tyrosine. These studies clearly demonstrate that the HO. radical is formed in the human oral cavity during betel quid chewing and is probably implicated in the genetic damage that has been observed in oral epithelial cells of chewers.

Generation of hydroxyl radical in isolated pea root cell wall, and the role of cell wall-bound peroxidase, Mn-SOD and phenolics in their production.

PubMed

Kukavica, Biljana; Mojovic, Milos; Vuccinic, Zeljko; Maksimovic, Vuk; Takahama, Umeo; Jovanovic, Sonja Veljovic

2009-02-01

The hydroxyl radical produced in the apoplast has been demonstrated to facilitate cell wall loosening during cell elongation. Cell wall-bound peroxidases (PODs) have been implicated in hydroxyl radical formation. For this mechanism, the apoplast or cell walls should contain the electron donors for (i) H(2)O(2) formation from dioxygen; and (ii) the POD-catalyzed reduction of H(2)O(2) to the hydroxyl radical. The aim of the work was to identify the electron donors in these reactions. In this report, hydroxyl radical (.OH) generation in the cell wall isolated from pea roots was detected in the absence of any exogenous reductants, suggesting that the plant cell wall possesses the capacity to generate .OH in situ. Distinct POD and Mn-superoxide dismutase (Mn-SOD) isoforms different from other cellular isoforms were shown by native gel electropho-resis to be preferably bound to the cell walls. Electron paramagnetic resonance (EPR) spectroscopy of cell wall isolates containing the spin-trapping reagent, 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO), was used for detection of and differentiation between .OH and the superoxide radical (O(2)(-).). The data obtained using POD inhibitors confirmed that tightly bound cell wall PODs are involved in DEPMPO/OH adduct formation. A decrease in DEPMPO/OH adduct formation in the presence of H(2)O(2) scavengers demonstrated that this hydroxyl radical was derived from H(2)O(2). During the generation of .OH, the concentration of quinhydrone structures (as detected by EPR spectroscopy) increased, suggesting that the H(2)O(2) required for the formation of .OH in isolated cell walls is produced during the reduction of O(2) by hydroxycinnamic acids. Cell wall isolates in which the proteins have been denaturated (including the endogenous POD and SOD) did not produce .OH. Addition of exogenous H(2)O(2) again induced the production of .OH, and these were shown to originate from the Fenton reaction with tightly bound metal ions. However, the appearance of the DEPMPO/OOH adduct could also be observed, due to the production of O(2)(-). when endogenous SOD has been inactivated. Also, O(2)(-). was converted to .OH in an in vitro horseradish peroxidase (HRP)/H(2)O(2) system to which exogenous SOD has been added. Taken together with the discovery of the cell wall-bound Mn-SOD isoform, these results support the role of such a cell wall-bound SOD in the formation of .OH jointly with the cell wall-bound POD. According to the above findings, it seems that the hydroxycinnamic acids from the cell wall, acting as reductants, contribute to the formation of H(2)O(2) in the presence of O(2) in an autocatalytic manner, and that POD and Mn-SOD coupled together generate .OH from such H(2)O(2).

Hydroxyl radical mediates cisplatin-induced apoptosis in human hair follicle dermal papilla cells and keratinocytes through Bcl-2-dependent mechanism.

PubMed

Luanpitpong, Sudjit; Nimmannit, Ubonthip; Chanvorachote, Pithi; Leonard, Stephen S; Pongrakhananon, Varisa; Wang, Liying; Rojanasakul, Yon

2011-08-01

Induction of massive apoptosis of hair follicle cells by chemotherapy has been implicated in the pathogenesis of chemotherapy-induced alopecia (CIA), but the underlying mechanisms of regulation are not well understood. The present study investigated the apoptotic effect of cisplatin in human hair follicle dermal papilla cells and HaCaT keratinocytes, and determined the identity and role of specific reactive oxygen species (ROS) involved in the process. Treatment of the cells with cisplatin induced ROS generation and a parallel increase in caspase activation and apoptotic cell death. Inhibition of ROS generation by antioxidants inhibited the apoptotic effect of cisplatin, indicating the role of ROS in the process. Studies using specific ROS scavengers further showed that hydroxyl radical, but not hydrogen peroxide or superoxide anion, is the primary oxidative species responsible for the apoptotic effect of cisplatin. Electron spin resonance studies confirmed the formation of hydroxyl radicals induced by cisplatin. The mechanism by which hydroxyl radical mediates the apoptotic effect of cisplatin was shown to involve down-regulation of the anti-apoptotic protein Bcl-2 through ubiquitin-proteasomal degradation. Bcl-2 was also shown to have a negative regulatory role on hydroxyl radical. Together, our results indicate an essential role of hydroxyl radical in cisplatin-induced cell death of hair follicle cells through Bcl-2 regulation. Since CIA is a major side effect of cisplatin and many other chemotherapeutic agents with no known effective treatments, the knowledge gained from this study could be useful in the design of preventive treatment strategies for CIA through localized therapy without compromising the chemotherapy efficacy.

Ultrasonic application to boost hydroxyl radical formation during Fenton oxidation and release organic matter from sludge

PubMed Central

Gong, Changxiu; Jiang, Jianguo; Li, De’an; Tian, Sicong

2015-01-01

We examined the effects of ultrasound and Fenton reagent on ultrasonic coupling Fenton oxidation (U+F) pre-treatment processes for the disintegration of wastewater treatment plant sludge. The results demonstrated that U+F treatment could significantly increase soluble chemical oxygen demand (SCOD), total organic carbon (TOC), and extracellular polymeric substances (EPS) concentrations in sludge supernatant. This method was more effective than ultrasonic (U) or Fenton oxidation (F) treatment alone. U+F treatment increased the release of SCOD by 2.1- and 1.4-fold compared with U and F alone, respectively. U+F treatment increased the release of EPS by 1.2-fold compared with U alone. After U+F treatment, sludge showed a considerably finer particle size and looser microstructure based on fluorescence microscopy, and the concentration of hydroxyl radicals (OH•) increased from 0.26 mM by F treatment to 0.43 mM by U+F treatment based on fluorescence spectrophotometer. This demonstrated that U+F treatment improves the release of organic matter from sludge. PMID:26066562

Antioxidant and quinone reductase-inducing constituents of black chokeberry (Aronia melanocarpa) fruits.

PubMed

Li, Jie; Deng, Ye; Yuan, Chunhua; Pan, Li; Chai, Heebyung; Keller, William J; Kinghorn, A Douglas

2012-11-21

Using in vitro hydroxyl radical-scavenging and quinone reductase-inducing assays, bioactivity-guided fractionation of an ethyl acetate-soluble extract of the fruits of the botanical dietary supplement, black chokeberry (Aronia melanocarpa), led to the isolation of 27 compounds, including a new depside, ethyl 2-[(3,4-dihydroxybenzoyloxy)-4,6-dihydroxyphenyl] acetate (1), along with 26 known compounds (2-27). The structures of the isolated compounds were identified by analysis of their physical and spectroscopic data ([α](D), NMR, IR, UV, and MS). Altogether, 17 compounds (1-4, 9, 15-17, and 19-27) showed significant antioxidant activity in the hydroxyl radical-scavenging assay, with hyperin (24, ED(50) = 0.17 μM) being the most potent. The new compound (1, ED(50) = 0.44 μM) also exhibited potent antioxidant activity in this assay. Three constituents of black chokeberry fruits doubled quinone reductase activity at concentrations <20 μM, namely, protocatechuic acid [9, concentration required to double quinone reductase activity (CD) = 4.3 μM], neochlorogenic acid methyl ester (22, CD = 6.7 μM), and quercetin (23, CD = 3.1 μM).

Calcium- and potassium-permeable plasma membrane transporters are activated by copper in Arabidopsis root tips: linking copper transport with cytosolic hydroxyl radical production.

PubMed

Rodrigo-Moreno, Ana; Andrés-Colás, Nuria; Poschenrieder, Charlotte; Gunsé, Benet; Peñarrubia, Lola; Shabala, Sergey

2013-04-01

Transition metals such as copper can interact with ascorbate or hydrogen peroxide to form highly reactive hydroxyl radicals (OH(•) ), with numerous implications to membrane transport activity and cell metabolism. So far, such interaction was described for extracellular (apoplastic) space but not cytosol. Here, a range of advanced electrophysiological and imaging techniques were applied to Arabidopsis thaliana plants differing in their copper-transport activity: Col-0, high-affinity copper transporter COPT1-overexpressing (C1(OE) ) seedlings, and T-DNA COPT1 insertion mutant (copt1). Low Cu concentrations (10 µm) stimulated a dose-dependent Gd(3+) and verapamil sensitive net Ca(2+) influx in the root apex but not in mature zone. C1(OE) also showed a fivefold higher Cu-induced K(+) efflux at the root tip level compared with Col-0, and a reduction in basal peroxide accumulation at the root tip after copper exposure. Copper caused membrane disruptions of the root apex in C1(OE) seedlings but not in copt1 plants; this damage was prevented by pretreatment with Gd(3+) . Our results suggest that copper transport into cytosol in root apex results in hydroxyl radical generation at the cytosolic side, with a consequent regulation of plasma membrane OH(•) -sensitive Ca(2+) and K(+) transport systems. © 2012 Blackwell Publishing Ltd.

Identification of intermediates and assessment of ecotoxicity in the oxidation products generated during the ozonation of clofibric acid.

PubMed

Rosal, Roberto; Gonzalo, María S; Boltes, Karina; Letón, Pedro; Vaquero, Juan J; García-Calvo, E

2009-12-30

The degradation of an aqueous solution of clofibric acid was investigated during catalytic and non-catalytic ozonation. The catalyst, TiO(2), enhanced the production of hydroxyl radicals from ozone and raised the fraction or clofibric acid degraded by hydroxyl radicals. The rate constant for the reaction of clofibric acid and hydroxyl radicals was not affected by the presence of the catalyst. The toxicity of the oxidation products obtained during the reaction was assessed by means of Vibrio fischeri and Daphnia magna tests in order to evaluate the potential formation of toxic by-products. The results showed that the ozonation was enhanced by the presence of TiO(2,) the clofibric acid being removed completely after 15 min at pH 5. The evolution of dissolved organic carbon, specific ultraviolet absorption at 254 nm and the concentration of carboxylic acids monitored the degradation process. The formation of 4-chlorophenol, hydroquinone, 4-chlorocatechol, 2-hydroxyisobutyric acid and three non-aromatic compounds identified as a product of the ring-opening reaction was assessed by exact mass measurements performed by liquid chromatography coupled to time-of-flight mass spectrometry (LC-TOF-MS). The bioassays showed a significant increase in toxicity during the initial stages of ozonation following a toxicity pattern closely related to the formation of ring-opening by-products.

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

Taylor, J.A.; Brasseur, G.P.; Zimmerman, P.R.

Using the hydroxyl radical field calibrated to the methyl chloroform observations, the globally averaged release of methane and its spatial and temporal distribution were investigated. Two source function models of the spatial and temporal distribution of the flux of methane to the atmosphere were developed. The first model was based on the assumption that methane is emitted as a proportion of net primary productivity (NPP). With the average hydroxyl radical concentration fixed, the methane source term was computed as {approximately}623 Tg CH{sub 4}, giving an atmospheric lifetime for methane {approximately}8.3 years. The second model identified source regions for methane frommore » rice paddies, wetlands, enteric fermentation, termites, and biomass burning based on high-resolution land use data. This methane source distribution resulted in an estimate of the global total methane source of {approximately}611 Tg CH{sub 4}, giving an atmospheric lifetime for methane {approximately}8.5 years. The most significant difference between the two models were predictions of methane fluxes over China and South East Asia, the location of most of the world's rice paddies. Using a recent measurement of the reaction rate of hydroxyl radical and methane leads to estimates of the global total methane source for SF1 of {approximately}524 Tg CH{sub 4} giving an atmospheric lifetime of {approximately}10.0 years and for SF2{approximately}514 Tg CH{sub 4} yielding a lifetime of {approximately}10.2 years.« less

Potent hydroxyl radical-scavenging activity of drought-induced type-2 metallothionein in wild watermelon.

PubMed

Akashi, Kinya; Nishimura, Noriyuki; Ishida, Yoshinori; Yokota, Akiho

2004-10-08

Wild watermelon (Citrullus lanatus sp.) has the ability to tolerate severe drought/high light stress conditions despite carrying out normal C3-type photosynthesis. Here, mRNA differential display was employed to isolate drought-responsive genes in the leaves of wild watermelon. One of the isolated genes, CLMT2, shared significant homology with type-2 metallothionein (MT) sequences from other plants. The second-order rate constant for the reaction between a recombinant CLMT2 protein and hydroxyl radicals was estimated to be 1.2 x 10(11) M(-1) s(-1), demonstrating that CLMT2 had an extraordinary high activity for detoxifying hydroxyl radicals. Moreover, hydroxyl radical-catalyzed degradation of watermelon genomic DNA was effectively suppressed by CLMT2 in vitro. This is the first demonstration of a plant MT with antioxidant properties. The results suggest that CLMT2 induction contributes to the survival of wild watermelon under severe drought/high light stress conditions. Copyright 2004 Elsevier Inc.

Ozone/graphene oxide catalytic oxidation: a novel method to degrade emerging organic contaminant N, N-diethyl-m-toluamide (DEET).

PubMed

Liu, Jia-Nan; Chen, Zhuo; Wu, Qian-Yuan; Li, Ang; Hu, Hong-Ying; Yang, Cheng

2016-08-11

N, N-diethyl-m-toluamide (DEET) is one of the important emerging contaminants that are being increasingly detected in reclaimed water as well as in drinking water sources. However, DEET is refractory to conventional biological treatment and pure ozone which is absent of hydroxyl radical. Current researches on the efficient removal of DEET are still quite limited. This study utilizes a novel method, namely ozone/graphene oxide (O3/GO), to investigate the effects on DEET removal in aqueous systems, especially in reclaimed water. The results indicate that the DEET degradation rate was significantly accelerated through the combined effect of GO and ozonation which can yield abundant hydroxyl radical, compared to pure ozone condition. According to hydroxyl radical scavenging experiments, hydroxyl radical was found to play a dominant role in synergistic removal of DEET. These findings can offer sound suggestions for future research on the removal of emerging organic contaminants. The information could also be beneficial to reclaimed water safety and sustainable management.

Thiaflavan scavenges radicals and inhibits DNA oxidation: a story from the ferrocene modification.

PubMed

Lai, Hai-Wang; Liu, Zai-Qun

2014-06-23

4-Thiaflavan is a sulfur-substituted flavonoid with a benzoxathiin scaffold. The aim of this work is to compare abilities of sulfur and oxygen atom, hydroxyl groups, and ferrocene moiety at different positions of 4-thiaflavan to trap radicals and to inhibit DNA oxidation. It is found that abilities of thiaflavans to trap radicals and to inhibit DNA oxidation are increased in the presence of ferrocene moiety and are further improved by the electron-donating group attaching to thiaflavan skeleton. It can be concluded that the ferrocene moiety plays the major role for thiaflavans to be antioxidants even in the absence of phenolic hydroxyl groups. On the other hand, the antioxidant effectiveness of phenolic hydroxyl groups in thiaflavans can be improved by the electron-donating group. The influences of sulfur and oxygen atoms in thiaflavans on the antioxidant property of para-hydroxyl group exhibit different manners when the thiaflavans are used to trap radicals and to inhibit DNA oxidation. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Photo-oxidation of PAHs with calcium peroxide as a source of the hydroxyl radicals

NASA Astrophysics Data System (ADS)

Kozak, Jolanta; Włodarczyk-Makuła, Maria

2018-02-01

The efficiency of the removal of selected PAHs from the pretreated coking wastewater with usage of CaO2, Fenton reagent (FeSO4) and UV rays are presented in this article. The investigations were carried out using coking wastewater originating from biological, industrial wastewater treatment plant. At the beginning of the experiment, the calcium peroxide (CaO2) powder as a source of hydroxyl radicals (OH•) and Fenton reagent were added to the samples of wastewater. Then, the samples were exposed to UV rays for 360 s. The process was carried out at pH 3.5-3.8. After photo-oxidation process a decrease in the PAHs concentration was observed. The removal efficiency of selected hydrocarbons was in the ranged of 89-98%. The effectiveness of PAHs degradation was directly proportional to the calcium peroxide dose.

Hydrogen peroxide contributes to the ultraviolet-B (280-315 nm) induced oxidative stress of plant leaves through multiple pathways.

PubMed

Czégény, Gyula; Wu, Min; Dér, András; Eriksson, Leif A; Strid, Åke; Hideg, Éva

2014-06-27

Solar UV-B (280-315 nm) radiation is a developmental signal in plants but may also cause oxidative stress when combined with other environmental factors. Using computer modeling and in solution experiments we show that UV-B is capable of photosensitizing hydroxyl radical production from hydrogen peroxide. We present evidence that the oxidative effect of UV-B in leaves is at least twofold: (i) it increases cellular hydrogen peroxide concentrations, to a larger extent in pyridoxine antioxidant mutant pdx1.3-1 Arabidopsis and; (ii) is capable of a partial photo-conversion of both 'natural' and 'extra' hydrogen peroxide to hydroxyl radicals. As stress conditions other than UV can increase cellular hydrogen peroxide levels, synergistic deleterious effects of various stresses may be expected already under ambient solar UV-B. Copyright © 2014 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Controlled Cross-Linking with Glucose Oxidase for the Enhancement of Gelling Potential of Pork Myofibrillar Protein.

PubMed

Wang, Xu; Xiong, Youling L; Sato, Hiroaki; Kumazawa, Yoshiyuki

2016-12-21

Differential oxidative modifications of myofibrillar protein (MP) by hydroxyl radicals generated in an enzymatic system with glucose oxidase (GluOx) in the presence of glucose/FeSO 4 versus a Fenton system (H 2 O 2 /FeSO 4 ) were investigated. Pork MP was modified at 4 °C and pH 6.25 with hydroxyl radicals produced from 1 mg/mL glucose in the presence of 80, 160, or 320 μg/mL GluOx and 10 μM FeSO 4 . Total sulfhydryl content, solubility, cross-linking pattern, and gelation properties of MP were measured. H 2 O 2 production proceeded linearly with the concentration of GluOx and increased with reaction time. GluOx- and H 2 O 2 -dose-dependent protein polymerization, evidenced by faded myosin heavy chain and actin in SDS-PAGE as well as significant decreases in sulfhydryls, coincided with protein solubility loss. Firmer and more elastic MP gels were produced by GluOx than by the Fenton system at comparable H 2 O 2 levels due to an altered radical reaction pathway.

Electrochemiluminescence sensors for scavengers of hydroxyl radical based on its annihilation in CdSe quantum dots film/peroxide system.

PubMed

Jiang, Hui; Ju, Huangxian

2007-09-01

This work elucidated the detailed electrochemiluminescence (ECL) process of the thioglycolic acid-capped CdSe quantum dots (QDs) film/peroxide aqueous system. The QDs were first electrochemically reduced to form electrons-injected QDs approximately -1.1 V, which then reduced hydrogen peroxide to produce OH* radical. The intermediate OH* radical was a key species for producing holes-injected QDs. The ECL emission with a peak at -1.114 V was demonstrated to come from the 1Se-1Sh transition emission. Using thiol compounds as the model molecules to annihilate the OH* radical, their quenching effects on ECL emission were studied. This effect led to a novel strategy for ECL sensing of the scavengers of hydroxyl radical. The detection results of thiol compounds showed high sensitivity, good precision, and acceptable accuracy, suggesting the promising application of the proposed method for quick detection of both scavengers and generators of hydroxyl radical in different fields.

Method and apparatus for the gas phase decontamination of chemical and biological agents

DOEpatents

O'Neill, Hugh J.; Brubaker, Kenneth L.

2003-10-07

An apparatus and method for decontaminating chemical and biological agents using the reactive properties of both the single atomic oxygen and the hydroxyl radical for the decontamination of chemical and biological agents. The apparatus is self contained and portable and allows for the application of gas reactants directly at the required decontamination point. The system provides for the use of ultraviolet light of a specific spectral range to photolytically break down ozone into molecular oxygen and hydroxyl radicals where some of the molecular oxygen is in the first excited state. The excited molecular oxygen will combine with water vapor to produce two hydroxyl radicals.

Methyl-esterified 3-hydroxybutyrate oligomers protect bacteria from hydroxyl radicals

USDA-ARS?s Scientific Manuscript database

Bacteria rely mainly on enzymes, glutathione and other low-molecular weight thiols to overcome oxidative stress. However, hydroxyl radicals are the most cytotoxic reactive oxygen species, and no known enzymatic system exists for their detoxification. We now show that methyl-esterified dimers and tri...

Antioxidant activities of chick embryo egg hydrolysates

PubMed Central

Sun, Hao; Ye, Ting; Wang, Yuntao; Wang, Ling; Chen, Yijie; Li, Bin

2014-01-01

Chick embryo egg hydrolysates (CEEH) were obtained by enzymatic hydrolysis of chick embryo egg in vitro-simulated gastrointestinal digestion. The antioxidant activities of CEEH were investigated by employing three in vitro assays, including the 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulfonate)/1,1-diphenyl-2-picrylhydrazyl (ABTS/DPPH)/hydroxyl radical-scavenging assays. The radical-scavenging effect of CEEH (1.0 mg/mL) was in a dose-dependent manner, with the highest trolox equivalent antioxidant capacity for ABTS, DPPH, and that of hydroxyl radicals found to be 569, 2097, and 259.6 μmol/L, respectively; whereas the trolox equivalent antioxidant capacity of unhatched egg for ABTS, DPPH, and that of hydroxyl radicals were found to be 199, 993, and 226.5 μmol/L, respectively. CEEH showed stronger scavenging activity than the hydrolysates of unhatched egg against free radicals such as ABTS, DPPH, and hydroxyl radicals. The antioxidant amino acid analysis indicated that the 14-day CEEH possess more antioxidant amino acids than that of the unhatched egg. In addition, essential amino acids analysis showed that the 14-day CEEH have the highest nutritional value. Combined with the results of the amino acid profiles, CEEH were believed to have higher nutritive value in addition to antioxidant activities than the unhatched egg. PMID:24804065

Synergistic disinfection and removal of biofilms by a sequential two-step treatment with ozone followed by hydrogen peroxide.

PubMed

Tachikawa, Mariko; Yamanaka, Kenzo

2014-11-01

Synergistic disinfection and removal of biofilms by ozone (O3) water in combination with hydrogen peroxide (H2O2) solution was studied by determining disinfection rates and observing changes of the biofilm structure in situ by confocal laser scanning microscopy (CLSM) using an established biofilm of Pseudomonas fluorescence. The sequential treatment with O3, 1.0-1.7 mg/L, followed by H2O2, 0.8-1.1%, showed synergistic disinfection effects, while the reversed treatment, first H2O2 followed by O3, showed only an additive effect. The decrease of synergistic disinfection effect by addition of methanol (CH3OH), a scavenger of hydroxyl radical (OH), into the H2O2 solution suggested generation of hydroxyl radicals on or in the biofilm by the sequential treatment with O3 followed by H2O2. The primary treatment with O3 increased disinfection rates of H2O2 in the secondary treatment, and the increase of O3 concentration enhanced the rates. The cold temperature of O3 water (14 °C and 8 °C) increased the synergistic effect, suggesting the increase of O3 adsorption and hydroxyl radical generation in the biofilm. CLSM observation showed that the sequential treatment, first with O3 followed by H2O2, loosened the cell connections and thinned the extracellular polysaccharides (EPS) in the biofilm. The hydroxyl radical generation in the biofilm may affect the EPS and biofilm structure and may induce effective disinfection with H2O2. This sequential treatment method may suggest a new practical procedure for disinfection and removal of biofilms by inorganic oxidants such as O3 and H2O2. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

PubMed

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

2018-05-15

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

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.

A unique dosing system for the production of OH under high vacuum for the study of environmental heterogeneous reactions

NASA Astrophysics Data System (ADS)

Brown, Matthew A.; Johánek, Viktor; Hemminger, John C.

2008-02-01

A unique dosing system for the production of hydroxyl radicals under high vacuum for the study of environmental heterogeneous reactions is described. Hydroxyl radicals are produced by the photodissociation of a hydrogen peroxide aqueous gas mixture with 254nm radiation according to the reaction H2O2+hν (254nm)→OH+OH. Under the conditions of the current design, 0.6% conversion of hydrogen peroxide is expected yielding a hydroxyl number density on the order of 1010molecules/cm3. The flux distribution of the dosing system is calculated using a Monte Carlo simulation method and compared with the experimentally determined results. The performance of this unique hydroxyl dosing system is demonstrated for the heterogeneous reaction with a solid surface of potassium iodide. Coupling of the hydroxyl radical dosing system to a quantitative surface analysis system should help provide molecular level insight into detailed reaction mechanisms.

Measurement of hydroxyl radical density generated from the atmospheric pressure bioplasma jet

NASA Astrophysics Data System (ADS)

Hong, Y. J.; Nam, C. J.; Song, K. B.; Cho, G. S.; Uhm, H. S.; Choi, D. I.; Choi, E. H.

2012-03-01

Atmospheric pressure bioplasmas are being used in a variety of bio-medical and material processing applications, surface modifications of polymers. This plasma can generate the various kinds of radicals when it contacs with the water. Especially, hydroxyl radical species have very important role in the biological and chemical decontamination of media in this situation. It is very important to investigate the hydroxyl radical density in needle-typed plasma jet since it plays a crucial role in interaction between the living body and plasma. We have generated the needle-typed plasma jet bombarding the water surface by using an Ar gas flow and investigated the emission lines by OES (optical emission spectroscopy). It is noted that the electron temperature and plasma density are measured to be about 1.7 eV and 3.4 × 1012 cm-3, respectively, under Ar gas flow ranged from 80 to 300 sccm (standard cubic centimeter per minute) in this experiment. The hydroxyl radical density has also been investigated and measured to be maximum value of 2.6 × 1015 cm-3 for the gas flow rate of 150 sccm in the needle-typed plasma jet by the ultraviolet optical absorption spectroscopy.

RELATIVE RATE CONSTANTS OF CONTAMINANT CANDIDATE LIST PESTICIDES WITH HYDROXYL RADICALS

EPA Science Inventory

The objective of this study was to establish the rate constants for the reactions of selected pesticides listed on the US EPA Contaminant Candidate List, with UV and hydroxyl radicals (·OH). Batch experiments were conducted in phosphate buffered solution at pH 7. All pestici...

PHOTOCHEICAL PRODUCTION OF HYDROXYL RADICAL IN NATURAL WATER - THE ROLE OF IRON AND DISSOLVED ORGANIC MATTER

EPA Science Inventory

Photochemical hydroxyl radical (OH) production was measured in several natural waters to investigate the importance of colored dissolved organic matter (CDOM) and iron-CDOM complexes as sources of OH. High rates of OH photoproduction in highly colored, iron-rich, acidic waters a...

Characterization and Neutralization of Arsenical-Based WWII Era Chemical Munition Fills

DTIC Science & Technology

2006-08-01

Fluorine 2.23 Hydroxyl Radical 2.06 Atomic Oxygen 1.78 Hydrogen Peroxide 1.31 Perhydroxyl Radical 1.25 Permanganate 1.24 Hypobromous Acid 1.17 Chlorine...containing carbon-carbon double bonds, aldehyde groups or hydroxyl groups. As an electrophile , the permanganate ion is strongly attracted to the

Formation of methemoglobin and phenoxyl radicals from p-hydroxyanisole and oxyhemoglobin.

PubMed

Stolze, K; Nohl, H

1991-01-01

The reaction of p-hydroxyanisole with oxyhemoglobin was investigated using electron spin resonance spectroscopy (ESR) and visible spectroscopy. As a reactive reaction intermediate we found the p-methoxyphenoxyl radical, the one-electron oxidation product of p-hydroxyanisole. Detection of this species required the rapid flow device elucidating the instability of this radical intermediate. The second reaction product formed is methemoglobin. Catalase or SOD had no effect upon the reaction kinetics. Accordingly, reactive oxygen species such as hydroxyl radicals or superoxide could not be observed although the spin trapping agent DMPO was used to make these short-lived species detectable. When the sulfhydryl blocking agents N-ethylmaleimide or mersalyl acid were used, an increase of the methemoglobin formation rate and of the phenoxyl radical concentration were observed. We have interpreted this observation in terms of a side reaction of free radical intermediates with thiol groups.

Synthesis and antioxidant properties of a new lipophilic ascorbic acid analogue.

PubMed

Cotelle, Philippe; Cotelle, Nicole; Teissier, Elisabeth; Vezin, Hervé

2003-03-20

4-(4-Hydroxyphenyl)-5-(4-hydroxyphenylmethyl)-2-hydroxyfurane-2-one 1 was prepared by an acidic dimerisation of 4-hydroxyphenylpyruvic acid and some of its antioxidant and spectroscopic properties have been measured and compared to that of ascorbic acid. 1 is as good an antioxidant as ascorbic acid in the DPPH (2,2-diphenyl-1-picryl hydrazyl radical) test and the inhibition of hydroxyl radical and a powerful inhibitor of the Cu(2+) or AAPH (2,2'-azobis-(2-amidinopropane) dihydrochloride) induced oxidation of human LDL. 1 gives a stable radical characterised by its ESR spectrum similarly to ascorbic acid but in lower concentration and with a different reactivity towards nitroxides. Theoretical calculations allow us to propose the structure for the radical formed from 1, to explain its lower stability than ascorbyl radical and to evaluate the lipophilicity of 1.

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.

Physico-chemical characterization, antioxidant and anticancer activities in vitro of a novel polysaccharide from Melia toosendan Sieb. Et Zucc fruit.

PubMed

He, Liang; Ji, Pengfei; Gong, Xingguo; Li, Weiqi; Cheng, Junwen; Qian, Hua; Song, Xianliang

2011-10-01

A novel water-soluble polysaccharide pMTPS-3, obtained from Melia toosendan Sieb. Et Zucc fruit by hot-water extraction and ethanol precipitation, was fractionated by DEAE-52 cellulose anion-exchange and Sephadex G-100 gel filtration chromatography. Its primary structural features and molecular weight were characterized by Fourier infrared spectrometry (FTIR), gel permeation chromatography (GPC) and gas chromatography (GC). And the antioxidant activities of pMTPS-3 in vitro were evaluated by 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging assay, superoxide radical scavenging assay and hydroxyl radical scavenging assay. The results suggested that pMTPS-3 was a heteropolysaccharide, composed of arabinose, glucose, mannose, and galactose in the molar ratio of 17.3:28.3:41.6:12.6 with molecular weight 26100Da. The purified pMTPS-3 was revealed to have notable scavenging activity against DPPH radical in a concentration-dependent manner and present a moderate inhibition of superoxide radicals with an IC(50) (5.6mg/ml), and potent inhibiting power for hydroxyl radical compared with crude polysaccharide. Further, it exhibited strong inhibition effect in vitro on the growth of human gastric cancer BGC-823 cells. It is strongly evidenced that pMTPS-3 purified from the crude polysaccharides of Melia toosendan Sieb. Et Zucc could be explored as a potential antioxidant and therapeutics. Copyright © 2011 Elsevier B.V. All rights reserved.

Detection and scavenging of hydroxyl radical via D-phenylalanine hydroxylation in human fluids.

PubMed

Biondi, Roberto; Brancorsini, Stefano; Poli, Giulia; Egidi, Maria Giulia; Capodicasa, Enrico; Bottiglieri, Livio; Gerli, Sandro; Brillo, Eleonora; Renzo, Gian Carlo Di; Cretoiu, Dragos; Micu, Romeo; Suciu, Nicolae

2018-05-01

Hydroxyl radical (.OH) is highly reactive, and therefore very short-lived. Finding new means to accurately detect .OH, and testing the ability of known .OH scavengers to neutralize them in human biological fluids would leverage our ability to more effectively counter oxidative (.OH) stress-mediated damage in human diseases. To achieve this, we pursued the evaluation of secondary products resulting from .OH attack, using a detection system based on Fenton reaction-mediated D-phenylalanine (D-Phe) hydroxylation. This reaction in turn generates o-tyrosine (o-tyr), m-tyrosine (m-tyr) and p-tyrosine (p-tyr). Here, these isomers were separated by HPLC, equipped with fluorescence detectors due to the natural fluorescence of these hydrotyrosines. By extension, we found that, adding radical scavengers competed with D-Phe on .OH attack, thus allowing to determine the .OH quenching capacity of a given compound expressed as inhibition ratio percent (IR%). Using a kinetic approach, we then tested the .OH scavenging capacity (OHSC) of well-known antioxidant molecules. In a test tube, N,N'-dimethylthiourea (DMTU) was the most efficient scavenger as compared to Trolox and N-Acethyl-L-cysteine, with NAC being the less effective. OHSC assay was then applied to biological fluid samples as seminal plasma, human serum from normal subjects and patients undergoing hemodialysis (HD), colostrum and human breast milk from mothers that received daily doses of 30g of chocolate (70% cocoa) during pregnancy. We found that a daily administration of dark chocolate during pregnancy almost doubled OHSC levels in breast milk (1.88 ± 0.12 times, p < 0.01). Furthermore, HD treatment determined a significant reduction of serum OHSC concentration (54.63 ± 2.82%, p < 0.001). Our results provide evidence that Fenton reaction-mediated D-Phe hydroxylation is a suitable method for routine and non-invasive evaluation of .OH detection and its scavenging in human biological fluids. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

Improvements in the Goddard balloon-borne lidar

NASA Technical Reports Server (NTRS)

Heaps, W. S.

1986-01-01

The Goddard balloon-borne lidar system for the measurement of stratospheric ozone and the hydroxyl radical has made three additional flights since the last laser radar conference. On September 27, 1984, a flight was made from Palestine, Texas obtaining a measurement of hydroxyl diurnal variation at 36 km. These data are presented on the plot which shows hydroxyl concentration as a function of GMT for the range cell closest to the instrument. Local noon corresponds to 18 hours on the plot. The rapid drop in concentration after noon is not predicted by models of stratospheric chemistry. It may represent the effects of contamination of the sample volume by hydrocarbons outgassed from the balloon. The more recent flights on June 30, 1985, and December 6, 1985, focussed on measurements of concentration in the lower stratosphere (less than 30 km). The June flight succeeded in obtaining an average concentration measurement (1.8 + or - 0.0000018 molecules/cubic cm) over the altitude range 21 to 26 km. The December flight obtained measurements down to 24 km with a better signal-to-noise ratio than that obtained in June. Prospects for further improvement in sensitivity and absolute calibration will be discussed.

Antioxidative and antiplatelet effects of aqueous inflorescence Piper betle extract.

PubMed

Lei, Daniel; Chan, Chiu-Po; Wang, Ying-Jan; Wang, Tong-Mei; Lin, Bor-Ru; Huang, Chun-Hsun; Lee, Jang-Jaer; Chen, Hsin-Ming; Jeng, Jiiang-Huei; Chang, Mei-Chi

2003-03-26

Piper betle, belonging to the Piperaceae family, is a tropical plant, and its leaf and inflorescence are popularly consumed by betel quid (BQ) chewers in Taiwan and many other South and Southeast Asian countries. However, little is known about the biochemical properties of inflorescence Piper betle (IPB) toward reactive oxygen species (ROS) and platelet functions. In the present work, aqueous IPB extract was shown to be a scavenger of H(2)O(2), superoxide radical, and hydroxyl radical with a 50% inhibitory concentration (IC(50)) of about 80, 28, and 73 microg/mL, respectively. IPB extract also prevented the hydroxyl radical induced PUC18 plasmid DNA breaks at concentrations higher than 40 microg/mL. Since ROS are crucial for platelet aggregation, we further found that IPB extract also inhibited the arachidonic acid (AA) induced and collagen-induced platelet aggregation, with an IC(50) of 207 and 335 microg/mL, respectively. IPB extract also inhibited the AA-, collagen- (>100 microg/mL of IPB), and thrombin (>250 microg/mL of IPB)-induced thromboxane B(2) (TXB(2)) production by more than 90%. However, IPB extract showed little effect on thrombin-induced aggregation. These results indicated that aqueous components of IPB are potential ROS scavengers and may prevent the platelet aggregation possibly via scavenging ROS or inhibition of TXB(2) production.

Antioxidant capacity and radical scavenging effect of polyphenol rich Mallotus philippenensis fruit extract on human erythrocytes: an in vitro study.

PubMed

Gangwar, Mayank; Gautam, Manish Kumar; Sharma, Amit Kumar; Tripathi, Yamini B; Goel, R K; Nath, Gopal

2014-01-01

Mallotus philippinensis is an important source of molecules with strong antioxidant activity widely used medicinal plant. Previous studies have highlighted their anticestodal, antibacterial, wound healing activities, and so forth. So, present investigation was designed to evaluate the total antioxidant activity and radical scavenging effect of 50% ethanol fruit glandular hair extract (MPE) and its role on Human Erythrocytes. MPE was tested for phytochemical test followed by its HPLC analysis. Standard antioxidant assays like DPPH, ABTS, hydroxyl, superoxide radical, nitric oxide, and lipid peroxidation assay were determined along with total phenolic and flavonoids content. Results showed that MPE contains the presence of various phytochemicals, with high total phenolic and flavonoid content. HPLC analysis showed the presence of rottlerin, a polyphenolic compound in a very rich quantity. MPE exhibits significant strong scavenging activity on DPPH and ABTS assay. Reducing power showed dose dependent increase in concentration absorption compared to standard, Quercetin. Superoxide, hydroxyl radical, lipid peroxidation, nitric oxide assay showed a comparable scavenging activity compared to its standard. Our finding further provides evidence that Mallotus fruit extract is a potential natural source of antioxidants which have a protective role on human Erythrocytes exhibiting minimum hemolytic activity and this justified its uses in folklore medicines.

Antioxidant Capacity and Radical Scavenging Effect of Polyphenol Rich Mallotus philippenensis Fruit Extract on Human Erythrocytes: An In Vitro Study

PubMed Central

Gautam, Manish Kumar; Sharma, Amit Kumar; Tripathi, Yamini B.; Goel, R. K.; Nath, Gopal

2014-01-01

Mallotus philippinensis is an important source of molecules with strong antioxidant activity widely used medicinal plant. Previous studies have highlighted their anticestodal, antibacterial, wound healing activities, and so forth. So, present investigation was designed to evaluate the total antioxidant activity and radical scavenging effect of 50% ethanol fruit glandular hair extract (MPE) and its role on Human Erythrocytes. MPE was tested for phytochemical test followed by its HPLC analysis. Standard antioxidant assays like DPPH, ABTS, hydroxyl, superoxide radical, nitric oxide, and lipid peroxidation assay were determined along with total phenolic and flavonoids content. Results showed that MPE contains the presence of various phytochemicals, with high total phenolic and flavonoid content. HPLC analysis showed the presence of rottlerin, a polyphenolic compound in a very rich quantity. MPE exhibits significant strong scavenging activity on DPPH and ABTS assay. Reducing power showed dose dependent increase in concentration absorption compared to standard, Quercetin. Superoxide, hydroxyl radical, lipid peroxidation, nitric oxide assay showed a comparable scavenging activity compared to its standard. Our finding further provides evidence that Mallotus fruit extract is a potential natural source of antioxidants which have a protective role on human Erythrocytes exhibiting minimum hemolytic activity and this justified its uses in folklore medicines. PMID:25525615

Comparison of chemiluminescence methods for analysis of hydrogen peroxide and hydroxyl radicals

NASA Astrophysics Data System (ADS)

Pehrman, R.; Amme, M.; Cachoir, C.

2006-01-01

Assessment of alpha radiolysis influence on the chemistry of geologically disposed spent fuel demands analytical methods for radiolytic product determination at trace levels. Several chemiluminescence methods for the detection of radiolytic oxidants hydrogen peroxide and hydroxyl radicals are tested. Two of hydrogen peroxide methods use luminol, catalyzed by either μ-peroxidase or hemin, one uses 10-methyl-9-(p-formylphenyl)-acridinium carboxylate trifluoromethanesulfonate and one potassium periodate. All recipes are tested as batch systems in basic conditions. For hydroxyl radical detection luminophores selected are 3-hydroxyphthalic hydrazide and rutin. Both methods are tested as batch systems. The results are compared and the applicability of the methods for near-field dissolution studies is discussed.

An association between the level of oxidative stress and the concentrations of NEFA and BHBA in the plasma of ketotic dairy cows.

PubMed

Li, Y; Ding, H Y; Wang, X C; Feng, S B; Li, X B; Wang, Z; Liu, G W; Li, X W

2016-10-01

The aim of this study was to evaluate the oxidative status in ketotic cows. We observed changes in the oxidative status and correlations between the oxidative and metabolic status in non-ketotic (n = 10), subclinical ketotic (n = 10) and ketotic cows (n = 10). Plasma samples were analysed by standard biochemical techniques and ELISA to determine traditional metabolic parameters: triglyceride (TG), phosphonium (P), calcium (Ca), aspartate aminotransferase (AST), alanine aminotransferase (ALT), alkaline phosphatase (ALP), total protein (TP), albumin (ALB), immune globulin (Ig), total cholesterol (TC), high-density lipoprotein (HDL), very low-density lipoprotein (VLDL) and lactate dehydrogenase (LDH); energy metabolism indices: glucose, β-hydroxybutyrate (BHBA) and non-esterified fatty acids (NEFA); and indices of oxidative status: malondialdehyde (MDA), hydrogen peroxide (H2 O2 ), vitamin C, vitamin E, superoxide dismutase (SOD), glutathione peroxidase (GSH-Px), catalase (CAT), xanthine oxidase (XOD) and total antioxidant capacity (TAOC). The results of this study showed that plasma glucose levels were lower in ketotic and subclinical ketotic cows than in non-ketotic cows; however, the plasma NEFA and BHBA concentrations were higher. In addition, significant decreases in TC, HDL and VLDL and significant increases in AST, ALT and LDH were observed in the plasma of the ketotic cows. The ketotic cows showed decreased plasma SOD, CAT, vitamin C and vitamin E, inhibited hydroxyl radical capacity and increased plasma H2 O2 and MDA. There were positive correlations between the plasma NEFA and ALT, AST, LDH and MDA and negative correlations between the plasma NEFA and TC, HDL, VLDL, SOD, vitamin C, vitamin E, 1542280 uric acid and inhibited hydroxyl radical capacity. In addition, there were positive correlations between BHBA concentrations and ALT, AST and LDH and negative correlations between plasma BHBA concentrations and TC, HDL, VLDL, vitamin E and inhibited hydroxyl radical capacity. Overall, ketotic dairy cows experience oxidative stress, which is presumably associated with hyperketonemia and higher NEFA. Journal of Animal Physiology and Animal Nutrition © 2016 Blackwell Verlag GmbH.

Kinetic Model for the Radical Degradation of Tri-Halonitromethane Disinfection Byproducts in Water

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

Stephen P. Mezyk; Bruce J. Mincher; William J. Cooper

The halonitromethanes (HNMs) are byproducts of the ozonation and chlorine/chloramine treatment of drinking waters. Although typically occurring at low concentrations HNMs have high cytotoxicity and mutagenicity, and may therefore represent a significant human health hazard. In this study, we have investigated the radical based mineralization of fully-halogenated HNMs in water using the congeners bromodichloronitromethane and chlorodibromonitromethane. We have combined absolute reaction rate constants for their reactions with the hydroxyl radical and the hydrated electron as measured by electron pulse radiolysis and analytical measurements of stable product concentrations obtained by 60Co steady-state radiolysis with a kinetic computer model that includes watermore » radiolysis reactions and halide/nitrogen oxide radical chemistry to fully elucidate the reaction pathways of these HNMs. These results are compared to our previous similar study of the fully chlorinated HNM chloropicrin. The full optimized computer model, suitable for predicting the behavior of this class of compounds in irradiated drinking water is provided.« less

Antioxidant activity and antibacterial activity of peach gum derived oligosaccharides.

PubMed

Yao, Xing-Cun; Cao, Yan; Wu, Sheng-Jun

2013-11-01

In this study, peach gum derived oligosaccharides (PGDO) were prepared from peach gum polysaccharides by hydrolysis using hydrogen peroxide (H2O2) under following conditions: time, 8h; temperature, 55 °C; H2O2 concentration, 4% (v/v); and NaOH concentration, 2.0 M. The antioxidant activity and antibacterial activity of PGDO were estimated. There were no significant chemical changes in the backbones of the peach gum polysaccharides treated with H2O2. The PGDO showed high hydroxyl radical scavenging activity (86.12%) and 2, 2-diphenyl-β-picrylhydrazyl radical scavenging activity (91.70%) at the concentration of 100 μg/mL as well as high reducing capacity at the concentration of 50 μg/mL. In addition the PGDO had high antibacterial activity against Bacillus subtilis, Staphylococcus aureus, and Escherichia coli at the concentration of 100 μg/mL. Copyright © 2013 Elsevier B.V. All rights reserved.

Processing pathway dependence of amorphous silica nanoparticle toxicity - colloidal versus pyrolytic

PubMed Central

Zhang, Haiyuan; Dunphy, Darren R.; Jiang, Xingmao; Meng, Huan; Sun, Bingbing; Tarn, Derrick; Xue, Min; Wang, Xiang; Lin, Sijie; Ji, Zhaoxia; Li, Ruibin; Garcia, Fred L.; Yang, Jing; Kirk, Martin L.; Xia, Tian; Zink, Jeffrey I; Nel, Andre; Brinker, C. Jeffrey

2012-01-01

We have developed structure/toxicity relationships for amorphous silica nanoparticles (NPs) synthesized through low temperature, colloidal (e.g. Stöber silica) or high temperature pyrolysis (e.g. fumed silica) routes. Through combined spectroscopic and physical analyses, we have determined the state of aggregation, hydroxyl concentration, relative proportion of strained and unstrained siloxane rings, and potential to generate hydroxyl radicals for Stöber and fumed silica NPs with comparable primary particle sizes (16-nm in diameter). Based on erythrocyte hemolytic assays and assessment of the viability and ATP levels in epithelial and macrophage cells, we discovered for fumed silica an important toxicity relationship to post-synthesis thermal annealing or environmental exposure, whereas colloidal silicas were essentially non-toxic under identical treatment conditions. Specifically, we find for fumed silica a positive correlation of toxicity with hydroxyl concentration and its potential to generate reactive oxygen species (ROS) and cause red blood cell hemolysis. We propose fumed silica toxicity stems from its intrinsic population of strained three-membered rings (3MRs) along with its chain-like aggregation and hydroxyl content. Hydrogen-bonding and electrostatic interactions of the silanol surfaces of fumed silica aggregates with the extracellular plasma membrane cause membrane perturbations sensed by the Nalp3 inflammasome, whose subsequent activation leads to secretion of the cytokine IL-1β. Hydroxyl radicals generated by the strained 3MRs in fumed silica but largely absent in colloidal silicas may contribute to the inflammasome activation. Formation of colloidal silica into aggregates mimicking those of fumed silica had no effect on cell viability or hemolysis. This study emphasizes that not all amorphous silica is created equal and that the unusual toxicity of fumed silica compared to colloidal silica derives from its framework and surface chemistry along with its fused chain-like morphology established by high temperature synthesis (>1300°C) and rapid thermal quenching. PMID:22924492

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.

Reactions of clofibric acid with oxidative and reductive radicals-Products, mechanisms, efficiency and toxic effects

NASA Astrophysics Data System (ADS)

Csay, Tamás; Rácz, Gergely; Salik, Ádám; Takács, Erzsébet; Wojnárovits, László

2014-09-01

The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O2-•/HO2• reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O2-•/HO2•. Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC-MS method was developed based on 18O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid.

Rovibrational intensities and electric dipole moment function of the X2 Pi hydroxyl radical

NASA Technical Reports Server (NTRS)

Chackerian, C., Jr.; Goorvitch, D.; Benidar, A.; Farrenq, R.; Guelachvili, G.; Martin, P. M.; Abrams, M. C.; Davis, S. P.

1992-01-01

Recent work aimed at determining the absolute rovibrational transition intensities for the ground electronic state of the hydroxyl radical is reviewed. Two new sets of Fourier transform emission spectra of OH are described which were recorded at the University of Paris and at the Kitt Peak National Solar Observatory.

Infrared Emission Spectrum of the Hydroxyl Radical: A Novel Experiment in Molecular Spectroscopy.

ERIC Educational Resources Information Center

Henderson, Giles; And Others

1982-01-01

Describes an experiment in which parameters from an "ab-initio" potential are used to calculate vibrational-rotational energy levels and construct a "stick spectrum" for the overtone emission of the hydroxyl radical. Provides background information on ab-initio spectrum, experimental procedures, and analysis of data. (Author/JN)

DNA Binding Hydroxyl Radical Probes.

PubMed

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

2012-01-01

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

New insights into the aquatic photochemistry of fluoroquinolone antibiotics: Direct photodegradation, hydroxyl-radical oxidation, and antibacterial activity changes.

PubMed

Ge, Linke; Na, Guangshui; Zhang, Siyu; Li, Kai; Zhang, Peng; Ren, Honglei; Yao, Ziwei

2015-09-15

The ubiquity and photoreactivity of fluoroquinolone antibiotics (FQs) in surface waters urge new insights into their aqueous photochemical behavior. This study concerns the photochemistry of 6 FQs: ciprofloxacin, danofloxacin, levofloxacin, sarafloxacin, difloxacin and enrofloxacin. Methods were developed to calculate their solar direct photodegradation half-lives (td,E) and hydroxyl-radical oxidation half-lives (tOH,E) in sunlit surface waters. The td,E values range from 0.56 min to 28.8 min at 45° N latitude, whereas tOH,E ranges from 3.24h to 33.6h, suggesting that most FQs tend to undergo fast direct photolysis rather than hydroxyl-radical oxidation in surface waters. However, a case study for levofloxacin and sarafloxacin indicated that the hydroxyl-radical oxidation induced risky photochlorination and resulted in multi-degradation pathways, such as piperazinyl hydroxylation and clearage. Changes in the antibacterial activity of FQs caused by photodegradation in various waters were further examined using Escherichia coli, and it was found that the activity evolution depended on primary photodegradation pathways and products. Primary intermediates with intact FQ nuclei retained significant antibacterial activity. These results are important for assessing the fate and risk of FQs in surface waters. Copyright © 2015. Published by Elsevier B.V.

Enhanced in vitro biological activity generated by surface characteristics of anodically oxidized titanium--the contribution of the oxidation effect.

PubMed

Wurihan; Yamada, A; Suzuki, D; Shibata, Y; Kamijo, R; Miyazaki, T

2015-05-20

Anodically oxidized titanium surfaces, prepared by spark discharge, have micro-submicron surface topography and nano-scale surface chemistry, such as hydrophilic functional groups or hydroxyl radicals in parallel. The complexity of the surface characteristics makes it difficult to draw a clear conclusion as to which surface characteristic, of anodically oxidized titanium, is critical in each biological event. This study examined the in vitro biological changes, induced by various surface characteristics of anodically oxidized titanium with, or without, release of hydroxyl radicals onto the surface. Anodically oxidized titanium enhanced the expression of genes associated with differentiating osteoblasts and increased the degree of matrix mineralization by these cells in vitro. The phenotypes of cells on the anodically oxidized titanium were the same with, or without, release of hydroxyl radicals. However, the nanomechanical properties of this in vitro mineralized tissue were significantly enhanced on surfaces, with release of hydroxyl radicals by oxidation effects. In addition, the mineralized tissue, produced in the presence of bone morphogenetic protein-2 on bare titanium, had significantly weaker nanomechanical properties, despite there being higher osteogenic gene expression levels. We show that enhanced osteogenic cell differentiation on modified titanium is not a sufficient indicator of enhanced in vitro mineralization. This is based on the inferior mechanical properties of mineralized tissues, without either being cultured on a titanium surface with release of hydroxyl radicals, or being supplemented with lysyl oxidase family members.

Reactivity of OHrad and e-aq from electron beam irradiation of aqueous solutions of EDTA and aminopolycarboxylic acids

NASA Astrophysics Data System (ADS)

Vel Leitner, N. Karpel; Guilbault, I.; Legube, B.

2003-05-01

Electron beam irradiation of aqueous solutions of EDTA, EDDA NN‧, NTA, IDA and Cu-EDTA was performed in the presence of scavengers for the hydroxyl radicals (methanol) or for the solvated electrons (hydrogen peroxide). Experiments showed that for each molecule, the G-value decreases as the radiation dose increases from 1 to 25 kGy, and for EDTA, when the initial concentration decreases from 10 to 0.1 mmol l-1. At pH 8 and for 5 kGy, the G-values of NTA, IDA, EDTA and EDDA NN‧ removal ascribed to OHrad radicals are, respectively, 0.06, 0.06, 0.15 and 0.20 μmol J-1, whereas for the solvated electrons the G-values were, respectively, 0.01, 0.01, 0.06 and 0.04 μmol J-1. The rate constants of hydroxyl radicals and solvated electrons were determined by comparison with one competitor. For each active species (hydroxyl radical or solvated electron), the reactivity is connected to the number of nitrogen atoms and acetate groups. The rate constants of OHrad radicals are above 1010 and 8.6×109 l mol-1 s-1 for EDDA NN‧ and EDTA, respectively, 2.1×109 l mol-1 s-1 for IDA and 6.1×108 l mol-1 s-1 for NTA. The reactivity of solvated electrons is smaller and the rate constants are in the range 1.9×106-3.7×106 l mol-1 s-1 for NTA, IDA and EDDA NN‧ and equal 1.4×107 l mol-1 s-1 for EDTA. The reactivity of the complex Cu-EDTA towards OHrad does not differ to a large extent from EDTA whereas with e-aq the reactivity of Cu-EDTA is better than EDTA since ke-/Cu-EDTA reaches 2.2×109 l mol-1 s-1. It follows that when both active entities (OHrad and e-aq) are involved in the electron beam irradiation process, the removal of free aminopolycarboxylic acids is mainly due to OHrad radicals. However, the complex Cu-EDTA is concerned by both e-aq and OHrad radicals.

Markedly Enhanced Surface Hydroxyl Groups of TiO2 Nanoparticles with Superior Water-Dispersibility for Photocatalysis

PubMed Central

Wu, Chung-Yi; Tu, Kuan-Ju; Deng, Jin-Pei; Lo, Yu-Shiu; Wu, Chien-Hou

2017-01-01

The benefits of increasing the number of surface hydroxyls on TiO2 nanoparticles (NPs) are known for environmental and energy applications; however, the roles of the hydroxyl groups have not been characterized and distinguished. Herein, TiO2 NPs with abundant surface hydroxyl groups were prepared using commercial titanium dioxide (ST-01) powder pretreated with alkaline hydrogen peroxide. Through this simple treatment, the pure anatase phase was retained with an average crystallite size of 5 nm and the surface hydroxyl group density was enhanced to 12.0 OH/nm2, estimated by thermogravimetric analysis, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. Especially, this treatment increased the amounts of terminal hydroxyls five- to six-fold, which could raise the isoelectric point and the positive charges on the TiO2 surface in water. The photocatalytic efficiency of the obtained TiO2 NPs was investigated by the photodegradation of sulforhodamine B under visible light irradiation as a function of TiO2 content, pH of solution, and initial dye concentration. The high surface hydroxyl group density of TiO2 NPs can not only enhance water-dispersibility but also promote dye sensitization by generating more hydroxyl radicals. PMID:28772926

Demonstration of the production of oxygen-centered free radicals during electrolysis using E.S.R. spin-trapping techniques: effects on cardiac function in the isolated rat heart.

PubMed

Lecour, S; Baouali, A B; Maupoil, V; Chahine, R; Abadie, C; Javouhey-Donzel, A; Rochette, L; Nadeau, R

1998-03-01

The present study was designed to identify the free radicals generated during the electrolysis of the solution used to perfuse isolated rat heart Langendorff preparations. The high reactivity and very short half-life of oxygen free radicals make their detection and identification difficult. A diamagnetic organic molecule (spin trap) can be used to react with a specific radical to produce a more stable secondary radical or "spin adduct" detected by electron spin resonance (ESR). Isovolumic left ventricular systolic pressure (LVSP) and left ventricular end diastolic pressure (LVEDP) were measured by a fluid-filled latex balloon inserted into the left ventricle. The coronary flow was measured by effluent collection. Electrolysis was performed with constant currents of 0.5, 1, 1.5, 3, 5, 7.5, and 10 mA generated by a Grass stimulator and applied to the perfusion solution for 1 min. A group of experiments was done using a 1.5 mA current and a Krebs-Henseleit (K-H) solution containing free radical scavengers (superoxide dismutase (SOD): 100 IU/ml or mannitol: 50 mM). Heart function rapidly declined in hearts perfused with K-H buffer that had been electrolyzed for 1 min. The addition of mannitol (50 mM) to the perfusion solution had no effect on baseline cardiac function before electrolysis while SOD (100 IU/ml) increased the coronary flow. However, SOD was more effective than the mannitol in protecting the heart against decreased of cardiac function, 5 min after the end of electrolysis. Samples of the K-H medium subjected to electrolysis were collected in cuvettes containing a final concentration of 125 mM 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and analyzed by spectroscopy. The ESR spectrum consisted of a quartet signal (hyperfine couplings aN = aH = 14.9 G) originating from the hydroxyl adduct signal, DMPO-OH. The intensity of the DMPO-OH signal remained stable during the 60 s of electrolysis and the quantity of free radicals induced by electrolysis was directly proportional to the intensity of the current. The addition of mannitol and SOD to the perfusate scavenged the hydroxyl radicals present in the solution, suggesting that both hydroxyl and superoxide radicals were formed during electrolysis.

Formation Of Nitrous Acid In Various Environments And Its Contribution To Hydroxyl Radical Budget

NASA Astrophysics Data System (ADS)

Li, X.; Lu, K.; Liu, Y.; Rohrer, F.; Häseler, R.; Bohn, B.; Fuchs, H.; Hofzumahaus, A.; Wahner, A.; Kiendler-Scharr, A.; Zeng, L.; Zhang, Y.

2017-12-01

Nitrous acid (HONO) is an important trace gas in the atmosphere due to its contribution to the cycles of nitrogen oxides (NOx) and hydrogen oxides (HOx). Yet the formation mechanism of HONO during daytime remains large uncertainty. In the past ten years, we performed ground HONO measurements using the LOPAP technique in different seasons in two major mega-city areas, i.e., North China Plain and Pearl River Delta. Spatial distribution of HONO over different regions in Europe was also observed by the same technique on-board the Zeppelin NT airship in 2012 and 2013. For all field observations, parameters (OH, HO2, NOx, photolysis frequencies, aerosols, etc.) influencing the HONO budget were measured simultaneous, which allows us to investigate the source of HONO and its contribution to the hydroxyl radical budget. In this presentation, we summarize the general features of HONO in the planetary boundary layer in terms of its daytime concentration, spatial distribution, and source strength, and contribution to the primary OH production. Various proposed HONO formation mechanisms have been tested in order to explain the widely exited missing daytime HONO production of 100 - 200 ppt h-1 . We will show that there is not a stand alone mechanism can be used for explaining the HONO formation in various environments. Design of field experiments which effectively separate different physical and chemical processes would be helpful to pin down the major daytime HONO source and to understand its influence on the hydroxyl radical budget.

Interaction of aromatic alcohols, aldehydes and acids with α-hydroxyl-containing carbon-centered radicals: A steady state radiolysis study

NASA Astrophysics Data System (ADS)

Samovich, S. N.; Brinkevich, S. D.; Shadyro, O. I.

2013-01-01

Benzaldehyde and its derivatives efficaciously oxidize in aqueous solutions α-hydroxyl-containing carbon-centered radicals (α-HCR) of various structures, suppressing thereby the radical recombination and fragmentation reactions. The compounds containing cinnamic moieties are capable of adding α-hydroxyethyl radicals (α-HER) to the carbon-carbon double bonds conjugated with the aromatic system to form molecular products identifiable by mass spectrometry. On radiolysis of aqueous ethanol solutions, reduction of α-HER by aromatic alcohols and acids has been shown to proceed via formation of their adducts with hydrated electron species.

Hydroxyl radical scavenging assay of phenolics and flavonoids with a modified cupric reducing antioxidant capacity (CUPRAC) method using catalase for hydrogen peroxide degradation.

PubMed

Ozyürek, Mustafa; Bektaşoğlu, Burcu; Güçlü, Kubilay; Apak, Reşat

2008-06-02

Hydroxyl radicals (OH) generated in the human body may play an important role in tissue injury at sites of inflammation in oxidative stress-originated diseases. As a more convenient, efficient, and less costly alternative to HPLC/electrochemical detection techniques and to the nonspecific, low-yield deoxyribose (TBARS) test, we used a salicylate probe for detecting OH generated by the reaction of iron(II)-EDTA complex with H(2)O(2). The produced hydroxyl radicals attack both the salicylate probe and the hydroxyl radical scavengers that are incubated in solution for 10 min. Added radical scavengers compete with salicylate for the OH produced, and diminish chromophore formation from Cu(II)-neocuproine. At the end of the incubation period, the reaction was stopped by adding catalase. With the aid of this reaction, a kinetic approach was adopted to assess the hydroxyl radical scavenging properties of polyphenolics, flavonoids and other compounds (e.g., ascorbic acid, glucose, mannitol). A second-order rate constant for the reaction of the scavenger with OH could be deduced from the inhibition of colour formation due to the salicylate probe. In addition to phenolics and flavonoids, five kinds of herbs were evaluated for their OH scavenging activity using the developed method. The modified CUPRAC (cupric ion reducing antioxidant capacity) assay proved to be efficient for ascorbic acid, gallic acid and chlorogenic acid, for which the deoxyribose assay test is basically nonresponsive. An important contribution of this developed assay is the inhibition of the Fenton reaction with catalase degradation of hydrogen peroxide so that the remaining H(2)O(2) would neither give a CUPRAC absorbance nor involve in redox cycling of phenolic antioxidants, enabling the rapid assay of polyphenolics.

Analysis of the saturation phenomena of the neutralization rate of positively charged 218Po in water vapor.

PubMed

Tan, Yanliang; Xiao, Detao; Shan, Jian; Zhou, Qingzhi; Qu, Jingnian

2014-09-01

Generally, 88% of the freshly generated 218Po ions decayed from 222Rn are positively charged. These positive ions become neutralized by recombination with negative ions, and the main source of the negative ions is the OH- ions formed by radiolysis of water vapor. However, the neutralization rate of positively charged 218Po versus the square root of the concentration of H2O will be a constant when the concentration of H2O is sufficiently high. Since the electron affinity of the hydroxyl radical formed by water vapor is high, the authors propose that the hydroxyl radical can grab an electron to become OH-. Because the average period of collision with other positively charged ions and the average life of the OH- are much longer than those of the electron, the average concentration of negative ions will grow when the water vapor concentration increases. The authors obtained a model to describe the growth of OH- ions. From this model, it was found that the maximum value of the OH- ion concentration is limited by the square root of the radon concentration. If the radon concentration is invariant, the OH- ion concentration should be approximately a constant when the water vapor concentration is higher than a certain value. The phenomenon that the neutralization rate of positively charged 218Po versus the square root of the water vapor concentration will be saturated when the water vapor concentration is sufficiently high can be explained by this mechanism. This mechanism can be used also to explain the phenomenon that the detection efficiency of a radon monitor based on the electrostatic collection method seems to be constant when the water vapor concentration is high.

POLYCHLORINATED DIBENZO-P-DIOXINS AND DIBENZOFURANS: GAS-PHASE HYDROXYL RADICAL REACTIONS AND RELATED ATMOSPHERIC REMOVAL. (R825377)

EPA Science Inventory

Gas-phase reactions with the hydroxyl radical (OH) are
expected to be an important removal pathway of polychlorinated dibenzo-p-dioxins and dibenzofurans
(PCDD/F)
in the atmosphere. Our laboratory recently developed
a system to measure the rate constants of ...

77 FR 5514 - Mandatory Reporting of Greenhouse Gases: Notice of Preliminary Determinations Regarding Requests...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-03

... the use of special characters, any form of encryption, and be free of any defects or viruses. Docket... such as hydroxyl radicals (OH), ozone (O 3 ), carbon monoxide (CO), and water). (iii) The radiative... of hydroxyl radicals (OH) or by deriving the lifetime of the short-lived (i.e., not well mixed...

Determination of Bimolecular Rate Constants for Reactions of Hydroxyl Radical with Pharmaceutical and Cosmetics Chemicals - Implications to the Fate in the Aquatic Environment

NASA Astrophysics Data System (ADS)

Nakajima, H.; Arakaki, T.; Anastasio, C.

2008-12-01

Large organic compounds such as hyaluronic acid and chondroitin sulfate are often used in pharmaceutical and cosmetics products, but their chemical degradation pathways are not well understood. To better elucidate their fate in the aquatic environment, we initiated a study to determine bimolecular rate constants between these organic compounds and hydroxyl radical (OH), which is a potent oxidant in the environment. The lifetimes of many organic compounds are determined by reactions with OH radicals, and the lifetime of OH is often controlled by reactions with organic compounds. To determine these bimolecular rate constants we used a competition kinetics technique with either hydrogen peroxide or nitrate as a source of OH and benzoate as the competing sink. Since the molecular weights of some of the large organic compounds we studied were not known, we used dissolved organic carbon (DOC) concentrations to determine mole-carbon based bimolecular rate constants, instead of the commonly used molar-based bimolecular rate constants. We will report the mole-carbon based bimolecular rate constants of OH, determined at room temperature, with hyaluronic acid, chondroitin sulfate and some other large organic compounds.

Hydrogen peroxide catalytic decomposition

NASA Technical Reports Server (NTRS)

Parrish, Clyde F. (Inventor)

2010-01-01

Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated through the use of concentrated hydrogen peroxide fed as a monopropellant into a catalyzed thruster assembly. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50%-70% by volume, and may be increased in concentration in a continuous process preceding decomposition in the thruster assembly. The exhaust of the thruster assembly, rich in hydroxyl and/or hydroperoxy radicals, may be fed into a stream containing oxidizable components, such as nitric oxide, to facilitate their oxidation.

Manganese Catalysts for C–H activation: An Experimental/Theoretical Study Identifies the Stereoelectronic Factor that Controls the Switch between Hydroxylation and Desaturation Pathways

PubMed Central

Hull, Jonathan F.; Balcells, David; Sauer, Effiette L. O.; Raynaud, Christophe; Brudvig, Gary W.; Crabtree, Robert H.; Eisenstein, Odile

2010-01-01

We describe competitive C–H activation chemistry of two types, desaturation and hydroxylation, using synthetic manganese catalysts with several substrates. 9,10-dihydrophenanthrene (DHP) gives the highest desaturation activity, the final products being phenanthrene (P1) and phenanthrene-9,10-oxide (P3), the latter being thought to arise from epoxidation of some of the phenanthrene. The hydroxylase pathway also occurs as suggested by the presence of the dione product, phenanthrene-9,10-dione (P2), thought to arise from further oxidation of hydroxylation intermediate 9-hydroxy-9,10-dihydrophenanthrene. The experimental work together with the DFT calculations shows that the postulated Mn oxo active species, [Mn(O)(tpp)(Cl)] (tpp = tetraphenyl porphyrin), can promote the oxidation of dihydrophenanthrene by either desaturation or hydroxylation pathways. The calculations show that these two competing reactions have a common initial step – radical H abstraction from one of the DHP sp3 C–H bonds. The resulting Mn hydroxo intermediate is capable of promoting not only OH rebound (hydroxylation) but also a second H abstraction adjacent to the first (desaturation). Like the active MnV=O species, this MnIV-OH species also has radical character on oxygen and can thus give H abstraction. Both steps have very low and therefore very similar energy barriers, leading to a product mixture. Since the radical character of the catalyst is located on the oxygen p orbital perpendicular to the MnIV-OH plane, the orientation of the organic radical with respect to this plane determines which reaction, desaturation or hydroxylation, will occur. Stereoelectronic factors such as the rotational orientation of the OH in the enzyme active site is thus likely to constitute the switch between hydroxylation and desaturation behavior. PMID:20481432

Detection of hydroxyl radicals by D-phenylalanine hydroxylation: a specific assay for hydroxyl radical generation in biological systems.

PubMed

Biondi, R; Xia, Y; Rossi, R; Paolocci, N; Ambrosio, G; Zweier, J L

2001-03-01

Hydroxylation of l-phenylalanine (Phe) by hydroxyl radical (*OH) yields 4-, 3-, and 2-hydroxyl-Phe (para-, meta-, and ortho-tyrosine, respectively). Phe derivative measurements have been employed to detect *OH formation in cells and tissues, however, the specificity of this assay is limited since Phe derivatives also arise from intracellular Phe hydroxylase. d-Phe, the d-type enantiomer, is not hydroxylated by Phe hydroxylase. We evaluate whether d-Phe reacts with *OH as well as l-Phe, providing a more reliable probe for *OH generation in biological systems. With *OH generated by a Fenton reaction or xanthine oxidase, d- and l-Phe equally gave rise to p, m, o-tyr and this could be prevented by *OH scavengers. Resting human neutrophils (PMNs) markedly converted l-Phe to p-tyr, through non-oxidant-mediated reactions, whereas d-Phe was unaffected. In contrast, when PMNs were stimulated in the presence of redox cycling iron the *OH formed resulted in more significant rise of p-tyr from d-Phe (9.4-fold) than l-Phe (3.6-fold) due to the significant background formation of p-tyr from l-Phe. Together, these data indicated that d- and l-Phe were equally hydroxylated by *OH. Using d-Phe instead of l-Phe can eliminate the formation of Phe derivatives from Phe hydroxylase and achieve more specific, sensitive measurement of *OH in biological systems.

Production and reactivity of the hydroxyl radical in homogeneous high pressure plasmas of atmospheric gases containing traces of light olefins

NASA Astrophysics Data System (ADS)

Magne, L.; Pasquiers, S.; Blin-Simiand, N.; Postel, C.

2007-05-01

A photo-triggered discharge has been used to study the production kinetic mechanisms and the reactivity of the hydroxyl radical in a N2/O2 mixture (5% oxygen) containing ethane or ethene for hydrocarbon concentration values in the range 1000-5000 ppm, at 460 mbar total pressure. The discharge (current pulse duration of 60 ns) has allowed the generation of a transient homogeneous non-equilibrium plasma, and the time evolution of the OH density has been measured (relative value) in the afterglow (up to 200 µs) by laser induced fluorescence (LIF). Experimental results have been explained using predictions of a self-consistent 0D discharge and plasma reactivity modelling, and reduced kinetic schemes for OH have been validated. It has been shown that recombination of H- and O-atoms, as well as reaction of O with the hydroperoxy radical HO2, plays a very important role in the production of OH radicals in the mixture with ethane. H is a key species for production of OH and HO2 radicals. As for ethane, O, H and HO2 are key species for the production of OH in the case of ethene, but carbonated radicals, following the partial oxidation of the hydrocarbon molecule by O, also play a non-negligible role. The rate constant for O- and H-atom recombination has been estimated to be 3 × 10-30 cm6 s-1 at near ambient temperature, consistent with LIF measurements on OH for both mixtures with ethane and ethene.

Phenolic extract of Dialium guineense pulp enhances reactive oxygen species detoxification in aflatoxin B₁ hepatocarcinogenesis.

PubMed

Adeleye, Abdulwasiu O; Ajiboye, Taofeek O; Iliasu, Ganiyat A; Abdussalam, Folakemi A; Balogun, Abdulazeez; Ojewuyi, Oluwayemisi B; Yakubu, Musa T

2014-08-01

This study investigated the effect of Dialium guineense pulp phenolic extract on aflatoxin B1 (AFB1)-induced oxidative imbalance in rat liver. Reactive oxygen species (ROS) scavenging potentials of free and bound phenolic extract of D. guineense (0.2-1.0 mg/mL) were investigated in vitro using 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical, superoxide ion (O2(-)), hydrogen peroxide (H2O2), hydroxyl radical, and ferric ion reducing system. In the in vivo study, 35 animals were randomized into seven groups of five rats each. Free and bound phenolic extract (1 mg/mL) produced 66.42% and 93.08%, 57.1% and 86.0%, 62.0% and 90.05%, and 60.11% and 72.37% scavenging effect on DPPH radical, O2(-) radical, H2O2, and hydroxyl radical, while ferric ion was significantly reduced. An AFB1-mediated decrease in the activities of ROS detoxifying enzymes (superoxide dismutase, catalase, glutathione peroxidase, glutathione reductase, and glucose 6 phosphate dehydrogenase) was significantly attenuated (P<.05). AFB1-mediated elevation in the concentrations of oxidative stress biomarkers; malondialdehyde, conjugated dienes, lipid hydroperoxides, protein carbonyl, and percentage DNA fragmentation were significantly lowered by D. guineense phenolic extract (P<.05). Overall, the in vitro and in vivo effects suggest that D. guineense phenolic extract elicited ROS scavenging and detoxification potentials, as well as the capability of preventing lipid peroxidation, protein oxidation, and DNA fragmentation.

Photoproduction of hydroxyl radicals in aqueous solution with algae under high-pressure mercury lamp.

PubMed

Liu, Xianli; Wu, Feng; Deng, Nansheng

2004-01-01

Photoproduction of hydroxyl radicals (*OH) could be induced in aqueous solution with algae (Nitzschia hantzschiana, etc.) and (or not) Fe3+ under high-pressure mercury lamp with an exposure time of 4 h. *OH was determined by HPLC using benzene as a probe. The photoproduction of *OH increased with increasing algae concentration. Fe3+ could enhance the photoproduction of *OH in aqueous solution with algae. The results showed that the photoproduction of *OH in algal solution with Fe3+ was greater than that in algal solution without Fe3+. The light intensity and pH affected the photoproduction of *OH in aqueous solution with algae with/without Fe3+. The photoproduction of *OH in aqueous solution with algae and Fe3+ under 250 W was greater than that under 125 W HPML. The photoproduction of *OH in algal solution (pH ranged from 4.0 to 7.0) with (or not) Fe3+ at pH 4 was the greatest.

Coplanar surface barrier discharge ignited in water vapor—a selective source of OH radicals proved by (TA)LIF measurement

NASA Astrophysics Data System (ADS)

Procházka, V.; Tučeková, Z.; Dvořák, P.; Kováčik, D.; Slavíček, P.; Zahoranová, A.; Voráč, J.

2018-01-01

Coplanar dielectric barrier discharge (DBD) was ignited in pure water vapor at atmospheric pressure in order to generate highly oxidizing plasma with one specific type of reactive radicals. In order to prevent water condensation the used plasma reactor was heated to 120 {}\\circ C. The composition of the radical species in the discharge was studied by methods based on laser-induced fluorescence (LIF) and compared with analogous measurements realized in the same coplanar DBD ignited in air. Fast collisional processes and laser-surface interaction were taken into account during LIF data processing. It was found that coplanar DBD ignited in water vapor produces hydroxyl (OH) radicals with concentration in the order of 1020 m-3, which is 10× higher than the value measured in discharge in humid air (40% relative humidity at 21 {}\\circ C). The concentration of atomic hydrogen radicals in the DBD ignited in water vapor was below the detection limit, which proves that the generation of oxidizing plasma with dominance of one specific type of reactive radicals was achieved. The temporal evolution, spatial distribution, power dependence and rotational temperature of the OH radicals was determined in the DBD ignited in both water vapor and air.

Release of free amino acids upon oxidation of peptides and proteins by hydroxyl radicals.

PubMed

Liu, Fobang; Lai, Senchao; Tong, Haijie; Lakey, Pascale S J; Shiraiwa, Manabu; Weller, Michael G; Pöschl, Ulrich; Kampf, Christopher J

2017-03-01

Hydroxyl radical-induced oxidation of proteins and peptides can lead to the cleavage of the peptide, leading to a release of fragments. Here, we used high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) and pre-column online ortho-phthalaldehyde (OPA) derivatization-based amino acid analysis by HPLC with diode array detection and fluorescence detection to identify and quantify free amino acids released upon oxidation of proteins and peptides by hydroxyl radicals. Bovine serum albumin (BSA), ovalbumin (OVA) as model proteins, and synthetic tripeptides (comprised of varying compositions of the amino acids Gly, Ala, Ser, and Met) were used for reactions with hydroxyl radicals, which were generated by the Fenton reaction of iron ions and hydrogen peroxide. The molar yields of free glycine, aspartic acid, asparagine, and alanine per peptide or protein varied between 4 and 55%. For protein oxidation reactions, the molar yields of Gly (∼32-55% for BSA, ∼10-21% for OVA) were substantially higher than those for the other identified amino acids (∼5-12% for BSA, ∼4-6% for OVA). Upon oxidation of tripeptides with Gly in C-terminal, mid-chain, or N-terminal positions, Gly was preferentially released when it was located at the C-terminal site. Overall, we observe evidence for a site-selective formation of free amino acids in the OH radical-induced oxidation of peptides and proteins, which may be due to a reaction pathway involving nitrogen-centered radicals.

CHEMISTRY OF FOG WATERS IN CALIFORNIA'S CENTRAL VALLEY: 1. IN SITU PHOTOFORMATION OF HYDROXYL RADICAL AND SINGLET MOLECULAR OXYGEN. (R825433)

EPA Science Inventory

The aqueous-phase photoformation of hydroxyl radical (OH) and singlet molecular oxygen (O₂(¹Δ_g) or ¹O^*

Structural Mass Spectrometry of Proteins Using Hydroxyl Radical Based Protein Footprinting

PubMed Central

Wang, Liwen; Chance, Mark R.

2011-01-01

Structural MS is a rapidly growing field with many applications in basic research and pharmaceutical drug development. In this feature article the overall technology is described and several examples of how hydroxyl radical based footprinting MS can be used to map interfaces, evaluate protein structure, and identify ligand dependent conformational changes in proteins are described. PMID:21770468

MEASUREMENT OF HYDROXYL RADICAL ACTIVITY IN A SOIL SLURRY USING THE SPIN TRAP A-(4-PYRIDYL-1-OXIDE)-N-TERT-BUTYLNITRONE

EPA Science Inventory

The spin trap compound a-(4-pyridyl-1-oxide)N-tert-butylnitrone (4-POBN) served as a probe to estimate the activity of Fenton-derived hydroxyl radicals (.OH) in a batch suspension comprised of silica sand and crushes goethite ore. The rate of probe disappearance was used to anal...

ROLE OF THE PHOTO-FENTON REACTION IN THE PRODUCTION OF HYDROXYL RADICALS AND PHOTOBLEACHING OF COLORED DISSOLVED ORGANIC MATTER IN A COASTAL RIVER OF THE SOUTHEASTERN UNITED STATES

EPA Science Inventory

Photochemical reactions involving colored dissolved organic matter (CDOM) in natural waters are important determinants of nutrient cycling, trace gas production and control of light penetration into the water column. In this study the role of the hydroxyl radical ((OH)-O-.) in CD...

Directed hydroxyl radical probing of the rRNA neighborhood of ribosomal protein S13 using tethered Fe(II).

PubMed Central

Heilek, G M; Noller, H F

1996-01-01

Directed hydroxyl radical probing was used to probe the rRNA neighborhood around protein S13 in the 30S ribosomal subunit. The unique cysteine at position 84 of S13 served as a tethering site for attachment of Fe(II)-1-(p-bromoacetamidobenzyl)-EDTA. Derivatized S13 (Fe-C84-S13) was then assembled into 30S ribosomal subunits by in vitro reconstitution with 16S rRNA and a mixture of the remaining 30S subunit proteins. Hydroxyl radicals generated from the tethered Fe(II) resulted in cleavage of the RNA backbone in two localized regions of the 3' major domain of 16S rRNA. One region spans nt 1308-1333 and is close to a site previously crosslinked to S13. A second set of cleavages is found in the 950/1230 helix. Both regions have been implicated in binding of S13 by previous chemical footprinting studies using base-specific chemical probes and solution-based hydroxyl radical probing. These results place both regions of 16S rRNA in proximity to position C84 of S13 in the three-dimensional structure of the 30S ribosomal subunit. PMID:8718688

Reaction mechanisms of DNT with hydroxyl radicals for advanced oxidation processes-a DFT study.

PubMed

Zhou, Yang; Yang, Zhilin; Yang, Hong; Zhang, Chaoyang; Liu, Xiaoqiang

2017-04-01

In advanced oxidation processes (AOPs), the detailed degradation mechanisms of a typical explosive of 2,4-dinitrotoluene (DNT) can be investigated by the density function theory (DFT) method at the SMD/M062X/6-311+G(d) level. Several possible degradation routes for DNT were explored in the current study. The results show that, for oxidation of the methyl group, the dominant degradation mechanism of DNT by hydroxyl radicals (•OH) is a series of sequential H-abstraction reactions, and the intermediates obtained are in good agreement with experimental findings. The highest activation energy barrier is less than 20 kcal mol -1 . Other routes are dominated by an addition-elimination mechanism, which is also found in 2,4,6-trinitrotoluene, although the experiment did not find the corresponding products. In addition, we also eliminate several impossible mechanisms, such as dehydration, HNO 3 elimination, the simultaneous addition of two •OH radials, and so on. The information gained about these degradation pathways is helpful in elucidating the detailed reaction mechanism between nitroaromatic explosives and hydroxyl radicals for AOPs. Graphical Abstract The degradation mechanism of an important explosive, 2,6-dinitrotoluene (DNT), by the hydroxyl radical for advanced oxidation progresses.

Combustion Processes Indoors: a Source of High OH Radical Concentrations Through the Photolysis of Hono

NASA Astrophysics Data System (ADS)

Bartolomei, V.; Gomez Alvarez, E.; Glor, M.; Gligorovski, S.; Temime-Roussel, B.; Quivet, E.; Strekowski, R.; Zetzsch, C.; Held, A. B.; Wortham, H.

2013-12-01

Hydroxyl radical (OH) is one of the most important oxidant species in the atmosphere controlling its self-oxidizing capacity. The main sources of OH radicals are photolysis of ozone and photolysis of nitrous acid (HONO), among the others. In the indoor air, the ozonolysis of alkenes has been suggested as the main OH formation pathway. The possibility for OH formation through photolytic pathways in the indoor environment has been, up to now, ignored (Gómez Alvarez et al., 2012). Models and indirect measurements to the present time predicted concentrations of OH radicals in the order of 104 -105 cm-3. Recently, by direct measurements we have detected high OH radical concentrations of 1.8 106 cm-3 in a classroom in Marseille and we demonstrated that its main source is the photolysis of HONO (Gómez Alvarez et al., 2013). The concentrations of HONO are quite high indoors, reaching levels in the order of a few tens of ppbV (Gómez Alvarez et al., 2013). This is mainly due to 1) direct combustion sources and 2) heterogeneous reactions of NO2 on the numerous surfaces present in the indoor environment. HONO levels of 30 ppb were measured in a previous campaign carried out in Bayreuth in July 2012 as direct emissions from the combustion of a candle. The combination between so high concentrations of HONO and higher than expected light transmissions indoors (or indoor artificial lighting) could have a significant impact on the OH concentrations indoors which could feasibly become considerably higher than we measured in our school campaign (Gomez Alvarez et al., 2013). In order to evaluate these upper limits under combustion conditions in the indoor environment, we have carried out a campaign in the LOTASC chamber (Bayreuth, Germany). For this aim, the exhaust fumes from the burning of a commonly used domestic candle have been introduced in the chamber. The chamber was irradiated under well research indoor lighting conditions. A thorough characterization of light intensities and span (wavelength distribution) indoors have been performed, which had been identified as a clear flaw in our knowledge restricting the advancement of indoor air quality models. OH concentration levels have been determined using d9-butanol as tracer, using the OH clock determination procedure by PTR-MS-TOF. The OH radical concentration was investigated using different light intensities representative from indoor conditions, both natural and artificial and also different levels of RH. The PSS model has been performed in order to evaluate the contribution of different sources to the OH radical concentrations indoors under these conditions. The obtained results from the PSS model clearly indicate that the main source of OH radical indoors under combustion conditions is the photolysis of HONO under typical indoor irradiation conditions. REFERENCES Gómez Alvarez E, Wortham H, Strekowski R, Zetzsch C, Gligorovski S (2012) Atmospheric photo-sensitized heterogeneous and multiphase reactions: From outdoors to indoors, Environ. Sci. Technol. 46, 1955-1963. Gómez Alvarez, E.; Amedro, D.; Afif, C. ; Gligorovski, S.; Schoemacker , C.; Fittschen, C. ; Doussin, J. F.; Wortham, H. (2013) Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid. Proc. Natl. Acad. Sci. USA Accepted.

Damage mechanism of hydroxyl radicals toward adenine—thymine base pair

NASA Astrophysics Data System (ADS)

Tan, Rong-Ri; Wang, Dong-Qi; Zhang, Feng-Shou

2014-02-01

The adenine—thymine base pair was studied in the presence of hydroxyl radicals in order to probe the hydrogen bond effect. The results show that the hydrogen bonds have little effect on the hydroxylation and dehydrogenation happened at the sites, which are not involved in a hydrogen bond, while at the sites involved in hydrogen bond formation in the base pair, the reaction becomes more difficult, both in view of the free energy barrier and the exothermicity. With a 6-311++G(d,p) level of description, both B3LYP and MP2 methods confirm that the C8 site of isolated adenine has the highest possibility to form covalent bond with the hydroxyl radicals, though with different energetics: B3LYP predicts a barrierless pathway, while MP2 finds a transition state with an energy of 106.1 kJ/mol. For the dehydrogenation reactions, B3LYP method predicts that the free energy barrier increases in the order of HN9 < HN61 < HN62 < H2 < H8.

Hydroxylated chalcones with dual properties: xanthine oxidase inhibitors and radical scavengers

PubMed Central

Hofmann, Emily; Webster, Jonathan; Do, Thuy; Kline, Reid; Snider, Lindsey; Hauser, Quintin; Higginbottom, Grace; Campbell, Austin; Ma, Lili; Paula, Stefan

2016-01-01

In this study, we evaluated the abilities of a series of chalcones to inhibit the activity of the enzyme xanthine oxidase (XO) and to scavenge radicals. 20 mono- and polyhydroxylated chalcone derivatives were synthesized by Claisen-Schmidt condensation reactions and then tested for inhibitory potency against XO, a known generator of reactive oxygen species (ROS). In parallel, the ability of the synthesized chalcones to scavenge a stable radical was determined. Structure-activity relationship analysis in conjunction with molecular docking indicated that the most active XO inhibitors carried a minimum of three hydroxyl groups. Moreover, the most effective radical scavengers had two neighboring hydroxyl groups on at least one of the two phenyl rings. Since it has been proposed previously that XO inhibition and radical scavenging could be useful properties for reduction of ROS-levels in tissue, we determined the chalcones’ effects to rescue neurons subjected to ROS-induced stress created by the addition of β-amyloid peptide. Best protection was provided by chalcones that combined good inhibitory potency with high radical scavenging ability in a single molecule, an observation that points to a potential therapeutic value of this compound class. PMID:26762836

Hydroxyl radical induced transformation of phenylurea herbicides: A theoretical study

NASA Astrophysics Data System (ADS)

Mile, Viktória; Harsányi, Ildikó; Kovács, Krisztina; Földes, Tamás; Takács, Erzsébet; Wojnárovits, László

2017-03-01

Aromatic ring hydroxylation reactions occurring during radiolysis of aqueous solutions are studied on the example of phenylurea herbicides by Density Functional Theory calculations. The effect of the aqueous media is taken into account by using the Solvation Model Based on Density model. Hydroxyl radical adds to the ring because the activation free energies (0.4-47.2 kJ mol-1) are low and also the Gibbs free energies have high negative values ((-27.4) to (-5.9) kJ mol-1). According to the calculations in most of cases the ortho- and para-addition is preferred in agreement with the experimental results. In these reactions hydroxycyclohexadienyl type radicals form. In a second type reaction, when loss of chlorine atom takes place, OH/Cl substitution occurs without cyclohexadienyl type intermediate.

Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling☆

PubMed Central

Riethmüller, Michaela; Burger, Nils; Bauer, Georg

2015-01-01

Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2.) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8, followed by caspase-8-mediated enhancement of NOX activity. The biochemical mechanisms described here might be considered as promising principle for the development of novel approaches in tumor therapy that specifically direct membrane-associated catalase of tumor cells and thus utilize tumor cell-specific apoptosis-inducing ROS signaling. PMID:26225731

Singlet oxygen treatment of tumor cells triggers extracellular singlet oxygen generation, catalase inactivation and reactivation of intercellular apoptosis-inducing signaling.

PubMed

Riethmüller, Michaela; Burger, Nils; Bauer, Georg

2015-12-01

Intracellular singlet oxygen generation in photofrin-loaded cells caused cell death without discrimination between nonmalignant and malignant cells. In contrast, extracellular singlet oxygen generation caused apoptosis induction selectively in tumor cells through singlet oxygen-mediated inactivation of tumor cell protective catalase and subsequent reactivation of intercellular ROS-mediated apoptosis signaling through the HOCl and the NO/peroxynitrite signaling pathway. Singlet oxygen generation by extracellular photofrin alone was, however, not sufficient for optimal direct inactivation of catalase, but needed to trigger the generation of cell-derived extracellular singlet oxygen through the interaction between H2O2 and peroxynitrite. Thereby, formation of peroxynitrous acid, generation of hydroxyl radicals and formation of perhydroxyl radicals (HO2(.)) through hydroxyl radical/H2O2 interaction seemed to be required as intermediate steps. This amplificatory mechanism led to the formation of singlet oxygen at a sufficiently high concentration for optimal inactivation of membrane-associated catalase. At low initial concentrations of singlet oxygen, an additional amplification step needed to be activated. It depended on singlet oxygen-dependent activation of the FAS receptor and caspase-8, followed by caspase-8-mediated enhancement of NOX activity. The biochemical mechanisms described here might be considered as promising principle for the development of novel approaches in tumor therapy that specifically direct membrane-associated catalase of tumor cells and thus utilize tumor cell-specific apoptosis-inducing ROS signaling. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

ROS Initiated Oxidation of Dopamine under Oxidative Stress Conditions in Aqueous and Lipidic Environments

PubMed Central

2011-01-01

Dopamine is known to be an efficient antioxidant and to protect neurocytes from oxidative stress by scavenging free radicals. In this work, we have carried out a systematic quantum chemistry and computational kinetics study on the reactivity of dopamine toward hydroxyl (•OH) and hydroperoxyl (•OOH) free radicals in aqueous and lipidic simulated biological environments, within the density functional theory framework. Rate constants and branching ratios for the different paths contributing to the overall reaction, at 298 K, are reported. For the reactivity of dopamine toward hydroxyl radicals, in water at physiological pH, the main mechanism of the reaction is proposed to be the sequential electron proton transfer (SEPT), whereas in the lipidic environment, hydrogen atom transfer (HAT) and radical adduct formation (RAF) pathways contribute almost equally to the total reaction rate. In both environments, dopamine reacts with hydroxyl radicals at a rate that is diffusion-controlled. Reaction with the hydroperoxyl radical is much slower and occurs only by abstraction of any of the phenolic hydrogens. The overall rate coefficients are predicted to be 2.23 × 105 and 8.16 × 105 M–1 s–1, in aqueous and lipidic environment, respectively, which makes dopamine a very good •OOH, and presumably •OOR, radical scavenger. PMID:21919526

Antioxidant capacity of flavanols and gallate esters: pulse radiolysis studies.

PubMed

Bors, W; Michel, C

1999-12-01

Reactivities of several proanthocyanidins (monomers of condensed tannins) and gallate esters (representing hydrolyzable tannins) with hydroxyl radicals, azide radicals, and superoxide anions were investigated using pulse radiolysis combined with kinetic spectroscopy. We determined the scavenging rate constants and the decay kinetics of the aroxyl radicals both at the wavelength of the semiquinone absorption (275 nm) and the absorption band of the gallate ester ketyl radical (400-420 nm). For most compounds second-order decay kinetics were observed, which reflect disproportionation of the semiquinones. In the case of the oligomeric hydrolysable tannins, pentagalloyl glucose and tannic acid, the decay kinetics were more complex involving sequential first-order and second-order reactions, which could only be resolved by kinetic modeling. A correlation of the reaction rates with hydroxyl radicals (k*OH) with the number of adjacent aromatic hydroxyl groups (i.e., representing catechol and/or pyrogallol structures) was obtained for both condensed and hydrolyzable tannins. Similar correlation for the reactions with azide radicals and superoxide anions are less obvious, but exist as well. We consider proanthocyanidins superior radical scavenging agents as compared with the monomeric flavonols and flavones and propose that these substances rather than the flavonoids proper represent the antioxidative principle in red wine and green tea.

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

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

Uhm, Han S., E-mail: hsuhm@kw.ac.kr

2015-12-15

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

Comparison of antioxidant and antiproliferation activities of polysaccharides from eight species of medicinal mushrooms.

PubMed

Chen, Peiying; Yong, Yangyang; Gu, Yifan; Wang, Zeliang; Zhang, Shizhu; Lu, Ling

2015-01-01

Polysaccharides from mushrooms including Pleurotus eryngii, P. ostreatus, P. nebrodensis, Lentinus edodes, Hypsizygus marmoreus, Flammulina velutipes, Ganoderma lucidum, and Hericium erinaceus were isolated by water extraction and alcohol precipitation. Our results suggest that all tested polysaccharides have the significant antioxidant capacities of scavenging free radicals (1,1-diphenyl-2-picrylhydrazyl and hydroxyl radicals). Among them, the H. erinaceus polysaccharide exhibits the highest 1,1-diphenyl-2-picrylhydrazyl radical-scavenging activity, whereas the L. edodes polysaccharide shows the strongest scavenging ability for hydroxyl radicals. Furthermore, using the MCF-7 breast cancer cell line and HeLa cells, all 8 selected polysaccharides are able to inhibit the proliferation of tumor cells, but the strength of inhibition varied depending on the mushroom species and the concentration used. Notably, G. lucidum polysaccharide shows the highest inhibition activity on MCF-7 cells. By comparison, H. erinaceus polysaccharide has the strongest inhibitory effect on HeLa cells. Moreover, high-performance liquid chromatography with a carbohydrate analysis column showed significant differences in polysaccharide components among these mushrooms. Thus our data suggest that the different species of mushrooms have the variable functions because of their own specific polysaccharide components. The 8 mushroom polysaccharides have the potential to be used as valuable functional food additives or sources of therapeutic agents for antioxidant and cancer treatments, especially polysaccharides from H. erinaceus, L. edodes, and G. lucidum.

Suppression of new particle formation from monoterpene oxidation by NOx

NASA Astrophysics Data System (ADS)

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

2013-10-01

The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory set up. At high NOx conditions (BVOC/NOx < 7, NOx > 23 ppb) no new particles were formed. Instead photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. As soon as [NO] was reduced to below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF orders of magnitude slower than in analogous experiments at low NOx conditions (NOx ~ 300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF suggesting that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent of approximately -2. This exponent indicated that the overall peroxy radical concentration must have been the same whenever NPF appeared. Thus permutation reactions of first generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy radical like molecules limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was less sensitive to NOx concentrations, if at all. Only at very high NOx concentrations yields were reduced by about an order of magnitude.

Suppression of new particle formation from monoterpene oxidation by NOx

NASA Astrophysics Data System (ADS)

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

2014-03-01

The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NOx conditions ([BVOC] / [NOx] < 7, [NOx] > 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NOx conditions ([NOx] ~300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching -2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NOx concentrations. If at all, yields were reduced by about an order of magnitude only at very high NOx concentrations.

Antioxidant and cytoprotective properties of D-tagatose in cultured murine hepatocytes.

PubMed

Paterna, J C; Boess, F; Stäubli, A; Boelsterli, U A

1998-01-01

D-Tagatose is a zero-energy producing ketohexose that is a powerful cytoprotective agent against chemically induced cell injury. To further explore the underlying mechanisms of cytoprotection, we investigated the effects of D-tagatose on both the generation of superoxide anion radicals and the consequences of oxidative stress driven by prooxidant compounds in intact cells. Primary cultures of hepatocytes derived from male C57BL/6 mice were exposed to the redox cycling drug nitrofurantoin (NFT). Lethal cell injury induced by 300 microM NFT was completely prevented by high concentrations (20 mM) of D-tagatose, whereas equimolar concentrations of glucose, mannitol, or xylose were ineffective. The extent of NFT-induced intracellular superoxide anion radical formation was not altered by D-tagatose, indicating that the ketohexose did not inhibit the reductive bioactivation of NFT. However, the NFT-induced decline of the intracellular GSH content was largely prevented by D-tagatose. The sugar also afforded complete protection against NFT toxicity in hepatocytes that had been chemically depleted of GSH. Furthermore, the ketohexose fully protected from increases in both membrane lipid peroxidation and protein carbonyl formation. In addition, D-tagatose completely prevented oxidative cell injury inflicted by toxic iron overload with ferric nitrilotriacetate (100 microM). In contrast, D-tagatose did not protect against lethal cell injury induced by tert-butyl hydroperoxide, a prooxidant which acts by hydroxyl radical-independent mechanisms and which is partitioned in the lipid bilayer. These results indicate that D-tagatose, which is a weak iron chelator, can antagonize the iron-dependent toxic consequences of intracellular oxidative stress in hepatocytes. The antioxidant properties of D-tagatose may result from sequestering the redox-active iron, thereby protecting more critical targets from the damaging potential of hydroxyl radical.

Hepatocyte or serum albumin protein carbonylation by oxidized fructose metabolites: Glyceraldehyde or glycolaldehyde as endogenous toxins?

PubMed

Dong, Qiang; Yang, Kai; Wong, Stephanie M; O'Brien, Peter J

2010-10-06

Excessive sugar intake in animal models may cause tissue damage associated with oxidative and carbonyl stress cytotoxicity as well as inflammation. Fructose became a 100-fold more cytotoxic if hepatocytes were exposed to a non-toxic infusion of H(2)O(2) so as to simulate H(2)O(2) released by Kupffer cells or infiltrating immune cells. In order to determine the molecular mechanisms involved, protein carbonylation of fructose and its metabolites were determined using the 2,4-dinitrophenylhydrazine method. In a cell-free system, fructose was found to carbonylate bovine serum albumin (BSA) only if low concentrations of FeII/H(2)O(2) were added. Protein carbonylation by the fructose metabolites glyceraldehyde or glycolaldehyde was also markedly increased by FeII/H(2)O(2). The protein carbonylation may be attributed to glyoxal formation by hydroxyl radicals as the glyoxal trapping agent aminoguanidine or hydroxyl radical scavengers prevented protein carbonylation. Glyoxal was also much more effective than other carbonyls at causing protein carbonylation. When BSA was replaced by isolated rat hepatocytes, fructose metabolite glyceraldehyde in the presence of non-toxic 2 microM FeII:8-hydroxyquinoline (HQ) and a H(2)O(2) generating system (glucose/glucose oxidase) markedly increased cytotoxicity, protein carbonylation and reactive oxygen species (ROS)/H(2)O(2) formation. Furthermore this was prevented by hydroxyl radical scavengers or aminoguanidine, a glyoxal scavenger. CuII: 8-hydroxyquinoline increased H(2)O(2) induced hepatocyte protein carbonylation less but was prevented by aminoguanidine. However, cytotoxicity and protein carbonylation induced by glyceraldehyde/CuII:HQ/H(2)O(2) were not affected by hydroxyl radical scavengers. Although fatty liver induced by an excessive sugar diet in animal models has been proposed as the first hit for non-alcoholic steatohepatitis (NASH) we propose that oxidative stress induced by the oxidation of fructose or fructose metabolites catalysed by Fenton FeII/H(2)O(2) could be a 'second hit'. A perpetual cycle of oxidative stress in hepatocytes could lead to cytotoxicity and contribute to NASH development. Copyright 2010 Elsevier Ireland Ltd. All rights reserved.

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation.

PubMed

Minero, Claudio; Maurino, Valter; Bono, Francesca; Pelizzetti, Ezio; Marinoni, Angela; Mailhot, Gilles; Carlotti, Maria Eugenia; Vione, Davide

2007-08-01

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.

[Correlation of Persistent Free Radicals, PCDD/Fs and Metals in Waste Incineration Fly Ash].

PubMed

Wang, Tian-jiao; Chen, Tong; Zhan, Ming-xiu; Guo, Ying; Li, Xiao-dong

2016-03-15

Environmentally persistent free radicals (EPFRs) are relatively highly stable and found in the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Recent studies have concentrated on model dioxin formation reactions and there are few studies on actual waste incineration fly ash. In order to study EPFRs and the correlation with dioxins and heavy metals in waste incineration fly ash, the spins of EPFRs, concentration of PCDD/Fs and metals in samples from 6 different waste incinerators were detected. The medical waste incineration fly ash from Tianjin, municipal solid waste incineration fly ash from Jiangxi Province, black carbon and slag from municipal solid waste incinerator in Lanxi, Zhejiang Province, all contained EPFRs. Above all the signal in Tianjin sample was the strongest. Hydroxyl radicals, carbon-center radicals and semiquinone radicals were detected. Compared with other samples, Jiangxi fly ash had the highest toxic equivalent quantity (TEQ) of dioxins, up to 7.229 4 ng · g⁻¹. However, the dioxin concentration in the Tianjin sample containing the strongest EPFR signals was only 0.092 8 ng · g⁻¹. There was perhaps little direct numeric link between EPFRs and PCDD/Fs. But the spins of EPFRs in samples presented an increasing trend as the metal contents increased, especially with Al, Fe, Zn. The signal strength of radicals was purposed to be related to the metal contents. The concentration of Zn (0.813 7% ) in the Tianjin sample was the highest and this sample contained much more spins of oxygen-center radicals. We could presume the metal Zn had a greater effect on the formation of EPFRs, and was easier to induce the formation of radicals with a longer half-life period.

The mechanism of the photochemical oxidation of water to oxygen with silver chloride colloids

NASA Astrophysics Data System (ADS)

Chandrasekaran, K.; Thomas, J. K.

1983-05-01

Photoexcitation of silver chloride colloids in the presence of excess silver ions, leads to the decomposition of water. Hydroxyl radicals were found to be intermediates in the decomposition process. Irradiation leads to hydroxyl radicals, which recombine to give hydrogen peroxide, on the colloidal particle surface. Subsequent decomposition of H 2O 2 to give O 2 is catalyzed by silver ions. Addition of alcohols such as methanol and isopropanol reduce the oxygen yield, as they react with OH radicals and reduce the H 2O 2 yield.

A kinetic study of enhancing effect by phenolic compounds on the hydroxyl radical generation during ozonation.

PubMed

Han, Y H; Ichikawa, K; Utsumi, H

2004-01-01

Ozone decomposition in aqueous solution proceeds through a radical type chain mechanism. These reactions involve the very reactive and catalytic intermediates O2- radical, OH radical, HO2 radical, OH-, H2O2, etc. OH radical is proposed as an important factor in the ozonation of water among them. In the present study, the enhancing effects of several phenolic compounds; phenol, 2-, 3-, 4-monochloro, 2,4-dichloro, 2,4,6-trichlorophenol on OH radical generation were mathematically evaluated using the electron spin resonance (ESR)/spin-trapping technique. OH radical was trapped with a 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a stable adduct, DMPO-OH. The initial velocities of DMPO-OH generation in ozonated water containing phenolic compounds were quantitatively measured using a combined system of ESR spectroscopy with stopped-flow apparatus, which was controlled by homemade software. The initial velocities of DMPO-OH generation increased as a function of the ozone concentration. The relation among ozone concentration, amount of phenolic compounds and the initial velocity (v0) of DMPO-OH generation was mathematically analyzed and the following equation was obtained, v0 (10(-6) M/s) = (A' x [PhOHs (10(-9) M)] + 0.0005) exp (60 x [ozone (10(-9) M)]). The equation fitted very well with the experimental results, and the correlation coefficient was larger than 0.98.

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.

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

TiO2 photocatalysis causes DNA damage via fenton reaction-generated hydroxyl radicals during the recovery period.

PubMed

Gogniat, Gaëtan; Dukan, Sam

2007-12-01

Here, we show that resistance of Escherichia coli to TiO2 photocatalysis involves defenses against reactive oxygen species. Results support the idea that TiO2 photocatalysis generates damage which later becomes deleterious during recovery. We found this to be partly due to DNA attack via hydroxyl radicals generated by the Fenton reaction during recovery.

KINETIC STUDIES OF THE REACTION OF HYDROXYL RADICALS WITH TRICHLOROETHYLENE AND TETRACHLOROETHYLENE. (R826169)

EPA Science Inventory

Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C₂HCl₃ (k₁) and C₂Cl₄ (k₂) over an extended temperature range at 740±10 Torr in a He bath gas. These...

Tropospheric OH and HO2 radicals: field measurements and model comparisons.

PubMed

Stone, Daniel; Whalley, Lisa K; Heard, Dwayne E

2012-10-07

The hydroxyl radical, OH, initiates the removal of the majority of trace gases in the atmosphere, and together with the closely coupled species, the hydroperoxy radical, HO(2), is intimately involved in the oxidation chemistry of the atmosphere. This critical review discusses field measurements of local concentrations of OH and HO(2) radicals in the troposphere, and in particular the comparisons that have been made with numerical model calculations containing a detailed chemical mechanism. The level of agreement between field measurements of OH and HO(2) concentrations and model calculations for a given location provides an indication of the degree of understanding of the underlying oxidation chemistry. We review the measurement-model comparisons for a range of different environments sampled from the ground and from aircraft, including the marine boundary layer, continental low-NO(x) regions influenced by biogenic emissions, the polluted urban boundary layer, and polar regions. Although good agreement is found for some environments, there are significant discrepancies which remain unexplained, a notable example being unpolluted, forested regions. OH and HO(2) radicals are difficult species to measure in the troposphere, and we also review changes in detection methodology, quality assurance procedures such as instrument intercomparisons, and potential interferences.

Enhanced decolorization of methyl orange in aqueous solution using iron-carbon micro-electrolysis activation of sodium persulfate.

PubMed

Li, Peng; Liu, Zhipeng; Wang, Xuegang; Guo, Yadan; Wang, Lizhang

2017-08-01

Reactivity of sodium persulfate (PS) in the decolorization of methyl orange (MO) in aqueous solution using an iron-carbon micro-electrolysis (ICE) method was investigated. The effects of sodium persulfate doses, pH, Fe-to-C mass ratios, initial MO concentration as well as the reaction temperature were comprehensively studied in batch experiments. The ICE-PS coupled process was more suitable for wide ranges of pH, initial MO concentration and reaction temperature, accompanied by the reduction of Fe compared ICE. The MO removal efficiency improved substantially by ICE-PS technique, 76.03% for ICE and 91.27% for ICE-PS at experimental conditions of pH 3.0, Fe-to-C mass ratio 3:1, PS addition 10 mM and initial MO concentration 0.61 mM. Furthermore, the biodegradability index (BI) dramatically increased from 0.26 to 0.65. The binary hydroxyl and sulfate radicals that non-selectively degrade MO to the derivatives with small molecules are ascribed to ICE-PS method as detected by the UV-vis spectra. The PS activation resource was Fe 2+ through the hydroxyl radical quenching reaction by the additive tert-butanol (TBA). This study provides an in-depth theoretical understanding of the development and wide commercial application of the ICE technology to refractory industrial dye wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Antioxidant Properties of Kynurenines: Density Functional Theory Calculations

PubMed Central

2016-01-01

Kynurenines, the main products of tryptophan catabolism, possess both prooxidant and anioxidant effects. Having multiple neuroactive properties, kynurenines are implicated in the development of neurological and cognitive disorders, such as Alzheimer's, Parkinson's, and Huntington's diseases. Autoxidation of 3-hydroxykynurenine (3HOK) and its derivatives, 3-hydroxyanthranilic acid (3HAA) and xanthommatin (XAN), leads to the hyperproduction of reactive oxygen species (ROS) which damage cell structures. At the same time, 3HOK and 3HAA have been shown to be powerful ROS scavengers. Their ability to quench free radicals is believed to result from the presence of the aromatic hydroxyl group which is able to easily abstract an electron and H-atom. In this study, the redox properties for kynurenines and several natural and synthetic antioxidants have been calculated at different levels of density functional theory in the gas phase and water solution. Hydroxyl bond dissociation enthalpy (BDE) and ionization potential (IP) for 3HOK and 3HAA appear to be lower than for xanthurenic acid (XAA), several phenolic antioxidants, and ascorbic acid. BDE and IP for the compounds with aromatic hydroxyl group are lower than for their precursors without hydroxyl group. The reaction rate for H donation to *O-atom of phenoxyl radical (Ph-O*) and methyl peroxy radical (Met-OO*) decreases in the following rankings: 3HOK ~ 3HAA > XAAOXO > XAAENOL. The enthalpy absolute value for Met-OO* addition to the aromatic ring of the antioxidant radical increases in the following rankings: 3HAA* < 3HOK* < XAAOXO* < XAAENOL*. Thus, the high free radical scavenging activity of 3HAA and 3HOK can be explained by the easiness of H-atom abstraction and transfer to O-atom of the free radical, rather than by Met-OO* addition to the kynurenine radical. PMID:27861556

The photocatalytic degradation of methylene blue by green semiconductor films that is induced by irradiation by a light-emitting diode and visible light.

PubMed

Yang, Chih-Chi; Doong, Ruey-An; Chen, Ku-Fan; Chen, Giin-Shan; Tsai, Yung-Pin

2018-01-01

This study develops a low-energy rotating photocatalytic contactor (LE-RPC) that has Cu-doped TiO 2 films coated on stainless-steel rotating disks, to experimentally evaluate the efficiency of the degradation and decolorization of methylene blue (MB) under irradiation from different light sources (visible 430 nm, light-emitting diode [LED] 460 nm, and LED 525 nm). The production of hydroxyl radicals is also examined. The experimental results show that the photocatalytic activity of TiO 2 that is doped with Cu 2+ is induced by illumination with visible light and an LED. More than 90% of methylene blue at a 10 mg/L concentration is degraded after illumination by visible light (430 nm) for 4 hr at 20 rpm. This study also demonstrates that the quantity of hydroxyl radicals produced is directly proportional to the light energy intensity. The greater the light energy intensity, the greater is the number of hydroxyl radicals produced. The CuO-doped anatase TiO 2 powder was successfully synthesized in this study by a sol-gel method. The catalytic abilities of the stainless-steel film were enhanced in the visible light regions. This study has successfully modified the nano-photocatalytic materials to drop band gap and has also successfully fixed the nano-photocatalytic materials on a substratum to effectively treat dye wastewater in the range of visible light. The results can be useful to the development of a low-energy rotating photocatalytic contactor for decontamination purposes.

A Surfactant-Free Synthesis Technique of Coral-Like Zno Hierarchical Structures for Photocatalytic Degradation of Resorcinol under UV Irradiation

NASA Astrophysics Data System (ADS)

Sin, Jin-Chung; Lam, Sze-Mun; Chin, Ying-Hui

2018-01-01

Hierarchical coral-like ZnO structures were successfully prepared by a surfactant-free wet chemical method. Various characterization tests were carried out to analyze the as-prepared ZnO samples. The coral-like ZnO was used to degrade resorcinol at three different solution pH values (pH 5.0, pH 8.0 and pH 11.0). It was observed that the resorcinol adsorption onto the ZnO was strongly dependent on the electrical charge properties of both photocatalyst and resorcinol. Photocatalytic degradation of resorcinol reached the highest at pH 11.0 due to high concentration of hydroxyl ions for hydroxyl radicals generation.

Chemical composition and antioxidant properties of clove leaf essential oil.

PubMed

Jirovetz, Leopold; Buchbauer, Gerhard; Stoilova, Ivanka; Stoyanova, Albena; Krastanov, Albert; Schmidt, Erich

2006-08-23

The antioxidant activity of a commercial rectified clove leaf essential oil (Eugenia caryophyllus) and its main constituent eugenol was tested. This essential oil comprises in total 23 identified constituents, among them eugenol (76.8%), followed by beta-caryophyllene (17.4%), alpha-humulene (2.1%), and eugenyl acetate (1.2%) as the main components. The essential oil from clove demonstrated scavenging activity against the 2,2-diphenyl-1-picryl hydracyl (DPPH) radical at concentrations lower than the concentrations of eugenol, butylated hydroxytoluene (BHT), and butylated hydroxyanisole (BHA). This essential oil also showed a significant inhibitory effect against hydroxyl radicals and acted as an iron chelator. With respect to the lipid peroxidation, the inhibitory activity of clove oil determined using a linoleic acid emulsion system indicated a higher antioxidant activity than the standard BHT.

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.

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.

Preparation and antioxidant activities of oligosaccharides from Crassostrea gigas.

PubMed

Wu, Shengjun; Huang, Xiaolian

2017-02-01

Oligosaccharides were prepared from Crassostrea gigas by hydrolysis of polysaccharide in C. gigas with peroxide oxygen (H2O2). The hydrolysates were cleared of protein, filtered, ultrafiltered and precipitated with absolute ethanol to give C. gigas oligosaccharides (CGOs). Factors affecting CGO yields, i.e., reaction time, temperature, and H2O2 concentration, were optimised as follows: 2.96h reaction time, 84.71°C reaction temperature, and 2.46% H2O2 concentration. Under these conditions, the maximum yield of CGOs reached 10.61%. The CGOs were then partially characterised by Fourier transform infrared spectroscopy, UV spectroscopy, monosaccharide composition, and antioxidant activities. Results indicate that CGOs possessed strong hydroxyl radical activity, 2,2-diphenyl-β-picrylhydrazyl-radical-scavenging activity and reducing capacity at a concentration of 100μg/mL. Copyright © 2016 Elsevier Ltd. All rights reserved.

Light absorption and the photoformation of hydroxyl radical and singlet oxygen in fog waters

NASA Astrophysics Data System (ADS)

Kaur, R.; Anastasio, C.

2017-09-01

The atmospheric aqueous-phase is a rich medium for chemical transformations of organic compounds, in part via photooxidants generated within the drops. Here we measure light absorption, photoformation rates and steady-state concentrations of two photooxidants - hydroxyl radical (•OH) and singlet molecular oxygen (1O2*) - in 8 illuminated fog waters from Davis, California and Baton Rouge, Louisiana. Mass absorption coefficients for dissolved organic compounds (MACDOC) in the samples are large, with typical values of 10,000-15,000 cm2 g-C-1 at 300 nm, and absorption extends to wavelengths as long as 450-600 nm. While nitrite and nitrate together account for an average of only 1% of light absorption, they account for an average of 70% of •OH photoproduction. Mean •OH photoproduction rates in fogs at the two locations are very similar, with an overall mean of 1.2 (±0.7) μM h-1 under Davis winter sunlight. The mean (±1σ) lifetime of •OH is 1.6 (±0.6) μs, likely controlled by dissolved organic compounds. Including calculated gas-to-drop partitioning of •OH, the average aqueous concentration of •OH is approximately 2 × 10-15 M (midday during Davis winter), with aqueous reactions providing approximately one-third of the hydroxyl radical source. At this concentration, calculated lifetimes of aqueous organics are on the order of 10 h for compounds with •OH rate constants of 1 × 1010 M-1 s-1 or higher (e.g., substituted phenols such as syringol (6.4 h) and guaiacol (8.4 h)), and on the order of 100 h for compounds with rate constants near 1 × 109 M-1 s-1 (e.g., isoprene oxidation products such as glyoxal (152 h), glyoxylic acid (58 h), and pyruvic acid (239 h)). Steady-state concentrations of 1O2* are approximately 100 times higher than those of •OH, in the range of (0.1-3.0) × 10-13 M. Since 1O2* is a more selective oxidant than •OH, it will only react appreciably with electron-rich species such as dimethyl furan (lifetime of 2.0 h) and substituted polycyclic aromatic hydrocarbons (e.g., 9,10-dimethylbenz[a]anthracene with a lifetime of 0.7 h). Comparing our current Davis samples with Davis fogs collected in the late 1990s shows a decrease in dissolved organic carbon content, similar mass absorption coefficients, lower •OH concentrations, but very similar 1O2* concentrations.

In vitro effects of coal fly ashes: hydroxyl radical generation, iron release, and DNA damage and toxicity in rat lung epithelial cells

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

van Maanen, J.M.; Borm, P.J.; Knaapen, A

1999-12-15

The authors measured iron release, acellular generation of hydroxyl radicals, and oxidative DNA damage and cytotoxicity in rat lung epithelial (RLE) cells by different coal fly ashes (CFA) that contain both quartz and iron. Seven samples of CFA with different particle size and quartz content (up to 14.1%) were tested along with silica (alpha-quartz), ground coal, and coal mine dust (respirable) as positive control particles, and fine TiO{sub 2} (anatase) as a negative control. Five test samples were pulverized fuel ashes (PFA), two samples were coal gasification (SCG) ashes (quartz content {lt} 0.1%), and one sample was a ground coal.more » No marked differences between SCG and PFA fly ashes were observed, and toxicity did not correlate with physicochemical characteristics or effect parameters. Stable surface radicals were only detected in the reference particles silica and coal mine dust, but not in CFA. On the other hand, hydroxyl radical generation by all fly ashes was observed in the presence of hydrogen peroxide. Also a relationship between acellular hydroxyl radical generation and oxidative DNA damage in RLE cells by CFA was observed. The respirable ashes (MAT023, 38, and 41) showed an extensive level of hydroxyl radical generation in comparison to nonrespirable fly ashes and respirable references. This was related to the iron mobilization from these particles. Themechanisms by which CFA and the positive references (silica, coal mine dust) affect rat lung epithelial cells seem to be different, and the data suggest that quartz in CFA does not act the same as quartz in silica or coal mine dust. However, the results indicate an important role for size and iron release in generation and subsequent effects of reactive oxygen species caused by CFA.« less

Radioprotective property of the ethanolic extract of Piper betel Leaf.

PubMed

Bhattacharya, Sayanti; Subramanian, Mahesh; Roychowdhury, Susri; Bauri, Ajay K; Kamat, Jaya P; Chattopadhyay, Subrata; Bandyopadhyay, Sandip Kumar

2005-06-01

The radioprotective activity of Piper betel ethanolic extract (PE) has been studied using rat liver mitochondria and pBR 322 plasmid DNA as two model in vitro systems. The extract effectively prevented gamma-ray induced lipid peroxidation as assessed by measuring thiobarbituric acid reactive substrates, lipid hydroperoxide and conjugated diene. Likewise, it prevented radiation-induced DNA strand breaks in a concentration dependent manner. The radioprotective activity of PE could be attributed to its hydroxyl and superoxide radicals scavenging property along with its lymphoproliferative activity. The radical scavenging capacity of PE was primarily due to its constituent phenolics, which were isolated and identified as chevibetol and allyl pyrocatechol.

Composition and antioxidant activities of four polysaccharides extracted from Herba Lophatheri.

PubMed

Ge, Qing; Mao, Jian-wei; Guo, Xiao-qing; Zhou, Yi-feng; Gong, Jing-yan; Mao, Shuang-rong

2013-09-01

Four polysaccharides (BLF80-A, BLF80-B, BLF80-C and BLF80-D) were isolated by hot-water extraction and purified from the leaves of Herba Lophatheri by DEAE-Sepharose fast flow. Their chemical and physical characteristics were determined and antioxidant activities were investigated on the basis of DPPH radical assay, hydroxyl radical assay and superoxide radical assay. The results showed that four polysaccharides exhibited antioxidant activities in a concentration-dependent manner, and the higher molecular weight, the stronger antioxidant activities of polysaccharides. Besides, the monosaccharide compositions of polysaccharides also influence their antioxidant activities. BLP80-D showed the strongest scavenging ability, followed by BLP80-C, BLP80-B and BLP80-A. Copyright © 2013 Elsevier B.V. All rights reserved.

Sonocatalytic-Fenton reaction for enhanced OH radical generation and its application to lignin degradation.

PubMed

Ninomiya, Kazuaki; Takamatsu, Hiromi; Onishi, Ayaka; Takahashi, Kenji; Shimizu, Nobuaki

2013-07-01

The present study demonstrated that the combined use of the sonocatalytic reaction (using ultrasound and titanium dioxide) and the Fenton reaction exhibited synergistically enhanced hydroxyl (OH) radical generation. Dihydroxybenzoic acid (DHBA) concentration as index of OH radical generation was 13 and 115 μM at 10 min in the sonocatalytic reaction and Fenton reaction, respectively. On the other hand, the DHBA concentration was 378 μM at 10 min in the sonocatalytic-Fenton reaction. The sonocatalytic-Fenton reaction was used for degradation of lignin. The lignin degradation ratio was 1.8%, 49.9%, and 60.0% at 180 min in the sonocatalytic reaction, Fenton reaction, and sonocatalytic-Fenton reaction, respectively. Moreover, the sonocatalytic-Fenton reaction was applied to pretreatment of lignocellulosic biomass to enhance subsequent enzymatic saccharification. The cellulose saccharification ratio was 11%, 14%, 16% and 25% at 360 min of pretreatment by control reaction, the sonocatalytic reaction, Fenton reaction, and sonocatalytic-Fenton reaction, respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Saturated laser fluorescence in turbulent sooting flames at high pressure

NASA Technical Reports Server (NTRS)

King, G. B.; Carter, C. D.; Laurendeau, N. M.

1984-01-01

The primary objective was to develop a quantitative, single pulse, laser-saturated fluorescence (LSF) technique for measurement of radical species concentrations in practical flames. The species of immediate interest was the hydroxyl radical. Measurements were made in both turbulent premixed diffusion flames at pressures between 1 and 20 atm. Interferences from Mie scattering were assessed by doping with particles or by controlling soot loading through variation of equivalence ratio and fuel type. The efficacy of the LSF method at high pressure was addressed by comparing fluorescence and adsorption measurements in a premixed, laminar flat flame at 1-20 atm. Signal-averaging over many laser shots is sufficient to determine the local concentration of radical species in laminar flames. However, for turbulent flames, single pulse measurements are more appropriate since a statistically significant number of laser pulses is needed to determine the probability function (PDF). PDFs can be analyzed to give true average properties and true local kinetics in turbulent, chemically reactive flows.

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.

[Resistance of Lactobacillus casei subsp. casei SY13 and Lactobacillus delbrueckii subsp. bulgaricus LJJ to reactive oxygen species].

PubMed

Zhang, Shuwen; Lv, Jiaping; Menghe, Bilige; Zhang, Heping; Zhang, Liyu; Song, Jinhui; Wang, Zhifei

2009-02-01

We evaluated antioxidative effect of two antioxidative strains, isolated from the traditional fermented dairy products. Both intact cells and cell-free extract of Lactobacillus casei subsp. casei SY13 and Lactobacillus delbrueckii subsp. bulgaricus LJJ were used to study the inhibited effect of linoleic acid peroxidation, the ability of scavenging 1,1-diphenyl-2-picrylhydrazyl radical, hydroxyl radical, superoxide anion radical,the ability of tolerancing hydrogen peroxide and the chelating capacity of ferrous ion and reducting activity. Lactobacillus casei subsp. casei SY13 and Lactobacillus delbrueckii subsp. bulgaricus LJJ demonstrated highest inhibition on linoleic acid peroxidation by 62.95% and 66.16%, respectively. The cell-free extract showed excellent scavenging superoxide anion and hydroxyl radicals activity. However, the intact cells of Lactobacillus delbrueckii subsp. bulgaricus LJJ scavenging superoxide and hydroxyl radicals capacity were not detected. The intact cells of Lactobacillus casei subsp. casei SY13 and Lactobacillus delbrueckii subsp. bulgaricus LJJ on 1,1-diphenyl-2-picrylhydrazyl radical scavenging ability and chelating ferrous ion capacity were superior to cell-free extract. The highest reduced activety was equivalent to 305 micromol/L and 294 micromol/L L-cysteine. Two latobacilli strains had good antioxidant capacity. As potential probiotics, it can be used in future.

The Hydroxyl Radical Reaction Rate Constant and Products of Cyclohexanol

DTIC Science & Technology

2007-10-01

Analysis Samples from kinetic studies were quantitativelymon- itored using a Hewlett-Packard (HP) gas chromato- graph (GC) 5890 with a flame ionization...excluded from the reaction mixture and the COL concentration was approximately doubled (4.9–9 ppm). Product Study Analysis Reactant mixtures and standards...from product identi- fication experiments were sampled by exposing a 100% polydimethylsiloxane solid phase microextrac- tion fiber (SPME) in the

In vitro evaluation of free radical scavenging activity of Codariocalyx motorius root extract.

PubMed

Chidambaram, Uma; Pachamuthu, Vanitha; Natarajan, Suganya; Elango, Bhakkiyalakshmi; Suriyanarayanan; Ramkumar, Kunga Mohan

2013-03-01

To determine the phenolic content in Codariocalyx motorius root extract and to evaluate its antioxidant properties using various in vitro assay systems. The antioxidant activity was evaluated based on scavenging of 1,1-diphenyl-2-picrylhydrazyl, hydroxyl radicals, superoxide anions, nitric oxide, hydrogen peroxide, peroxynitrite, reducing power and by inhibition of lipid peroxidation which was estimated in terms of thiobarbituric acid reactive substances. The root extract of the Codariocalyx motorius (C. motorius) exhibited potent total antioxidant activity that increased with increasing amount of extract concentration, which was compared with standard drug such as quercetin, butylated hydroxytoluene, tocopherol at different concentrations. The different concentrations of the extracts showed inhibition on lipid peroxidation. In addition, the extracts had effective reducing power, free radical scavenging, super oxide anion scavenging, nitric oxide scavenging, lipid peroxidation, and total phenolic content depending on concentration. High correlation between total phenolic contents and scavenging potential of different reactive oxygen species (r(2)=0.831-0.978) indicated the polyphenols as the main antioxidants. Codariocalyx motorius (C. motorius) root possess the highly active antioxidant substance which can be used for the treatment of oxidative stress-related diseases. Copyright © 2013 Hainan Medical College. Published by Elsevier B.V. All rights reserved.

Relationships between the structure of natural organic matter and its reactivity towards molecular ozone and hydroxyl radicals

USGS Publications Warehouse

Westerhoff, P.; Aiken, G.; Amy, G.; Debroux, J.

1999-01-01

Oxidation reaction rate parameters for molecular ozone (O3) and hydroxyl (HO) radicals with a variety of hydrophobic organic acids (HOAs) isolated from different geographic locations were determined from batch ozonation studies. Rate parameter values, obtained under equivalent dissolved organic carbon concentrations in both the presence and absence of non-NOM HO radical scavengers, varied as a function of NOM structure. First-order rate constants for O3 consumption (k(O3)) averaged 8.8 x 10-3 s-1, ranging from 3.9 x 10-3 s-1 for a groundwater HOA to > 16 x 10-3 s-1 for river HOAs with large terrestrial carbon inputs. The average second-order rate constant (k(HO,DOC) between HO radicals and NOM was 3.6 x 108 l (mol C)-1 s-1; a mass of 12 g C per mole C was used in all calculations. Specific ultraviolet absorbance (SUVA) at 254 or 280 nm of the HOAs correlated well (r > 0.9) with O3 consumption rate parameters, implying that organic ??-electrons strongly and selectively influence oxidative reactivity. HO radical reactions with NOM were less selective, although correlation between k(HO,DOC) and SUVA existed. Other physical-chemical properties of NOM, such as aromatic and aliphatic carbon content from 13C-NMR spectroscopy, proved less sensitive for predicting oxidation reactivity than SUVA. The implication of this study is that the structural nature of NOM varies temporally and spatially in a water source, and both the nature and amount of NOM will influence oxidation rates.

Total Phenol Content and In Vitro Antioxidant Potential of Helicanthus elastica (Desr.) Danser-A Less-explored Indian Mango Mistletoe

PubMed Central

Sunil Kumar, Koppala Narayana; Saraswathy, Ariyamuthu; Amerjothy, Swaminathan; Susan, Thomas; Ravishankar, Basaviah

2014-01-01

Natural products are an important source of antioxidant molecules like tannins, phenolic compounds, flavonoids, etc., Helicanthus elastica (Desr.) Danser (Loranthaceae) is one such plant belonging to the category of mistletoe, and grows commonly on the mango trees in India. In the present study, an attempt has been made to assess the antioxidant properties of the plant. Ethanol extract of H. elastica growing on mango tree was studied using different in vitro models. Shade-dried whole plant material was extracted with ethanol by cold percolation. Fifty milligrams of the alcohol extract of H. elastica was weighed and dissolved in 10 ml of methanol. The resultant 5 mg/ml solution was suitably diluted to obtain different concentrations. Total phenol content, reducing power assay, and scavenging of free radicals like nitric oxide, hydroxyl, hydrogen peroxide, and 1,1-diphenyl-2-picrylhydrazyl were studied by standardized in vitro chemical methods using ascorbic acid as the standard. The total phenol content of the plant was found to be 1.89% w/w. The extract showed good reducing power as well as scavenging of free radicals (nitric oxide, hydroxyl, superoxide anion, and hydrogen peroxide) at concentrations ranging from 5 to 100 μg/ml. The study revealed the antioxidant potential of H. elastica. PMID:25379473

Enhanced photocatalytic degradation of norfloxacin in aqueous Bi2WO6 dispersions containing nonionic surfactant under visible light irradiation.

PubMed

Tang, Lin; Wang, Jiajia; Zeng, Guangming; Liu, Yani; Deng, Yaocheng; Zhou, Yaoyu; Tang, Jing; Wang, Jingjing; Guo, Zhi

2016-04-05

Photocatalytic degradation is an alternative method to remove pharmaceutical compounds in water, however it is hard to achieve efficient rate because of the poor solubility of pharmaceutical compounds in water. This study investigated the photodegradation of norfloxacin in a nonionic surfactant Triton-X100 (TX100)/Bi2WO6 dispersion under visible light irradiation (400-750nm). It was found that the degradation of poorly soluble NOF can be strongly enhanced with the addition of TX100. TX100 was adsorbed strongly on Bi2WO6 surface and accelerated NOF photodegradation at the critical micelle concentration (CMC=0.25mM). Higher TX100 concentration (>0.25mM) lowered the degradation rate. In the presence of TX100, the degradation rate reached the maximum value when the pH value was 8.06. FTIR analyses demonstrated that the adsorbed NOF on the catalyst was completely degraded after 2h irradiation. According to the intermediates identified by HPLC/MS/MS, three possible degradation pathways were proposed to include addition of hydroxyl radical to quinolone ring, elimination of piperazynilic ring in fluoroquinolone molecules, and replacement of F atoms on the aromatic ring by hydroxyl radicals. Copyright © 2015 Elsevier B.V. All rights reserved.

Isoprene photochemistry over the Amazon rainforest.

PubMed

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

2016-05-31

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

Isoprene photochemistry over the Amazon rainforest

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Chemical composition and antioxidant/antimicrobial activities in supercritical carbon dioxide fluid extract of Gloiopeltis tenax.

PubMed

Zheng, Jiaojiao; Chen, Yicun; Yao, Fen; Chen, Weizhou; Shi, Ganggang

2012-12-01

Gloiopeltis tenax (G. tenax) is widely distributed along the Chinese coastal areas and is commonly used in the treatment of diarrhea and colitis. This study aimed at investigating the bioactivities of the volatile constituents in G. tenax. We extracted the essential constituents of G. tenax by supercritical carbon dioxide extraction (CO₂-SFE), then identified and analyzed the constituents by gas chromatography-mass spectrometry (GC-MS). In total, 30 components were identified in the G. tenax extract. The components showed remarkable antioxidant activity (radical scavenging activity of 2,2-diphenyl-1-picrylhydrazyl (DPPH)), lipid peroxidation inhibition capacity (in a β-carotene/linoleic acid-coupled oxidation reaction), and hydroxyl radical-scavenging activity (by deoxyribose degradation by iron-dependent hydroxyl radical), compared to butylated hydroxytoluene. In microdilution assays, G. tenax extracts showed a moderate inhibitory effects on Staphyloccocus aureus (minimum inhibitory concentration (MIC) = 3.9 mg/mL), Enterococcus faecalis (7.8 mg/mL), Pseudomonas aeruginosa (15.6 mg/mL), and Escherichia coli (3.9 mg/mL). Antioxidant and antimicrobial activities of G. tenax were related to the active chemical composition. These results suggest that the CO₂-SFE extract from G. tenax has potential to be used as a natural antioxidant and antimicrobial agent in food processing.

Chemical Composition and Antioxidant/Antimicrobial Activities in Supercritical Carbon Dioxide Fluid Extract of Gloiopeltis tenax

PubMed Central

Zheng, Jiaojiao; Chen, Yicun; Yao, Fen; Chen, Weizhou; Shi, Ganggang

2012-01-01

Gloiopeltis tenax (G. tenax) is widely distributed along the Chinese coastal areas and is commonly used in the treatment of diarrhea and colitis. This study aimed at investigating the bioactivities of the volatile constituents in G. tenax. We extracted the essential constituents of G. tenax by supercritical carbon dioxide extraction (CO2-SFE), then identified and analyzed the constituents by gas chromatography-mass spectrometry (GC-MS). In total, 30 components were identified in the G. tenax extract. The components showed remarkable antioxidant activity (radical scavenging activity of 2,2-diphenyl-1-picrylhydrazyl (DPPH)), lipid peroxidation inhibition capacity (in a β-carotene/linoleic acid-coupled oxidation reaction), and hydroxyl radical-scavenging activity (by deoxyribose degradation by iron-dependent hydroxyl radical), compared to butylated hydroxytoluene. In microdilution assays, G. tenax extracts showed a moderate inhibitory effects on Staphyloccocus aureus (minimum inhibitory concentration (MIC) = 3.9 mg/mL), Enterococcus faecalis (7.8 mg/mL), Pseudomonas aeruginosa (15.6 mg/mL), and Escherichia coli (3.9 mg/mL). Antioxidant and antimicrobial activities of G. tenax were related to the active chemical composition. These results suggest that the CO2-SFE extract from G. tenax has potential to be used as a natural antioxidant and antimicrobial agent in food processing. PMID:23342386

Oxidation of benzoic acid by heat-activated persulfate: Effect of temperature on transformation pathway and product distribution.

PubMed

Zrinyi, Nick; Pham, Anh Le-Tuan

2017-09-01

Heat activates persulfate (S 2 O 8 2- ) into sulfate radical (SO 4 - ), a powerful oxidant capable of transforming a wide variety of contaminants. Previous studies have shown that an increase in temperature accelerates the rates of persulfate activation and contaminant transformation. However, few studies have considered the effect of temperature on contaminant transformation pathway. The objective of this study was to determine how temperature (T = 22-70 °C) influences the activation of persulfate, the transformation of benzoic acid (i.e., a model compound), and the distribution of benzoic acid oxidation products. The time-concentration profiles of the products suggest that benzoic acid was transformed via decarboxylation and hydroxylation mechanisms, with the former becoming increasingly important at elevated temperatures. The pathway through which the products were further oxidized was also influenced by the temperature of persulfate activation. Our findings suggest that the role of temperature in the persulfate-based treatment systems is not limited only to controlling the rates of sulfate and hydroxyl radical generation. The ability of sulfate radical to initiate decarboxylation reactions and, more broadly, fragmentation reactions, as well as the effect of temperature on these transformation pathways could be important to the transformation of a number of organic contaminants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Antioxidative properties of harmane and beta-carboline alkaloids.

PubMed

Tse, S Y; Mak, I T; Dickens, B F

1991-07-15

beta-Carboline alkaloids are derived as a result of condensation between indoleamine (e.g. tryptamine) and short-chain carboxylic acid (e.g. pyruvic acid) or aldehyde (e.g. acetaldehyde), a reaction that occurs readily at room temperature. These compounds have been found endogenously in human and animal tissues and may be formed as a byproduct of secondary metabolism: their endogenous functions however, are not well understood. Indoles and tryptophan derivatives exhibit antioxidative actions by scavenging free radicals and forming resonance stabilized indolyl radicals. Harmane and related compounds exhibited concentration-dependent inhibition of lipid peroxidation (measured as thiobarbiturate reactive products) in a hepatic microsomal preparation incubated with either enzymatic dependent (Fe3+ ADP/NADPH) or non-enzymatic dependent (Fe3+ ADP/dihydroxyfumarate) oxygen radical producing systems. Alkaloids with hydroxyl substitution and a partially desaturated pyridyl ring were found to have the highest antioxidative potencies. Substitution of a hydroxyl group by a methoxyl group at the 6-position resulted in a decrease of greater than 10-fold in the antioxidative activities. Harmane showed high efficacy in an enzymatic system but low efficacy in a non-enzymatic system. The antioxidative effects of harmane in the former system may be attributed to its ability to inhibit oxidative enzymes in the microsomal system. These results suggest that beta-carbolines may also serve as endogenous antioxidants.

A mechanism for the production of hydroxyl radical at surface defect sites on pyrite

NASA Astrophysics Data System (ADS)

Borda, Michael J.; Elsetinow, Alicia R.; Strongin, Daniel R.; Schoonen, Martin A.

2003-03-01

A previous contribution from our laboratory reported the formation of hydrogen peroxide (H 2O 2) upon addition of pyrite (FeS 2) to O 2-free water. It was hypothesized that a reaction between adsorbed H 2O and Fe(III), at a sulfur-deficient defect site, on the pyrite surface generates an adsorbed hydroxyl radical (OH •). ≡Fe(III) + H 2O (ads) → ≡Fe(II) + OH •(ads) + H + The combination of two OH • then produces H 2O 2. In the present study, we show spectroscopic evidence consistent with the conversion of Fe(III) to Fe(II) at defect sites, the origin of H 2O 2 from H 2O, and the existence of OH • in solution. To demonstrate the iron conversion at the surface, X-ray photoelectron spectroscopy (XPS) was employed. Using a novel mass spectrometry method, the production of H 2O 2 was evaluated. The aqueous concentration of OH • was measured using a standard radical scavenger method. The formation of OH • via the interaction of H 2O with the pyrite surface is consistent with several observations in earlier studies and clarifies a fundamental step in the oxidation mechanism of pyrite.

Method of making a membrane having hydrophilic and hydrophobic surfaces for adhering cells or antibodies by using atomic oxygen or hydroxyl radicals

NASA Technical Reports Server (NTRS)

Koontz, Steven L. (Inventor); Spaulding, Glenn F. (Inventor)

1994-01-01

A portion of an organic polymer article such as a membrane is made hydrophilic by exposing a hydrophobic surface of the article to a depth of about 50 to about 5000 angstroms to atomic oxygen or hydroxyl radicals at a temperature below 100C., preferably below 40 C, to form a hydrophilic uniform surface layer of hydrophilic hydroxyl groups. The atomic oxygen and hydroxyl radicals are generated by a flowing afterglow microwave discharge, and the surface is outside of a plasma produced by the discharge. A membrane having both hydrophilic and hydrophobic surfaces can be used in an immunoassay by adhering antibodies to the hydrophobic surface. In another embodiment, the membrane is used in cell culturing where cells adhere to the hydrophilic surface. Prior to adhering cells, the hydrophilic surface may be grafted with a compatibilizing compound. A plurality of hydrophilic regions bounded by adjacent hydrophobic regions can be produced such that a maximum of one cell per each hydrophilic region adheres.

Drying effects on the antioxidant properties of polysaccharides obtained from Agaricus blazei Murrill.

PubMed

Wu, Songhai; Li, Feng; Jia, Shaoyi; Ren, Haitao; Gong, Guili; Wang, Yanyan; Lv, Zesheng; Liu, Yong

2014-03-15

Three polysaccharides (ABMP-F, ABMP-V, ABMP-A) were obtained from Agaricus blazei Murrill via methods such as freeze drying, vacuum drying and air drying, respectively. Their chemical compositions were examined, and antioxidant activities were investigated on the basis of assay for hydroxyl radical, DPPH radical, ABTS free radical scavenging ability and assay for Fe(2+)-chelating ability. Results showed that the three ABMPs have different physicochemical and antioxidant properties. Compared with air drying and vacuum drying methods, freeze drying method resulted to ABMP with higher neutral sugar, polysaccharide yield, uronic acid content, and stronger antioxidant abilities of hydroxyl radical, DPPH radical, ABTS radical scavenging and Fe(2+)-chelating. As a result, Agaricus blazei Murrill polysaccharides are natural antioxidant and freeze drying method serves as a good choice for the preparation of such polysaccharides and should be used to produce antioxidants for food industry. Copyright © 2014. Published by Elsevier Ltd.

On-line separation and characterization of hyaluronan oligosaccharides derived from radical depolymerization

PubMed Central

Zhao, Xue; Yang, Bo; Li, Lingyun; Zhang, Fuming; Linhardt, Robert J.

2013-01-01

Hydroxyl radicals are widely implicated in the oxidation of carbohydrates in biological and industrial processes and are often responsible for their structural modification resulting in functional damage. In this study, the radical depolymerization of the polysaccharide hyaluronan was studied in a reaction with hydroxyl radicals generated by Fenton Chemistry. A simple method for isolation and identification of the resulting non-sulfated oligosaccharide products of oxidative depolymerization was established. Hyaluronan oligosaccharides were analyzed using ion-pairing reversed phase high performance liquid chromotography coupled with tandem electrospray mass spectrometry. The sequence of saturated hyaluronan oligosaccharides having even- and odd-numbers of saccharide units, afforded through oxidative depolymerization, were identified. This study represents a simple, effective ‘fingerprinting’ protocol for detecting the damage done to hyaluronan by oxidative radicals. This study should help reveal the potential biological outcome of reactive-oxygen radical-mediated depolymerization of hyaluronan. PMID:23768593

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

PubMed

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

2011-01-01

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

Balloon stratospheric research flights, April 1976 to December 1976

NASA Technical Reports Server (NTRS)

Allen, N. C.

1977-01-01

These flights were designed to measure the vertical concentration profile of trace stratospheric species which form major links in the chlorine photochemical system of the upper atmosphere, to measure the vertical concentration profiles of atomic oxygen, the hydroxyl radical and ozone in the stratosphere. An overview of the scientific goals of the program, a statement of program management and support functions, a brief description of the instrumentation flown, pertinent engineering and payload operations data, and a summary of the scientific data obtained for four flights are presented.

Vibrational Study of Melatonin and its Radioprotective Activity towards Hydroxyl Radical

NASA Astrophysics Data System (ADS)

Singh, Gurpreet; Kaur, Sarvpreet; Saini, G. S. S.

2011-12-01

Vibrational study of Melatonin (N-acetyl 5-methoxytrypatamin) was done using FTIR and Raman spectroscopy. DFT calculations were employed to the structural analysis of melatonin and to the end products. The theoretical calculations confirmed the different observed vibrational modes. The optimized structure energy calculations of the different end products confirmed the most probable site of the hydroxyl radical attack is the hydrogen attached to nitrogen present in the indole ring.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Kinetics and mechanism for the sonochemical degradation of a nonionic surfactant.

PubMed

Singla, Ritu; Grieser, Franz; Ashokkumar, Muthupandian

2009-03-26

The sonolytic degradation of the nonionic surfactant, octaethylene glycol monododecyl ether (C(12)E(8)), has been studied at various initial concentrations below and above its critical micelle concentration (CMC). It has been observed that the degradation rate increases with an increase in the initial concentration of the surfactant until the CMC is reached. Above the CMC an almost constant degradation rate is observed, suggesting that the surfactant in its monomer form is involved in the degradation process. The degradation process of C(12)E(8) involves two distinct primary processes occurring at the bubble/solution interface: (a) hydroxylation/oxidation of the surfactant and (b) pyrolytic fragmentation of the surfactant. The oxidative cleavage of ethylene oxide units provides evidence for OH radical attack. Hydroxylation of the ethoxy chain gives rise to various short-chain carboxyalkyl-polyethylene glycol intermediates. The polyethylene glycol chain formed, due to the scission of the C(12)E(8) molecule, undergoes rapid hydroxylation/oxidation to yield simple compounds that have the potential to undergo further degradation. The detection of multiple intermediates indicates that several processes affect the complete degradation pathways of the surfactant molecule. TOC analysis, however, indicates that the sonolytic mineralization of the surfactant is difficult to achieve at reasonable rates due to the relatively low surface activity of the degradation products formed during sonolysis.

The effects of hyaluronan and its fragments on lipid models exposed to UV irradiation.

PubMed

Trommer, Hagen; Wartewig, Siegfried; Böttcher, Rolf; Pöppl, Andreas; Hoentsch, Joachim; Ozegowski, Jörg H; Neubert, Reinhard H H

2003-03-26

The effects of hyaluronan and its degradation products on irradiation-induced lipid peroxidation were investigated. Liposomal skin lipid models with increasing complexity were used. Hyaluronan and its fragments were able to reduce the amount of lipid peroxidation secondary products quantified by the thiobarbituric acid (TBA) assay. The qualitative changes were studied by mass spectrometry. To elucidate the nature of free radical involvement electron paramagnetic resonance (EPR) studies were carried out. The influence of hyaluronan and its fragments on the concentration of hydroxyl radicals generated by the Fenton system was examined using the spin trapping technique. Moreover, the mucopolysaccharide's ability to react with stable radicals was checked. The quantification assay of 2,2-diphenyl-1-picrylhydrazyl hydrate (DPPH) showed no concentration changes of the stable radical caused by hyaluronan. Hyaluronan was found to exhibit prooxidative effects in the Fenton assay in a concentration dependent manner. A transition metal chelation was proposed as a mechanism of this behavior. Considering human skin and its constant exposure to UV light and oxygen and an increased pool of iron in irradiated skin the administration of hyaluronan or its fragments in cosmetic formulations or sunscreens could be helpful for the protection of the human skin. Copyright 2003 Elsevier Science B.V.

On the quantification of the dissolved hydroxyl radicals in the plasma-liquid system using the molecular probe method

NASA Astrophysics Data System (ADS)

Ma, Yupengxue; Gong, Xinning; He, Bangbang; Li, Xiaofei; Cao, Dianyu; Li, Junshuai; Xiong, Qing; Chen, Qiang; Chen, Bing Hui; Huo Liu, Qing

2018-04-01

Hydroxyl (OH) radical is one of the most important reactive species produced by plasma-liquid interactions, and the OH in liquid phase (dissolved OH radical, OHdis) takes effect in many plasma-based applications due to its high reactivity. Therefore, the quantification of the OHdis in a plasma-liquid system is of great importance, and a molecular probe method usually used for the OHdis detection might be applied. Herein, we investigate the validity of using the molecular probe method to estimate the [OHdis] in the plasma-liquid system. Dimethyl sulfoxide is used as the molecular probe to estimate the [OHdis] in an air plasma-liquid system, and usually the estimation of [OHdis] is deduced by quantifying the OHdis-induced derivative, the formaldehyde (HCHO). The analysis indicates that the true concentration of the OHdis should be estimated from the sum of three terms: the formed HCHO, the existing OH scavengers, and the H2O2 formed from the OHdis. The results show that the measured [HCHO] needs to be corrected since the HCHO consumption is not negligible in the plasma-liquid system. We conclude from the results and the analysis that the molecular probe method generally underestimates the [OHdis] in the plasma-liquid system. If one wants to obtain the true concentration of the OHdis in the plasma-liquid system, one needs to know the consumption behavior of the OHdis-induced derivatives, the information of the OH scavengers (such as hydrated electron, atomic hydrogen besides the molecular probe), and also the knowledge of the H2O2 formed from the OHdis.

Volatile organic compound conversion by ozone, hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and impacts of oxidant sources

NASA Astrophysics Data System (ADS)

Waring, Michael S.; Wells, J. Raymond

2015-04-01

Indoor chemistry may be initiated by reactions of ozone (O3), the hydroxyl radical (OH), or the nitrate radical (NO3) with volatile organic compounds (VOC). The principal indoor source of O3 is air exchange, while OH and NO3 formation are considered as primarily from O3 reactions with alkenes and nitrogen dioxide (NO2), respectively. Herein, we used time-averaged models for residences to predict O3, OH, and NO3 concentrations and their impacts on conversion of typical residential VOC profiles, within a Monte Carlo framework that varied inputs probabilistically. We accounted for established oxidant sources, as well as explored the importance of two newly realized indoor sources: (i) the photolysis of nitrous acid (HONO) indoors to generate OH and (ii) the reaction of stabilized Criegee intermediates (SCI) with NO2 to generate NO3. We found total VOC conversion to be dominated by reactions both with O3, which almost solely reacted with D-limonene, and also with OH, which reacted with D-limonene, other terpenes, alcohols, aldehydes, and aromatics. VOC oxidation rates increased with air exchange, outdoor O3, NO2 and D-limonene sources, and indoor photolysis rates; and they decreased with O3 deposition and nitric oxide (NO) sources. Photolysis was a strong OH formation mechanism for high NO, NO2, and HONO settings, but SCI/NO2 reactions weakly generated NO3 except for only a few cases.

Elucidation of hydroxyl groups-antioxidant relationship in mono- and dihydroxyflavones based on O-H bond dissociation enthalpies.

PubMed

Treesuwan, Witcha; Suramitr, Songwut; Hannongbua, Supa

2015-06-01

Radical scavenging potential is the key to anti-oxidation of hydroxyflavones which generally found in fruits and vegetables. The objective of this work was to investigate the influence of hydroxyl group on the O-H bond dissociation enthalpies (BDE) from a series of mono- and dihydroxyflavones. Calculation at the B3LYP/6-31G(d,p) level reveals the important roles of an additional one hydroxyl group to boost the BDE of hydroxyflavones that were a stabilization of the generated radicals through attractive H-bond interactions, an ortho- and para-dihydroxyl effect, and a presence of the 3-OH in dihydroxyflavones. On the other hand, the meta-dihydroxyl effect and range-hydroxyl effect especially associated with the either 5-OH or 8-OH promoted greater BDE. Results did not only confirm that dihydroxyflavones had lower BDE than monohydroxyflavones but also suggest the selective potent hydroxyflavone molecules that are the 6'-hydroxyflavone (for monohydroxyflavone) and the 5',6'-, 7,8- and 3',4'-dihydroxyflavone which the corresponding radical preferable generated at C6'-O•, C8-O• and C4'-O•, respectively. Electron distribution was limited only over the two connected rings of hydroxyflavones while the expansion distribution into C-ring could be enhanced if the radical was formed especially for the 2',3'- and 5',6'dihydroxyflavone radicals. The delocalized bonds were strengthened after radical was generated. However the 5-O• in 5,6-dihydroxyflavone and the 3-O• in 3,6'-dihydroxyflavone increased the bond order at C4-O11 which might interrupt the conjugated delocalized bonds at the keto group.

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.

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.

Hydroxyl radical concentrations and Kuwait oil fire emission rates for March 1991

NASA Astrophysics Data System (ADS)

McKenna, D. S.; Hord, C. J.; Kent, J. M.

1995-12-01

Toward the end of the Gulf War, Iraqi troops damaged several hundred oil wells in Kuwait setting many of them on fire. Measurements made in March 1991, a few weeks after most of the fires had started (Johnson et al., 1991), were used to estimated the total burn rate and the emission rates of individual pollutants. Measurements of the principal carbon species in the plume, obtained from flask samples collected at the same time as continuous measurements of SO2 have been used to derive an "effective" sulphur content of the smoke of 2.4%, almost a third lower than the previous estimate. This sulphur content of 2.4% combined with the capping history of the fires has been used to revise the earlier estimates and provide more detailed information on the speciation of the emissions. It is now estimated that 139×106 t of crude oil were burnt during an 8-month period, resulting in the release of 112×106 t of carbon in carbon dioxide, 3×106 t of carbon in soot, 1.6×106 t of carbon in carbon monoxide, 1.3×106 t of carbon in nonmethane hydrocarbons, 0.11×106 t of nitrogen in nitrogen oxides, and 3.11×106 t of sulphur in sulphur dioxide. In addition to measurements made close to the source of the plume, one flight successfully sampled a plume some 600 km from the fires which had experienced significant photochemical aging. These observations provided a unique data set with which to estimate the rate at which hydrocarbon pollutants in the plume degrade and to infer the hydroxyl radical concentrations which cause that degradation. Most of the aliphatic hydrocarbon concentrations determined from flask samples collected at a range of distances from the Kuwait source conform to a simple loss process proportional to hydrocarbon hydroxyl reactivity and imply a diurnally averaged hydroxyl radical concentration within the plume of 1×106 molecules cm-3. Finally, it is shown that, although theoretically, hydrocarbon concentrations can be combined to predict the difference ratio of hydrocarbon reactivity, that is, (k1 - k2)/(k3 - k4), in practice experimental error can give rise to apparent discrepancies between theory and observations. Earlier studies found similar discrepancies and have speculated that these arise from differences in "photochemical age" for different hydrocarbons, a parameter those studies could not determine. We have shown similar discrepancies but have been able to determine photochemical ages for several hydrocarbons and have shown that the hydrocarbon reductions are consistent with a single photochemical age (3% precision), precluding the earlier explanations. However, even though the photochemical lifetime may be determined very precisely, consideration of the computational stability of the procedures involved suggest that unavoidable experimental precision may lead to factors of 2 errors in the determination of the difference ratio, which is more than sufficient to explain the known discrepancies.

Comparison of gel properties and biochemical characteristics of myofibrillar protein from bighead carp (Aristichthys nobilis) affected by frozen storage and a hydroxyl radical-generation oxidizing system.

PubMed

Lu, Han; Zhang, Longteng; Li, Qingzheng; Luo, Yongkang

2017-05-15

We wanted to clarify whether gel properties can be affected by in vivo or in vitro myofibrillar protein oxidation and, thus, to provide relevant information and a scientific foundation for the processing of gel products. To accomplish this, we measured the changes in sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), total disulfide (SS) content, surface hydrophobicity (So-ANS), carbonyl content, and gel texture and water-holding capacity (WHC) of isolated myofibrillar protein from bighead carp fillets during frozen storage and under different H 2 O 2 concentrations, which were used to represent in vivo and in vitro conditions, respectively. The results indicated that a certain range in content of disulfide crosslinks (0.91mol/10 5 g protein) would promote gel hardness. Mild protein oxidation caused by a certain degree of frozen storage and hydroxyl radicals can promote gel texture and WHC. Based on those results, freezing bighead carp for a certain period can be used to produce gel products. Copyright © 2016 Elsevier Ltd. All rights reserved.

A novel turn-on fluorescent strategy for sensing ascorbic acid using graphene quantum dots as fluorescent probe.

PubMed

Liu, Hua; Na, Weidan; Liu, Ziping; Chen, Xueqian; Su, Xingguang

2017-06-15

In this paper, a facile and rapid fluorescence turn-on assay for fluorescent detection of ascorbic acid (AA) was developed by using the orange emission graphene quantum dots (GQDs). In the presence of horse radish peroxidase (HRP) and hydrogen peroxide (H 2 O 2 ), catechol can be oxidized by hydroxyl radicals and converted to o-benzoquinone, which can significantly quench the fluorescence of GQDs. However, when AA present in the system, it can consume part of H 2 O 2 and hydroxyl radicals to inhibit the generation of o-benzoquinone, resulting in fluorescence recovery. Under the optimized experimental conditions, the fluorescence intensity was linearly correlated with the concentration of H 2 O 2 in the range of 3.33-500µM with a detection limit of 1.2µM. The linear detection for AA was in the range from 1.11 to 300µM with a detection limit of 0.32µM. The proposed method was applied to the determination of AA in human serum samples with satisfactory results. Copyright © 2017. Published by Elsevier B.V.

Morin Flavonoid Adsorbed on Mesoporous Silica, a Novel Antioxidant Nanomaterial

PubMed Central

Arriagada, Francisco; Correa, Olosmira; Günther, Germán; Nonell, Santi; Mura, Francisco; Olea-Azar, Claudio

2016-01-01

Morin (2´,3, 4´,5,7-pentahydroxyflavone) is a flavonoid with several beneficial health effects. However, its poor water solubility and it sensitivity to several environmental factors avoid its use in applications like pharmaceutical and cosmetic. In this work, we synthetized morin-modified mesoporous silica nanoparticles (AMSNPs-MOR) as useful material to be used as potential nanoantioxidant. To achieve this, we characterized its adsorption kinetics, isotherm and the antioxidant capacity as hydroxyl radical (HO•) scavenger and singlet oxygen (1O2) quencher. The experimental data could be well fitted with Langmuir, Freundlich and Temkin isotherm models, besides the pseudo-second order kinetics model. The total quenching rate constant obtained for singlet oxygen deactivation by AMSNPs-MOR was one order of magnitude lower than the morin rate constant reported previously in neat solvents and lipid membranes. The AMSNPs-MOR have good antioxidant properties by itself and exhibit a synergic effect with morin on the antioxidant property against hydroxyl radical. This effect, in the range of concentrations studied, was increased when the amount of morin adsorbed increased. PMID:27812111

Halogen radicals contribute to photooxidation in coastal and estuarine waters

PubMed Central

Parker, Kimberly M.; Mitch, William A.

2016-01-01

Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl− and Br− by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters. PMID:27162335

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.

Formation of Hydroxylamine from Ammonia and Hydroxyl Radicals

NASA Astrophysics Data System (ADS)

Krim, Lahouari; Zins, Emilie-Laure

2014-06-01

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

Lunar Dust and Lunar Simulant Activation, Monitoring, Solution and Cellular Toxicity Properties

NASA Technical Reports Server (NTRS)

Jeevarajan, A.S.; Wallace, W.T.

2009-01-01

During the Apollo missions, many undesirable situations were encountered that must be mitigated prior to returning humans to the moon. Lunar dust (that part of the lunar regolith less than 20 m in diameter) was found to produce several problems with astronaut s suits and helmets, mechanical seals and equipment, and could have conceivably produced harmful physiological effects for the astronauts. For instance, the abrasive nature of the dust was found to cause malfunctions of various joints and seals of the spacecraft and suits. Additionally, though efforts were made to exclude lunar dust from the cabin of the lunar module, a significant amount of material nonetheless found its way inside. With the loss of gravity correlated with ascent of the lunar module from the lunar surface to rendezvous with the command module, much of the major portions of the contaminating soil and dust began to float, irritating the astronaut s eyes and being inhaled into their lungs. Our goal has been to understand some of the properties of lunar dust that could lead to possible hazards for humans. Due to the lack of an atmosphere, there is nothing to protect the lunar soil from ultraviolet radiation, solar wind, and meteorite impacts. These processes could all serve to activate the soil, or produce reactive surface species. In order to understand the possible toxic effects of the reactive dust, it is necessary to reactivate the dust, as samples returned during the Apollo missions were exposed to the atmosphere of the Earth. We have used grinding and UV exposure to mimic some of the processes occurring on the Moon. The level of activation has been monitored using two methods: fluorescence spectroscopy and electron paramagnetic resonance spectroscopy (EPR). These techniques allow the monitoring of hydroxyl radical production in solution. We have found that grinding of lunar dust produces 2-3 times the concentration of hydroxyl radicals as lunar simulant and 10 times that of quartz. Exposure of the lunar dust to UV radiation under vacuum was also found to lead to hydroxyl radical production. After grinding, we have also monitored loss of reactivity of the dusts by exposing them to conditions of known humidity and temperature. From these tests, it was found that the reactivity half-life of lunar simulant is approximately 3 hours, while that of quartz is approximately 2 hours. Placing lunar dust in solution could lead to effects on mechanical and physiological systems, as well as other biological systems. For instance, while it is known that lunar dust is highly abrasive and caused a variety of problems with suits and equipment during Apollo, it is unknown as to how these properties might be affected in the presence of water or other liquids. It is possible that the dust may release minerals (e.g., metallic nanophase Fe) into solution that could speed corrosion or rust. Also, as lunar dust produces hydroxyl radicals (and possibly other reactive oxygen species) in solution, these radicals could also lead to the breakdown of suit or habitat materials. In the body (i.e., in lung solution), the effects could be two-fold. First, if the lunar dust dissolves, it may release an excess of elements (such as zero-valence metallic Fe) that are necessary for bodily functions but only in certain concentration ranges. For lunar dust, the presence of nanophase iron being released into the body is a concern. Secondly, the hydroxyl radicals or other reactive oxygen species produced by the dust in solution could conceivably interact with cells, leading to various problems. We have studied the dissolution of both ground and unground lunar simulant in buffer solutions of different pH. The concentration of a number of species was determined using mass spectrometry. These studies showed that lowering the pH of the solution causes a dramatic increase in the amount of each element released into solution and that grinding also produces higher concentrations. Finally, we have perfmed initial tests aimed at understanding the effects of lunar simulant on cellular systems. Alveolar epithelial cells were cultured and exposed to different concentrations of dust suspended in cell culture media. After predetermined amounts of time, the media was removed and the concentrations of important inflammatory cytokines (IL6, IL8, and TNF-alpha ) were measured. The results of these tests are being used to develop the correct protocols for tests to be performed using lunar dust samples.

Studies on free radical scavenging, cancer cell antiproliferation, and calf thymus DNA interaction of Schiff bases.

PubMed

da Silva, Cleiton M; Silva, Marina M; Reis, Fabiano S; Ruiz, Ana Lúcia T G; de Carvalho, João E; Santos, Josué C C; Figueiredo, Isis M; Alves, Rosemeire B; Modolo, Luzia V; de Fátima, Ângelo

2017-07-01

Thirty-nine Schiff bases were synthesized by performing microwave-assisted condensation of the corresponding aldehydes and aromatic amines. Their reactive nitrogen species (RNS) scavenging activity and inhibitory effects against cancer cell growth were then subsequently investigated. Additionally, the interaction between the calf thymus DNA (ctDNA) and selected Schiff bases was evaluated using fluorescence spectroscopy, and their binding parameters were determined. The yields of the various compounds ranged from moderate to excellent (43-99%) after only a 2-min reaction. The hydroxylated Schiff bases 2, 8, 15, 16, 18, 20, 29, 32, 34, and 37 were found to be potent scavengers of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals with half-maximal scavenging concentration (SC 50 ) values lower than that of the positive control, resveratrol. The presence of hydroxyl substituents on the aromatic rings also proved essential to the cytotoxicity of the compounds. The binding constants (K b ) obtained using fluorescence spectroscopy ranged from 0.37 to 3.07×10 5 Lmol -1 , and were strongly influenced by the structure and hydroxylation degree. Schiff bases 3 and 8 showed promising cytotoxic activity, with half-maximal growth inhibitory (GI 50 ) values in the same order of magnitude as those exhibited by the reference drug, doxorubicin against various cell lines. Interestingly, these compounds also showed the highest K b , suggesting that the cytotoxic activity could be related to their interaction with the DNA of the tumor cells. The results of this study highlighted some Schiff bases as potential lead compounds for the design of new free radical scavengers and anticancer agents. Copyright © 2017 Elsevier B.V. All rights reserved.

Partial characterization and antioxidant and antiproliferative activities of the aqueous extracellular polysaccharides from the thermophilic microalgae Graesiella sp.

PubMed

Trabelsi, Lamia; Chaieb, Olfa; Mnari, Amira; Abid-Essafi, Salwa; Aleya, Lotfi

2016-07-12

For thousands of years, Tunisian geothermal water has been used in bathing. Indeed, thermal baths "Hammam" were recommended in the treatment of different type of illnesses as, for instance, for relaxing joints and soothing. The ability of microalgae to sustain at the high temperature makes them potential producers of high value thermostable bio-products. This study aimed to explore the therapeutic potential of the aqueous extracellular polysaccharides (AEPS) of the Tunisian thermophilic microalgae Graesiella sp. and to evaluate its physico-chemical characteristics. Different parameters were used to characterize the AEPS. The dry weight, volatile dry weight, elemental analysis, monosaccharide composition and IR-spectroscopy analysis. Carbohydrate, uronic acid, ester sulfate and protein concentrations were also determined using colorimetric assay. AEPS was analyzed for its antioxidant propriety by means of total antioxidant capacity, DPPH radicals scavenging assay, ferrous chelating ability and hydroxyl and superoxide radical scavenging activity. The antiproliferative activity of AEPS was evaluated for HepG2 and Caco-2 cells using the MTT assay. The Graesiella sp. AEPS is found to be a hetero-sulfated-anionic polysaccharides that contain carbohydrate (52 %), uronic acids (23 %), ester sulfate (11 %) and protein (12 %). The carbohydrate fraction was formed by eight neutral sugars glucose, galactose, mannose, fucose, rhamnose, xylose, arabinose and ribose. The FT-IR revealed the presence of carboxyl, hydroxyl, amine and sulfate groups. AEPS showed high activity as reducing agent, high ferrous chelating capacity and caused a significant decrease in a concentration-dependent manner of hydroxyl radical. A moderate DPPH scavenging activity and a poor superoxide radical scavenging ability were also observed. AEPS treatment (from 0.01 to 2.5 mg/ml) caused also a clear decrease of cell viabilities in a dose-dependent manner. The IC50 values obtained in HepG2 and Caco-2 cells were 1.06 mg/ml and 0.3 mg/ml respectively. This study evidenced that the Graesiella sp. AEPS exhibits antioxidant and antiproliferative activities. The biological activities of this extract depend on its fine structural features. Further work will identify and purify the active polysaccharides to enhance our understanding of their complete structure and relationships with its function.

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

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

Cohen, N.; Koffend, J.B.

1998-02-01

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

Measurement of Hydroxyl Radicals in Plasma Pencil by Laser Induced Fluorescence

DTIC Science & Technology

2013-07-01

31st ICPIG, July 14-19, 2013, Granada , Spain Topic number 6 Measurement of hydroxyl radicals in plasma pencil by laser induced fluorescence J...International Conference on Phenomena in Ionized Gases (31st) (ICPIG) Held in Granada , Spain on 14-19 July 2013, The original document contains color images. 14...Prescribed by ANSI Std Z39-18 31st ICPIG, July 14-19, 2013, Granada , Spain Topic number 6 camera. The fluorescence signal was significantly stronger

Chain-breaking antioxidant activity of hydroxylated and methoxylated magnolol derivatives: the role of H-bonds.

PubMed

Baschieri, Andrea; Pulvirenti, Luana; Muccilli, Vera; Amorati, Riccardo; Tringali, Corrado

2017-07-26

Chemical modification of magnolol, an uncommon dimeric neolignan contained in Magnolia genus trees, provides a unique array of polyphenols having interesting biological activity potentially related to radical scavenging. The chain-breaking antioxidant activity of four new hydroxylated and methoxylated magnolol derivatives was explored by experimental and computational methods. The measurement of the rate constant of the reaction with ROO˙ radicals (k inh ) in an apolar solvent showed that the introduction of hydroxyl groups ortho to the phenolic OH in magnolol increased the k inh value, being 2.4 × 10 5 M -1 s -1 and 3.3 × 10 5 M -1 s -1 for the mono and the dihydroxy derivatives respectively (k inh of magnolol is 6.1 × 10 4 M -1 s -1 ). The di-methoxylated derivative is less reactive than magnolol (k inh = 1.1 × 10 4 M -1 s -1 ), while the insertion of both hydroxyl and methoxyl groups showed no effect (6.0 × 10 4 M -1 s -1 ). Infrared spectroscopy and theoretical calculations allowed a rationalization of these results and pointed out the crucial role of intramolecular H-bonds. We also show that a correct estimation of the rate constant of the reaction with ROO˙ radicals, by using BDE(OH) calculations, requires that the geometry of the radical is as close as possible to that of the parent phenol.

Application of a hydroxyl-radical-based disinfection system for ballast water.

PubMed

Bai, Mindong; Tian, Yiping; Yu, Yixuan; Zheng, Qilin; Zhang, Xiaofang; Zheng, Wu; Zhang, Zhitao

2018-06-02

A hydroxyl radical (OH) ballast water treatment system (BWTS) was developed and applied to inactivate entrained organisms in a 10,000-ton oceanic ship, where OH was produced by a strong ionization discharge combined with a water jet cavitation effect. The calculated OH generation rate was 1373.4 μM min -1 in ballast water, which is much higher than that in other advanced oxidative processes such as photocatalysis. As a result, non-indigenous red tide algae were inactivated to meet the ballast water discharge standards (<10 cells mL -1 ) of the International Maritime Organization. The ratio of variable fluorescence to maximum fluorescence (F v /F m ) for algal chlorophyll rapidly decreased to zero within a contact time of only 6 s, indicating complete inactivation of algae. Observation under a scanning electron microscope showed no cellular materials were released by algal cells upon OH inactivation. A risk assessment of the OH treatment system was conducted, and the ratios of predicted environmental concentrations to predicted no effect concentrations of all detected disinfection byproducts were less than 1, even at a worst-case oxidant concentration of 2.41 mg L -1 . Ship ballast water treated using OH inactivation is safe for marine environments. Finally, the energy consumption and operational costs of the OH BWTS were found to be 0.033 kWh m -3 and CNY 0.03 m -3 , respectively. Copyright © 2018 Elsevier Ltd. All rights reserved.

Induction of oxidative DNA damage by mesalamine in the presence of copper: a potential mechanism for mesalamine anticancer activity.

PubMed

Zimmerman, Ryan P; Jia, Zhenquan; Zhu, Hong; Vandjelovic, Nathan; Misra, Hara P; Wang, Jianmin; Li, Yunbo

2011-02-27

Mesalamine is the first line pharmacologic intervention for patients with ulcerative colitis, and recent epidemiologic studies have demonstrated a protective association between therapeutic use of the drug and colorectal carcinoma. However, the mechanism by which this protection is afforded has yet to be elucidated. Because copper is found at higher than normal concentrations in neoplastic cell nuclei and is known to interact with phenolic compounds to generate reactive oxygen species, we investigated whether the reaction of mesalamine/copper was able to induce oxidative DNA strand breaks in φX-174 RF I plasmid DNA, and the various components of the mechanism by which the reaction occurred. Plasmid DNA strand breaks were induced by pharmacologically relevant concentrations of mesalamine in the presence of a micromolar concentration of Cu(II), and damage was inhibited by bathocuproinedisulfonic acid (BCS) and catalase. Further, we showed that the reaction of copper with mesalamine consumed molecular oxygen, which was inhibited by BCS. Electron paramagnetic resonance spectral analysis of the reaction of copper/mesalamine indicated the presence of the hydroxyl radical, which was inhibited by both BCS and catalase. This study demonstrates for the first time that through a copper-redox cycling mechanism, the copper-mediated oxidation of mesalamine is a pro-oxidant interaction that generates hydroxyl radicals which may participate in oxidative DNA damage. These results demonstrate a potential mechanism of the anticancer effects of mesalamine in patients with ulcerative colitis. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Evaluation of Antioxidant and Free Radical Scavenging Capacities of Polyphenolics from Pods of Caesalpinia pulcherrima

PubMed Central

Hsu, Feng-Lin; Huang, Wei-Jan; Wu, Tzu-Hua; Lee, Mei-Hsien; Chen, Lih-Chi; Lu, Hsiao-Jen; Hou, Wen-Chi; Lin, Mei-Hsiang

2012-01-01

Thirteen polyphenolics were isolated from fresh pods of Caesalpinia pulcherrima using various methods of column chromatography. The structures of these polyphenolics were elucidated as gallic acid (1), methyl gallate (2), 6-O-galloyl-d-glucoside (3), methyl 6-O-galloyl-β-d-glucoside (4), methyl 3,6-di-O-galloyl-α-d-glucopyranoside (5), gentisic acid 5-O-α-d-(6′-O-galloyl)glucopyranoside (6), guaiacylglycerol 4-O-β-d-(6′-O-galloyl)glucopyranoside (7), 3-methoxy-4-hydroxyphenol 1-O-β-d-(6′-O-galloyl) glucopyranoside (8), (+)-gallocatechin (9), (+)-catechin (10), (+)-gallocatechin 3-O-gallate (11), myricetin 3-rhamnoside (12), and ampelopsin (13). All isolated compounds were tested for their antioxidant activities in the 1,1-diphenyl-2-picrylhydrazyl (DPPH), hydroxyl, and peroxynitrite radicals scavenging assays. Among those compounds, 11, 12, and 2 exhibited the best DPPH-, hydroxyl-, and peroxynitrite radical-scavenging activities, respectively. Compound 7 is a new compound, and possesses better scavenging activities towards DPPH but has equivalent hydroxyl radical scavenging activity when compared to BHT. The paper is the first report on free radical scavenging properties of components of the fresh pods of Caesalpinia pulcherrima. The results obtained from the current study indicate that the free radical scavenging property of fresh pods of Caesalpinia pulcherrima may be one of the mechanisms by which this herbal medicine is effective in several free radical mediated diseases. PMID:22754350

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

PubMed Central

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

2018-01-01

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

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

PubMed

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

2018-02-27

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

Purification and characterization of novel antioxidant peptides from enzymatic hydrolysates of tilapia (Oreochromis niloticus) skin gelatin.

PubMed

Zhang, Yufeng; Duan, Xiu; Zhuang, Yongliang

2012-11-01

To obtain hydrolysates with high degree of hydrolysis (DH) and scavenging radical activity, tilapia skin gelatin (TSG) was hydrolyzed by properase E and multifect neutral. The optimum hydrolysis condition of each enzyme was determined using the orthogonal experiment, and double-enzyme hydrolysis was further applied. The results showed the tilapia skin gelatin hydrolysate (TSGH) obtained by progressive hydrolysis using multifect neutral and properase E had the highest DH and hydroxyl radical scavenging activity. The IC(50) values of TSGH on scavenging 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, superoxide anion radical (·O(2)) and hydroxyl radical (·OH) activities were also determined. TSGH was further purified using gel filtration chromatography, ion exchange chromatography, and RP-HPLC. The peptides were identified using nano-LC-ESI mass spectrometry. Finally, two antioxidant peptides were identified and the amino acid sequences were Glu-Gly-Leu (317.33 Da) and Tyr-Gly-Asp-Glu-Tyr (645.21 Da), respectively. The IC(50) values of two peptides on hydroxyl radical scavenging activities were 4.61 μg mL(-1)and 6.45 μg mL(-1), respectively. Therefore, the results demonstrated that the hydrolysates of TSG prepared by multifect neutral and properase E could serve as a source of peptides with high antioxidant activity. It provided a scientific basis for the preparation of antioxidant peptides. Copyright © 2012 Elsevier Inc. All rights reserved.

Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions

PubMed Central

Donahue, Neil M.; Henry, Kaytlin M.; Mentel, Thomas F.; Kiendler-Scharr, Astrid; Spindler, Christian; Bohn, Birger; Brauers, Theo; Dorn, Hans P.; Fuchs, Hendrik; Tillmann, Ralf; Wahner, Andreas; Saathoff, Harald; Naumann, Karl-Heinz; Möhler, Ottmar; Leisner, Thomas; Müller, Lars; Reinnig, Marc-Christopher; Hoffmann, Thorsten; Salo, Kent; Hallquist, Mattias; Frosch, Mia; Bilde, Merete; Tritscher, Torsten; Barmet, Peter; Praplan, Arnaud P.; DeCarlo, Peter F.; Dommen, Josef; Prévôt, Andre S.H.; Baltensperger, Urs

2012-01-01

The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models. PMID:22869714

Antioxidant and Hypoglycemic Activities of Exopolysaccharide by Submerged Culture of Inocutus Hispidus.

PubMed

Liu, S H; Sun, S W; Tian, Z F; Wu, J Y; Li, X L; Xu, C P

2015-01-01

This work was to investigate the hypoglycemic and antioxidant activities of the exopolysaccharides produced in a stirred-tank bioreactor by Inocutus hispidus. The exopolysaccharides showed significant antioxidant activities, up to 70.7±2.5% inhibition of hydroxyl radicals, 50% inhibition of 2,2-diphenyl-1-picrylhydrazyl radicals, and a Trolox equivalent antioxidant capacity of 3.3 mM. The exopolysaccharide also showed notable hypoglycemic effects in streptozotocin-induced diabetic mice, reducing the plasma glucose, total cholesterol and triacylglycerol concentrations by 18.2±1.5, 20.9±0.8 and 14.4±0.4, respectively. The results demonstrated the potential of this EPS for human health protection against oxidative damage and hyperglycemia.

Moringa oleifera Lam. seed extract prevents fat diet induced oxidative stress in mice and protects liver cell-nuclei from hydroxyl radical mediated damage.

PubMed

Das, Nilanjan; Ganguli, Debdutta; Dey, Sanjit

2015-12-01

High fat diet (HFD) prompts metabolic pattern inducing reactive oxygen species (ROS) production in mitochondria thereby triggering multitude of chronic disorders in human. Antioxidants from plant sources may be an imperative remedy against this disorder. However, it requires scientific validation. In this study, we explored if (i) Moringa oleifera seed extract (MoSE) can neutralize ROS generated in HFD fed mice; (ii) protect cell-nuclei damage developed by Fenton reaction in vitro. Swiss mice were fed with HFD to develop oxidative stress model (HFD group). Other groups were control, seed extract alone treated, and MoSE simultaneously (HS) treated. Treatment period was of 15 days. Antioxidant enzymes with tissue nitrite content (TNC) and lipid peroxidation (LPO) were estimated from liver homogenate. HS group showed significantly higher (P < 0.05) superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), reduced glutathione (GSH) activity, and ferric reducing antioxidant power (FRAP) compared to only HFD fed group. Further, TNC and LPO decreased significantly (P < 0.05) in HS group compared to HFD fed group. MoSE also protected hepatocytes nuclei from the hydroxyl radicals generated by Fenton reaction. MoSE was found to be polyphenol rich with potent reducing power, free radicals and hydroxyl radicals scavenging activity. Thus, MoSE exhibited robust antioxidant prospective to neutralize ROS developed in HFD fed mice and also protected the nuclei damage from hydroxyl radicals. Hence, it can be used as herbal medication against HFD induced ROS mediated disorders.

Effects of salicylate on 3,4-methylenedioxymethamphetamine (MDMA)-induced neurotoxicity in rats.

PubMed

Yeh, S Y

1997-11-01

The drug 3,4-methylenedioxymethamphetamine (MDMA) is a serotonergic neurotoxicant that causes hyperthermia and depletion of serotonin (5-HT) and 5-hydroxy-indole-3-acetic acid (5-HIAA) in the central nervous system. Formation of neurotoxic metabolites of MDMA, e.g., 2,4,5-trihydroxy-methamphetamine and 2,4,5-trihydroxyamphetamine, involves hydroxyl and/or superoxide free radicals. The present study was designed to determine whether the hydroxyl free-radical-trapping agent salicylate could provide protection against MDMA neurotoxicity in rats. In the acute studies, sodium salicylate (12.5-400 mg/kg, calculated as free acid) was injected interperitoneally (i.p.) 1 h before subcutaneous (s.c.) injections of MDMA (20 mg/kg as base). In the chronic studies, sodium salicylate (3.1-100 mg/kg) was injected i.p. 1 h before repeated s.c. injections of MDMA (10 mg/kg as base, twice daily, at 0830 and 1730 h for 4 consecutive days). Repeated MDMA administration depleted contents of 5-HT and 5-HIAA in the frontal cortex, hippocampus and striatum. Coadministration of salicylate plus MDMA did not significantly alter MDMA-induced depletion of 5-HT and 5-HIAA in these tissues. Thus, salicylate, a hydroxyl free-radical-trapping agent, does not protect against MDMA-induced hyperthermia and depletion of 5-HT and 5-HIAA. These observations suggest that MDMA-induced neurotoxicity may occur mainly through the production of superoxide or other radicals rather than hydroxyl free radicals. Salicylate actually potentiated MDMA-induced hyperthermia and lethality, findings that might be of clinical relevance.

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.

Cloud condensation nuclei activity of aliphatic amine secondary aerosol

USDA-ARS?s Scientific Manuscript database

Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The resulting particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate ...

Destruction of microcystins (cyanotoxins) by UV-254 nm-based direct photolysis and advanced oxidation processes (AOPs): influence of variable amino acids on the degradation kinetics and reaction mechanisms.

PubMed

He, Xuexiang; de la Cruz, Armah A; Hiskia, Anastasia; Kaloudis, Triantafyllos; O'Shea, Kevin; Dionysiou, Dionysios D

2015-05-01

Hepatotoxic microcystins (MCs) are the most frequently detected group of cyanobacterial toxins. This study investigated the degradation of common MC variants in water, MC-LR, MC-RR, MC-YR and MC-LA, by UV-254 nm-based processes, UV only, UV/H2O2, UV/S2O8(2-) and UV/HSO5(-). Limited direct photolysis of MCs was observed, while the addition of an oxidant significantly improved the degradation efficiency with an order of UV/S2O8(2-) > UV/HSO5(-) > UV/H2O2 at the same initial molar concentration of the oxidant. The removal of MC-LR by UV/H2O2 appeared to be faster than another cyanotoxin, cylindrospermopsin, at either the same initial molar concentration or the same initial organic carbon concentration of the toxin. It suggested a faster reaction of MC-LR with hydroxyl radical, which was further supported by the determined second-order rate constant of MCs with hydroxyl radical. Both isomerization and photohydration byproducts were observed in UV only process for all four MCs; while in UV/H2O2, hydroxylation and diene-Adda double bond cleavage byproducts were detected. The presence of a tyrosine in the structure of MC-YR significantly promoted the formation of monohydroxylation byproduct m/z 1061; while the presence of a second arginine in MC-RR led to the elimination of a guanidine group and the absence of double bond cleavage byproducts. It was therefore demonstrated in this study that the variable amino acids in the structure of MCs influenced not only the degradation kinetics but also the preferable reaction mechanisms. Copyright © 2015 Elsevier Ltd. All rights reserved.

Elevated free nitrotyrosine levels, but not protein-bound nitrotyrosine or hydroxyl radicals, throughout amyotrophic lateral sclerosis (ALS)-like disease implicate tyrosine nitration as an aberrant in vivo property of one familial ALS-linked superoxide dismutase 1 mutant.

PubMed

Bruijn, L I; Beal, M F; Becher, M W; Schulz, J B; Wong, P C; Price, D L; Cleveland, D W

1997-07-08

Mutations in superoxide dismutase 1 (SOD1; EC 1.15.1.1) are responsible for a proportion of familial amyotrophic lateral sclerosis (ALS) through acquisition of an as-yet-unidentified toxic property or properties. Two proposed possibilities are that toxicity may arise from imperfectly folded mutant SOD1 catalyzing the nitration of tyrosines [Beckman, J. S., Carson, M., Smith, C. D. & Koppenol, W. H. (1993) Nature (London) 364, 584] through use of peroxynitrite or from peroxidation arising from elevated production of hydroxyl radicals through use of hydrogen peroxide as a substrate [Wiedau-Pazos, M., Goto, J. J., Rabizadeh, S., Gralla, E. D., Roe, J. A., Valentine, J. S. & Bredesen, D. E. (1996) Science 271, 515-518]. To test these possibilities, levels of nitrotyrosine and markers for hydroxyl radical formation were measured in two lines of transgenic mice that develop progressive motor neuron disease from expressing human familial ALS-linked SOD1 mutation G37R. Relative to normal mice or mice expressing high levels of wild-type human SOD1, 3-nitrotyrosine levels were elevated by 2- to 3-fold in spinal cords coincident with the earliest pathological abnormalities and remained elevated in spinal cord throughout progression of disease. However, no increases in protein-bound nitrotyrosine were found during any stage of SOD1-mutant-mediated disease in mice or at end stage of sporadic or SOD1-mediated familial human ALS. When salicylate trapping of hydroxyl radicals and measurement of levels of malondialdehyde were used, there was no evidence throughout disease progression in mice for enhanced production of hydroxyl radicals or lipid peroxidation, respectively. The presence of elevated nitrotyrosine levels beginning at the earliest stages of cellular pathology and continuing throughout progression of disease demonstrates that tyrosine nitration is one in vivo aberrant property of this ALS-linked SOD1 mutant.

Cisplatin enhances the formation of DNA single- and double-strand breaks by hydrated electrons and hydroxyl radicals.

PubMed

Rezaee, Mohammad; Sanche, Léon; Hunting, Darel J

2013-03-01

The synergistic interaction of cisplatin with ionizing radiation is the clinical rationale for the treatment of several cancers including head and neck, cervical and lung cancer. The underlying molecular mechanism of the synergy has not yet been identified, although both DNA damage and repair processes are likely involved. Here, we investigate the indirect effect of γ rays on strand break formation in a supercoiled plasmid DNA (pGEM-3Zf-) covalently modified by cisplatin. The yields of single- and double-strand breaks were determined by irradiation of DNA and cisplatin/DNA samples with (60)Co γ rays under four different scavenging conditions to examine the involvement of hydrated electrons and hydroxyl radicals in inducing the DNA damage. At 5 mM tris in an N2 atmosphere, the presence of an average of two cisplatins per plasmid increased the yields of single- and double-strand breaks by factors of 1.9 and 2.2, respectively, relative to the irradiated unmodified DNA samples. Given that each plasmid of 3,200 base pairs contained an average of two cisplatins, this represents an increase in radiosensitivity of 3,200-fold on a per base pair basis. When hydrated electrons were scavenged by saturating the samples with N2O, these enhancement factors decreased to 1.5 and 1.2, respectively, for single- and double-strand breaks. When hydroxyl radicals were scavenged using 200 mM tris, the respective enhancement factors were 1.2 and 1.6 for single- and double-strand breaks, respectively. Furthermore, no enhancement in DNA damage by cisplatin was observed after scavenging both hydroxyl radicals and hydrated electrons. These findings show that hydrated electrons can induce both single- and double-strand breaks in the platinated DNA, but not in unmodified DNA. In addition, cisplatin modification is clearly an extremely efficient means of increasing the formation of both single- and double-strand breaks by the hydrated electrons and hydroxyl radicals created by ionizing radiation.

Method of cross-linking polyvinyl alcohol and other water soluble resins

NASA Technical Reports Server (NTRS)

Phillipp, W. H.; May, C. E.; Hsu, L. C.; Sheibley, D. W. (Inventor)

1980-01-01

A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.

Antioxidative Activity of Colostrum and Human Milk: Effects of Pasteurization and Storage.

PubMed

Marinković, Vesna; Ranković-Janevski, Milica; Spasić, Snežana; Nikolić-Kokić, Aleksandra; Lugonja, Nikoleta; Djurović, Dijana; Miletić, Srdjan; Vrvić, Miroslav M; Spasojević, Ivan

2016-06-01

Milk banks collect, pasteurize, and freeze/store human milk. The processing may alter redox properties of milk, but the effects have not been fully examined. We collected 10 mature milk and 10 colostrum samples and applied a battery of biochemical assays and electron paramagnetic resonance spectroscopy to inspect changes that milk undergoes with pasteurization and 30 days storage at -20°C. Pasteurization and storage of raw milk did not affect total nonenzymatic antioxidative capacity, but specific components and features were altered. Urate radical and ascorbyl radical emerge as products of exposure of milk to hydroxyl radical-generating system. Processing shifted the load of antioxidative activity from ascorbate to urate and lowered the capacity of milk to diminish hydroxyl radical. Pasteurization caused a significant drop in the activity of 2 major antioxidative enzymes-superoxide dismutase and glutathione peroxidase, whereas freezing/storage of raw milk affected only superoxide dismutase. Colostrum showed drastically higher total nonenzymatic antioxidative capacity, hydroxyl radical scavenging ability, and glutathione reductase activity compared with mature milk. Pasteurization and storage affect nonenzymatic and enzymatic antioxidative agents in human milk. It appears that nonenzymatic antioxidative systems in colostrum and milk are different. The effects of processing may be partially compensated by fortification/spiking with ascorbate before use.

De Novo Emergence of Genetically Resistant Mutants of Mycobacterium tuberculosis from the Persistence Phase Cells Formed against Antituberculosis Drugs In Vitro

PubMed Central

Sebastian, Jees; Swaminath, Sharmada; Nair, Rashmi Ravindran; Jakkala, Kishor; Pradhan, Atul

2016-01-01

ABSTRACT Bacterial persisters are a subpopulation of cells that can tolerate lethal concentrations of antibiotics. However, the possibility of the emergence of genetically resistant mutants from antibiotic persister cell populations, upon continued exposure to lethal concentrations of antibiotics, remained unexplored. In the present study, we found that Mycobacterium tuberculosis cells exposed continuously to lethal concentrations of rifampin (RIF) or moxifloxacin (MXF) for prolonged durations showed killing, RIF/MXF persistence, and regrowth phases. RIF-resistant or MXF-resistant mutants carrying clinically relevant mutations in the rpoB or gyrA gene, respectively, were found to emerge at high frequency from the RIF persistence phase population. A Luria-Delbruck fluctuation experiment using RIF-exposed M. tuberculosis cells showed that the rpoB mutants were not preexistent in the population but were formed de novo from the RIF persistence phase population. The RIF persistence phase M. tuberculosis cells carried elevated levels of hydroxyl radical that inflicted extensive genome-wide mutations, generating RIF-resistant mutants. Consistent with the elevated levels of hydroxyl radical-mediated genome-wide random mutagenesis, MXF-resistant M. tuberculosis gyrA de novo mutants could be selected from the RIF persistence phase cells. Thus, unlike previous studies, which showed emergence of genetically resistant mutants upon exposure of bacteria for short durations to sublethal concentrations of antibiotics, our study demonstrates that continuous prolonged exposure of M. tuberculosis cells to lethal concentrations of an antibiotic generates antibiotic persistence phase cells that form a reservoir for the generation of genetically resistant mutants to the same antibiotic or another antibiotic. These findings may have clinical significance in the emergence of drug-resistant tubercle bacilli. PMID:27895008

Isoprene photochemistry over the Amazon rainforest

DOE PAGES

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.; ...

2016-05-31

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO 2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK +more » MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. Also, a value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). In conclusion, this abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.« less

Isoprene photochemistry over the Amazon rainforest

PubMed Central

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

2016-01-01

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

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

Liu, Yingjun; Brito, Joel; Dorris, Matthew R.

Isoprene photooxidation is a major driver of atmospheric chemistry over forested regions. Isoprene reacts with hydroxyl radicals (OH) and molecular oxygen to produce isoprene peroxy radicals (ISOPOO). These radicals can react with hydroperoxyl radicals (HO 2) to dominantly produce hydroxyhydroperoxides (ISOPOOH). They can also react with nitric oxide (NO) to largely produce methyl vinyl ketone (MVK) and methacrolein (MACR). Unimolecular isomerization and bimolecular reactions with organic peroxy radicals are also possible. There is uncertainty about the relative importance of each of these pathways in the atmosphere and possible changes because of anthropogenic pollution. Herein, measurements of ISOPOOH and MVK +more » MACR concentrations are reported over the central region of the Amazon basin during the wet season. The research site, downwind of an urban region, intercepted both background and polluted air masses during the GoAmazon2014/5 Experiment. Under background conditions, the confidence interval for the ratio of the ISOPOOH concentration to that of MVK + MACR spanned 0.4–0.6. This result implies a ratio of the reaction rate of ISOPOO with HO2 to that with NO of approximately unity. Also, a value of unity is significantly smaller than simulated at present by global chemical transport models for this important, nominally low-NO, forested region of Earth. Under polluted conditions, when the concentrations of reactive nitrogen compounds were high (>1 ppb), ISOPOOH concentrations dropped below the instrumental detection limit (<60 ppt). In conclusion, this abrupt shift in isoprene photooxidation, sparked by human activities, speaks to ongoing and possible future changes in the photochemistry active over the Amazon rainforest.« less

DNA damage during glycation of lysine by methylglyoxal: assessment of vitamins in preventing damage.

PubMed

Suji, G; Sivakami, S

2007-11-01

Amino acids react with methylglyoxal to form advanced glycation end products. This reaction is known to produce free radicals. In this study, cleavage to plasmid DNA was induced by the glycation of lysine with methylglyoxal in the presence of iron(III). This system was found to produce superoxide as well as hydroxyl radicals. The abilities of various vitamins to prevent damage to plasmid DNA were evaluated. Pyridoxal-5-phosphate showed maximum protection, while pyridoxamine showed no protection. The protective abilities could be directly correlated to inhibition of production of hydroxyl and superoxide radicals. Pyridoxal-5-phosphate exhibited low radical scavenging ability as evaluated by its TEAC, but showed maximum protection probably by interfering in free radical production. Pyridoxamine did not inhibit free radical production. Thiamine and thiamine pyrophosphate, both showed protective effects albeit to different extents. Tetrahydrofolic acid showed better antioxidant activity than folic acid but was found to damage DNA by itself probably by superoxide generation.

The oxygen-centered radicals scavenging activity of sulfasalazine and its metabolites. A direct protection of the bowel.

PubMed

Prónai, L; Yukinobu, I; Láng, I; Fehér, J

1992-01-01

Oxygen-centered radicals, such as superoxide (O2-) and hydroxyl radicals (.OH) generated by phagocytes have been suggested to be involved in the pathogenesis of chronic inflammations of the bowel, such as Crohn's disease and colitis ulcerosa. Recently, sulfasalazine (SASP) and its metabolites have been reported to exert their effects as a direct scavenger of oxygen-centered radicals in the bowel. To scavenge oxygen-centered radicals in vivo, however, SASP and its metabolites have to react with O2- and/or .OH in vitro very rapidly, furthermore they have to reach an appropriate (possible millimolar) concentration range at the site of inflammation. To test this possibility, we investigated the direct O2- and .OH scavenging activity of SASP and its metabolites using the specific electron paramagnetic resonance/spin trapping method, and we compared the 50% inhibition rates of SASP and its metabolites with their known concentrations in the bowel and in the human plasma. It was found that SASP and its metabolites, such as 5-amino-salicylic acid (5-ASA), and acetyl-5-amino-salicylic acid (AC-5-ASA), but not sulfapyridine (SP) and acetyl-sulfapyridine (Ac-SP) have a direct O2- and .OH scavenging activity in vitro systems. Among the compounds, SASP and 5-ASA can reach a concentration which is appropriate to scavenge oxygen-centered radicals in the bowel but not in the human plasma. It was concluded that the in vivo antiinflammatory effects of SASP and its metabolites are, at least partly, due to the direct oxygen-centered scavenging activity of these drugs.

Expression of the phycoerythrin gene of Gracilaria lemaneiformis (Rhodophyta) in E. coli and evaluation of the bioactivity of recombinant PE

NASA Astrophysics Data System (ADS)

Wen, Ruobing; Sui, Zhenghong; Zhang, Xuecheng; Zhang, Shuang; Qin, Song

2007-10-01

Phycoerythrin (PE) is one of the most important proteins involved in light capturing during photosynthesis in red algae. Its potential biological activities had gained wide concerns. In the present study, tumor cytotoxic and hydroxyl radical assay were preformed to detect the bioactivity of recombinant PE. Recombinant plasmids pGEX-PE and pBGL were transformed into E. coli BL21 to make two recombinant strains BEX (pGEX-PE) and BGL (pBGL). PE expressing in BEX (pGEX-PE) was validated by SDS-PAGE and Western blotting analysis. SDS-PAGE analysis indicated that the PE-GST fusion protein was mostly inclusion bodies. Specific expression of PE was confirmed by Western blotting analysis. The recombinant E. coli BEX (pGEX-PE) cells were collected and sonicated. The supernatants were reserved for the tumor cytotoxic experiments. The result of tumor cytotoxic assay indicated that the supernatants containing PE had the activity of inhibiting the growth of Hela cells and with the increase of protein concentration, the inhibiting rate increased from 37.31% to 63.26%, which showed significant difference from the control. Hydroxyl radical scavenging effect was tested with supernatants of BEX (pGEX-PE) and BGL (pBGL) cell lysates treated with sonication and heating. For the sonication samples, the scavenging rates of the supernatants of BEX (pGEX-PE) and BGL (pBGL) cell lysates were significantly higher than the negative control BL21(pGEX-4T) ( P<0.02), and the scavenging rates increased slowly following the increase of the protein content. For the heating samples, except for the 0.2 mg mL-1 BGL (pBGL) products, the scavenging effects of the supernatants of BEX (pGEX-PE) and BGL (pBGL) cell lysates were stronger than that of negative control BL21(pGEX-4T). However, the effect intensity was not positively correlated with the increase of the protein concentration. Though a partially decreased hydroxyl radical scavenging activity was led by heating, the biological activity was still retained and conspicuous. This research showed that phycoerythrin protein expressing in E. coli has the potential medical and sanitarian value.

Variation of a Lightning NOx Indicator for National Climate Assessment

NASA Technical Reports Server (NTRS)

Koshak, William; Vant-Hull, B.; McCaul, E. W.; Peterson, H. S.

2014-01-01

Lightning nitrogen oxides (LNOx) indirectly influences our climate since these molecules are important in controlling the concentration of ozone (O3) and hydroxyl radicals (OH) in the atmosphere [Huntrieser et al., 1998]. In support of the National Climate Assessment (NCA) program, satellite Lightning Imaging Sensor (LIS; Christian et al. [1999]; Cecil et al. [2014]) data is used to estimate LNOx production over the southern portion of the conterminous US for the 16 year period 1998-2013.

Reductive and oxidative degradation of iopamidol, iodinated X-ray contrast media, by Fe(III)-oxalate under UV and visible light treatment.

PubMed

Zhao, Cen; Arroyo-Mora, Luis E; DeCaprio, Anthony P; Sharma, Virender K; Dionysiou, Dionysios D; O'Shea, Kevin E

2014-12-15

Iopamidol, widely employed as iodinated X-ray contrast media (ICM), is readily degraded in a Fe(III)-oxalate photochemical system under UV (350 nm) and visible light (450 nm) irradiation. The degradation is nicely modeled by pseudo first order kinetics. The rates of hydroxyl radical (OH) production for Fe(III)-oxalate/H2O2/UV (350 nm) and Fe(III)-oxalate/H2O2/visible (450 nm) systems were 1.19 ± 0.12 and 0.30 ± 0.01 μM/min, respectively. The steady-state concentration of hydroxyl radical (OH) for the Fe(III)-oxalate/H2O2/UV (350 nm) conditions was 10.88 ± 1.13 × 10(-14) M and 2.7 ± 0.1 × 10(-14) M for the Fe(III)-oxalate/H2O2/visible (450 nm). The rate of superoxide anion radical (O2(-)) production under Fe(III)-oxalate/H2O2/UV (350 nm) was 0.19 ± 0.02 μM/min with a steady-state concentration of 5.43 ± 0.473 × 10(-10) M. Detailed product studies using liquid chromatography coupled to Q-TOF/MS demonstrate both reduction (multiple dehalogenations) and oxidation (aromatic ring and side chains) contribute to the degradation pathways. The reduction processes appear to be initiated by the carbon dioxide anion radical (CO2(-)) while oxidation processes are consistent with OH initiated reaction pathways. Unlike most advanced oxidation processes the Fe(III)-oxalate/H2O2/photochemical system can initiate to both reductive and oxidative degradation processes. The observed reductive dehalogenation is an attractive remediation strategy for halogenated organic compounds as the process can dramatically reduce the formation of the problematic disinfection by-products often associated with oxidative treatment processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Growth, metabolism of Phanerochaete chrysosporium and route of lignin degradation in response to cadmium stress in solid-state fermentation.

PubMed

Zhao, Meihua; Zhang, Chaosheng; Zeng, Guangming; Huang, Danlian; Xu, Piao; Cheng, Min

2015-11-01

This study examines the growth, metabolism of Phanerochaete chrysosporium (P. chrysosporium) and route of lignin degradation in response to cadmium (Cd) stress in solid-state fermentation of rice straw. Less living fungi biomass was found under Cd exposure, suggesting that Cd had strong toxicity to P. chrysosporium. The maximum values of lignin peroxidase and manganese peroxidase were 0.34 and 5.21 U g(-1) at the Cd concentration of 32 mg kg(-1), respectively, lower than that in control, which indicated Cd stress would inhibit ligninolytic enzymes. The production of reactive oxygen species (ROS) including hydroxyl radicals (OH), superoxide anion radical (O2(-)) and hydrogen peroxide (H2O2) increased after Cd exposure. Higher concentration of oxalate was detected at high Cd concentrations. Cd stress also had influence on the rates of lignocelluloses degradation and the route of lignin degradation. Partial Cd could be removed by P. chrysosporium. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

Free radical scavenging abilities of polypeptide from Chlamys farreri

NASA Astrophysics Data System (ADS)

Han, Zhiwu; Chu, Xiao; Liu, Chengjuan; Wang, Yuejun; Mi, Sun; Wang, Chunbo

2006-09-01

We investigated the radical scavenging effect and antioxidation property of polypeptide extracted from Chlamys farreri (PCF) in vitro using chemiluminescence and electron spin resonance (ESR) methods. We examined the scavenging effects of PCF on superoxide anions (O{2/-}), hydroxyl radicals (OH·), peroxynitrite (ONOO-) and the inhibiting capacity of PCF on peroxidation of linoleic acid. Our experiment suggested that PCF could scavenge oxygen free radicals including superoxide anions (O{2/-}) (IC50=0.3 mg/ml), hydroxyl radicals (OH·) (IC50=0.2 μg/ml) generated from the reaction systems and effectively inhibit the oxidative activity of ONOO- (IC50=0.2 mg/ml). At 1.25 mg/ml of PCF, the inhibition ratio on lipid peroxidation of linoleic acid was 43%. The scavenging effect of PCF on O{2/-}, OH· and ONOO- free radicals were stronger than those of vitamin C but less on lipid peroxidation of linoleic acid. Thus PCF could scavenge free radicals and inhibit the peroxidation of linoleic acid in vitro. It is an antioxidant from marine products and potential for industrial production in future.

Protective effect of Rehmannia glutinosa on the cisplatin-induced damage of HEI-OC1 auditory cells through scavenging free radicals.

PubMed

Yu, Hyeon-Hee; Seo, Se-Jeong; Kim, Yeon-Hwa; Lee, Hae-Youn; Park, Rae-Kil; So, Hong-Seob; Jang, Seon Ll; You, Yong-Ouk

2006-10-11

The steamed root of Rehmannia glutinosa has been used in traditional Oriental Medicine for treatment of inner ear diseases, such as tinnitus and hearing loss. In the present study, we showed that the ethanol extract of steamed roots of Rehmannia glutinosa (SRG) protected HEI-OC1 auditory cells from cisplatin cytotoxicity in a dose-dependent fashion. In addition, to investigate the protection mechanism of SRG on cisplatin cytotoxicity towards HEI-OC1, we measured the effects of SRG on lipid peroxidation of cisplatin treated cells as well as scavenging activities against superoxide radical, hydroxyl radical, hydrogen peroxide, and DPPH radical. SRG (5-100 microg/ml) had protective effect against the cisplatin-induced HEI-OC1 cell damage and reduced lipid peroxidation in a dose-dependent manner. Furthermore, SRG showed strong scavenging activity against superoxide radical, hydroxyl radical, hydrogen peroxide, and DPPH radical. These results indicate that SRG protects cisplatin-induced HEI-OC1 cell damage through inhibition of lipid peroxidation and scavenging activities of free radials.

Effect of Molecular Interactions on Electron-Transfer and Antioxidant Activity of Bis(alkanol)selenides: A Radiation Chemical Study.

PubMed

Kumar, Pavitra V; Singh, Beena G; Phadnis, Prasad P; Jain, Vimal K; Priyadarsini, K Indira

2016-08-16

Understanding electron-transfer processes is crucial for developing organoselenium compounds as antioxidants and anti-inflammatory agents. To find new redox-active selenium antioxidants, we have investigated one-electron-transfer reactions between hydroxyl ((.) OH) radical and three bis(alkanol)selenides (SeROH) of varying alkyl chain length, using nanosecond pulse radiolysis. (.) OH radical reacts with SeROH to form radical adduct, which is converted primarily into a dimer radical cation (>Se∴Se<)(+) and α-{bis(hydroxyl alkyl)}-selenomethine radical along with a minor quantity of an intramolecularly stabilized radical cation. Some of these radicals have been subsequently converted to their corresponding selenoxide, and formaldehyde. Estimated yield of these products showed alkyl chain length dependency and correlated well with their antioxidant ability. Quantum chemical calculations suggested that compounds that formed more stable (>Se∴Se<)(+) , produced higher selenoxide and lower formaldehyde. Comparing these results with those for sulfur analogues confirmed for the first time the distinctive role of selenium in making such compounds better antioxidants. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The fate of the hydroxyl radical in the earth's primitive atmosphere and implications for the production of molecular oxygen

NASA Technical Reports Server (NTRS)

Vander Wood, T. B.; Thiemens, M. H.

1980-01-01

Behavior of the hydroxyl radical produced by the photolysis of water vapor in the earth's early atmosphere is examined. Because of the substantial OH radical reactivity with trace species (CO, HCl, SO2, H2S, NH3, and CH4) the formation of molecular oxygen may be prevented, even at a trace species mixing ratio. The photolysis rate of H2O, with corrections for hydrogen exospheric escape, is capable of describing the oxidation of the atmosphere and crust but may not be used to determine the rate of molecular oxygen generation without consideration of the various OH-trace species reactions.

Sulfur Dioxide Accelerates the Heterogeneous Oxidation Rate of Organic Aerosol by Hydroxyl Radicals

DOE PAGES

Richards-Henderson, Nicole K.; Goldstein, Allen H.; Wilson, Kevin R.

2016-03-08

There remains considerable uncertainty in how anthropogenic gas phase emissions alter the oxidative aging of organic aerosols in the troposphere. Here we observe a 10-20 fold acceleration in the effective heterogeneous OH oxidation rate of organic aerosol in the presence of SO 2. This acceleration originates from the radical chain reactions propagated by alkoxy radicals, which are formed efficiently inside the particle by the reaction of peroxy radicals with SO 2. As the OH approaches atmospheric concentrations, the radical chain length increases, transforming the aerosol at rates predicted to be up to 10 times the OH-aerosol collision frequency. Model predictions,more » constrained by experiments over orders of magnitude changes in [OH] and [SO 2], suggest that in polluted regions the heterogeneous processing of organic aerosols by OH ([SO 2] ≥ 40 ppb) occur on similar time scales as analogous gas-phase oxidation reactions. These results provide evidence for a previously unidentified mechanism by which organic aerosol oxidation is enhanced by anthropogenic gas phase emissions. (Chemical Equation Presented).« less

Ozone-mist spray sterilization for pest control in agricultural management

NASA Astrophysics Data System (ADS)

Ebihara, Kenji; Mitsugi, Fumiaki; Ikegami, Tomoaki; Nakamura, Norihito; Hashimoto, Yukio; Yamashita, Yoshitaka; Baba, Seiji; Stryczewska, Henryka D.; Pawlat, Joanna; Teii, Shinriki; Sung, Ta-Lun

2013-02-01

We developed a portable ozone-mist sterilization system to exterminate pests (harmful insects) in agricultural field and greenhouse. The system is composed of an ozone generator, an ozone-mist spray and a small container of ozone gas. The ozone generator can supply highly concentrated ozone using the surface dielectric barrier discharge. Ozone-mist is produced using a developed nozzle system. We studied the effects of ozone-mist spray sterilization on insects and agricultural plants. The sterilization conditions are estimated by monitoring the behavior of aphids and observing the damage of the plants. It was shown that aphids were exterminated in 30 s without noticeable damages of the plant leaves. The reactive radicals with strong oxidation potential such as hydroxyl radical (*OH), hydroperoxide radical (*HO2), the superoxide ion radical (*O2‒) and ozonide radical ion (*O3‒) can increase the sterilization rate for aphids. Contribution to the Topical Issue "13th International Symposium on High Pressure Low Temperature Plasma Chemistry (Hakone XIII)", Edited by Nicolas Gherardi, Henryca Danuta Stryczewska and Yvan Ségui.

Protective effect of D-002, a mixture of beeswax alcohols, against indomethacin-induced gastric ulcers and mechanism of action.

PubMed

Pérez, Yohani; Oyárzabal, Ambar; Mas, Rosa; Molina, Vivian; Jiménez, Sonia

2013-01-01

D-002, a mixture of higher aliphatic beeswax alcohols, produces gastroprotective and antioxidant effects. To investigate the gastroprotective effect of D-002 against indomethacin-induced ulcers, oxidative variables and myeloperoxidase (MPO) activity in the rat gastric mucosa were examined. Rats were randomized into six groups: a negative vehicle control and five indomethacin (50 mg/kg) treated groups, comprising a positive control, three groups treated orally with D-002 (5, 25 and 100 mg/kg) and one group with omeprazole 20 mg/kg intraperitoneally (ip). The contents of malondialdehyde (MDA), protein carbonyl groups (PCG), hydroxyl radical generation and catalase (CAT), glutathione peroxidase (GSH-PX), superoxide dismutase (SOD) and MPO enzyme activities in the rat gastric mucosa were assessed. Indomethacin increased the content of MDA and PCG, the generation of *OH radical and MPO enzyme activity, while it decreased the CAT, GSH-PX and SOD activities as compared to the negative controls. D-002 (5-100 mg/kg) significantly and dose-dependently reduced indomethacin-induced ulceration to 75 %. Also, D-002 decreased the content of MDA and PCG, the generation of hydroxyl radicals and MPO activity as compared to the positive controls. The highest dose of D-002 (100 mg/kg) increased significantly GSH-PX and SOD activities, while all doses used increased CAT activities. Omeprazole 20 mg/kg, the reference drug, reduced significantly the ulcers (93 %), MDA and PCG, the generation of hydroxyl radicals and MPO activity, and increased the CAT, GSH-PX and SOD activities. D-002 treatment produced gastroprotective effects against indomethacin-induced gastric ulceration, which can be related to the reduction of hydroxyl radical generation, lipid peroxidation, protein oxidation and MPO activity, and to the increase of the antioxidant enzymes activities in the rat gastric mucosa.

Modelling On Photogeneration Of Hydroxyl Radical In Surface Waters And Its Reactivity Towards Pharmaceutical Wastes

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

Das, Radha; Dipartimento di Chimica Analitica, Universita degli Studi di Torino, Via Pietro Giuria 5, Torino; Vione, Davide

2010-10-26

This paper reports a simple model to describe the formation and reactivity of hydroxyl radicals in the whole column of freshwater lakes. It is based on empirical irradiation data and is a function of the water chemical composition (the photochemically significant parameters NPOC, nitrate, nitrite, carbonate and bicarbonate), the lake conformation best expressed as the average depth, and the water absorption spectrum in a simplified Lambert-Beer approach. The purpose is to derive the lifetime of dissolved molecules, due to reaction with OH, on the basis of their second-order rate constants with the hydroxyl radical. The model was applied to twomore » compounds of pharmaceutical wastes ibuprofen and carbamazepine, for which the second-order rate constants for reaction with the hydroxyl radical were measured by means of the competition kinetics with 2-propanol. The measured values of the rate constants are 1.0x10{sup 10} and 1.6x10{sup 10} M{sup -1} s{sup -1} for ibuprofen and carbamazepine, respectively. The model suggests that the lifetime of a given compound can be very variable in different lakes, even more than the lifetime of different compounds in the same lake. It can be concluded that as far as the reaction with OH, is concerned the concepts of photolability and photostability, traditionally attached to definite compounds, are ecosystem-dependent at least as much as they depend on the molecule under consideration.« less

Comparison of the Composition and Antioxidant Activities of Phenolics from the Fruiting Bodies of Cultivated Asian Culinary-Medicinal Mushrooms.

PubMed

Lin, Shaoling; Ching, Lai Tsz; Ke, Xinxin; Cheung, Peter Chi Keung

2016-01-01

The composition profile and the antioxidant properties of phenolics in water extracts obtained from the fresh fruiting bodies of 4 common cultivated Asian edible mushrooms-Agrocybe aegerita, Pleurotus ostreatus, P. eryngii, and Pholiota nameko were compared. The water extract from A. aegerita (AaE) had the highest total phenolic content (TPC) at 54.18 ± 0.27 gallic acid equivalents (μmol/L)/mg extract (P < 0.05), as measured by the Folin-Ciocalteu method, and consisted of the largest number (including gallic acid, protocatechuic acid, chlorogenic acid, ferulic acid, and sinapic acid) and total amounts of phenolic acids identified by Fourier transform-ion cyclotron resonance mass spectrometry. The water extract of Ph. nameko was found to have the second-highest TPC (43.55 ± 0.10 gallic acid equivalents [μmol/L]/mg extract), followed by the water extract of P. eryngii and the water extract of P. ostreatus (39.55 ± 0.25 and 39.02 ± 0.30 gallic acid equivalents/mg extract, respectively). The scavenging activities of the water extracts from these mushrooms were evaluated against 2,2-diphenyl-l-(2,4,6-trinitrophenyl) hydrazyl diphenylpicrylhydrazyl (DPPH), superoxide anion radicals, hydroxyl radicals, and hydrogen peroxide. Based on halfmaximal effective concentrations, AaE was more effective in scavenging hydrogen peroxide (<0.05), followed by DPPH (0.51 mg/mL), superoxide anion radicals (0.85 mg/mL) and hydroxyl radicals (5.94 mg/mL), then the other mushroom water extracts. The differences in the half-maximal effective concentrations of individual mushroom water extracts were probably the result of the different numbers and amounts of individual phenolic acids in the extracts. The antioxidant activities of the mushroom water extracts were correlated with their TPC. The strongest antioxidant properties of AaE were consistent with its highest TPC and with the largest number and amount of phenolics identified in the extract. These results indicated that cultivated edible mushrooms could be a potential source of natural antioxidants with free radical scavenging properties for application as a functional food ingredient.

Antioxidant and prooxidant effects of polyphenol compounds on copper-mediated DNA damage.

PubMed

Perron, Nathan R; García, Carla R; Pinzón, Julio R; Chaur, Manuel N; Brumaghim, Julia L

2011-05-01

Inhibition of copper-mediated DNA damage has been determined for several polyphenol compounds. The 50% inhibition concentration values (IC(50)) for most of the tested polyphenols are between 8 and 480 μM for copper-mediated DNA damage prevention. Although most tested polyphenols were antioxidants under these conditions, they generally inhibited Cu(I)-mediated DNA damage less effectively than Fe(II)-mediated damage, and some polyphenols also displayed prooxidant activity. Because semiquinone radicals and hydroxyl radical adducts were detected by EPR spectroscopy in solutions of polyphenols, Cu(I), and H(2)O(2), it is likely that weak polyphenol-Cu(I) interactions permit a redox-cycling mechanism, whereby the necessary reactants to cause DNA damage (Cu(I), H(2)O(2), and reducing agents) are regenerated. The polyphenol compounds that prevent copper-mediated DNA damage likely follow a radical scavenging pathway as determined by EPR spectroscopy. Copyright © 2011 Elsevier Inc. All rights reserved.

Experimental and theoretical study on chemical reactions and species diffusion by a nano-pulse discharged bubble for water treatment

NASA Astrophysics Data System (ADS)

He, Yuchen; Uehara, Satoshi; Takana, Hidemasa; Nishiyama, Hideya

2018-01-01

Advanced oxidation processes using hydroxyl radicals (ṡOH) generated inside bubbles in water has drawn widely interest for the high oxidation potential of OH radical to decompose persistent organic pollutants such as dioxins and humic acid for water purification. In this study, a two-dimensional diffusion model for a nano-pulse discharged bubble in water is established. Based on the experimental results of streamer propagation inside a bubble, the diffusion processes around the bubble interface and reactions of chemical species in liquids are simulated. The simulation results show that OH radicals can diffuse only several micrometers away from the bubble interface in water. Furthermore, the optimal operating voltage and frequency conditions for OH generation is obtained by comparing the OH concentration in water obtained from numerical simulation with that measured by spectroscopy in experiment.

Radiolysis of paracetamol in dilute aqueous solution

NASA Astrophysics Data System (ADS)

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

2012-09-01

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

Hydroxyl Radical Modification of Collagen Type II Increases Its Arthritogenicity and Immunogenicity

PubMed Central

Shahab, Uzma; Ahmad, Saheem; Moinuddin; Dixit, Kiran; Habib, Safia; Alam, Khursheed; Ali, Asif

2012-01-01

Background The oxidation of proteins by endogenously generated free radicals causes structural modifications in the molecules that lead to generation of neo-antigenic epitopes that have implications in various autoimmune disorders, including rheumatoid arthritis (RA). Collagen induced arthritis (CIA) in rodents (rats and mice) is an accepted experimental model for RA. Methodology/Principal Findings Hydroxyl radicals were generated by the Fenton reaction. Collagen type II (CII) was modified by •OH radical (CII-OH) and analysed by ultraviolet-visible (UV-VIS), fluorescence and circular dichroism (CD) spectroscopy. The immunogenicity of native and modified CII was checked in female Lewis rats and specificity of the induced antibodies was ascertained by enzyme linked immunosorbent assay (ELISA). The extent of CIA was evaluated by visual inspection. We also estimated the oxidative and inflammatory markers in the sera of immunized rats. A slight change in the triple helical structure of CII as well as fragmentation was observed after hydroxyl radical modification. The modified CII was found to be highly arthritogenic and immunogenic as compared to the native form. The CII-OH immunized rats exhibited increased oxidative stress and inflammation as compared to the CII immunized rats in the control group. Conclusions/Significance Neo-antigenic epitopes were generated on •OH modified CII which rendered it highly immunogenic and arthritogenic as compared to the unmodified form. Since the rodent CIA model shares many features with human RA, these results illuminate the role of free radicals in human RA. PMID:22319617

Reaction Mechanisms and Structural and Physicochemical Properties of Caffeic Acid Grafted Chitosan Synthesized in Ascorbic Acid and Hydroxyl Peroxide Redox System.

PubMed

Liu, Jun; Pu, Huimin; Chen, Chong; Liu, Yunpeng; Bai, Ruyu; Kan, Juan; Jin, Changhai

2018-01-10

The ascorbic acid (AA) and hydroxyl peroxide (H 2 O 2 ) redox pair induced free radical grafting reaction is a promising approach to conjugate phenolic groups with chitosan (CS). In order to reveal the exact mechanisms of the AA/H 2 O 2 redox pair induced grafting reaction, free radicals generated in the AA/H 2 O 2 redox system were compared with hydroxyl radical ( • OH) produced in the Fe 2+ /H 2 O 2 redox system. Moreover, the structural and physicochemical properties of caffeic acid grafted CS (CA-g-CS) synthesized in these two redox systems were compared. Results showed that only ascorbate radical (Asc •- ) was produced in the AA/H 2 O 2 system. The reaction between Asc •- and CS produced novel carbon-centered radicals, whereas no new free radicals were detected when • OH reacted with CS. Thin layer chromatography, UV-vis, Fourier transform infrared, and nuclear magnetic resonance spectroscopic analyses all confirmed that CA was successfully grafted onto CS through Asc •- . However, CA could be hardly grafted onto CS via • OH. CA-g-CS synthesized through Asc •- exhibited lower thermal stability and crystallinity than the reaction product obtained through • OH. For the first time, our results demonstrated that the synthesis of CA-g-CS in the AA/H 2 O 2 redox system was mediated by Asc •- rather than • OH.

Hydroxyl radical generation by photosystem II.

PubMed

Pospísil, Pavel; Arató, András; Krieger-Liszkay, Anja; Rutherford, A William

2004-06-01

The photogeneration of hydroxyl radicals (OH(*)) in photosystem II (PSII) membranes was studied using EPR spin-trapping spectroscopy. Two kinetically distinguishable phases in the formation of the spin trap-hydroxyl (POBN-OH) adduct EPR signal were observed: the first phase (t(1/2) = 7.5 min) and the second phase (t(1/2) = 30 min). The generation of OH(*) was found to be suppressed in the absence of the Mn-complex, but it was restored after readdition of an artificial electron donor (DPC). Hydroxyl radical generation was also lost in the absence of oxygen, whereas it was stimulated when the oxygen concentration was increased. The production of OH(*) during the first kinetic phase was sensitive to the presence of SOD, whereas catalase and EDTA diminished the production of OH(*) during the second kinetic phase. The POBN-OH adduct EPR signal during the first phase exhibits a similar pH-dependence as the ability to oxidize the non-heme iron, as monitored by the Fe(3+) (g = 8) EPR signal: both EPR signals gradually decreased as the pH value was lowered below pH 6.5 and were absent at pH 5. Sodium formate decreases the production of OH(*) in intact and Mn-deleted PSII membranes. Upon illumination of PSII membranes, both superoxide, as measured by EPR signal from the spin trap-superoxide (EMPO-OOH) adduct, and H(2)O(2), measured colormetrically, were generated. These results indicated that OH(*) is produced on the electron acceptor side of PSII by two different routes, (1) O(2)(*)(-), which is generated by oxygen reduction on the acceptor side of PSII, interacts with a PSII metal center, probably the non-heme iron, to form an iron-peroxide species that is further reduced to OH(*) by an electron from PSII, presumably via Q(A)(-), and (2) O(2)(*)(-) dismutates to form free H(2)O(2) that is then reduced to OH(*) via the Fenton reaction in the presence of metal ions, the most likely being Mn(2+) and Fe(2+) released from photodamaged PSII. The two different routes of OH(*) generation are discussed in the context of photoinhibition.

Fluorescent Carbon Dots Derived from Maillard Reaction Products: Their Properties, Biodistribution, Cytotoxicity, and Antioxidant Activity.

PubMed

Li, Dongmei; Na, Xiaokang; Wang, Haitao; Xie, Yisha; Cong, Shuang; Song, Yukun; Xu, Xianbing; Zhu, Bei-Wei; Tan, Mingqian

2018-02-14

Food-borne nanoparticles have received great attention because of their unique physicochemical properties and potential health risk. In this study, carbon dots (CDs) formed during one of the most important chemical reactions in the food processing field, the Maillard reaction from the model system including glucose and lysine, were investigated. The CDs purified from Maillard reaction products emitted a strong blue fluorescence under ultraviolet light with a fluorescent quantum yield of 16.30%. In addition, they were roughly spherical, with sizes of around 4.3 nm, and mainly composed of carbon, oxygen, hydrogen, and nitrogen. Their surface groups such as hydroxyl, amino, and carboxyl groups were found to possibly enable CDs to scavenge DPPH and hydroxyl radicals. Furthermore, the cytotoxicity assessment of CDs showed that they could readily enter HepG2 cells while causing negligible cell death at low concentration. However, high CDs concentrations were highly cytotoxic and led to cell death via interference of the glycolytic pathway.

Effect of Oxygen Gas on the Decomposition of Dye by Pulsed Discharge in Water Droplet Spray

NASA Astrophysics Data System (ADS)

Nose, Taisuke; Yokoyama, Yuzo; Nakamura, Akira; Minamitani, Yasushi

Effect of O2 on the decolorization of indigo carmine and on the production of dissolved species such as NO2-, NO3-, O3 and H2O2 in the treatment water by pulsed discharge in water droplet spray was investigated by controlling the O2/N2 ratios as carrier gases in the reactor. The decolorization rate gradually increased with rise in O2 ratio, which reached a constant value in the range of 50% to 90% O2 ratio and decreased in pure O2. The maximum value was about 2 times as high as that of 20% O2 ratio. The decolorization efficiency was not affected by gas flow rate in the range of 4 L/min to 50 L/min. NO2- in the treatment water was only detected in pure N2, but NO3- was produced in O2/N2. NO2- added to the treatment water was not oxidized in pure N2, but was perfectly converted to NO3- in O2/N2. These results implied that hydroxyl radical produced in gas phase does not directly contribute to the oxidation of substances in water. O3 concentration gradually increased with rise in O2 ratio, whereas H2O2 concentration decreased. In the range of 50 to 80% O2 ratio, O3 and H2O2 concentrations were approximately constant value, similar to the trend of decolorization rate. Moreover rate constants on various gas mixing ratio of O2/N2 were determined from the kinetics study. These results suggested that hydroxyl radical produced in the treatment water by the chain reactions of O3 and hydroperoxy radical (HO2·) plays an important role of the decomposition of molecules in water.

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.

Hydroxyl radical observations during the wintertime in Beijing and comparison with steady state model calculations.

NASA Astrophysics Data System (ADS)

Slater, E.; Whalley, L.; Woodward-Massey, R.; Ye, C.; Crilley, L.; Kramer, L. J.; Vu, T.; Bloss, W.; Squires, F. A.; Dunmore, R.; Lee, J. D.; Heard, D. E.

2017-12-01

In Beijing poor urban air quality has a demonstrable effect on human health. During the wintertime, anthropogenic emissions from fossil fuel combustion can lead to high aerosol loadings and haze events. A high oxidation capacity on hazy days has previously been inferred from the significant contribution secondary organic aerosol (SOA) make to total PM2.5 (Huang et al., 2014). The hydroxyl radical (OH) mediates virtually all of the oxidative chemistry in the atmosphere, being responsible for the transformation of primary emissions into secondary pollutants such as NO2, O3 and SOA. Understanding the sources and sinks of OH in the atmosphere is essential in improving predictions of the lifetimes and chemical processing of pollutants and their transport within urban areas. We will present OH and HO2 measurements made in central Beijing during the recent `An Integrated Study of AIR Pollution PROcesses in Beijing (AIRPRO)' project which took place in November and December 2016. OH measurements were made using the FAGE (Fluorescence Assay by Gas Expansion) technique, with the use of an inlet pre injector (IPI) which provides an alternative method to determine the background by injecting a scavenger (propane) to remove ambient OH. The OH measurements were made over a range of meteorological conditions including a number of haze days, with the average maximum OH concentration measured for the campaign being 2.5 x 106 cm-3 and for haze days the OH concentration reached levels of 3.5 x 106 cm-3 which is comparable to OH levels in non-haze days. We will compare the OH observations to steady state calculations constrained to the total OH reactivity and key OH precursors that were measured alongside OH. Through this comparison we will identify the major OH sources which sustain the wintertime oxidation capacity. The current understanding is that gas-phase oxidation via the OH radical becomes less important in haze events due to lower light and ozone levels, making photochemistry less important (Wang et al.,(2016). However, we will present evidence by comparing the dependence of the OH radical concentrations with PM2.5 levels that the OH concentration persists throughout haze events, and that there may be a missing source of HOx under haze conditions. This finding implies an uncertainty in oxidation capacity during haze events.

Antioxidation activities of low-molecular-weight gelatin hydrolysate isolated from the sea cucumber Stichopus japonicus

NASA Astrophysics Data System (ADS)

Wang, Jingfeng; Wang, Yuming; Tang, Qingjuan; Wang, Yi; Chang, Yaoguang; Zhao, Qin; Xue, Changhu

2010-03-01

Gelatin extracted from the body wall of the sea cucumber ( Stichopus japonicus) was hydrolyzed with flavourzyme. Low-molecular-weight gelatin hydrolysate (LMW-GH) of 700-1700 Da was produced using an ultrafiltration membrane bioreactor system. Chemiluminescence analysis revealed that LMW-GH scavenges high free radicals in a concentration-dependent manner; IC50 value for superoxide and hydroxyl radicals was 442 and 285 μg mL-1, respectively. LMW-GH exhibited excellent inhibitory characteristics against melanin synthesis and tyrosinase activity in B16 cells. Furthermore, LMW-GH notably increased intracellular glutathione (GSH), which in turn suppressed melanogenesis. LMW-GH performs antioxidation activity, holding the potential of being used as a valuable ingredient in function foods, cosmetics and pharmaceuticals or nutriceuticals.

Antioxidant activity and oxidative stress protection of duck proteins hydrolysates in SK-N-SH cells.

PubMed

Guo, Yuxing; Pan, Daodong; Wu, Zhen; Zhao, Chuanchuan; Cao, Jinxuan

2013-02-26

Studies have found that natural antioxidants, which are free-radical scavengers, can reduce the risk of diseases caused by free radicals. This work investigated the antioxidant properties of duck proteins hydrolysates. The free-radical scavenging function of CP-1 (M(r) > 10 kDa), CP-2 (5 kDa < M(r) < 10 kDa) and CP-3 (M(r) < 5 kDa), obtained through ultrafiltration and gel filtration were evaluated. The results showed that the lower molecular weight fraction exhibited a stronger free-radical scavenging ability. The highest free-radical scavenging activity was detected in the fraction of p4 purified from CP-3 using Sephadex G-15 column chromatography. The 50% inhibitory value (IC(50)) of p4 for scavenging radicals of superoxide, hydroxyl and 1,1-diphenyl-2-pycrylhydrazyl (DPPH) were, respectively, 0.97 mg mL(-1), 0.84 mg mL(-1) and 1.84 mg mL(-1). Furthermore, the p4 fraction at a concentration of 10 μg mL(-1) increased cell viability from 84.8% to 94% under antioxidative stress in neuroblastoma SK-N-SH cells.

Assessment of antioxidant potential, total phenolics and flavonoids of different solvent fractions of monotheca buxifolia fruit.

PubMed

Jan, Shumaila; Khan, Muhammad Rashid; Rashid, Umbreen; Bokhari, Jasia

2013-10-01

This study was conducted to investigate the antioxidant potential of methanol extract and its derived fractions (hexane, ethyl acetate, butanol, and aqueous) of fruits of Monotheca buxifolia (Falc.) Dc., a locally used fruit in Pakistan. Dried powder of the fruit of M. buxifolia was extracted with methanol and the resultant was fractionated with solvents having escalating polarity; n-hexane, chloroform, ethyl acetate, n-butanol and the residual soluble aqueous fraction. Total phenolic and total flavonoid contents were estimated for the methanol and various fractions. These fractions were also subjected to various in vitro assays to estimate the scavenging activity for 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), superoxide, hydroxyl, hydrogen peroxide and reductive ability for ferric ions and phosphomolybdate assay. The n-butanol, aqueous and methanol fractions possessed high amount of phenolics and flavonoids compared with other fractions, and subsequently showed a pronounced scavenging activity on DPPH, ABTS, superoxide, hydroxyl and hydrogen peroxide radicals and had a potent reductive ability on ferric ion and phosphomolybdate assay. There was a found significant correlation between total phenolic and flavonoid contents and EC50 of DPPH, superoxide, hydrogen peroxide radical and phosphomolybdate assays, whereas a nonsignificant correlation was found with the hydroxyl radical and ABTS radical assay. M. buxifolia fruit can be used as natural antioxidant source to prevent damage associated with free radicals.

Spectroscopic studies on the antioxidant activity of p-coumaric acid

NASA Astrophysics Data System (ADS)

Kiliç, Ismail; Yeşiloğlu, Yeşim

2013-11-01

p-coumaric acid (4-hydroxycinnamic acid), a phenolic acid, is a hydroxyl derivative of cinnamic acid. It decreases low density lipoprotein (LDL) peroxidation and reduces the risk of stomach cancer. In vitro radical scavenging and antioxidant capacity of p-coumaric acid were clarified using different analytical methodologies such as total antioxidant activity determination by ferric thiocyanate, hydrogen peroxide scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging, 2,2‧-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) radical scavenging activity and superoxide anion radical scavenging, ferrous ions (Fe2+) chelating activity and ferric ions (Fe3+) reducing ability. p-Coumaric acid inhibited 71.2% lipid peroxidation of a linoleic acid emulsion at 45 μg/mL concentration. On the other hand, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), α-tocopherol and ascorbic acid displayed 66.8%, 69.8%, 64.5% and 59.7% inhibition on the peroxidation of linoleic acid emulsion at the same concentration, respectively. In addition, p-coumaric acid had an effective DPPHrad scavenging, ABTSrad + scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, ferric ions (Fe3+) reducing power and ferrous ions (Fe2+) chelating activities. Also, those various antioxidant activities were compared to BHA, BHT, α-tocopherol and ascorbic acid as references antioxidant compounds. These results suggested that p-coumaric acid can be used in the pharmacological and food industry because of these properties.

Evaluation of the ability of Eleutherine americana crude extract as natural food additive in cooked pork.

PubMed

Ifesan, B O T; Siripongvutikorn, S; Hutadilok-Towatana, N; Voravuthikunchai, S P

2009-09-01

The scavenging activities of crude ethanolic extract from Eleutherine americana, on 2,2-diphenyl-1-picrylhydrazyl (DPPH) and hydroxyl free radicals were investigated. The results revealed that the extract produced IC(50) values of 8.4 microg/mL and 0.78 mg/mL on DPPH and hydroxyl free radicals, respectively. The total phenolic content of the extract was determined using the Folin-Ciocalteu reagent and the crude extract yielded high phenolic content of 4.56 mumol gallic acid equivalent per milligram dried extract. The extract, at different concentrations, was incorporated into pork, cooked in the microwave, and stored at 4 degrees C for 9 d. The crude extract demonstrated antioxidant activity, which increases with increased extract concentrations and retarded lipid oxidation in the cooked pork. Antibacterial activity of the extract against Staphylococcus aureus in the cooked pork revealed that at a concentration of 10.8 mg/100 g, the extract reduced the bacterial population by 0.57 log compared to control at 9 d of storage. The sensory results revealed that the pork samples treated with the extract and the control sample were not significantly different from day 0 to 6; however, on day 9 the treatments were significantly scored higher than the control. Furthermore, addition of the extract led to an increase in the redness values of the pork and this was acceptable from the sensory point of view. E. americana crude extract could be a promising novel antioxidant to prevent lipid oxidation and a potential natural color enhancer of red meat and meat products.

A model of CO-CH4 global transport/chemistry. I - Chemistry model

NASA Technical Reports Server (NTRS)

Peters, L. K.; Kitada, T.

1980-01-01

A simplified chemistry model was developed to incorporate the CO-CH4 chemistry into the global transport model of these compounds. CO is important because of its effects on atmospheric chemistry and is partly responsible for controlling the hydroxyl radical (OH) concentration in the troposphere. The model includes the photodissociation rate coefficients expressed as functions of solar zenith angle and altitude, and it was applied to determine the sensitivity of the OH concentration to trace gaseous species, such as NOx, O3, and H2O. Also, the concentrations and diurnal variations of OH and HO2, and the contribution of individual reactions to OH generation and consumption were calculated.

The temperature dependence of the rate constant for the reaction of hydroxyl radicals with nitric acid

NASA Technical Reports Server (NTRS)

Kurylo, M. J.; Cornett, K. D.; Murphy, J. L.

1982-01-01

The rate constant for the reaction of hydroxyl radicals with nitric acid in the 225-443 K temperature range has been measured by means of the flash photolysis resonance fluorescence technique. Above 300 K, the rate constant levels off in a way that can only be explained by the occurrence of two reaction channels, of which one, operative at low temperatures, proceeds through the formation of an adduct intermediate. The implications of these rate constant values for stratospheric reaction constants is discussed.

Hemoglobin detection using carbon dots as a fluorescence probe.

PubMed

Barati, Ali; Shamsipur, Mojtaba; Abdollahi, Hamid

2015-09-15

Herein, we have described the application of high fluorescent carbon dots (CDs) without any surface modification as a simple and fast responding fluorescence probe for sensitive and selective determination of hemoglobin (Hb) in the presence of H2O2. Although Hb itself was able to quench the fluorescence of CDs, based on the inner filter effect (IFE) of the protein that affects both excitation and emission spectra of CDs, the presence of H2O2 resulted in further improvement of the sensitivity of Hb detection. The assay is based on the reaction of Hb with H2O2 that generates reactive oxygen species including hydroxyl (OH•) and superoxide (O2(•-)) radicals under heme degradation and/or iron release from Hb and the subsequent reaction of hydroxyl radicals, as strong oxidizing agents, with CDs resulting in high fluorescence quenching. The proposed probe was used for determination of Hb in concentration range of 1-100 nM with a detection limit of 0.4 nM. The method was successfully applied to the determination of Hb in human blood samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Remote monitoring of emission activity level from NPP using radiofrequencies 1420, 1665, 1667 MHz in real time.

PubMed

Kolotkov, Gennady; Penin, Sergei

2013-01-01

The Fukushima nuclear accident showed the importance of timely monitoring and detection of radioactive emissions released from enterprises of the nuclear fuel cycle. Nuclear power plants (NPP) working continuously are a stationary source of gas-aerosol emissions which presented in a ground surface layer persistently. Following radioactive emission, untypical effects can be observed, for example: the occurrences of areas with increased ionization, and increased concentration of some gases caused by photochemical reactions. The gases themselves and their characteristic radiation can be markers of radioactivity and can be monitored by a passive method. Hydrogen atom (H) and hydroxyl radical (OH) are formed in a radioactive plume by radiolysis of water molecules and other hydrogen-containing air components by the high energy electrons from beta-decay of radionuclides. The hydrogen atom and hydroxyl radical can spontaneously radiate at 1420 MHz and 1665-1667 MHz respectively. The passive method of remote monitoring of radiation levels using radio-frequencies of H and OH from radioactive emissions of NPP is described. The model data is indicative of the monitoring of radiation levels using these frequencies. Crown Copyright © 2012. Published by Elsevier Ltd. All rights reserved.

Study of photocatalytic degradation of tributyltin, dibutylin and monobutyltin in water and marine sediments.

PubMed

Brosillon, Stephan; Bancon-Montigny, Chrystelle; Mendret, Julie

2014-08-01

This study reports on the first assessment of the treatment of sediments contaminated by organotin compounds using heterogeneous photocatalysis. Photocatalysis of organotins in water was carried out under realistic concentration conditions (μgL(-1)). Degradation compounds were analyzed by GC-ICP-MS; a quasi-complete degradation of tributyltin (TBT) in water (99.8%) was achieved after 30min of photocatalytic treatment. The degradation by photolysis was about (10%) in the same conditions. For the first time decontamination of highly polluted marine sediments (certified reference material and harbor sediments) by photocatalysis proves that the use of UV and the production of hydroxyl radicals are an efficient way to treat organotins adsorbed onto marine sediment despite the complexity of the matrix. In sediment, TBT degradation yield ranged from 32% to 37% after only 2h of irradiation (TiO2-UV) and the by-products: dibutyltin (DBT) and monobutyltin (MBT) were degraded very rapidly in comparison with TBT. It was shown that during photocatalysis of organotins in sediments, the hydroxyl radical attack and photolysis are the two ways for the degradation of adsorbed TBT. Copyright © 2014 Elsevier Ltd. All rights reserved.

Decomposition of gas-phase trichloroethene by the UV/TiO2 process in the presence of ozone.

PubMed

Shen, Y S; Ku, Y

2002-01-01

The decomposition of gas-phase trichloroethene (TCE) in air streams by direct photolysis, the UV/TiO2 and UV/O3 processes was studied. The experiments were carried out under various UV light intensities and wavelengths, ozone dosages, and initial concentrations of TCE to investigate and compare the removal efficiency of the pollutant. For UV/TiO2 process, the individual contribution to the decomposition of TCE by direct photolysis and hydroxyl radicals destruction was differentiated to discuss the quantum efficiency with 254 and 365 nm UV lamps. The removal of gaseous TCE was found to reduce by UV/TiO2 process in the presence of ozone possibly because of the ozone molecules could scavenge hydroxyl radicals produced from the excitation of TiO2 by UV radiation to inhibit the decomposition of TCE. A photoreactor design equation for the decomposition of gaseous TCE by the UV/TiO2 process in air streams was developed by combining the continuity equation of the pollutant and the surface catalysis reaction rate expression. By the proposed design scheme, the temporal distribution of TCE at various operation conditions by the UV/TiO2 process can be well modeled.

ROS production in homogenate from the body wall of sea cucumber Stichopus japonicus under UVA irradiation: ESR spin-trapping study.

PubMed

Qi, Hang; Dong, Xiu-fang; Zhao, Ya-ping; Li, Nan; Fu, Hui; Feng, Ding-ding; Liu, Li; Yu, Chen-xu

2016-02-01

Sea cucumber Stichopus japonicus (S. japonicus) shows a strong ability of autolysis, which leads to severe deterioration in sea cucumber quality during processing and storage. In this study, to further characterize the mechanism of sea cucumber autolysis, hydroxyl radical production induced by ultraviolet A (UVA) irradiation was investigated. Homogenate from the body wall of S. japonicas was prepared and subjected to UVA irradiation at room temperature. Electron Spin Resonance (ESR) spectra of the treated samples were subsequently recorded. The results showed that hydroxyl radicals (OH) became more abundant while the time of UVA treatment and the homogenate concentration were increased. Addition of superoxide dismutase (SOD), catalase, EDTA, desferal, NaN3 and D2O to the homogenate samples led to different degrees of inhibition on OH production. Metal cations and pH also showed different effects on OH production. These results indicated that OH was produced in the homogenate with a possible pathway as follows: O2(-) → H2O2 → OH, suggesting that OH might be a critical factor in UVA-induced S. japonicus autolysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

What makes a natural clay antibacterial?

USGS Publications Warehouse

Williams, Lynda B.; Metge, David W.; Eberl, Dennis D.; Harvey, Ronald W.; Turner, Amanda G.; Prapaipong, Panjai; Port-Peterson, Amisha T.

2011-01-01

Chemical analyses of E. coli killed by aqueous leachates of an antibacterial clay show that intracellular concentrations of Fe and P are elevated relative to controls. Phosphorus uptake by the cells supports a regulatory role of polyphosphate or phospholipids in controlling Fe2+. Fenton reaction products can degrade critical cell components, but we deduce that extracellular processes do not cause cell death. Rather, Fe2+ overwhelms outer membrane regulatory proteins and is oxidized when it enters the cell, precipitating Fe3+ and producing lethal hydroxyl radicals.

Hydroxyl radicals' production and ECG parameters during ischemia and reperfusion in rat, guinea pig and rabbit isolated heart.

PubMed

Paulova, Hana; Stracina, Tibor; Jarkovsky, Jiri; Novakova, Marie; Taborska, Eva

2013-06-01

Ischemic and reperfusion injury is a serious condition related to numerous biochemical and electrical abnormalities of the myocardium. It has been repeatedly studied in various animal models. In this study, the production of hydroxyl radicals and electrophysiological parameters were compared in three species. Rat, guinea pig and rabbit isolated hearts were perfused according to Langendorff under strictly identical conditions. The heart rate and arrhythmia were monitored during ischemia and reperfusion periods at defined time intervals; the production of hydroxyl radical was determined by HPLC as 2.5-dihydroxybenzoic acid (2.5-DHBA) formed by salicylic acid hydroxylation. Relationship between arrhythmias and production of 2.5-DHBA was studied. The inter-species differences were observed in timing of arrhythmias onset and their severity, and in the production of 2.5-DHBA in both ischemia and reperfusion. The most considerable changes were observed in rats, where arrhythmias appeared early and with highest severity during ischemia on one side and the regular rhythm was restored early and completely during reperfusion. The corresponding changes in the production of 2.5-DHBA were observed. It can be concluded that rat isolated heart is the most suitable model for evaluation of ischemia/reperfusion injury under given experimental conditions.

Analytical chemical kinetic investigation of the effects of oxygen, hydrogen, and hydroxyl radicals on hydrogen-air combustion

NASA Technical Reports Server (NTRS)

Carson, G. T., Jr.

1974-01-01

Quantitative values were computed which show the effects of the presence of small amounts of oxygen, hydrogen, and hydroxyl radicals on the finite-rate chemical kinetics of premixed hydrogen-air mixtures undergoing isobaric autoignition and combustion. The free radicals were considered to be initially present in hydrogen-air mixtures at equivalence ratios of 0.2, 0.6, 1.0, and 1.2. Initial mixture temperatures were 1100 K, 1200 K, and 1500 K, and pressures were 0.5, 1.0, 2.0, and 4.0 atm. Of the radicals investigated, atomic oxygen was found to be the most effective for reducing induction time, defined as the time to 5 percent of the total combustion temperature rise. The reaction time, the time between 5 percent and 95 percent of the temperature rise, is not decreased by the presence of free radicals in the initial hydrogen-air mixture. Fuel additives which yield free radicals might be used to effect a compact supersonic combustor design for efficient operation in an otherwise reaction-limited combustion regime.

Degradation of lipid regulators by the UV/chlorine process: Radical mechanisms, chlorine oxide radical (ClO•)-mediated transformation pathways and toxicity changes.

PubMed

Kong, Xiujuan; Wu, Zihao; Ren, Ziran; Guo, Kaiheng; Hou, Shaodong; Hua, Zhechao; Li, Xuchun; Fang, Jingyun

2018-06-15

Degradation of three lipid regulators, i.e., gemfibrozil, bezafibrate and clofibric acid, by a UV/chlorine treatment was systematically investigated. The chlorine oxide radical (ClO • ) played an important role in the degradation of gemfibrozil and bezafibrate with second-order rate constants of 4.2 (±0.3) × 10 8  M -1  s -1 and 3.6 (±0.1) × 10 7  M -1  s -1 , respectively, whereas UV photolysis and the hydroxyl radical (HO • ) mainly contributed to the degradation of clofibric acid. The first-order rate constants (k') for the degradation of gemfibrozil and bezafibrate increased linearly with increasing chlorine dosage, primarily due to the linear increase in the ClO • concentration. The k' values for gemfibrozil, bezafibrate, and clofibric acid degradation decreased with increasing pH from 5.0 to 8.4; however, the contribution of the reactive chlorine species (RCS) increased. Degradation of gemfibrozil and bezafibrate was enhanced in the presence of Br - , whereas it was inhibited in the presence of natural organic matter (NOM). The presence of ammonia at a chlorine: ammonia molar ratio of 1:1 resulted in decreases in the k' values for gemfibrozil and bezafibrate of 69.7% and 7%, respectively, but led to an increase in that for clofibric acid of 61.8%. Degradation of gemfibrozil by ClO • was initiated by hydroxylation and chlorine substitution on the benzene ring. Then, subsequent hydroxylation, bond cleavage and chlorination reactions led to the formation of more stable products. Three chlorinated intermediates were identified during ClO • oxidation process. Formation of the chlorinated disinfection by-products chloral hydrate and 1,1,1-trichloropropanone was enhanced relative to that of other by-products. The acute toxicity of gemfibrozil to Vibrio fischeri increased significantly when subjected to direct UV photolysis, whereas it decreased when oxidized by ClO • . This study is the first to report the transformation pathway of a micropollutant by ClO • . Copyright © 2018 Elsevier Ltd. All rights reserved.

Characterization and Neutralization of Recovered Lewisite Munitions

DTIC Science & Technology

2006-12-01

chlorine being rated as 1.0.51 Oxidative Species Relative Oxidizing Strength* Fluorine 2.23 Hydroxyl Radical 2.06 Atomic Oxygen 1.78 Hydrogen...containing carbon-carbon double bonds, aldehyde groups or hydroxyl groups. As an electrophile , the permnanganate ion is strongly attracted to the electrons

Chemisorption of hydrogen atoms and hydroxyl groups on stretched graphene: A coupled QM/QM study

NASA Astrophysics Data System (ADS)

Katin, Konstantin P.; Prudkovskiy, Vladimir S.; Maslov, Mikhail M.

2017-09-01

Using the density functional theory coupled with the nonorthogonal tight-binding model, we analyze the chemisorption of hydrogen atoms and hydroxyl groups on the unstrained and stretched graphene sheets. Drawback of finite cluster model of graphene for the chemisorption energy calculation in comparison with the QM/QM approach applied is discussed. It is shown that the chemisorption energy for the hydroxyl group is sufficiently lower than for hydrogen at stretching up to 7.5%. The simultaneous paired chemisorption of hydrogen and hydroxyl groups on the same hexagon has also been examined. Adsorption of two radicals in ortho and para positions is found to be more energetically favorable than those in meta position at any stretching considered. In addition the energy difference between adsorbent pairs in ortho and para positions decreases as the stretching rises. It could be concluded that the graphene stretching leads to the loss of preferred mutual arrangement of two radicals on its surface.

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.

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).

Chemical determination of free radical-induced damage to DNA.

PubMed

Dizdaroglu, M

1991-01-01

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

Pueraria thunbergiana inhibits cisplatin-induced damage of HEI-OC1 auditory cells through scavenging free radicals.

PubMed

Yu, Hyeon-Hee; Jung, Su-Young; Shin, Mee-Kyung; Park, Raekil; So, Hong-Seob; You, Yong-Ouk

2010-06-01

The radix of Pueraria thunbergiana (P. thunbergiana) is traditionally prescribed to attenuate the clinical manifestation of inner ear dysfunction and various clinical situations including fevers, gastrointestinal disorders, skin problems, migraine headaches, lowering cholesterol, and treating chronic alcoholism in oriental medicine. In the present study, we examined the protective effect of ethanol extract of the radix of P. thunbergiana (RPT) on cisplatin-induced damage of HEI-OC1 auditory hair cells. When the cells were cultured in the medium containing 5-100 microg/mL of RPT, RPT showed protective effect against the cisplatin-induced HEI-OC1 cell damage. We also measured the effects of RPT on lipid peroxidation of cisplatin-treated cells as well as scavenging activities against superoxide radical, hydroxyl radical, hydrogen peroxide, and DPPH radical. RPT reduced cisplatin-induced lipid peroxidation in a dose-dependent manner. Furthermore, RPT showed strong scavenging activity against superoxide radical, hydroxyl radical, hydrogen peroxide, and DPPH radical. These results indicate that RPT protects cisplatin-induced HEI-OC1 cell damage through inhibition of lipid peroxidation and scavenging activities of free radials. (c) 2009 John Wiley & Sons, Ltd.

Glycerol dehydratation by the B12-independent enzyme may not involve the migration of a hydroxyl group: a computational study.

PubMed

Feliks, Mikolaj; Ullmann, G Matthias

2012-06-21

A combination of continuum electrostatic and density functional calculations has been employed to study the mechanism of the B(12)-independent glycerol dehydratase, a novel glycyl-radical enzyme involved in the microbial conversion of glycerol to 3-hydroxylpropionaldehyde. The calculations indicate that the dehydratation of glycerol by the B(12)-independent enzyme does not need to involve a mechanistically complicated migration of the middle hydroxyl group to one of the two terminal positions of a molecule, as previously suggested. Instead, the reaction can proceed in three elementary steps. First, a radical transfer from the catalytically active Cys433 to the ligand generates a substrate-related intermediate. Second, a hydroxyl group splits off at the middle position of the ligand and is protonated by the neighboring His164 to form a water molecule. The other active site residue Glu435 accepts a proton from one of the terminal hydroxyl groups of the ligand and a C═O double bond is created. Third, the reaction is completed by a radical back transfer from the product-related intermediate to Cys433. On the basis of our calculations, the catalytic functions of the active site residues have been suggested. Cys433 is a radical relay site; His164 and Glu435 make up a proton accepting/donating system; Asn156, His281, and Asp447 form a network of hydrogen bonds responsible for the electrostatic stabilization of the transition state. A synergistic participation of these residues in the reaction seems to be crucial for the catalysis.

Sources of Nitrous Acid, Formaldehyde, and Hydroxyl Radical in Doha, Qatar.

NASA Astrophysics Data System (ADS)

Ackermann, Luis; Rappenglueck, Bernhard; Ayoub, Mohammed

2017-04-01

One of the most important species in the atmosphere is the hydroxyl radical (OH), due to its role controlling the oxidizing capacity of an air shed. The main formation processes of OH include the photolysis of ozone (O3), nitrous acid (HONO), formaldehyde (HCHO), and the ozonolysis of alkenes. Still, the sources of HONO in the atmosphere are not sufficiently well known, with indications that heterogeneous reactions on surfaces may contribute to the observed concentrations. The city of Doha in Qatar presents a unique opportunity to explore photochemical processes including the effects of high particulates concentrations under extreme weather conditions (high temperatures and humidity) and complex emission sources. Two Intensive Observational Periods (IOP) were conducted in Doha in 2016, one during the winter and the other during the summer. These consisted of meteorological measurements, ozone (O3), nitrous acid (HONO), formaldehyde (HCHO), nitrogen monoxide (NO), direct nitrogen dioxide (NO2), sulfur dioxide (SO2), carbon monoxide (CO), as well as particulate matter with an aerodynamic diameter ≤ 10 μm and 2.5 μm (PM10 and PM2.5). In addition photolysis rates of HONO, HCHO, NO2, and singlet oxygen (O1D) were measured. The photostationary state concentration of OH was calculated from its known sources and sinks. The maximum hourly average concentration of OH was determined to be around 1.1 ppt for summer and 0.5 ppt for winter IOP. For the 24-hr average, the photolysis of HONO was the main precursor for OH production with 54.3 % and 72.7 % (summer and winter IOP), while the photolysis of O3 was responsible for 23.8 % and 19.7 % and the photolysis of HCHO accounted for 21.9 % and 7.6 % (summer and winter IOP, respectively). In this study we present source apportionment analysis for the radical precursors HONO and HCHO during the winter and summer IOP and its diurnal variation and elucidate their impact on OH production. We also infer NOx vs VOC limitation of O3 production from NO2 and HCHO observations.

Oxidation of As(III) to As(V) using ozone microbubbles.

PubMed

Khuntia, Snigdha; Majumder, Subrata Kumar; Ghosh, Pallab

2014-02-01

The use of ozone in the treatment of water and wastewater is rapidly increasing due to its high oxidizing power. Arsenic is one the most toxic elements found in water. As(III) and As(V) are the major sources of arsenic poisoning. It is known that As(V) can be more easily removed from water by adsorptive methods than As(III). In this work, oxidation of more toxic As(III) to less toxic As(V) was studied in a pilot-plant by using ozone microbubbles. The microbubbles were effective in dissolving ozone in water. The oxidation was fast over a wide range of pH (e.g., 4-9). The role of hydroxyl radical in the oxidation of As(III) under acidic conditions was investigated by using 2-propanol as the hydroxyl radical scavenger. Under acidic conditions, the addition of 2-propanol slowed down the oxidation, which proves that hydroxyl radicals were involved in the oxidation process. The effect of carbonate ions on the rate of oxidation was investigated. It was found that the generation of carbonate ion radical from the carbonate ion accelerated the oxidation of As(III). The kinetics of oxidation of As(III) by ozone was studied. Copyright © 2013 Elsevier Ltd. All rights reserved.

Oxidation Inhibits Iron-Induced Blood Coagulation

PubMed Central

Pretorius, Etheresia; Bester, Janette; Vermeulen, Natasha; Lipinski, Boguslaw

2013-01-01

Blood coagulation under physiological conditions is activated by thrombin, which converts soluble plasma fibrinogen (FBG) into an insoluble clot. The structure of the enzymatically-generated clot is very characteristic being composed of thick fibrin fibers susceptible to the fibrinolytic degradation. However, in chronic degenerative diseases, such as atherosclerosis, diabetes mellitus, cancer, and neurological disorders, fibrin clots are very different forming dense matted deposits (DMD) that are not effectively removed and thus create a condition known as thrombosis. We have recently shown that trivalent iron (ferric ions) generates hydroxyl radicals, which subsequently convert FBG into abnormal fibrin clots in the form of DMDs. A characteristic feature of DMDs is their remarkable and permanent resistance to the enzymatic degradation. Therefore, in order to prevent thrombotic incidences in the degenerative diseases it is essential to inhibit the iron-induced generation of hydroxyl radicals. This can be achieved by the pretreatment with a direct free radical scavenger (e.g. salicylate), and as shown in this paper by the treatment with oxidizing agents such as hydrogen peroxide, methylene blue, and sodium selenite. Although the actual mechanism of this phenomenon is not yet known, it is possible that hydroxyl radicals are neutralized by their conversion to the molecular oxygen and water, thus inhibiting the formation of dense matted fibrin deposits in human blood. PMID:23170793

A facile preparation of TiO2/ACF with Csbnd Ti bond and abundant hydroxyls and its enhanced photocatalytic activity for formaldehyde removal

NASA Astrophysics Data System (ADS)

Liu, R. F.; Li, W. B.; Peng, A. Y.

2018-01-01

The quantum yields and efficiency(ACF) was prepared via a modified deposition-precipitation method to facilitate its photon absorption and of photogenerated charge carriers have been the major issues for photocatalysis on titania catalyst. The TiO2/ACF catalyst with anatase TiO2 uniformly dispersed on activated carbon fibers electron transfer, thus improve the quantum yields and efficiency of the photogenerated electrons and holes. XPS analysis on the catalyst demonstrates the existence of Ti3+ and Ti2+ species, Csbnd Ti bond and abundant hydroxyls, which are also proved by UV-vis DRS and TG-DSC analysis. It is believed that the acid environment in preparation plays an essential role in the formation of Csbnd Ti bond and surface hydroxyls, which can be tuned by changing hydrothermal synthesis time. The Csbnd Ti bond can improve the electron transfer in the catalyst and the substantial surface hydroxyls lead to high absorption for UV lines and enhanced adsorption of water and formaldehyde, resulting in more active OH free radicals and the outstanding photocatalytic activity of TiO2/ACF, which is much higher than the titania powder for photocatalytic removal of low concentration formaldehyde. The essential role of surface hydroxyls for photocatalytic activity was confirmed surpassing that of chemical bond between carbon and titanium in TiO2-carbon composite for the first time.

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

PubMed

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

2013-09-01

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

Investigation of the rates of surface and bulk ROS-generating reactions using indigo dye as an indicator

NASA Astrophysics Data System (ADS)

Anderson, Carly; Clark, Douglas; Graves, David

2014-10-01

We present evidence for the existence of two distinct processes that contribute to the generation of reactive oxygen and nitrogen species (RONS) in liquids exposed to cold atmospheric plasma (CAP) in air. At the plasma-liquid interface, there exists a fast surface reaction zone where RONS from the gas phase interact with species in the liquid. RONS can also be produced by ``slow'' chemical reactions in the bulk liquid, even long after plasma exposure. To separate the effects of these processes, we used indigo dye as an indicator of ROS production; specifically generation of hydroxyl radical. The rate of indigo decolorization while in direct contact with CAP is compared with the expected rate of hydroxyl radical generation at the liquid surface. When added to aqueous solutions after CAP exposure, indigo dye reacts on a time scale consistent with the production of peroxynitrous acid, ONOOH, which is known to decompose to hydroxyl radical below a pH of 6.8. In this study, the CAP used was a air corona discharge plasma run in a positive streamer mode.

Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.

PubMed

Komaszylo Née Siedlecka, Joanna; Kania, Magdalena; Masnyk, Marek; Cmoch, Piotr; Lozinska, Iwona; Czarnocki, Zbigniew; Skorupinska-Tudek, Karolina; Danikiewicz, Witold; Swiezewska, Ewa

2016-02-01

Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents--reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol-2 and -10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy-, peroxy- and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI-MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI-MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time.

Hydrogen gas treatment prolongs replicative lifespan of bone marrow multipotential stromal cells in vitro while preserving differentiation and paracrine potentials.

PubMed

Kawasaki, Haruhisa; Guan, Jianjun; Tamama, Kenichi

2010-07-02

Cell therapy with bone marrow multipotential stromal cells/mesenchymal stem cells (MSCs) represents a promising approach in the field of regenerative medicine. Low frequency of MSCs in adult bone marrow necessitates ex vivo expansion of MSCs after harvest; however, such a manipulation causes cellular senescence with loss of differentiation, proliferative, and therapeutic potentials of MSCs. Hydrogen molecules have been shown to exert organ protective effects through selective reduction of hydroxyl radicals. As oxidative stress is one of the key insults promoting cell senescence in vivo as well as in vitro, we hypothesized that hydrogen molecules prevent senescent process during MSC expansion. Addition of 3% hydrogen gas enhanced preservation of colony forming early progenitor cells within MSC preparation and prolonged the in vitro replicative lifespan of MSCs without losing differentiation potentials and paracrine capabilities. Interestingly, 3% hydrogen gas treatment did not decrease hydroxyl radical, protein carbonyl, and 8-hydroxydeoxyguanosine, suggesting that scavenging hydroxyl radical might not be responsible for these effects of hydrogen gas in this study. Copyright 2010 Elsevier Inc. All rights reserved.

Sequestering ability of butylated hydroxytoluene, propyl gallate, resveratrol, and vitamins C and E against ABTS, DPPH, and hydroxyl free radicals in chemical and biological systems.

PubMed

Soares, Daniele G; Andreazza, Ana C; Salvador, Mirian

2003-02-12

The antioxidant capacity of butylated hydroxytoluene (BHT; 2,6-di-tert-butyl-p-cresol), propyl gallate (3,4,5-trihydroxybenzoic acid n-propyl ester), resveratrol (trans-3,4',5-trihydroxystilbene), and vitamins C (l-ascorbic acid) and E [(+)-alpha-tocopherol] was studied in chemical and biological systems. The chemical assays evaluated the capacity of these antioxidants to sequester 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS.) and 1,1 diphenyl-2-picrylhydrazyl (DPPH.). A new colorimetric method to determine hydroxyl radical scavenging is also described. The biological tests use the eucaryotic cells of Saccharomyces cerevisiae treated with the antioxidants in the presence of the stressing agents apomorphine, hydrogen peroxide, and paraquat dichloride (methylviologen; 1,1'-dimethyl-4,4'-bipyridinium dichloride). The results in chemical systems showed that all of the antioxidants were able to significantly inhibit the oxidation of beta-carotene by hydroxyl free radicals. The assays in yeast showed that the antioxidant activity of the tested compounds depended on the stressing agent used and the mechanism of action of the antioxidant.

Different catalytic effects of a single water molecule: the gas-phase reaction of formic acid with hydroxyl radical in water vapor.

PubMed

Anglada, Josep M; Gonzalez, Javier

2009-12-07

The effect of a single water molecule on the reaction mechanism of the gas-phase reaction between formic acid and the hydroxyl radical was investigated with high-level quantum mechanical calculations using DFT-B3LYP, MP2 and CCSD(T) theoretical approaches in concert with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction between HCOOH and HO has a very complex mechanism involving a proton-coupled electron transfer process (pcet), two hydrogen-atom transfer reactions (hat) and a double proton transfer process (dpt). The hydroxyl radical predominantly abstracts the acidic hydrogen of formic acid through a pcet mechanism. A single water molecule affects each one of these reaction mechanisms in different ways, depending on the way the water interacts. Very interesting is also the fact that our calculations predict that the participation of a single water molecule results in the abstraction of the formyl hydrogen of formic acid through a hydrogen atom transfer process (hat).

Hydrogen gas treatment prolongs replicative lifespan of bone marrow multipotential stromal cells in vitro while preserving differentiation and paracrine potentials

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

Kawasaki, Haruhisa; Davis Heart and Lung Research Institute, The Ohio State University, Columbus, OH 43210; Guan, Jianjun

2010-07-02

Cell therapy with bone marrow multipotential stromal cells/mesenchymal stem cells (MSCs) represents a promising approach in the field of regenerative medicine. Low frequency of MSCs in adult bone marrow necessitates ex vivo expansion of MSCs after harvest; however, such a manipulation causes cellular senescence with loss of differentiation, proliferative, and therapeutic potentials of MSCs. Hydrogen molecules have been shown to exert organ protective effects through selective reduction of hydroxyl radicals. As oxidative stress is one of the key insults promoting cell senescence in vivo as well as in vitro, we hypothesized that hydrogen molecules prevent senescent process during MSC expansion.more » Addition of 3% hydrogen gas enhanced preservation of colony forming early progenitor cells within MSC preparation and prolonged the in vitro replicative lifespan of MSCs without losing differentiation potentials and paracrine capabilities. Interestingly, 3% hydrogen gas treatment did not decrease hydroxyl radical, protein carbonyl, and 8-hydroxydeoxyguanosine, suggesting that scavenging hydroxyl radical might not be responsible for these effects of hydrogen gas in this study.« less

UVA-induced reset of hydroxyl radical ultradian rhythm improves temporal lipid production in Chlorella vulgaris.

PubMed

Balan, Ranjini; Suraishkumar, G K

2014-01-01

We report for the first time that the endogenous, pseudo-steady-state, specific intracellular levels of the hydroxyl radical (si-OH) oscillate in an ultradian fashion (model system: the microalga, Chlorella vulgaris), and also characterize the various rhythm parameters. The ultradian rhythm in the endogenous levels of the si-OH occurred with an approximately 6 h period in the daily cycle of light and darkness. Further, we expected that the rhythm reset to a shorter period could rapidly switch the cellular redox states that could favor lipid accumulation. We reset the endogenous rhythm through entrainment with UVA radiation, and generated two new ultradian rhythms with periods of approximately 2.97 h and 3.8 h in the light phase and dark phase, respectively. The reset increased the window of maximum lipid accumulation from 6 h to 12 h concomitant with the onset of the ultradian rhythms. Further, the saturated fatty acid content increased approximately to 80% of total lipid content, corresponding to the peak maxima of the hydroxyl radical levels in the reset rhythm. © 2014 American Institute of Chemical Engineers.

Structural features, kinetics and SAR study of radical scavenging and antioxidant activities of phenolic and anilinic compounds

PubMed Central

2013-01-01

Background Phenolic compounds are widely distributed in plant kingdom and constitute one of the most important classes of natural and synthetic antioxidants. In the present study fifty one natural and synthetic structurally variant phenolic, enolic and anilinic compounds were examined as antioxidants and radical scavengers against DPPH, hydroxyl and peroxyl radicals. The structural diversity of the used phenolic compounds includes monophenols with substituents frequently present in natural phenols e.g. alkyl, alkoxy, ester and carboxyl groups, besides many other electron donating and withdrawing groups, in addition to polyphenols with 1–3 hydroxyl groups and aminophenols. Some common groups e.g. alkyl, carboxyl, amino and second OH groups were incorporated in ortho, meta and para positions. Results SAR study indicates that the most important structural feature of phenolic compounds required to possess good antiradical and antioxidant activities is the presence of a second hydroxyl or an amino group in o- or p-position because of their strong electron donating effect in these positions and the formation of a stable quinone-like products upon two hydrogen-atom transfer process; otherwise, the presence of a number of alkoxy (in o or p-position) and /or alkyl groups (in o, m or p-position) should be present to stabilize the resulted phenoxyl radical and reach good activity. Anilines showed also similar structural feature requirements as phenols to achieve good activities, except o-diamines which gave low activity because of the high energy of the resulted 1,2-dimine product upon the 2H-transfer process. Enols with ene-1,2-diol structure undergo the same process and give good activity. Good correlations were obtained between DPPH inhibition and inhibition of both OH and peroxyl radicals. In addition, good correlations were obtained between DPPH inhibition and antioxidant activities in sunflower oil and liver homogenate systems. Conclusions In conclusion, the structures of good anti radical and antioxidant phenols and anilines are defined. The obtained good correlations imply that measuring anti DPPH activity can be used as a simple predictive test for the anti hydroxyl and peroxyl radical, and antioxidant activities. Kinetic measurements showed that strong antioxidants with high activity have also high reaction rates indicating that factors stabilizing the phenoxyl radicals lower also the activation energy of the hydrogen transfer process. PMID:23497653

Role of nitrite in the photochemical formation of radicals in the snow.

PubMed

Jacobi, Hans-Werner; Kleffmann, Jörg; Villena, Guillermo; Wiesen, Peter; King, Martin; France, James; Anastasio, Cort; Staebler, Ralf

2014-01-01

Photochemical reactions in snow can have an important impact on the composition of the atmosphere over snow-covered areas as well as on the composition of the snow itself. One of the major photochemical processes is the photolysis of nitrate leading to the formation of volatile nitrogen compounds. We report nitrite concentrations determined together with nitrate and hydrogen peroxide in surface snow collected at the coastal site of Barrow, Alaska. The results demonstrate that nitrite likely plays a significant role as a precursor for reactive hydroxyl radicals as well as volatile nitrogen oxides in the snow. Pollution events leading to high concentrations of nitrous acid in the atmosphere contributed to an observed increase in nitrite in the surface snow layer during nighttime. Observed daytime nitrite concentrations are much higher than values predicted from steady-state concentrations based on photolysis of nitrate and nitrite indicating that we do not fully understand the production of nitrite and nitrous acid in snow. The discrepancy between observed and expected nitrite concentrations is probably due to a combination of factors, including an incomplete understanding of the reactive environment and chemical processes in snow, and a lack of consideration of the vertical structure of snow.

The advanced EctoSys electrolysis as an integral part of a ballast water treatment system.

PubMed

Echardt, J; Kornmueller, A

2009-01-01

A full-scale 500 m(3)/h ballast water treatment system was tested according to the landbased type approval procedure of the International Maritime Organization (IMO). The system consists of disc filters followed by the advanced EctoSys electrolysis as an integral part for disinfection. The test water quality exceeded by far the minimum requirements for type approval testing. Due to the properties of the special electrodes used together with the striking disinfection effect, the disinfectants assumed to be produced inline by the EctoSys cell in river water were hydroxyl radicals, while in brackish water additionally chlorine and consequently the more stable bromine were formed. In river water, no residual oxidants could be detected in accordance with the assumed production of not responding, highly-reactive and short-living hydroxyl radicals. Accordingly, disinfection byproduct (DBP) formation was very low and close to the limit of quantification in river water. While in brackish water, initial residual oxidant concentrations were maximum 2 mg/L as chlorine and mostly brominated DBP (especially bromoform and bromate) were found. Overall considering this worst case test approach, the DBP concentrations of the treated effluents were below or in the range of the WHO Drinking Water Guideline values and therefore evaluated as acceptable for discharge to the environment. The stringent discharge standard by IMO concerning viable organisms was fully met in river and brackish water, proving the disinfection efficiency of the EctoSys electrolysis against smaller plankton and bacteria.

Reduction of paraquat-induced renal cytotoxicity by manganese and copper complexes of EGTA and EHPG.

PubMed

Samai, Mohamed; Hague, Theresa; Naughton, Declan P; Gard, Paul R; Chatterjee, Prabal K

2008-02-15

Superoxide anion generation plays an important role in the development of paraquat toxicity. Although superoxide dismutase mimetics (SODm) have provided protection against organ injury involving generation of superoxide anions, they often suffer problems, e.g., regarding their bioavailability or potential pro-oxidant activity. The aim here was to investigate and compare the therapeutic potential of two novel SODm, manganese(II) and copper(II) complexes of the calcium chelator ethylenebis(oxyethylenenitrilo)tetraacetic acid (EGTA) and of the contrast agent ethylenebis(hydroxyphenylglycine) (EHPG), against paraquat-induced renal toxicity in vitro. Incubation of renal NRK-52E cells with paraquat (1 mM) for 24 h produced submaximal, yet significant, reduction in cellular viability and cell death and produced significant increases in superoxide anion and hydroxyl radical generation. Manganese and copper complexes of EGTA (10-100 microM) and EHPG (30-100 microM) reduced paraquat-induced renal cell toxicity and reduced superoxide anion and hydroxyl radical generation significantly. Manganese complexes displayed greater efficacy than copper complexes and, at equivalent concentrations, manganese complexed with EHPG provided the greatest protection. Furthermore, these metal complexes did not interfere with the uptake of [methyl-(14)C]paraquat into NRK-52E cells, suggesting that they provided protection against paraquat cytotoxicity via intracellular mechanisms. These complexes did not display cytotoxicity at the concentrations examined. Together, these results suggest that manganese and copper complexes of EGTA and EHPG, and especially the manganese-EHPG complex, could provide benefit against paraquat nephrotoxicity.

Antioxidant and free radical scavenging activity of Spondias pinnata

PubMed Central

Hazra, Bibhabasu; Biswas, Santanu; Mandal, Nripendranath

2008-01-01

Background Many diseases are associated with oxidative stress caused by free radicals. Current research is directed towards finding naturally-occurring antioxidants of plant origin. The aim of the present study was to evaluate the in vitro antioxidant activities of Spondias pinnata stem bark extract. Methods A 70% methanol extract of Spondias pinnata stem bark was studied in vitro for total antioxidant activity, for scavenging of hydroxyl radicals, superoxide anions, nitric oxide, hydrogen peroxide, peroxynitrite, singlet oxygen and hypochlorous acid, and for iron chelating capacity, reducing power, and phenolic and flavonoid contents. Results The extract showed total antioxidant activity with a trolox equivalent antioxidant concentration (TEAC) value of 0.78 ± 0.02. The IC50 values for scavenging of free radicals were 112.18 ± 3.27 μg/ml, 13.46 ± 0.66 μg/ml and 24.48 ± 2.31 μg/ml for hydroxyl, superoxide and nitric oxide, respectively. The IC50 for hydrogen peroxide scavenging was 44.74 ± 25.61 mg/ml. For the peroxynitrite, singlet oxygen and hypochlorous acid scavenging activities the IC50 values were 716.32 ± 32.25 μg/ml, 58.07 ± 5.36 μg/ml and 127.99 ± 6.26 μg/ml, respectively. The extract was found to be a potent iron chelator with IC50 = 66.54 ± 0.84 μg/ml. The reducing power was increased with increasing amounts of extract. The plant extract (100 mg) yielded 91.47 ± 0.004 mg/ml gallic acid-equivalent phenolic content and 350.5 ± 0.004 mg/ml quercetin-equivalent flavonoid content. Conclusion The present study provides evidence that a 70% methanol extract of Spondias pinnata stem bark is a potential source of natural antioxidants. PMID:19068130

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.

Activation of Peroxymonosulfate by Subsurface Minerals.

PubMed

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

2016-08-01

In situ chemical oxidation (ISCO) has become a widely used technology for the remediation of soil and groundwater. Although peroxymonosulfate is not a common oxidant source for ISCO, its chemical structure is similar to the ISCO reagents hydrogen peroxide and persulfate, suggesting that peroxymonosulfate may have the beneficial properties of each of these oxidants. Peroxymonosulfate activation in the presence of subsurface minerals was examined as a basis for ISCO, and possible reactive species (hydroxyl radical, sulfate radical, and reductants+nucleophiles) generated in the mineral-activated peroxymonosulfate systems were investigated. Rates of peroxymonosulfate decomposition and generation rates of reactive species were studied in the presence of three iron oxides, one manganese oxide, and three soil fractions. The iron oxide hematite-activated peroxymonosulfate system most effectively degraded the hydroxyl radical probe nitrobenzene. Reductants+nucleophiles were not generated in mineral-activated peroxymonosulfate systems. Use of the probe compound anisole in conjunction with scavengers demonstrated that both sulfate radical and hydroxyl radical are generated in mineral-activated peroxymonosulfate systems. In order to confirm the activation of peroxymonosulfate by subsurface minerals, one natural soil and associated two soil fractions were evaluated as peroxymonosulfate catalysts. The natural soil did not effectively promote the generation of oxidants; however, the soil organic matter was found to promote the generation of reductants + nucleophiles. The results of this research show that peroxymonosulfate has potential as an oxidant source for ISCO applications, and would be most effective in treating halogenated contaminants when soil organic matter is present in the subsurface. Copyright © 2016. Published by Elsevier B.V.

Iodine-enhanced ultrasound degradation of sulfamethazine in water.

PubMed

Yang, Xiao-Yu; Wei, Hong; Li, Ke-Bin; He, Qiang; Xie, Jian-Cang; Zhang, Jia-Tong

2018-04-01

This study investigated sulfamethazine (SMT) ultrasound degradation, enhanced by iodine radicals, generated by potassium iodide (KI) and hydrogen peroxide (H 2 O 2 ) in situ. The results showed that the ultrasound/H 2 O 2 /KI (US/H 2 O 2 /KI) combination treatment achieved an 85.10 ± 0.45% SMT removal (%) in 60 min under the following conditions: pH = 3.2, ultrasound power of 195 W, initial SMT concentration of 0.04 mmol·L -1 , H 2 O 2 concentration of 120 mmol·L -1 , and KI concentration of 2.4 mmol·L -1 . UV-Vis spectrophotometric monitoring of molecular iodine (I 2 ) and triiodide (I 3 - ) revealed a correlation between the SMT degradation and the iodine change in the solution. Quenching experiments using methanol, t-butanol and thiamazole as radical scavengers indicated that iodine radicals, such as I and I 2 - , were more important than hydroxyl radicals (HO) for SMT degradation. SMT degradation under the US/H 2 O 2 /KI treatment followed pseudo-first order reaction kinetics. The activation energy (E a ) of SMT degradation was 7.75 ± 0.61 kJ·mol -1 , which suggested the reaction was controlled by the diffusion step. Moreover, TOC removal was monitored, and the obtained results revealed that it was not as effective as SMT degradation under the US/H 2 O 2 /KI system. Copyright © 2017 Elsevier B.V. All rights reserved.

Transport and Distribution of Hydroxyl Radicals and Oxygen Atoms from H2O Photodissociation in the Inner Coma of Comet 67P/Churyumov-Gerasimenko

NASA Astrophysics Data System (ADS)

Lai, Ian-Lin; Su, Cheng-Chin; Ip, Wing-Huen; Wei, Chen-En; Wu, Jong-Shinn; Lo, Ming-Chung; Liao, Ying; Thomas, Nicolas

2016-03-01

With a combination of the Direct Simulation Monte Carlo (DSMC) calculation and test particle computation, the ballistic transport process of the hydroxyl radicals and oxygen atoms produced by photodissociation of water molecules in the coma of comet 67P/Churyumov-Gerasimenko is modelled. We discuss the key elements and essential features of such simulations which results can be compared with the remote-sensing and in situ measurements of cometary gas coma from the Rosetta mission at different orbital phases of this comet.

Mucuna pruriens attenuates haloperidol-induced orofacial dyskinesia in rats.

PubMed

Pathan, Amjadkhan A; Mohan, Mahalaxmi; Kasture, Ameya S; Kasture, Sanjay B

2011-04-01

Neuroleptic-induced tardive dyskinesia (TD) is a motor disorder of the orofacial region resulting from chronic neuroleptic treatment. The agents improving dopaminergic transmission improve TD. Mucuna pruriens seed contains levodopa and amino acids. The effect of methanolic extract of M. pruriens seeds (MEMP) was studied on haloperidol-induced TD, alongside the changes in lipid peroxidation, reduced glutathione, superoxide dismutase (SOD) and catalase levels. The effect of MEMP was also evaluated in terms of the generation of hydroxyl and 1,1-diphenyl,2-picrylhydrazyl (DPPH) radical. MEMP (100 and 200 mg kg⁻¹) inhibited haloperidol-induced vacuous chewing movements, orofacial bursts and biochemical changes. MEMP also inhibited hydroxyl radical generation and DPPH. The results of the present study suggest that MEMP by virtue of its free radical scavenging activity prevents neuroleptic-induced TD.

Chemical analysis and antioxidant activity in vitro of polysaccharides extracted from Boletus edulis.

PubMed

Zhang, Anqiang; Xiao, Nannan; He, Pengfei; Sun, Peilong

2011-12-01

Boletus edulis is a well-known delicious mushroom. In this study, three crude polysaccharides (BEPF30, BEPF60 and BEPF80) were isolated from the fruiting bodies of B. edulis with boiling water. Chemical and physical characteristics of the three crude polysaccharides were investigated by the combination of chemical and instrumental analysis methods. Their antioxidant activities were investigated in vitro systems including hydroxyl assay, superoxide radical assay, reducing power and chelating activity. Among these three polysaccharides, BEPF60 showed more significant reducing power and chelating activity; and highest inhibitory effects on superoxide radical and hydroxyl radical. These results indicated that polysaccharides extracted from B. edulis might be employed as ingredients in healthy and functional food to alleviate the oxidative stress. Copyright © 2011 Elsevier B.V. All rights reserved.

Observations of the Hydroxyl Radical in C/2013 US10 (Catalina) at 18 cm Wavelength

NASA Astrophysics Data System (ADS)

Wang, Zhen; Chen, Xi; Gao, Feng; Zhang, Shaobo; Zheng, Xing-Wu; Ip, Wing-Huen; Wang, Na; Liu, Xiang; Zuo, Xiu-Ting; Gou, Wei; Chang, Sheng-Qi

2017-12-01

The hydroxyl (OH) radical produced by photodissociation of water molecule is one of the most important indicators for cometary outgassing activity. The absorption lines of the OH radical at 1665 and 1667 MHz in the coma of comet C/2013 US10 Catalina were detected between 2015 December 3 and 5 by the Tian Ma Radio Telescope of Shanghai Astronomical Observatory. The source flux intensity was derived to be about -209 mJy km s-1 and -86 mJy km s-1 at 1665 MHz and 1667 MHz, respectively. The corresponding gas production rate was estimated to be (8.78 ± 1.47) × 1028 H2O s-1 and (5.94 ± 1.27) × 1028 H2O s-1, accordingly.

RELATIVE REACTIVITY OF CONTAMINANT CANDIDATE LIST PESTICIDES TO OH RADICAL OXIDATION

EPA Science Inventory

Advanced oxidation processes (AOPs) represent those technologies that bring about enhanced oxidative degradation of pollutants in aqueous solution by the generation of hydroxyl radical (•OH). US Environmental Protection Agency (EPA) published, in February 2005, the second Contam...

Extraction, purification and antioxidant activities of the polysaccharides from maca (Lepidium meyenii).

PubMed

Zha, Shenghua; Zhao, Qingsheng; Chen, Jinjin; Wang, Liwei; Zhang, Guifeng; Zhang, Hong; Zhao, Bing

2014-10-13

Water-soluble polysaccharides were separated from maca (Lepidium meyenii) aqueous extract (MAE). The crude polysaccharides were deproteinized by Sevag method. During the preparation process of maca polysaccharides, amylase and glucoamylase effectively removed starch in maca polysaccharides. Four Lepidium meyenii polysaccharides (LMPs) were obtained by changing the concentration of ethanol in the process of polysaccharide precipitation. All of the LMPs were composed of rhamnose, arabinose, glucose and galactose. Antioxidant activity tests revealed that LMP-60 showed good capability of scavenging hydroxyl free radical and superoxide radical at 2.0mg/mL, the scavenging rate was 52.9% and 85.8%, respectively. Therefore, the results showed that maca polysaccharides had a high antioxidant activity and could be explored as the source of bioactive compounds. Copyright © 2014 Elsevier Ltd. All rights reserved.

Inhibitory effect of green tea on injury to a cultured renal epithelial cell line, LLC-PK1.

PubMed

Yokozawa, T; Dong, E; Chung, H Y; Oura, H; Nakagawa, H

1997-01-01

When cells from a cultured renal epithelial cell line, LLC-PK1, were cultured under hypoxic conditions (oxygen concentration of 2% or less) before reoxygenation was applied (95% air, 5% CO2), the leakage of lactate dehydrogenase (LDH) into the medium increased. This phenomenon was inhibited in the presence of dimethyl sulfoxide, a hydroxyl radical scavenger, suggesting the involvement of free radicals. Such oxidative stress was significantly inhibited by a green tea extract, and more potently by a tannin mixture. On the other hand, under ordinary culture conditions (95%, air, 5% CO2), there was cell injury, although the LDH leakage was less than that under hypoxia/reoxygenation, and such injury was inhibited by the green tea extract and the tannin mixture.

Antioxidant activities of polysaccharides from Lentinus edodes and their significance for disease prevention.

PubMed

Chen, Huoliang; Ju, Ying; Li, Junjie; Yu, Min

2012-01-01

The crude polysaccharide (LEP) was extracted by hot water from the fruiting bodies of Lentinus edodes, and further purified by DEAE-cellulose and Sepharose CL-6B chromatography, giving three polysaccharide fractions coded as LEPA1, LEPB1 and LEPC1. In this study, their chemical and physical characteristics of polysaccharide fractions and antioxidant capacities, including scavenging activity against hydroxyl radicals, superoxide radicals and Fe(2+)-chelating ability, were valuated. The results showed that LEPC1 exhibited significantly antioxidant activity at a concentration-dependent manner. Therefore these results indicated that the water-extractable polysaccharide fraction was a potent antioxidant and could be developed to be new health medicine for fighting against various human diseases. Copyright © 2011 Elsevier B.V. All rights reserved.

Cellulase-assisted extraction and antioxidant activity of polysaccharides from Rhizoma imperata.

PubMed

Jiang, Long-Fa

2014-08-08

In this study, the cellulase-assisted extraction and antioxidant activity of the polysaccharides from Rhizoma imperata were investigated. To improve the yield of R. Imperata polysaccharides (RPs), the extraction conditions were optimized as follows: time, 69.48 min; temperature, 45.36°C; pH, 4.58; cellulase amount, 1,200 U/g. Under these optimum conditions, the yield of RPs reached 0.67% (w/w), and was higher than that of the traditionally aqueous extraction method. The sugar content in the RPs product reached up to 93.25% (w/w). The RPs product has high antioxidant activity including hydroxyl radical scavenging activity and 2,2-diphenyl-β-picrylhydrazyl radical scavenging activity at the concentration of 100mg/mL. Copyright © 2014 Elsevier Ltd. All rights reserved.

Key role of persistent free radicals in hydrogen peroxide activation by biochar: implications to organic contaminant degradation.

PubMed

Fang, Guodong; Gao, Juan; Liu, Cun; Dionysiou, Dionysios D; Wang, Yu; Zhou, Dongmei

2014-01-01

We investigated the activation of hydrogen peroxide (H2O2) by biochars (produced from pine needles, wheat, and maize straw) for 2-chlorobiphenyl (2-CB) degradation in the present study. It was found that H2O2 can be effectively activated by biochar, which produces hydroxyl radical ((•)OH) to degrade 2-CB. Furthermore, the activation mechanism was elucidated by electron paramagnetic resonance (EPR) and salicylic acid (SA) trapping techniques. The results showed that biochar contains persistent free radicals (PFRs), typically ∼ 10(18) unpaired spins/gram. Higher trapped [(•)OH] concentrations were observed with larger decreases in PFRs concentration, when H2O2 was added to biochar, indicating that PFRs were the main contributor to the formation of (•)OH. This hypothesis was supported by the linear correlations between PFRs concentration and trapped [(•)OH], as well as kobs of 2-CB degradation. The correlation coefficients (R(2)) were 0.723 and 0.668 for PFRs concentration vs trapped [(•)OH], and PFRs concentration vs kobs, respectively, when all biochars pyrolyzed at different temperatures were included. For the same biochar washed by different organic solvents (methanol, hexane, dichloromethane, and toluene), the correlation coefficients markedly increased to 0.818-0.907. Single-electron transfer from PFRs to H2O2 was a possible mechanism for H2O2 activation by biochars, which was supported by free radical quenching studies. The findings of this study provide a new pathway for biochar implication and insight into the mechanism of H2O2 activation by carbonaceous materials (e.g., activated carbon and graphite).

Evaluation of the Antioxidant Activity of Extracts and Active Principles of Commonly Consumed Indian Spices.

PubMed

Patra, Kartick; Jana, Samarjit; Mandal, Deba Prasad; Bhattacharjee, Shamee

2016-01-01

Accumulating evidence suggests that free radical reactions play a key part in the development of degenerative diseases and that an antioxidant-rich diet is a major defense against these free radical reactions. In this study, we explore comparative antioxidant capacities of extracts of some commonly used in Indian spices (anise, cardamom, Ceylon cinnamon, and clove) along with their purified components (anethole, eucalyptol, cinnamaldehyde, and eugenol, respectively). Eugenol shows the highest 1,1-diphenyl-2-picrylhydrazyl, hydroxyl, and superoxide scavenging and reducing power activity in terms of weight; however, this was not found when compared in terms of equivalence. Extracts of the other three spices were found to be more potent antioxidants than their corresponding active components. Interestingly, clove extract, despite possessing the highest phenol and flavonoid content, is not the most potent radical scavenger. At low concentrations, both the crude extracts and their purified components (except for anethole and eugenol) have low hemolytic activity, but at higher concentrations purified components are more toxic than their respective crude extract. This study suggests that spices as a whole are more potent antioxidants than their purified active components, perhaps reflecting the synergism among different phytochemicals present in spice extracts.

Effect of drying temperatures on structural performance and photocatalytic activity of BiOCl synthesized by a soft chemical method

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

Guang, Lu, E-mail: lu_g@163.com; Hui, Wang; Xuejun, Zou

2016-07-15

A group of BiOCl photocatalysts with different drying temperatures were prepared by a soft chemical method. The effects of drying temperatures on the crystalline phase, morphology, surface area and optical property of as-prepared samples were investigated in detail by XRD, SEM, N{sub 2} absorption–desorption and DRS. Moreover, their photocatalytic activities on the degradation of rhodamine B were evaluated under visible light irradiation. It was found that the sample dried at 120 °C had the best photocatalytic activity, which was mainly attributed to the highest exposing proportion of {001} facets correspond to BiOCl, largest BET and minimum bandgap. The degradation mechanismmore » was explored that superoxide radicals were mainly contributed to the degradation of chromophore, however, holes and hydroxyl were mainly contributed to the photo degradation. Moreover, holes and hydroxyl dominated the degradation of RhB. - Graphical abstract: Holes, hydroxyl and superoxide radicals can attribute to the degradation process but take different degradation pathways. Superoxide radicals mainly contribute to the degradation of chromophore, however, holes and hydroxyl mainly contribute to the photo degradation. Display Omitted - Highlights: • BiOCl nanosheets were prepared by a soft chemical method. • Effect of drying temperatures on as-prepared BiOCl samples was studied. • The highest removal efficiency of RhB was obtained over the sample dried at 120 °C.« less

Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

PubMed

Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

2016-02-01

The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC.

Enhanced antioxidant activity of gold nanoparticle embedded 3,6-dihydroxyflavone: a combinational study

NASA Astrophysics Data System (ADS)

Medhe, Sharad; Bansal, Prachi; Srivastava, Man Mohan

2014-02-01

The antioxidative effect of selected dietary compounds (3,6-dihydroxyflavone, lutein and selenium methyl selenocysteine) was determined in single and combination using DPPH (2,2-diphenyl-l-picrylhydrazyl), OH (hydroxyl), H2O2 (hydrogen peroxide) and NO (nitric oxide) radical scavenging assays. Radical scavenging effect of the dietary phytochemicals individually are found to be in the order: ascorbic acid (standard) > lutein > 3,6-dihydroxyflavone > selenium methyl selenocysteine, at concentration 100 μg/ml, confirmed by all the four bioassays (p < 0.05). Among the various combinations studied, the triplet combination of 3,6-dihydroxyflavone, lutein and selenium methyl selenocysteine (1:1:1), exhibited enhancement in the target activity at same concentration level. Synthesized gold nanoparticle embedded 3,6-dihydroxyflavone further enhanced the target antioxidant activity. The combinational study including gold nanoparticle embedded 3,6-dihydroxyflavone with other native dietary nutrients showed remarkable increase in antioxidant activity at the same concentration level. The present in vitro study on combinational and nanotech enforcement of dietary phytochemicals shows the utility in the architecture of nanoparticle embedded phytoproducts having a wide range of applications in medical science.

Behavior of the potential antitumor V(IV)O complexes formed by flavonoid ligands. 3. Antioxidant properties and radical production capability.

PubMed

Sanna, Daniele; Ugone, Valeria; Fadda, Angela; Micera, Giovanni; Garribba, Eugenio

2016-08-01

The radical production capability and the antioxidant properties of some V(IV)O complexes formed by flavonoid ligands were examined. In particular, the bis-chelated species of quercetin (que), [VO(que)2](2-), and morin (mor), [VO(mor)2], were evaluated for their capability to reduce the stable radical 1,1-diphenyl-2-picrylhydrazyl (DPPH) and produce the hydroxyl radical (•)OH by Fenton-like reactions, where the reducing agent is V(IV)O(2+). The results were compared with those displayed by other V(IV)O complexes, such as [VO(H2O)5](2+), [VO(acac)2] (acac=acetylacetonate) and [VO(cat)2](2-) (cat=catecholate). The capability of the V(IV)O flavonoids complexes to reduce DPPH is much larger than that of the V(IV)O species formed by non-antioxidant ligands and it is due mainly to the flavonoid molecule. Through the 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin trapping assay of the hydroxyl radical it was possible to demonstrate that in acidic solution V(IV)O(2+) has an effectiveness in producing (•)OH radicals comparable to that of Fe(2+). When V(IV)O complexes of flavonoids were taken into account, the amount of hydroxyl radicals produced in Fenton-like reactions depends on the specific structure of the ligand and on their capability to reduce H2O2 to give (•)OH. Both the formation of reactive oxygen species (ROS) under physiological conditions by V(IV)O complexes of flavonoid ligands and their radical scavenging capability can be put in relationship with their antitumor effectiveness and it could be possible to modulate these actions by changing the features of the flavonoid coordinated to the V(IV)O(2+) ion, such as the entity, nature and position of the substituents and the number of phenolic groups. Copyright © 2016 Elsevier Inc. All rights reserved.

Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site

NASA Astrophysics Data System (ADS)

Arsene, C.; Bougiatioti, A.; Kanakidou, M.; Bonsang, B.; Mihalopoulos, N.

2007-05-01

In situ continuous hourly measurements of C2-C8 non-methane hydrocarbons (NMHCS) have been performed from March to October 2006 at two coastal locations on the island of Crete, in the Eastern Mediterranean. Well defined diurnal variations were observed for several short lived NMHCS (including ethene, propene, n-butane, n-pentane, n-hexane, 2-methyl-pentane). The daytime concentration of hydroxyl (OH) radicals estimated from these experimental data varied from 1.3×106 to ~4.0×106 radical cm-3, in good agreement with box-model simulations. In addition the relative variability of various hydrocarbon pairs (at least 7) was used to derive the tropospheric levels of Cl atoms. The Cl atom concentration has been estimated to range between 0.6×104 and 4.7×104 atom cm-3, in good agreement with gaseous hydrochloric acid (HCl) observations in the area. Such levels of Cl atoms can be of considerable importance for the oxidation capacity of the troposphere on a regional scale.

RELATIVE REACTIVITY OF CONTAMINANT CANDIDATE LIST PESTICIDES TO OH RADICAL OXIDATION ABSTRACT

EPA Science Inventory

Advanced oxidation processes (AOPs) represent those technologies that bring about enhanced oxidative degradation of pollutants in aqueous solution by the generation of hydroxyl radical (•OH). US Environmental Protection Agency (EPA) published, in February 2005, the second Contami...

Spectroscopic studies on the antioxidant activity of p-coumaric acid.

PubMed

Kiliç, Ismail; Yeşiloğlu, Yeşim

2013-11-01

p-coumaric acid (4-hydroxycinnamic acid), a phenolic acid, is a hydroxyl derivative of cinnamic acid. It decreases low density lipoprotein (LDL) peroxidation and reduces the risk of stomach cancer. In vitro radical scavenging and antioxidant capacity of p-coumaric acid were clarified using different analytical methodologies such as total antioxidant activity determination by ferric thiocyanate, hydrogen peroxide scavenging, 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH) scavenging, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) radical scavenging activity and superoxide anion radical scavenging, ferrous ions (Fe(2+)) chelating activity and ferric ions (Fe(3+)) reducing ability. p-Coumaric acid inhibited 71.2% lipid peroxidation of a linoleic acid emulsion at 45μg/mL concentration. On the other hand, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), α-tocopherol and ascorbic acid displayed 66.8%, 69.8%, 64.5% and 59.7% inhibition on the peroxidation of linoleic acid emulsion at the same concentration, respectively. In addition, p-coumaric acid had an effective DPPH scavenging, ABTS(+) scavenging, superoxide anion radical scavenging, hydrogen peroxide scavenging, ferric ions (Fe(3+)) reducing power and ferrous ions (Fe(2+)) chelating activities. Also, those various antioxidant activities were compared to BHA, BHT, α-tocopherol and ascorbic acid as references antioxidant compounds. These results suggested that p-coumaric acid can be used in the pharmacological and food industry because of these properties. Copyright © 2013 Elsevier B.V. All rights reserved.

Purification and in vitro antioxidative effects of giant squid muscle peptides on free radical-mediated oxidative systems.

PubMed

Rajapakse, Niranjan; Mendis, Eresha; Byun, Hee-Guk; Kim, Se-Kwon

2005-09-01

Low molecular weight peptides obtained from ultrafiltration (UF) of giant squid (Dosidicus gigas) muscle protein were studied for their antioxidative effects in different in vitro oxidative systems. The most potent two peptides, Asn-Ala-Asp-Phe-Gly-Leu-Asn-Gly-Leu-Glu-Gly-Leu-Ala (1307 Da) and Asn-Gly-Leu-Glu-Gly-Leu-Lys (747 Da), exhibited their antioxidant potential to act as chain-breaking antioxidants by inhibiting radical-mediated peroxidation of linoleic acid, and their activities were closer to highly active synthetic antioxidant, butylated hydroxytoluene. Addition of these peptides could enhance the viability of cytotoxic embryonic lung fibroblasts significantly (P<.05) at a low concentration of 50 microg/ml, and it was presumed due to the suppression of radical-induced oxidation of membrane lipids. Electron spin trapping studies revealed that the peptides were potent scavengers of free radicals in the order of carbon-centered (IC(50) 396.04 and 304.67 microM), hydroxyl (IC(50) 497.32 and 428.54 microM) and superoxide radicals (IC(50) 669.34 and 573.83 microM). Even though the exact molecular mechanism for scavenging of free radicals was unclear, unusually high hydrophobic amino acid composition (more than 75%) of giant squid muscle peptides was presumed to be involved in the observed activities.

HOx Radical Chemistry in an Indiana Forest Environment: Measurement and Model Comparison

NASA Astrophysics Data System (ADS)

Lew, M.; Bottorff, B.; Sigler, P. S. R.; Stevens, P. S.; Sklaveniti, S.; Leonardis, T.; Locoge, N.; Dusanter, S.; Kundu, S.; Deming, B.; Wood, E. C. D.; Gentner, D. R.

2015-12-01

Reactions of the hydroxyl (OH) and peroxy radicals (HO2 and RO2) play a central role in the chemistry of the atmosphere. In addition to controlling the lifetimes of many trace gases important to issues of global climate change, OH radical reactions initiate the oxidation of volatile organic compounds (VOCs) which can lead to the production of ozone and secondary organic aerosols in the atmosphere. Previous measurements of these radicals in forest environments characterized by high mixing ratios of isoprene and low mixing ratios of NOx have shown serious discrepancies with modeled concentrations. These results bring into question our understanding of the atmospheric chemistry of isoprene and other biogenic VOCs under low NOx conditions. In the summer of 2015, HOx radicals were measured using Laser-Induced Fluorescence Fluorescence Assay by Gas Expansion (LIF-FAGE) technique as part of the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC). This campaign took place in a forested area at the Indiana Research and Teaching Preserve (IURTP) near the Bloomington campus characterized by high mixing ratios of isoprene and low mixing ratios of NOx. Supporting measurements of photolysis rates, volatile organic compounds, nitrogen oxides, and other species were used to constrain a zero-dimensional box model based on the Regional Atmospheric Chemistry Mechanism (RACM2) and the Master Chemical Mechanism (MCM).

Dynamics and density estimation of hydroxyl radicals in a pulsed corona discharge

NASA Astrophysics Data System (ADS)

Ono, Ryo; Oda, Tetsuji

2002-09-01

Hydroxyl radicals generated by a pulsed corona discharge are measured by laser-induced fluorescence (LIF) with a tunable KrF excimer laser. The discharge with 35 kV voltage and 100 ns pulse current occurs between needle and plate electrodes in H2O/O2/N2 mixture at atmospheric pressure. The density and decay profile of OH radicals are studied. OH radicals decay with time after the discharge with a time constant of about 30-60 µs. The OH density is estimated to be about 7×1014 cm-3 in H2O(2.4%)/N2 mixture 10 µs after the discharge. The OH density is approximately proportional to the energy dissipated in the discharge. The O2 content influences the OH production. When the O2 content is varied in H2O(2.4%)/O2/N2 mixture, the OH density is maximum at an O2 content of 2%. The spatial distribution of OH density shows that OH radicals are produced in the streamers under positive discharge.

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2011 CFR

2011-07-01

.... (1985). (13) Mill T., Hendry D.G., Richardson H. “Free radical oxidants in natural waters.” Science, 207...)(7) of this section); peroxy radicals (RO2−) (Mill et al. (1981) under paragraph (f)(9) of this section; Mill et al. (1983) under paragraph (f)(8) of this section); hydroxyl radicals (HO−) (Mill et al...

40 CFR 795.70 - Indirect photolysis screening test: Sunlight photolysis in waters containing dissolved humic...

Code of Federal Regulations, 2010 CFR

2010-07-01

.... (1985). (13) Mill T., Hendry D.G., Richardson H. “Free radical oxidants in natural waters.” Science, 207...)(7) of this section); peroxy radicals (RO2−) (Mill et al. (1981) under paragraph (f)(9) of this section; Mill et al. (1983) under paragraph (f)(8) of this section); hydroxyl radicals (HO−) (Mill et al...

Formation and chemical aging of secondary organic aerosol during the β-caryophyllene oxidation

NASA Astrophysics Data System (ADS)

Tasoglou, A.; Pandis, S. N.

2015-06-01

The secondary organic aerosol (SOA) production during the oxidation of β-caryophyllene by ozone (O3) and hydroxyl radicals (OH) and the subsequent chemical aging of the products during reactions with OH were investigated. Experiments were conducted with ozone and with hydroxyl radicals at low NOx (zero added NOx) and at high NOx (hundreds of parts per billion). The SOA mass yield at 10 μg m-3 of organic aerosol was 27% for the ozonolysis, 20% for the reaction with OH at low NOx, and 38% at high NOx under dry conditions, 20 °C, and ozone excess. Parameterizations of the fresh SOA yields have been developed. The average fresh SOA atomic O : C ratio varied from 0.24 to 0.34 depending on the oxidant and the NOx level, while the H : C ratio was close to 1.5 for all systems examined. An average density of 1.06 ± 0.1 μg m-3 of the β-caryophyllene SOA was estimated. The exposure to UV light had no effect on the β-caryophyllene SOA concentration and aerosol mass spectrometer (AMS) measurements. The chemical aging of the β-caryophyllene SOA produced was studied by exposing the fresh SOA to high concentrations (107 molecules cm-3) of OH for several hours. These additional reactions increased the SOA concentration by 15-40% and O : C by approximately 25%. A limited number of experiments suggested that there was a significant impact of the relative humidity on the chemical aging of the SOA. The evaporation rates of β-caryophyllene SOA were quantified by using a thermodenuder allowing us to estimate the corresponding volatility distributions and effective vaporization enthalpies.

Ultrasonic degradation, mineralization and detoxification of diclofenac in water: optimization of operating parameters.

PubMed

Naddeo, V; Belgiorno, V; Kassinos, D; Mantzavinos, D; Meric, S

2010-01-01

The 20 kHz ultrasound-induced degradation of non-steroidal, anti-inflammatory drug diclofenac (DCF) was investigated. Several operating conditions, such as power density (25-100 W/L), substrate concentration (2.5-80 mg/L), initial solution pH (3.5-11), liquid bulk temperature and the type of sparging gas (air, oxygen, argon), were tested concerning their effect on DCF degradation (as assessed measuring absorbance at 276 nm) and hydroxyl radicals generation (as assessed measuring H(2)O(2) concentration). Sample mineralization (in terms of TOC and COD removal), aerobic biodegradability (as assessed by the BOD(5)/COD ratio) and ecotoxicity to Daphnia magna and Artemia salina were followed too. DCF conversion is enhanced at increased applied power densities and liquid bulk temperatures, acidic conditions and in the presence of dissolved air or oxygen. The reaction rate increases with increasing DCF concentration in the range 2.5-5mg/L but it remains constant in the range 40-80 mg/L, indicating different kinetic regimes (i.e. first and zero order, respectively). H(2)O(2) production rates in pure water are higher than those in DCF solutions, implying that decomposition basically proceeds through hydroxyl radical reactions. Mineralization is a slow process as reaction by-products are more stable than DCF to total oxidation; nonetheless, they are also more readily biodegradable. Toxicity to D. magna increases during the early stages of the reaction and then decreases progressively upon degradation of reaction by-products; nevertheless, complete toxicity elimination cannot be achieved at the conditions in question. Neither the original nor the treated DCF samples are toxic to A. salina.

Human Umbilical Cord Wharton's Jelly Stem Cell Conditioned Medium Induces Tumoricidal Effects on Lymphoma Cells Through Hydrogen Peroxide Mediation.

PubMed

Lin, Hao Daniel; Fong, Chui-Yee; Biswas, Arijit; Choolani, Mahesh; Bongso, Ariff

2016-09-01

Several groups have reported that human umbilical cord Wharton's jelly stem cells (hWJSCs) possess unique tumoricidal properties against many cancers. However, the exact mechanisms as to how hWJSCs inhibit tumor growth are not known. Recent evidence suggests that exposure of cancer cells to high hydrogen peroxide (H2 O2 ) levels from H2 O2 -releasing drugs causes their death. We therefore explored whether the tumoricidal effect of hWJSCs on lymphoma cells was mediated via H2 O2 . We first exposed lymphoma cells to six different molecular weight cut-off (MWCO) concentrates of hWJSC-conditioned medium (hWJSC-CM) (3, 5, 10, 30, 50, 100 kDa) for 48 h. Since, the 3 kDa-MWCO concentrate showed the greatest cell inhibition we then investigated whether the tumoricidal effect of the specific 3 kDa-MWCO concentrate on two different lymphoma cell lines (Ramos and Toledo) was mediated via accumulation of H2 O2 . We used a battery of assays (MTT, propidium iodide, mitochondria membrane potential, apoptosis, cell cycle, oxidative stress enzymes, hydrogen peroxide, mitochondrial superoxide, hydroxyl radical, peroxynitrile anion, and lipid peroxidation) to test this mechanism. The hWJSC-CM-3 kDa MWCO concentrate significantly decreased cell viability and mitochondrial membrane potential and increased cell death and apoptosis in both lymphoma cell lines. There were significant increases in superoxide dismutase with concomitant decreases in glutathione peroxidase, catalase, and thioredoxin peroxidase activities. H2 O2 levels, mitochondrial superoxide, hydroxyl radical, peroxynitrile anion, and lipid peroxidation were also significantly increased in both lymphoma cell lines. The results suggested that the hWJSC-CM-3 kDa MWCO concentrate regulates cellular H2 O2 leading to a tumoricidal effect and may thus be a promising anti-lymphoma agent. J. Cell. Biochem. 117: 2045-2055, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Sensitivity of Ca2+ transport of mitochondria to reactive oxygen species.

PubMed

Yang, Z W; Yang, F Y

1997-12-01

The relationship between Ca2+ transport and energy transduction of myocardial mitochondria in the presence of reactive oxygen species was investigated. Following treatment with oxygen free radicals [superoxide(O2.-) or hydroxyl radical (.OH)], lipid free radicals in myocardial mitochondrial membrane could be detected by using the method of EPR spin trap. Simultaneously there were obvious alterations in the free Ca2+ ([Ca2+]m) in the mitochondrial matrix; the physical state of membrane lipid; the efficiency of oxidative phosphorylation (ADP/O); the value of the respiratory control ratio (RCR); and the membrane potential of the inner membrane of myocardial mitochondria. If the concentrations of reactive oxygen species were reduced by about 30%, the alterations in the physical state of the membrane lipid and energy transduction of myocardial mitochondria were not observed, but the changes in Ca2+ homeostasis remained. We conclude that Ca2+ transport by myocardial mitochondria is more sensitive to agents such as O2.- or OH, etc. than are oxidation phosphorylation and the respiratory chain.

Curculigo orchioides protects cisplatin-induced cell damage.

PubMed

Kang, Tong Ho; Hong, Bin Na; Jung, Su-Young; Lee, Jeong-Han; So, Hong-Seob; Park, Raekil; You, Yong-Ouk

2013-01-01

Cisplatin is commonly used as a chemotherapeutic agent against many human cancers. However, it generates reactive oxygen species (ROS) and has serious dose-limiting side effects, including ototoxicity. The roots of Curculigo orchioides (C. orchioides) have been used to treat auditory diseases such as tinnitus and hearing loss in Chinese traditional medicine. In the present study, we investigated the protective effects of an ethanol extract obtained from C. orchioides rhizome (COR) on cisplatin-induced cell damage in auditory cells (HEI-OC1). COR (2.5-25 μg/ml) inhibited cisplatin-induced HEI-OC1 cell damage in a dose-dependent manner. To investigate the protective mechanism of COR on cisplatin cytotoxicity in HEI-OC1 cells, we measured the effects of COR on ROS generation and lipid peroxidation in cisplatin-treated cells as well as its scavenging activities against superoxide radicals, hydroxyl radicals, hydrogen peroxide, and DPPH radicals. COR (1-25 μg/ml) had scavenging activities against superoxide radicals, hydroxyl radicals, hydrogen peroxide, and DPPH radicals, as well as reduced lipid peroxidation. In in vivo experiments, COR was shown to reduce cochlear and peripheral auditory function impairments through cisplatin-induced auditory damage in mice. These results indicate that COR protects from cisplatin-induced auditory damage by inhibiting lipid peroxidation and scavenging activities against free radicals.

Antioxidant capacities vary substantially among cultivars of rabbiteye blueberry (Vaccinium ashei Reade)

USDA-ARS?s Scientific Manuscript database

Fruit from forty-two blueberry cultivars, including thirty-six rabbiteye (Vaccinium ashei Reade), three V. ashei hybrid derivatives and three northern highbush (V. corymbosum L.) were evaluated for their antioxidant activities against peroxyl free radicals, hydroxyl radicals, hydrogen peroxide, supe...

An ab initio investigation of possible intermediates in the reaction of the hydroxyl and hydroperoxyl radicals

NASA Technical Reports Server (NTRS)

Jackels, C. F.

1985-01-01

Ab initio quantum chemical techniques are used to investigate covalently-bonded and hydrogen-bonded species that may be important intermediates in the reaction of hydroxyl and hydroperoxyl radicals. Stable structures of both types are identified. Basis sets of polarized double zeta quality and large scale configuration interaction wave functions are utilized. Based on electronic energies, the covalently bonded HOOOH species is 26.4 kcal/mol more stable than the OH and HO2 radicals. Similarly, the hydrogen bonded HO---HO2 species has an electronic energy 4.7 kcal/mol below that of the component radicals, after correction is made for the basis set superposition error. The hydrogen bonded form is planar, possesses one relatively normal hydrogen bond, and has the lowest energy 3A' and 1A' states that are essentially degenerate. The 1A" and 3A" excited states produced by rotation of the unpaired OH electron into the molecular plane are very slightly bound.

A novel detection approach based on chromophore-decolorizing with free radical and application to photometric determination of copper with acid chrome dark blue.

PubMed

Gao, Hong-Wen; Chen, Fang-Fang; Chen, Ling; Zeng, Teng; Pan, Lu-Ting; Li, Jian-Hua; Luo, Hua-Fei

2007-03-21

A novel detection approach named chromophore-decolorizing with free radicals is developed for determination of trace heavy metal. The hydroxyl radicals (HO) generated from Fe(III) and hydrogen peroxide will oxidize the free chromophore into almost colorless products. The copper-acid chrome dark blue (ACDB) complexation was investigated at pH 5.07. In the presence of Fe(III) and hydrogen peroxide, the excess ACDB was decolorized in the Cu-ACDB reaction solution, and the final solution contained only one color compound, the Cu-ACDB complex. After oxidation of free hydroxyl radicals, the complexation becomes sensitive and selective and it has been used for the quantitation of trace amounts of Cu(II) dissolved in natural water. Beer's law is obeyed in the range from 0 to 0.500 microg mL(-1) Cu(II) and the limit of detection is only 6 microg L(-1) Cu(II). Besides, the Cu-ACDB complex formed was characterized.

Isolation, purification and characterization of antioxidative peptide of pearl millet (Pennisetum glaucum) protein hydrolysate.

PubMed

Agrawal, Himani; Joshi, Robin; Gupta, Mahesh

2016-08-01

Pearl millet (Pennisetum glaucum) is a rich source of protein, used for present study to hydrolyze protein, peptide separation and its functional activity. Antioxidative bioactive peptide was successfully identified from pearl millet using trypsin enzyme. Different antioxidative potential of isolated peptide were assessed based on activity of DPPH radical, ABTS radical, hydroxyl radical, Fe(2+) chelating ability and reducing power. Bioactive peptide separated by gel-filtration chromatography, showed the higher antioxidant activity as tested by different free radicals. The activity of pearl millet protein hydrolysate fraction was found for DPPH assay (67.66%), ABTS assay (78.81%), Fe(2+) chelating ability (51.20%), hydroxyl assay (60.95%) and reducing power (0.375nm) was further purified using reversed-phase UFLC and subjected to matrix assisted laser desorption/ionization time-of-flight/time-of-flight mass spectrometry (MALDI-TOF/TOF-MS) for sequential identification of the peptide. The sequence SDRDLLGPNNQYLPK was identified as antioxidant peptide. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparative antioxidant and anti-inflammatory effects of [6]-gingerol, [8]-gingerol, [10]-gingerol and [6]-shogaol.

PubMed

Dugasani, Swarnalatha; Pichika, Mallikarjuna Rao; Nadarajah, Vishna Devi; Balijepalli, Madhu Katyayani; Tandra, Satyanarayana; Korlakunta, Jayaveera Narsimha

2010-02-03

Zingiber officinale Rosc. (Zingiberaceae) has been traditionally used in Ayurvedic, Chinese and Tibb-Unani herbal medicines for the treatment of various illnesses that involve inflammation and which are caused by oxidative stress. Although gingerols and shogaols are the major bioactive compounds present in Zingiber officinale, their molecular mechanisms of actions and the relationship between their structural features and the activity have not been well studied. The aim of the present study was to examine and compare the antioxidant and anti-inflammatory activities of gingerols and their natural analogues to determine their structure-activity relationship and molecular mechanisms. The in vitro activities of the compounds [6]-gingerol, [8]-gingerol, [10]-gingerol and [6]-shogaol were evaluated for scavenging of 1,1-diphenyl-2-picyrlhydrazyl (DPPH), superoxide and hydroxyl radicals, inhibition of N-formyl-methionyl-leucyl-phenylalanine (f-MLP) induced reactive oxygen species (ROS) production in human polymorphonuclear neutrophils (PMN), inhibition of lipopolysaccharide induced nitrite and prostaglandin E(2) production in RAW 264.7 cells. In the antioxidant activity assay, [6]-gingerol, [8]-gingerol, [10]-gingerol and [6]-shogaol exhibited substantial scavenging activities with IC(50) values of 26.3, 19.47, 10.47 and 8.05 microM against DPPH radical, IC(50) values of 4.05, 2.5, 1.68 and 0.85 microM against superoxide radical and IC(50) values of 4.62, 1.97, 1.35 and 0.72 microM against hydroxyl radical, respectively. The free radical scavenging activity of these compounds also enhanced with increasing concentration (P<0.05). On the other hand, all the compounds at a concentration of 6 microM have significantly inhibited (P<0.05) f-MLP-stimulated oxidative burst in PMN. In addition, production of inflammatory mediators (NO and PGE(2)) has been inhibited significantly (P<0.05) and dose-dependently. 6-Shogaol has exhibited the most potent antioxidant and anti-inflammatory properties which can be attributed to the presence of alpha,beta-unsaturated ketone moiety. The carbon chain length has also played a significant role in making 10-gingerol as the most potent among all the gingerols. This study justifies the use of dry ginger in traditional systems of medicine. Copyright 2009 Elsevier Ireland Ltd. All rights reserved.

Advancements and Application of Microsecond Synchrotron X-ray Footprinting at the Advanced Light Source

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

Gupta, Sayan; Celestre, Rich; Feng, Jun

2016-01-02

The method of synchrotron X-ray protein footprinting (XF-MS) is used to determine protein conformational changes, folding, protein-protein and protein-ligand interactions, providing information which is often difficult to obtain using X-ray crystallography and other common structural biology methods [1 G. Xu and M.R. Chance, Chemical Reviews 107, 3514–3543 (2007). [CrossRef], [PubMed], [Web of Science ®], [Google Scholar] –3 V.N. Bavro, Biochem Soc Trans 43, 983–994 (2015). [CrossRef], [PubMed], [Web of Science ®], [Google Scholar] ]. The technique uses comparative in situ labeling of solvent-accessible side chains by highly reactive hydroxyl radicals (•OH) in buffered aqueous solution under different assay conditions. Inmore » regions where a protein is folded or binds a partner, these •OH susceptible sites are inaccessible to solvent, and therefore protected from labeling. The •OH are generated by the ionization of water using high-flux-density X-rays. High-flux density is a key factor for XF-MS labeling because obtaining an adequate steady-state concentration of hydroxyl radical within a short irradiation time is necessary to minimize radiation-induced secondary damage and also to overcome various scavenging reactions that reduce the yield of labeled side chains.« less

An Experimental Approach to Controllably Vary Protein Oxidation While Minimizing Electrode Adsorption for Boron-Doped Diamond Electrochemical Surface Mapping Applications

PubMed Central

McClintock, Carlee S; Hettich, Robert L.

2012-01-01

Oxidative protein surface mapping has become a powerful approach for measuring the solvent accessibility of folded protein structures. A variety of techniques exist for generating the key reagent – hydroxyl radicals – for these measurements; however, these approaches range significantly in their complexity and expense of operation. This research expands upon earlier work to enhance the controllability of boron-doped diamond (BDD) electrochemistry as an easily accessible tool for producing hydroxyl radicals in order to oxidize a range of intact proteins. Efforts to modulate oxidation level while minimizing the adsorption of protein to the electrode involved the use of relatively high flow rates to reduce protein residence time inside the electrochemical flow chamber. Additionally, a different cell activation approach using variable voltage to supply a controlled current allowed us to precisely tune the extent of oxidation in a protein-dependent manner. In order to gain perspective on the level of protein adsorption onto the electrode surface, studies were conducted to monitor protein concentration during electrolysis and gauge changes in the electrode surface between cell activation events. This report demonstrates the successful use of BDD electrochemistry for greater precision in generating a target number of oxidation events upon intact proteins. PMID:23210708

Soil organic matter-hydrogen peroxide dynamics in the treatment of contaminated soils and groundwater using catalyzed H2O2 propagations (modified Fenton's reagent).

PubMed

Bissey, Lauren L; Smith, Jeffrey L; Watts, Richard J

2006-07-01

The interactions between catalyzed H(2)O(2) propagations (CHP-i.e. modified Fenton's reagent) and soil organic matter (SOM) during the treatment of contaminated soils and groundwater was studied in a well-characterized surface soil. The fate of two fractions of SOM, particulate organic matter (POM) and nonparticulate organic matter (NPOM), during CHP reactions was evaluated using concentrations of hydrogen peroxide from 0.5 to 3M catalyzed by soluble iron (III), an iron (III)-ethylenediamine tetraacetic acid (EDTA) chelate, or naturally-occurring soil minerals. The destruction of total SOM in CHP systems was directly proportional to the hydrogen peroxide dosage, and was significantly greater at pH 3 than at neutral pH; furthermore, SOM destruction occurred predominantly in the NPOM fraction. At pH 3, SOM did not affect hydrogen peroxide decomposition rates or hydroxyl radical activity in CHP reactions. However, at neutral pH, increasing the mass of SOM decreased the hydrogen peroxide decomposition rate and increased the rate of hydroxyl radical generation in CHP systems. These results show that, while CHP reactions destroy some of the organic carbon pools, SOM does not have a significant effect on the CHP treatment of soils and groundwater.

Direct and indirect photodegradation of estriol in the presence of humic acid, nitrate and iron complexes in water solutions.

PubMed

Chen, Yong; Zhang, Kai; Zuo, Yuegang

2013-10-01

The photochemical behavior of a natural estrogen estriol (E3) was investigated in the presence of the natural photoreactive constituents including nitrate, iron(III), and humic acid (HA). The direct photodegradation of E3 increased with increasing incident light intensity, decreasing initial concentration of E3 and increasing pH in the range of 6.0 to 10.0. The direct photodegradation of the deprotonated speciation of E3 was much faster than that of its protonated form. The presence of NO3(-) and iron(III) promoted the photochemical loss of E3 in the aqueous solutions. The quenching experiments verified that hydroxyl radicals were predominantly responsible for the indirect photodegradation of E3. HA could act as photosensitizer, light screening agent and free radical quencher. For the first time, the enhancement or inhibition effect of HA on photodegradation was found to depend on the irradiation light intensity. HA enhanced the photodegradation of E3 under sunlight or weak irradiation of simulated sunlight. In contrast, under high irradiation light intensity, HA inhibited the photodegradation. The hydroxylation photoproducts were identified using GC-MS and the photodegradation pathway of E3 was proposed. Copyright © 2013 Elsevier B.V. All rights reserved.

Oxidant-induced DNA damage of target cells.

PubMed Central

Schraufstätter, I; Hyslop, P A; Jackson, J H; Cochrane, C G

1988-01-01

In this study we examined the leukocytic oxidant species that induce oxidant damage of DNA in whole cells. H2O2 added extracellularly in micromolar concentrations (10-100 microM) induced DNA strand breaks in various target cells. The sensitivity of a specific target cell was inversely correlated to its catalase content and the rate of removal of H2O2 by the target cell. Oxidant species produced by xanthine oxidase/purine or phorbol myristate acetate-stimulated monocytes induced DNA breakage of target cells in proportion to the amount of H2O2 generated. These DNA strand breaks were prevented by extracellular catalase, but not by superoxide dismutase. Cytotoxic doses of HOCl, added to target cells, did not induce DNA strand breakage, and myeloperoxidase added extracellularly in the presence of an H2O2-generating system, prevented the formation of DNA strand breaks in proportion to its H2O2 degrading capacity. The studies also indicated that H2O2 formed hydroxyl radical (.OH) intracellularly, which appeared to be the most likely free radical responsible for DNA damage: .OH was detected in cells exposed to H2O2; the DNA base, deoxyguanosine, was hydroxylated in cells exposed to H2O2; and intracellular iron was essential for induction of DNA strand breaks. PMID:2843565

Pyrrole Alkaloids with Potential Cancer Chemopreventive Activity Isolated from a Goji Berry-Contaminated Commercial Sample of African Mango

PubMed Central

2015-01-01

Bioassay-guided fractionation of a commercial sample of African mango (Irvingia gabonensis) that was later shown to be contaminated with goji berry (Lycium sp.) led to the isolation of a new pyrrole alkaloid, methyl 2-[2-formyl-5-(hydroxymethyl)-1H-pyrrol-1-yl]propanoate, 1, along with seven known compounds, 2–8. The structures of the isolated compounds were established by analysis of their spectroscopic data. The new compound 1g showed hydroxyl radical-scavenging activity with an ED50 value of 16.7 μM, whereas 4-[formyl-5-(methoxymethyl)-1H-pyrrol-1-yl]butanoic acid (2) was active in both the hydroxyl radical-scavenging (ED50 11.9 μM) and quinone reductase-induction [CD (concentration required to double QR activity) 2.4 μM)] assays used. The isolated compounds were shown to be absent in a taxonomically authenticated African mango sample but present in three separate authentic samples of goji berry (Lycium barbarum) using LC-MS and 1H NMR fingerprinting analysis, including one sample that previously showed inhibitory activity in vivo in a rat esophageal cancer model induced with N-nitrosomethylbenzylamine. Additionally, microscopic features characteristic of goji berry were observed in the commercial African mango sample. PMID:24792835

Insights into the Role of Humic Acid on Pd-catalytic Electro-Fenton Transformation of Toluene in Groundwater

PubMed Central

Liao, Peng; Al-Ani, Yasir; Malik Ismael, Zainab; Wu, Xiaohui

2015-01-01

A recently developed Pd-based electro-Fenton (E-Fenton) process enables efficient in situ remediation of organic contaminants in groundwater. In the process, H2O2, Fe(II), and acidic conditions (~pH 3) are produced in situ to facilitate the decontamination, but the role of ubiquitous natural organic matters (NOM) remain unclear. This study investigated the effect of Aldrich humic acid (HA) on the transformation of toluene by the Pd-based E-Fenton process. At pH 3 with 50 mA current, the presence of HA promoted the efficiency of toluene transformation, with pseudo-first-order rate constants increase from 0.01 to 0.016 as the HA concentration increases from 0 to 20 mg/L. The HA-enhanced toluene transformation was attributed to the accelerated thermal reduction of Fe(III) to Fe(II), which led to production of more hydroxyl radicals. The correlation of the rate constants of toluene transformation and HA decomposition validated hydroxyl radical (·OH) as the predominant reactive species for HA decomposition. The finding of this study highlighted that application of the novel Pd-based E-Fenton process in groundwater remediation may not be concerned by the fouling from humic substances. PMID:25783864

Insights into the role of humic acid on Pd-catalytic electro-Fenton transformation of toluene in groundwater.

PubMed

Liao, Peng; Al-Ani, Yasir; Malik Ismael, Zainab; Wu, Xiaohui

2015-03-18

A recently developed Pd-based electro-Fenton (E-Fenton) process enables efficient in situ remediation of organic contaminants in groundwater. In the process, H₂O₂, Fe(II), and acidic conditions (~pH 3) are produced in situ to facilitate the decontamination, but the role of ubiquitous natural organic matters (NOM) remain unclear. This study investigated the effect of Aldrich humic acid (HA) on the transformation of toluene by the Pd-based E-Fenton process. At pH 3 with 50 mA current, the presence of HA promoted the efficiency of toluene transformation, with pseudo-first-order rate constants increase from 0.01 to 0.016 as the HA concentration increases from 0 to 20 mg/L. The HA-enhanced toluene transformation was attributed to the accelerated thermal reduction of Fe(III) to Fe(II), which led to production of more hydroxyl radicals. The correlation of the rate constants of toluene transformation and HA decomposition validated hydroxyl radical (·OH) as the predominant reactive species for HA decomposition. The finding of this study highlighted that application of the novel Pd-based E-Fenton process in groundwater remediation may not be concerned by the fouling from humic substances.

2,4,8-trihydroxybicyclo [3.2.1]octan-3-one scavenges free radicals and protects against xenobiotic-induced cytotoxicity.

PubMed

Srivastava, Anup; Jagan Mohan Rao, L; Shivanandappa, T

2012-03-01

Currently, there is a great deal of interest in the study of natural compounds with free-radical-scavenging activity because of their potential role in maintaining human health and preventing diseases. In this paper, we report the antioxidant and cytoprotective properties of 2,4,8-trihydroxybicyclo [3.2.1]octan-3-one (TBO) isolated from the aqueous extract of Decalepis hamiltonii roots. Our results show that TBO is a potent scavenger of superoxide (O(2)·-), hydroxyl (·OH), nitric oxide (·NO) and lipid peroxide (LOO·) - physiologically relevant free radicals with IC(50) values in nmolar (42-281) range. TBO also exhibited concentration-dependent secondary antioxidant activities such as reducing power, metal-chelating activity and inhibition of protein carbonylation. Further, TBO at nmolar concentration prevented CuSO(4)-induced human LDL oxidation. Apart from the in vitro free-radical-scavenging activity, TBO demonstrated cytoprotective activity in primary hepatocytes and Ehrlich ascites tumour (EAT) cells against oxidative-stress-inducing xenobiotics. The mechanism of cytoprotective action involved maintaining the intracellular glutathione (GSH), scavenging of reactive oxygen species (ROS) and inhibiting lipid peroxidation (LPO). Based on the results, it is suggested that TBO is a novel bioactive molecule with implications in both prevention and amelioration of diseases involving oxidative stress as well as in the general well-being.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Studies on the preparation of Caro’s acid by ultrasonic enhanced electrochemistry

NASA Astrophysics Data System (ADS)

Li, Linbo; Yu, Zeli; Hong, Tao; Fang, Zhao; Peng, Jishi; Yang, Zhao

2017-06-01

Ultrasonic cavitation effects can generate hydroxyl radicals and high energy, which is widely applied in the field of oxidation currently. Ultrasound-enhanced electrochemical is used to prepare Caro’s acid, which improves the generate rate of Caro’s acid. In this article, the influences of ultrasonic frequency and ultrasonic power on the electrolysis voltage, electrolyte temperature, electrolyte concentration and the concentration of additive in the process of electrochemical preparation of Caro’s acid was studied. And the optimal production conditions were determined. The research results showed that ultrasonic can significantly improve the production of Caro’s acid and the product can increase by about 20 g/L under the best condition.

One- or two-electron water oxidation, hydroxyl radical, or H 2O 2 evolution

DOE PAGES

Siahrostami, Samira; Li, Guo -Ling; Viswanathan, Venkatasubramanian; ...

2017-02-23

Electrochemical or photoelectrochemcial oxidation of water to form hydrogen peroxide (H 2O 2) or hydroxyl radicals (•OH) offers a very attractive route to water disinfection, and the first process could be the basis for a clean way to produce hydrogen peroxide. A major obstacle in the development of effective catalysts for these reactions is that the electrocatalyst must suppress the thermodynamically favored four-electron pathway leading to O 2 evolution. Here, we develop a thermochemical picture of the catalyst properties that determine selectivity toward the one, two, and four electron processes leading to •OH, H 2O 2, and O 2.

Time resolved study of hydroxyl radical oxidation of oleic acid at the air-water interface

NASA Astrophysics Data System (ADS)

Zhang, Xinxing; Barraza, Kevin M.; Upton, Kathleen T.; Beauchamp, J. L.

2017-09-01

The ubiquity of oleic acid (OA) renders it a poster child for laboratory investigations of environmental oxidation chemistry. In the current study, mechanistic details of the oxidation of OA by hydroxyl radicals at the air-water interface are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Products from OH oxidation of both unsaturated and saturated carbon atoms are identified, and mechanisms for both types of oxidation processes are proposed. Uptake of oxygen in the interfacial layer increases linearly with time, consistent with Langmuir-Hinshelwood reaction kinetics. These results provide fundamental knowledge relating to OH initiated degradation of fatty acids in atmospheric aerosols.

Aromatic hydroxylation by cytochrome P450: model calculations of mechanism and substituent effects.

PubMed

Bathelt, Christine M; Ridder, Lars; Mulholland, Adrian J; Harvey, Jeremy N

2003-12-10

The mechanism and selectivity of aromatic hydroxylation by cytochrome P450 enzymes is explored using new B3LYP density functional theory computations. The calculations, using a realistic porphyrin model system, show that rate-determining addition of compound I to an aromatic carbon atom proceeds via a transition state with partial radical and cationic character. Reactivity is shown to depend strongly on ring substituents, with both electron-withdrawing and -donating groups strongly decreasing the addition barrier in the para position, and it is shown that the calculated barrier heights can be reproduced by a new dual-parameter equation based on radical and cationic Hammett sigma parameters.

A characterization of the two-step reaction mechanism of phenol decomposition by a Fenton reaction

NASA Astrophysics Data System (ADS)

Valdés, Cristian; Alzate-Morales, Jans; Osorio, Edison; Villaseñor, Jorge; Navarro-Retamal, Carlos

2015-11-01

Phenol is one of the worst contaminants at date, and its degradation has been a crucial task over years. Here, the decomposition process of phenol, in a Fenton reaction, is described. Using scavengers, it was observed that decomposition of phenol was mainly influenced by production of hydroxyl radicals. Experimental and theoretical activation energies (Ea) for phenol oxidation intermediates were calculated. According to these Ea, phenol decomposition is a two-step reaction mechanism mediated predominantly by hydroxyl radicals, producing a decomposition yield order given as hydroquinone > catechol > resorcinol. Furthermore, traces of reaction derived acids were detected by HPLC and GS-MS.

Influence of pH, buffers and role of quinolinic acid, a novel iron chelating agent, in the determination of hydroxyl radical scavenging activity of plant extracts by Electron Paramagnetic Resonance (EPR).

PubMed

Fadda, Angela; Barberis, Antonio; Sanna, Daniele

2018-02-01

The Fenton reaction is used to produce hydroxyl radicals for the evaluation of the antioxidant activity of plant extracts. In this paper the parameters affecting the production of hydroxyl radicals and their spin trapping with DMPO were studied. The use of quinolinic acid (Quin) as an Fe(II) ligand was proposed for antioxidant activity determination of Green tea, orange juice and asparagus extracts. Quin, buffers and pH affect the DMPO-OH signal intensity of the EPR spectra. Quin/Fe(II) and low pH enhance the OH generation. Phosphate and Tris-HCl buffers decrease the signal intensity measured in Fe(II)-sulfate and Fe(II)-Quin systems. The extracts were analyzed with Fenton systems containing Fe(II)-sulfate and Fe(II)-Quin with and without buffer. The highest activity was shown with Fe(II)-Quin without buffer, this system being less influenced by pH and chelating agents present in the extracts. This paper will help researchers to better design spin trapping experiments for food matrices. Copyright © 2017 Elsevier Ltd. All rights reserved.

Physical and chemical properties of pyropheophorbide-a methyl ester in ethanol, phosphate buffer and aqueous dispersion of small unilamellar dimyristoyl-L-alpha-phosphatidylcholine vesicles.

PubMed

Delanaye, Lisiane; Bahri, Mohamed Ali; Tfibel, Francis; Fontaine-Aupart, Marie-Pierre; Mouithys-Mickalad, Ange; Heine, Bélinda; Piette, Jacques; Hoebeke, Maryse

2006-03-01

The aggregation process of pyropheophorbide-a methyl ester (PPME), a second-generation photosensitizer, was investigated in various solvents. Absorption and fluorescence spectra showed that the photosensitizer was under a monomeric form in ethanol as well as in dimyristoyl-L-alpha-phosphatidylcholine liposomes while it was strongly aggregated in phosphate buffer. A quantitative determination of reactive oxygen species production by PPME in these solvents has been undertaken by electron spin resonance associated with spin trapping technique and absorption spectroscopy. In phosphate buffer, both electron spin resonance and absorption measurements led to the conclusion that singlet oxygen production was not detectable while hydroxyl radical production was very weak. In liposomes and ethanol, singlet oxygen and hydroxyl radical production increased highly; the singlet oxygen quantum yield was determined to be 0.2 in ethanol and 0.13 in liposomes. The hydroxyl radical production origin was also investigated. Singlet oxygen was formed from PPME triplet state deactivation in the presence of oxygen. Indeed, the triplet state formation quantum yield of PPME was found to be about 0.23 in ethanol, 0.15 in liposomes (too small to be measured in PBS).

Modelling of The Atmospheric Chemistry of Organic Nitrates

NASA Astrophysics Data System (ADS)

Winsland, N.

Organic nitrates are linked to the formation of tropospheric ozone and the cycling and transport of nitrogen-containing species in the atmosphere. Few laboratory stud- ies have been carried out on the reactions of organic nitrates. Photolysis quantum yield studies and UV absorption spectra have been carried out for the simple alkyl nitrates and PAN. Studies of PAN and ethyl nitrate with other atmospheric components (the hydroxyl radical - OH - and the chlorine atom - Cl) have been carried out to mea- sure their rates of reaction. However, the products and mechanisms of these reactions are poorly understood. We present here the results of modelling the reactions of the C1-C8 alkyl nitrates and PAN with the hydroxyl radical. These models are based on information from current literature and from photochemical reactor studies carried out at the Environment Institute, EU Joint Research Centre, Ispra, Italy. These studies give us a more detailed understanding of the mechanisms and products of the atmospheric loss of organic nitrates due to reaction with the hydroxyl radical. Preliminary studies show that the major products are aldehydes, ketones, nitro-oxy aldehydes, nitro-oxy ketones, NOx and nitric acid.

Importance of Extracellular Processes in the Oxygen Enhancement of Radiation Lethality.

DTIC Science & Technology

1982-03-08

radical oxygen toxicity superoxide dismutases methyl viologen hydroxyl radical pyocyanine o. Lactobacillus plantarum manganese Streptococcus sanguis gene...Against Oxygen Toxicity in Lactobacillus plantarum . F. S. Archibald and I. Fridovich. Superoxide Dismutases: Detoxication of a Free Radical. H. M. Hassan...S. Archibald and I. Fridovich 7 Investigations of the State of the Manganese in Lactobacillus plantarum . F. S. Archibald and I. Fridovich Superoxide

EMERGING TECHNOLOGY BULLETIN: REMOVAL OF PHENOL FROM AQUEOUS SOLUTIONS USING HIGH ENERGY ELECTRON BEAM IRRADIATION

EPA Science Inventory

Irradiation of aqueous solutions with high-energy electrons results in the formation of the aqueous electron, hydrogen radical, H-, and the hydroxyl radical, OH-. These reactive transient species initiate chemical reactions capable of destroying organic compounds in aqueous solut...

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.

New evidence on the formation of oxidizing species in corona discharge in contact with liquid and their reactions with organic compounds.

PubMed

Magureanu, M; Dobrin, D; Bradu, C; Gherendi, F; Mandache, N B; Parvulescu, V I

2016-12-01

The objective of these investigations is to understand in more detail how organic compounds in water are degraded during plasma treatment. The formation of oxidizing species (ozone (O 3 ), hydrogen peroxide (H 2 O 2 ) and hydroxyl radicals (OH)) in a pulsed corona discharge in contact with liquid is investigated. The degradation of a target organic compound (methylparaben) in aqueous solution was increased when combining plasma treatment with ozonation, using the O 3 generated in the discharge. Enhanced mass transfer of O 3 obtained in this plasma+O 3 configuration leads to a six fold increase of MeP oxidation rate. The evolution of oxidants concentration during treatment of MeP solutions provides information on their consumption in reactions with MeP and its oxidation products. The correlation of MeP degradation results (MeP removal and mineralization) with O 3 consumption and the identified reaction products confirms that although O 3 plays an important role in the degradation, for the mineralization OH radicals have an essential contribution. The concentration of OH radicals is diminished in the solutions containing MeP as compared to plasma-treated water, indicating OH consumption in reactions with the target compound and its degradation products. The concentration of H 2 O 2 in the liquid can be either increased or reduced in the presence of MeP, depending on its initial concentration. On the one hand, decomposition of H 2 O 2 by OH or O 3 is suppressed in the presence of MeP, but on the other hand less OH radicals are available for its formation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Amyloid beta-Cu2+ complexes in both monomeric and fibrillar forms do not generate H2O2 catalytically but quench hydroxyl radicals.

PubMed

Nadal, Rebecca C; Rigby, Stephen E J; Viles, John H

2008-11-04

Oxidative stress plays a key role in Alzheimer's disease (AD). In addition, the abnormally high Cu(2+) ion concentrations present in senile plaques has provoked a substantial interest in the relationship between the amyloid beta peptide (Abeta) found within plaques and redox-active copper ions. There have been a number of studies monitoring reactive oxygen species (ROS) generation by copper and ascorbate that suggest that Abeta acts as a prooxidant producing H2O2. However, others have indicated Abeta acts as an antioxidant, but to date most cell-free studies directly monitoring ROS have not supported this hypothesis. We therefore chose to look again at ROS generation by both monomeric and fibrillar forms of Abeta under aerobic conditions in the presence of Cu(2+) with/without the biological reductant ascorbate in a cell-free system. We used a variety of fluorescence and absorption based assays to monitor the production of ROS, as well as Cu(2+) reduction. In contrast to previous studies, we show here that Abeta does not generate any more ROS than controls of Cu(2+) and ascorbate. Abeta does not silence the redox activity of Cu(2+/+) via chelation, but rather hydroxyl radicals produced as a result of Fenton-Haber Weiss reactions of ascorbate and Cu(2+) rapidly react with Abeta; thus the potentially harmful radicals are quenched. In support of this, chemical modification of the Abeta peptide was examined using (1)H NMR, and specific oxidation sites within the peptide were identified at the histidine and methionine residues. Our studies add significant weight to a modified amyloid cascade hypothesis in which sporadic AD is the result of Abeta being upregulated as a response to oxidative stress. However, our results do not preclude the possibility that Abeta in an oligomeric form may concentrate the redox-active copper at neuronal membranes and so cause lipid peroxidation.

Significant HONO concentration at a semi-rural site in the Pearl River Delta during a severe pollution period and its impact on atmospheric oxidation capacity

NASA Astrophysics Data System (ADS)

Yun, H.; Wang, T.; Wang, W.; Yu, C.; Xia, M.; Xue, L.; Wang, Z.; Zhang, N.; Poon, S.; Zhou, Y.; Yue, D.; Zhai, Y.

2017-12-01

Nitrous acid (HONO) is an important source of hydroxyl radical (OH) in the boundary layer, and has considerable impact on atmospheric oxidation capacity and ozone formation. However, the abundance of HONO and subsequent effects under severe pollution conditions, especially in winter, has not been thoroughly investigated. We conducted an intensive observation at a semi-rural site (Heshan) in the center of the Pearl River Delta (PRD) in January 2017. Extremely high HONO concentrations (up to 9.0 ppbv) were observed with a LOng-Path Absorption Photometer (LOPAP) in a severe pollution episode with especially high PM2.5 ( 400 μg m-3) and O3 ( 160 ppbv). HONO sustained at a relatively high level in the morning and had peaks even in the afternoon. An observation-based box model (OBM) built on Master Chemical Mechanism (MCM v3.3.1) was used to simulate the formation of HONO and its contribution to the radical concentrations. The results showed that HONO was the dominant source of primary radicals (= OH+HO2+RO2) and governed the in-situ production of ozone. Currently-identified HONO sources were added into the model to reveal the formation process of HONO during both the nighttime and daytime, and the relative importance of these sources will be discussed.

Spectroscopic study of degradation products of ciprofloxacin, norfloxacin and lomefloxacin formed in ozonated wastewater.

PubMed

Liu, Chen; Nanaboina, Venkateswarlu; Korshin, Gregory V; Jiang, Wenju

2012-10-15

This study addressed the formation and properties of degradation products of ciprofloxacin, norfloxacin and lomefloxacin formed during ozonation of secondary wastewater effluent containing these fluoroquinolone antibiotics. The generation of the degradation products was interpreted in the context of transformations of effluent organic matter (EfOM) tracked via absorbance measurements. The structures of 20 degradation products were elucidated for ciprofloxacin and norfloxacin, respectively. 27 degradation products were identified for lomefloxacin. The prevalent oxidation pathways were suggested based on the structures of the identified products formed in the absence and presence of the hydroxyl radical scavenger t-butanol. These pathways were largely similar for all studied fluoroquinolones and involved attacks on the piperazine ring and the quinolone structure. The quinolone ring remained intact in the presence of t-butanol thus indicating that this functional group could only be oxidized by OH radicals while the piperazine ring was readily oxidized by molecular ozone. The cleavage of the quinolone moiety that resulted in several identified degradation products occurred via the attack by hydroxyl radicals on the carbon-carbon double bond adjacent to the carboxylic acid group. Lomefloxacin had more diverse oxidation products due to the presence of a methyl group on its piperazinyl ring. The concentrations of the identified degradation products behaved non-monotonically as a function of ozone dose or treatment time, yet exhibited interpretable correlations versus changes of EfOM absorbance. Examination of these correlations allowed developing a novel approach for elucidating the transformations of fluoroquinolone antibiotics during ozonation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Photochemical behavior of carbon nanotubes in natural waters: reactive oxygen species production and effects on •OH generation by Suwannee River fulvic acid, nitrate, and Fe (III).

PubMed

Zhou, Lei; Zhang, Ya; Wang, Qi; Ferronato, Corinne; Yang, Xi; Chovelon, Jean-Marc

2016-10-01

The photochemical activities of three kinds of carbon nanotubes (CNTs) were investigated in the present study. Efficient procedures of dispersing the three kinds of carbon nanotubes in water were established, and the quantitative analysis methods were also developed by TOC-absorbance method. High pH value or low ionic strength of the colloidal solutions facilitated the dispersion of CNTs. The suspensions of three kinds of CNTs could generate singlet oxygen ((1)O2) and hydroxyl radical (•OH) under irradiation of simulated sunlight, while superoxide radical (O2 (•-)) was not detected. The steady-state concentrations of (1)O2 and •OH generated by these CNTs were also determined. The presence of CNTs in natural waters can affect the photochemical behavior of water constituents, such as nitrate, dissolved organic matter, and Fe(3+). Specifically, in nitrate solution, the presence of CNTs could inhibit the generation of •OH by nitrate through light screening effect, while the quenching effect of hydroxyl radicals by CNTs was not observed. Besides light screening effect, the three kinds of CNTs used in the experiments also have a strong inhibiting effect on the ability of DOM to produce •OH by binding to the active sites. Moreover, the adsorption of Fe(3+) on MWCNT-OH and MWCNT-COOH could lead to its inactivation of formation of •OH in acidic conditions. However, the presence of the three kinds of CNTs did not affect the ligand-to-metal charge transfer (LMCT) reaction of DOM-Fe (III) complex.

Sulfated polysaccharides with antioxidant and anticoagulant activity from the sea cucumber Holothuria fuscogliva

NASA Astrophysics Data System (ADS)

Li, Rongfeng; Yu, Huahua; Yue, Yang; Liu, Song; Xing, Rong'e.; Chen, Xiaolin; Li, Pengcheng

2017-07-01

Sea cucumber is a traditional nutritional food and medicinal resource with many bioactive components in China. Holothuria fuscogliva is a big sea cucumber with a rich of bioactive polysaccharides. To investigate the bioactivities of the polysaccharides from sea cucumber H. fuscogliva, we prepared the sulfated polysaccharides (HfP) from sea cucumber H. fuscogliva using a protease hydrolysis method. Antioxidant activities of HfP were investigated, including hydroxyl radical scavenging activity and superoxide radical scavenging activity. And, the anticoagulant activities of HfP were studied, including the activated partial thromboplastin time (APTT), prothrombin time (PT) and thrombin time (TT). The average molecular weight was 1 867.1 Da, with a sulfate content of 20.7%. In addition, the molar ratio of monosaccharide composition of HfP was Man: Rha: Glc A: Glc: Gal: Xyl: Fuc=0.083 6: 0.437: 0.134: 0:1.182: 0.748: 1. It had a strong antioxidant activity, the hydroxyl and superoxide radical scavenging activity EC50 of HfP was 3.74 and 0.037 mg/mL, respectively. It also showed a good anticoagulant activity in our study. The APTT of HfP was much higher than that of heparin sodium, and the PT and TT of HfP was close to that of heparin sodium at a low concentration. Therefore, HfP shows a good antioxidant and anticoagulant activity and it may become a potential candidate of the natural antioxidant and anticoagulant and will have a good application future in health product or medicine industry.

Comparative antioxidant activity of cultivated and wild Vaccinium species investigated by EPR, human neutrophil burst and COMET assay.

PubMed

Braga, P C; Antonacci, R; Wang, Y Y; Lattuada, N; Dal Sasso, M; Marabini, L; Fibiani, M; Lo Scalzo, R

2013-01-01

The Vaccinium (V.) spp. berries are considered a source of antioxidants, mainly belonging to polyphenols, specifically flavonoids and anthocyanins. Wild genotypes generally contain more antioxidants than cultivated counterparts. So, seven different antioxidants assays on extracts from cultivated and wild Vaccinium berries were performed, to evaluate their difference in terms of bioactivity on oxidative protection and minimum dosage to have a significant action. Four cell-free antioxidant assays (ABTS radical scavenging and electronic paramagnetic resonance using Fremy's salt, superoxide anion and hydroxyl radical), and three assays on human cells (two luminol amplified chemiluminescence, LACL, one on DNA damage, COMET) were used to measure the effects of cultivated blueberry (V. corymbosum) and wild bilberry (V. myrtillus) on the differently induced oxidative stress. Concentrations vs activity patterns were obtained by successive dilutions of extracts in order to identify both EC50 and minimum significant activity (MSA). All the assays (except for the hydroxyl radical scavenging) showed a good relationship mainly with anthocyanin and polyphenol content and the significant greater activity of wild Vaccinium extracts. In fact, LACL data gave an EC50 of 11.8 and an MSA of 5.2 g were calculated as fresh weight dosage in cultivated berries, compared with lower doses in wild berries, EC50 of 5.7 g and MSA of 3.4 g. Wild Vaccinium extracts averaged 3.04 and 2.40 fold more activity than cultivated extracts by EC50 and MSA, respectively. COMET assay confirmed the stronger action on DNA protection in wild samples.

Cytotoxic and radioprotective effects of Podophyllum hexandrum.

PubMed

Shukla, Sandeep Kumar; Chaudhary, Pankaj; Prem Kumar, Indracanti; Afrin, Farhat; Puri, Satish Chandra; Qazi, Ghulam Nabi; Sharma, Rakesh Kumar

2006-07-01

Podophyllum hexandrum, a herb thriving in Himalayas has already been reported to exhibit antitumor and radioprotective properties. Present study was undertaken to unravel the possible mechanism responsible for the cytotoxic and radioprotective properties of REC-2001, a fraction isolated from the rhizome of P. hexandrum using murine peritoneal macrophages and plasmid DNA as model systems. Cell death, levels of intracellular reactive oxygen species (ROS) and apoptosis were studied employing trypan blue exclusion assay, dichlorofluorescein diacetate and DNA fragmentation assay, respectively. Superoxide anions, hydroxyl radicals and DNA damage were estimated following nitroblue tetrazolium, 2-deoxyribose degradation and plasmid DNA relaxation assays, respectively. Pre-irradiation administration of REC-2001 to peritoneal macrophages in the concentration range of 25-200μg/ml significantly reduced radiation induced ROS generation, DNA damage, apoptosis and cell killing in comparison to radiation control group indicating radioprotective potential. Studies with plasmid DNA indicated the ability of REC-2001 to inhibit 20Gy induced single and double strand breaks further supporting the antioxidative potential. However, REC-2001 in a dose-dependent fashion induced cell death, ROS and DNA fragmentation indicating the cytotoxic nature. REC-2001, in presence of 100μM copper sulfate, generated significant amount of hydroxyl radicals and superoxide anions indicating ability to act as a pro-oxidant in presence of metal ions. The superoxide anion generation was found to be sensitive to metal chelators like EDTA and deferoxamine mesylate (DFR). These results suggest that the ability of REC-2001 to act as a pro-oxidant in presence of metal ions and antioxidant in presence of free radicals might be responsible for cytotoxic and radioprotective properties.

Would Phoenix Dactyflera Pollen (palm seed) be considered as a treatment agent against Males' infertility? A systematic review.

PubMed

Fallahi, Soghra; Rajaei, Minoo; Malekzadeh, Kianoosh; Kalantar, Seyed Mehdi

2015-12-01

Oxidative stress is a key factor involved in male infertility, which is due to an unnatural increase in environmental free radicals. In the majority of cases, this has a negative effect on a male's ability to impregnate a female. Currently, it is believed that spermatozoa can be protected against the damages induced by oxidative stress by saturating sperm with antioxidants. The antioxidant role of phoenix dactylifera pollen is capable of collecting the reactive oxygen and neutralizing it in and out of body cells. The present research provides a review of the antioxidant roles of phoenix dactylifera pollen on male infertility. This research is based on English-Language studies and articles found by comprehensively reviewing electronic databases, websites, books, and academic articles over the last 10 years. The phenolic compounds of phoenix dactylifera pollen, due to the existing polyphenols, are strong chelators of heavy metals. Therefore, they are effective in eliminating environmental hydroxyl radicals. Moreover, these plants have high capacities of eliminating hydroxyl free radicals, picrylhydrazyl, diphenyl and phoenix dactylifera pollen and also inhibiting glutathione-S-transferase (GST). Currently, the use of herbal antioxidants to neutralize reactive oxygen species (ROS) and reduce the negative effects of oxidative stress on body cells and tissues has attracted researchers' attention. Various substances, such as flavonoids and catechins, perform their antioxidant role by increasing the concentration of glutathione peroxidase. The final product of this process is an increase in the number of motile sperm, which can have significant effects on fertility.

Powerful bacterial killing by buckwheat honeys is concentration-dependent, involves complete DNA degradation and requires hydrogen peroxide.

PubMed

Brudzynski, Katrina; Abubaker, Kamal; Wang, Tony

2012-01-01

Exposure of bacterial cells to honey inhibits their growth and may cause cell death. Our previous studies showed a cause-effect relationship between hydroxyl radical generated from honey hydrogen peroxide and growth arrest. Here we explored the role of hydroxyl radicals as inducers of bacterial cells death. The bactericidal effect of ·OH on antibiotic-resistant clinical isolates of MRSA and VRE and standard bacterial strains of E. coli and B. subtiles was examined using a broth microdilution assay supplemented with 3'-(p-aminophenyl) fluorescein (APF) as the ·OH trap, followed by colony enumeration. Bactericidal activities of eight honeys (six varieties of buckwheat, blueberry and manuka honeys) were analyzed. The MBC/MIC ratio ≤4 and the killing curves indicated that honeys exhibited powerful, concentration-dependent bactericidal effect. The extent of killing depended on the ratio of honey concentration to bacterial load, indicating that honey dose was critical for its bactericidal efficacy. The killing rate and potency varied between honeys and ranged from over a 6-log(10) to 4-log(10) CFU/ml reduction of viable cells, equivalent to complete bacterial eradication. The maximal killing was associated with the extensive degradation of bacterial DNA. Honey concentration at which DNA degradation occurred correlated with cell death observed in the concentration-dependent cell-kill on agar plates. There was no quantitative relationship between the ·OH generation by honey and bactericidal effect. At the MBC, where there was no surviving cells and no DNA was visible on agarose gels, the ·OH levels were on average 2-3x lower than at Minimum Inhibitory Concentration (MICs) (p < 0.0001). Pre-treatment of honey with catalase, abolished the bactericidal effect. This raised possibilities that either the abrupt killing prevented accumulation of ·OH (dead cells did not generate ·OH) or that DNA degradation and killing is the actual footprint of ·OH action. In conclusion, honeys of buckwheat origin exhibited powerful, concentration-dependent bactericidal effect. The killing and DNA degradation showed a cause-effect relationship. Hydrogen peroxide was an active part of honey killing mechanism.

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

Mount, G.H.; Harder, J.W.

The determination of the concentration of the hydroxyl radical in the troposphere is of fundamental importance to an understanding of the chemistry of the lower atmosphere. Described here are experiments located at Fritz Peak Observatory, Colorado, that measure of OH concentration to a sensitivity limit of about 5 X 10{sup 5} cm{sup {minus}3} (0.025 pptv) with absolute error approximately {+-}30% and, simultaneously, measure the concentrations of H{sub 2}O, SO{sub 2}, CH{sub 2}O, NO{sub 2}, NO{sub 3}, HONO, O{sub 3}, and other trace gases in the troposphere that affect OH concentration to provide a test of photochemical theories of OH formationmore » and destruction. An informal OH intercomparison campaign that occurred at Fritz Peak in 1991 and the 1993 Tropospheric OH Photochemistry Experiment are discussed. 33 refs., 14 figs., 2 tabs.« less

INCREASED 8-HYDROXY GUANINE CONTENT OF CHLOROPLAST DNA FROM OZONE TREATED PLANTS

EPA Science Inventory

The mechanism of ozone-mediated plant injury is not know but has been postulated to involve oxygen free radicals. Hydroxyl free radicals react with DNA causing formation of many products, one of which is 8-hydroxyguanine. By using high performance liquid chromatography with elect...

Rate Constant and Temperature Dependence for the Reaction of Hydroxyl Radicals with 2-Flouropropane (FC-281ea) and Comparison with an Estimated Rate Constant

NASA Technical Reports Server (NTRS)

DeMore, W.; Wilson, E., Jr.

1998-01-01

Relative rate experiments were used to measure the rate constant and temperature dependence of the reaction of OH radicals with 2-fluoropropane (HFC-281ea), using ethane, propane, ethyl chloride as reference standards.

Free radical-scavenging delta-lactones from Boletus calopus.

PubMed

Kim, Jin-Woo; Yoo, Ick-Dong; Kim, Won-Gon

2006-12-01

The methanol extracts from the fruiting body of the mushroom Boletus calopus showed free radical-scavenging activity. Bioactivity-guided fractionation of the methanol extracts led to a new hydroxylated calopin named calopin B, along with the known delta-lactones calopin and cyclocalopin A. The structure of the new calopin analogue was elucidated by spectroscopic methods. All compounds showed potent free radical-scavenging activity against superoxide, DPPH, and ABTS radicals with IC (50) values of 1.2 - 5.4 microg/mL.

Lunar Dust and Lunar Simulant Activation and Monitoring

NASA Technical Reports Server (NTRS)

Wallace, W. T.; Hammond, D. K.; Jeevarajan, A. S.

2008-01-01

Prior to returning to the moon, understanding the effects of lunar dust on both human physiology and mechanical equipment is a pressing concern, as problems related to lunar dust during the Apollo missions have been well documented (J.R. Gaier, The Effects of Lunar Dust on EVA Systems During the Apollo Missions. 2005, NASA-Glenn Research Center. p. 65). While efforts were made to remove the dust before reentering the lunar module, via brushing of the suits or vacuuming, a significant amount of dust was returned to the spacecraft, causing various problems. For instance, astronaut Harrison Schmitt complained of hay fever effects caused by the dust, and the abrasive nature of the material was found to cause problems with various joints and seals of the spacecraft and suits. It is clear that, in order to avoid potential health and performance problems while on the lunar surface, the reactive properties of lunar dust must be quenched. It is likely that soil on the lunar surface is in an activated form, i.e. capable of producing oxygen-based radicals in a humidified air environment, due to constant exposure to meteorite impacts, UV radiation, and elements of the solar wind. An activated silica surface serves as a good example. An oxygen-based radical species arises from the breaking of Si-OSi bonds. This system is comparable to that expected for the lunar dust system due to the large amounts of agglutinic glass and silicate vapor deposits present in lunar soil. Unfortunately, exposure to the Earth s atmosphere has passivated the active species on lunar dust, leading to efforts to reactivate the dust in order to understand the true effects that will be experienced by astronauts and equipment on the moon. Electron spin resonance (ESR) spectroscopy is commonly used for the study of radical species, and has been used previously to study silicon- and oxygen-based radicals, as well as the hydroxyl radicals produced by these species in solution (V. Vallyathan, et al., Am. Rev. Respir. Dis. 138 (1988) 1213-1219). The size and cost of these instruments makes them unattractive for the monitoring of lunar dust activity. A more suitable technique is based on the change in fluorescence of a molecule upon reaction with a hydroxyl radical (or other radical species). Fluorescence instruments are much less costly and bulky than ESR spectrometers, and small fluorescence sensors for space missions have already been developed (F. Gao, et al., J. Biomed. Opt. 10 (2005) 054005). For the current fluorescence studies, the terephthalate molecule has been chosen for monitoring the production of hydroxyl radicals in solution. As shown in Scheme 1, the reaction between the non-fluorescent terephthalate molecule and a hydroxyl radical produces the highly-fluorescent 2-hydroxyterephthalate molecule.

Total OH reactivity as a constraint of model calculated peroxy radical production, and the catalytic efficiency of NOx in O3 production in a boreal forest environment.

NASA Astrophysics Data System (ADS)

Javed, M. U.; Hens, K.; Martinez, M.; Kubistin, D.; Novelli, A.; Beygi, Z. H.; Axinte, R.; Nölscher, A. C.; Sinha, V.; Song, W.; Johnson, A. M.; Auld, J.; Bohn, B.; Sander, R.; Taraborrelli, D.; Williams, J.; Fischer, H.; Lelieveld, J.; Harder, H.

2016-12-01

Peroxy radicals play a key role in ozone (O3) production and hydroxyl (OH) recycling influencing the self-cleansing capacity and air quality. Organic peroxy radical (RO2) concentrations are estimated by three different approaches for a boreal forest, based on the field campaign HUMPPA-COPEC 2010 in Southern Finland. RO2 concentrations were simulated by a box model constrained by the comprehensive dataset from the campaign and cross-checked against the photostationary state (PSS) of NOx [= nitric oxide (NO) + nitrogen dioxide (NO2)] calculations. The model simulated RO2 concentrations appear too low to explain the measured PSS of NOx. As the atmospheric RO2 production is proportional to OH loss, the total OH loss rate frequency (total OH reactivity) in the model is underestimated compared to the measurements. The total OH reactivity of the model is tuned to match the observed total OH reactivity by increasing the biogenic volatile organic compound (BVOCs) concentrations for the model simulations. The new-found simulated RO2 concentrations based on the tuned OH reactivity explain the measured PSS of NOx reasonably well. Furthermore, the sensitivity of the NOx lifetime and the catalytic efficiency of NOx (CE) in O3 production, in the context of organic alkyl nitrate (RONO2) formation, was also investigated. Based on the campaign data, it was found that the lifetime of NOx and the CE are reduced and are sensitive to the RONO2 formation under low-NOx conditions, which matches a previous model-based study.

Organic pollutants removal in wastewater by heterogeneous photocatalytic ozonation.

PubMed

Xiao, Jiadong; Xie, Yongbing; Cao, Hongbin

2015-02-01

Heterogeneous photocatalysis and ozonation are robust advanced oxidation processes for eliminating organic contaminants in wastewater. The combination of these two methods is carried out in order to enhance the overall mineralization of refractory organics. An apparent synergism between heterogeneous photocatalysis and ozonation has been demonstrated in many literatures, which gives rise to an improvement of total organic carbon removal. The present overview dissects the heterogeneous catalysts and the influences of different operational parameters, followed by the discussion on the kinetics, mechanism, economic feasibility and future trends of this integrated technology. The enhanced oxidation rate mainly results from a large amount of hydroxyl radicals generated from a synergistically induced decomposition of dissolved ozone, besides superoxide ion radicals and the photo-induced holes. Six reaction pathways possibly exist for the generation of hydroxyl radicals in the reaction mechanism of heterogeneous photocatalytic ozonation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Kinetic and mechanistic reactivity. Isoprene impact on ozone levels in an urban area near Tijuca Forest, Rio de Janeiro.

PubMed

da Silva, Cleyton Martins; da Silva, Luane Lima; Corrêa, Sergio Machado; Arbilla, Graciela

2016-12-01

Volatile organic compounds (VOCs) play a central role in atmospheric chemistry. In this work, the kinetic and mechanistic reactivities of VOCs are analyzed, and the contribution of the organic compounds emitted by anthropogenic and natural sources is estimated. VOCs react with hydroxyl radicals and other photochemical oxidants, such as ozone and nitrate radicals, which cause the conversion of NO to NO 2 in various potential reaction paths, including photolysis, to form oxygen atoms, which generate ozone. The kinetic reactivity was evaluated based on the reaction coefficients for hydroxyl radicals with VOCs. The mechanistic reactivity was estimated using a detailed mechanism and the incremental reactivity scale that Carter proposed. Different scenarios were proposed and discussed, and a minimum set of compounds, which may describe the tropospheric reactivity in the studied area, was determined. The role of isoprene was analyzed in terms of its contribution to ozone formation.

Photooxidation of carbofuran by a polychromatic UV irradiation without and with hydrogen peroxide

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

Benitez, F.J.; Beltran-Heredia, J.; Gonzalez, T.

The photodegradation of carbofuran aqueous solutions has been conducted with direct photolysis provided by a polychromatic UV radiation source and by the combination of this UV radiation with hydrogen peroxide. In both processes, the decomposition level obtained as a function of the operating variables is reported, and the presence of tert-butyl alcohol, a scavenger of free radicals, is discussed. While the contribution of hydroxyl radicals is negligible in the direct photolysis, its reactions in the UV/H{sub 2}O{sub 2} system clearly increase the carbofuran decomposition and therefore must be taken into account in the reaction rate equation for the total degradation.more » From the mechanisms proposed, the quantum yields for the direct photolysis and the kinetic constants for the reaction between carbofuran and the hydroxyl radicals generated in the H{sub 2}O{sub 2} photolysis in the combined process are respectively evaluated.« less

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

Tang, Mingyi; Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com; Wu, Tao

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

Antioxidant activity of different fractions of Spirulina platensis protean extract.

PubMed

Piñero Estrada, J E; Bermejo Bescós, P; Villar del Fresno, A M

2001-01-01

Spirulina platensis, planktonic blue-green algae, is gaining increasing attention because of its nutritional and medicinal properties. This microalgae contains phycobiliproteins (phycocyanin and allophycocyanin). Previous reports from our laboratory have shown that a protean extract of S. platensis is a potent free-radical scavenger (hydroxyl and peroxyl radicals) and inhibits microsomal lipid peroxidation. The aim of this study was to purify and characterize phycocyanin of S. platensis. Besides, we tried to demonstrate that one of the main components responsible for this antioxidant activity is a biliprotein phycocyanin. For this purpose, we studied the antioxidant activity of different fractions obtained during the phycocyanin purification process, through the scavenger activity of hydroxyl radical. We also observed that an increase in phycocyanin content was related to an increase in the antioxidant activity in different fractions, and therefore phycobiliprotein phycocyanin is the component mainly responsible for the antioxidant activity.

[In vitro anti-inflammatory and free radical scavenging activities of flavans from Ilex centrochinensis].

PubMed

Li, Lu-jun; Yu, Li-juan; Li, Yan-ci; Liu, Meng-yuan; Wu, Zheng-zhi

2015-04-01

This study was carried out to evaluate the anti-inflammatory and free radical scavenging activities of flavans from flex centrochinensis S. Y. Hu in vitro and their structure-activity relationship. LPS-stimulated RAW 264.7 macrophage was used as inflammatory model. MTT assay for cell availability, Griess reaction for nitric oxide (NO) production, the content of TNF-alpha, IL-1beta, IL-6 and PGE, were detected with ELISA kits; DPPH, superoxide anion and hydroxyl free radicals scavenging activities were also investigated. According to the result, all flavans tested exhibited anti-inflammatory effect in different levels. Among them, compounds 1, 3, 4 and 6 showed potent anti-inflammatory effect through the inhibition of NO, TNF-alpha, IL-lp and IL-6, of which 1 was the most effective inhibitor, however, 2 and 5 were relatively weak or inactive. The order of free radical scavenging activities was similar to that of anti-inflammatory activities. Therefore, these results suggest that 3, 4 and 6, especially of 1, were,in part responsible for the anti-inflammatory and free radical scavenging activity of Ilex centrochinensis. Hydroxyl group at 4'-position of B-ring plays an important role in the anti-inflammatory and free radical scavenging capacities.

Investigation of OH Radical Regeneration from Isoprene Oxidation Across Different NOx Regimes in the Atmosphere Simulation Chamber SAPHIR

NASA Astrophysics Data System (ADS)

Novelli, A.; Bohn, B.; Dorn, H. P.; Häseler, R.; Hofzumahaus, A.; Kaminski, M.; Yu, Z.; Li, X.; Tillmann, R.; Wegener, R.; Fuchs, H.; Kiendler-Scharr, A.; Wahner, A.

2017-12-01

The hydroxyl radical (OH) is the dominant daytime oxidant in the troposphere. It starts the degradation of volatile organic compounds (VOC) originating from both anthropogenic and biogenic emissions. Hence, it is a crucial trace species in model simulations as it has a large impact on many reactive trace gases. Many field campaigns performed in isoprene dominated environment in low NOx conditions have shown large discrepancies between the measured and the modelled OH radical concentrations. These results have contributed to the discovery of new regeneration paths for OH radicals from isoprene-OH second generation products with maximum efficiency at low NO. The current chemical models (e.g. MCM 3.3.1) include this novel chemistry allowing for an investigation of the validity of the OH regeneration at different chemical conditions. Over 11 experiments focusing on the OH oxidation of isoprene were performed at the SAPHIR chamber in the Forschungszentrum Jülich. Measurements of VOCs, NOx, O3, HONO were performed together with the measurement of OH radicals (by both LIF-FAGE and DOAS) and OH reactivity. Within the simulation chamber, the NO mixing ratio was varied between 0.05 to 2 ppbv allowing the investigation of both the "new" regeneration path for OH radicals and the well-known NO+HO2 mechanism. A comparison with the MCM 3.3.1 that includes the upgraded LIM1 mechanism showed very good agreement (within 10%) for the OH data at all concentrations of NOx investigated. Comparison with different models, without LIM1 and with updated rates for the OH regeneration, will be presented together with a detailed analysis of the impact of this study on results from previous field campaigns.

Laboratory and Ambient Studies of the Products of Gas-Phase Hydroxyl and Nitrate Ion Radical-Initiated Reactions with Selected PAHs

NASA Astrophysics Data System (ADS)

Zimmermann, Kathryn Jean

Nitrated polycyclic aromatic hydrocarbon (nitro-PAH) product distributions from the gas-phase hydroxyl (OH) and nitrate (NO3) radical-initiated reactions with selected PAHs, as well as the heterogeneous reactions of surface-bound PAHs with N2O5 and HNO3, were investigated. Chapter 2 presents formation yields of nitro-PAHs from the gas-phase OH radical-initiated reactions of 1,7- and 2,7-dimethylnaphthalene (DMN) as a function of NO 2 concentration over the range 0.04-0.14 ppmv. The measured formation yields of dimethylnitronaphthalenes (DMNNs) under conditions that the OH-DMN adducts reacted solely with NO2 were 0.252 ± 0.094% for Σ1,7-DMNNs and 0.010 ± 0.005% for Σ2,7-DMNNs. 1,7-dimethyl-5-nitronaphthalene (1,7DM5NN) was the major nitro-isomer formed, with a limiting high-NO 2 concentration yield of 0.212 ± 0.080% and with equal reactions of the 1,7-DMN-OH adduct with NO2 and O2 occurring in air at 60 ± 39 ppbv of NO2, indicating that the OH-DMN adduct reaction with NO2 can be important at NO2 concentrations commonly found in urban atmospheres. Although the yields of the DMNNs are low, ≤0.3%, the DMNN (and ethylnitronaphthalene) profiles from chamber experiments match well with those observed in polluted urban areas under conditions where OH radical-initiated chemistry is dominant, such as Mexico City, Mexico. Chapter 3 examines the nitro-PAH products of gas-phase OH and NO 3 radicals and heterogeneous N2O5 reactions with fluoranthene, pyrene, benz[a]anthracene, chrysene, and triphenylene. Analysis of nitro-PAHs in the NIST diesel particulate SRM (1975) and selected ambient samples are also presented. 2-Nitrofluoranthene (2-NFL) was the most abundant nitro-PAH in Riverside, CA and Mexico City, and the mw 273 nitro-PAHs were observed in lower concentrations. However, in Tokyo, Japan, concentrations of 1- + 2-nitrotriphenylene (NTP) were more similar to those of 2-NFL. Comparing specific nitro-PAH ratios in ambient particulate samples from Tokyo, Mexico City, and Riverside, and in diesel particles with those from chamber experiments confirms the atmospheric formation of 2-NFL and 2-nitropyrene (2-NPY) via gas-phase radical-initiated reactions. Heterogeneous nitration of ambient particle-bound PAHs is investigated in Chapter 4. Ambient particulate samples collected in Beijing, China, and from four sites within the Los Angeles air basin (Los Angeles, Azusa, Riverside, and Banning), along with filter-bound deuterated PAHs, were exposed to a gas-phase equilibrium mixture of N2O5, NO3 radicals, and NO2 in an environmental chamber at ambient pressure and temperature. For the majority of these reactions 1-nitropyrene was the nitro-PAH formed in the greatest amount and was determined to occur heterogeneously (and not in the gas-phase) by using isomer distribution patterns of deuterated nitro-PAHs either formed on filter surfaces or collected from the chamber in the gas-phase. Chapter 5 investigates the contributions of atmospheric formation (OH versus NO3 chemistry) and direct emissions (electrophilic nitration products) to ambient gas-phase and particulate nitro-PAHs sampled in the Los Angeles air basin and Mexico City, Mexico, over several sampling campaigns using a combination of several marker ratios of volatile and semi-volatile nitro-PAHs. Ratios of 2-nitrofluoranthene (2-NFL)/2-nitropyrene (2-NPY), 2-methyl-4-nitronaphthalene (2M4NN)/1-methyl-5-nitronaphthalene (1M5NN), and 2,7-dimethyl-4-nitronaphthalene (2,7DM4NN)/1,7-dimethyl-5-nitronaphthalene (1,7DM5NN) were used to assess the contribution of OH radical chemistry versus NO3 radical chemistry to ambient nitro-PAHs from 50 particle-phase and gas-phase samples. (Abstract shortened by UMI.).

Free radical scavenging activities measured by electron spin resonance spectroscopy and B16 cell antiproliferative behaviors of seven plants.

PubMed

Calliste, C A; Trouillas, P; Allais, D P; Simon, A; Duroux, J L

2001-07-01

In an effort to discover new antioxidant natural compounds, seven plants that grow in France (most of them in the Limousin countryside) were screened. Among these plants, was the extensively studied Vitis vinifera as reference. For each plant, sequential percolation was realized with five solvents of increasing polarities (hexane, chloroform, ethyl acetate, methanol, and water). Free radical scavenging activities were examined in different systems using electron spin resonance (ESR) spectroscopy. These assays were based on the stable free radical 1,1-diphenyl-2-picrylhydrazyl (DPPH), the hydroxyl radicals generated by a Fenton reaction, and the superoxide radicals generated by the X/XO system. Antiproliferative behavior was studied on B16 melanoma cells. ESR results showed that three plants (Castanea sativa, Filipendula ulmaria, and Betula pendula) possessed, for the most polar fractions (presence of phenolic compounds), high antioxidant activities in comparison with the Vitis vinifera reference. Gentiana lutea was the only one that presented a hydroxyl scavenging activity for the ethyl acetate and chloroform fractions. The antiproliferative test results showed that the same three plants are the most effective, but for the apolar fractions (chloroform and hexane).

Extraction and free radical scavenging activity of polysaccharide from 'Anji Baicha' (Camellia sinensis (L.) O. Kuntze).

PubMed

Zhang, Zhongshan; Wang, Xiaomei; Li, Jingfen; Wang, Guozhi; Mao, Genxiang

2016-03-01

In this study, the optimization of the extraction conditions of polysaccharide from 'Anji Baicha' (Camellia sinensis (L.) O. Kuntze) (AP) was investigated by response surface methodology (RSM). Three main independent variables (extraction temperature, time, ratio of water to raw material) were taken into consideration. And then the free radical scavenging activities of the sample were investigated including scavenging effects of superoxide and hydroxyl radicals. The RSM analysis showed good correspondence between experimental and predicted values.. The optimal condition to obtain the highest yield of AP was determined as follows: temperature 76.79 °C, time 2.48 h, ratio of water to material 22.53 mL/g. For the free radical scavenging activity, the IC50 values of Vc and AP were 7.78 and 83.25 μg/mL. And for the scavenging effect on hydroxyl radical, that of AP and Vc were 1.80 and 1.69 mg/mL. AP showed excellent antioxidant activity. This exhibited AP had a good potential for antioxidant. The purification and structure needs to be study in further. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2018-01-01

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

Hydrogen peroxide-induced reduction of delayed rectifier potassium current in hippocampal neurons involves oxidation of sulfhydryl groups.

PubMed

Hasan, Sonia M K; Redzic, Zoran B; Alshuaib, Waleed B

2013-07-03

This study examined the effect of H2O2 on the delayed rectifier potassium current (IKDR) in isolated hippocampal neurons. Whole-cell voltage-clamp experiments were performed on freshly dissociated hippocampal CA1 neurons of SD rats before and after treatment with H2O2. To reveal the mechanism behind H2O2-induced changes in IKDR, cells were treated with different oxidizing and reducing agents. External application of membrane permeable H2O2 reduced the amplitude and voltage-dependence of IKDR in a concentration dependent manner. Desferoxamine (DFO), an iron-chelator that prevents hydroxyl radical (OH) generation, prevented H2O2-induced reduction in IKDR. Application of the sulfhydryl-oxidizing agent 5,5 dithio-bis-nitrobenzoic acid (DTNB) mimicked the effect of H2O2. Sulfhydryl-reducing agents dithiothreitol (DTT) and glutathione (GSH) alone did not affect IKDR; however, DTT and GSH reversed and prevented the H2O2-induced inhibition of IKDR, respectively. Membrane impermeable agents GSH and DTNB showed effects only when added intracellularly identifying intracellular sulfhydryl groups as potential targets for hydroxyl-mediated oxidation. However, the inhibitory effects of DTNB and H2O2 at the positive test potentials were completely and partially abolished by DTT, respectively, suggesting an additional mechanism of action for H2O2, that is not shared by DTNB. In summary, this study provides evidence for the redox modulation of IKDR, identifies hydroxyl radical as an intermediate oxidant responsible for the H2O2-induced decrease in current amplitude and identifies intracellular sulfhydryl groups as an oxidative target. Copyright © 2013 Elsevier B.V. All rights reserved.

Protective properties of butanolic extract of the Calendula officinalis L. (marigold) against lipid peroxidation of rat liver microsomes and action as free radical scavenger.

PubMed

Cordova, Clarissa A S; Siqueira, Ionara R; Netto, Carlos A; Yunes, Rosendo A; Volpato, Ana M; Cechinel Filho, Valdir; Curi-Pedrosa, Rozangela; Creczynski-Pasa, Tânia B

2002-01-01

Calendula officinalis (marigold) has many pharmacological properties. It is used for the treatment of skin disorders, pain and also as a bactericide, antiseptic and anti-inflammatory. Reactive oxygen species (ROS) and reactive nitrogen species (RNS) are known to participate in the pathogenesis of various human diseases and may be involved in the conditions which C. officinalis is used to treat. The aim of this study was to investigate the relationship between the beneficial properties of this plant and its antioxidant action. The butanolic fraction (BF) was studied because it is non-cytotoxic and is rich in a variety of bioactive metabolites including flavonoids and terpenoids. Superoxide radicals (O(2)(*-)) and hydroxyl radicals (HO(*)) are observed in decreasing concentrations in the presence of increasing concentrations of BF with IC(50) values of 1.0 +/- 0.09 mg/ml and 0.5 +/- 0.02 mg/ml, respectively, suggesting a possible free radical scavenging effect. Lipid peroxidation in liver microsomes induced by Fe(2+)/ascorbate was 100% inhibited by 0.5 mg/ml of BF (IC(50) = 0.15 mg/ml). Its total reactive antioxidant potential (TRAP) (in microM Trolox equivalents) was 368.14 +/- 23.03 and its total antioxidant reactivity (TAR) was calculated to be 249.19 +/- 14.5 microM. The results obtained suggest that the butanolic fraction of C. officinalis possesses a significant free radical scavenging and antioxidant activity and that the proposed therapeutic efficacy of this plant could be due, in part, to these properties.

Sulfur and selenium antioxidants: challenging radical scavenging mechanisms and developing structure-activity relationships based on metal binding.

PubMed

Zimmerman, Matthew T; Bayse, Craig A; Ramoutar, Ria R; Brumaghim, Julia L

2015-04-01

Because sulfur and selenium antioxidants can prevent oxidative damage, numerous animal and clinical trials have investigated the ability of these compounds to prevent the oxidative stress that is an underlying cause of cardiovascular disease, Alzheimer's disease, and cancer, among others. One of the most common sources of oxidative damage is metal-generated hydroxyl radical; however, very little research has focused on determining the metal-binding abilities and structural attributes that affect oxidative damage prevention by sulfur and selenium compounds. In this review, we describe our ongoing investigations into sulfur and selenium antioxidant prevention of iron- and copper-mediated oxidative DNA damage. We determined that many sulfur and selenium compounds inhibit Cu(I)-mediated DNA damage and that DNA damage prevention varies dramatically when Fe(II) is used in place of Cu(I) to generate hydroxyl radical. Oxidation potentials of the sulfur or selenium compounds do not correlate with their ability to prevent DNA damage, highlighting the importance of metal coordination rather than reactive oxygen species scavenging as an antioxidant mechanism. Additional gel electrophoresis, mass spectrometry, and UV-visible studies confirmed sulfur and selenium antioxidant binding to Cu(I) and Fe(II). Ultimately, our studies established that both the hydroxyl-radical-generating metal ion and the chemical environment of the sulfur or selenium significantly affect DNA damage prevention and that metal coordination is an essential mechanism for these antioxidants. Copyright © 2015 Elsevier Inc. All rights reserved.

Comparative study on the antioxidant activity of peptides from pearl oyster ( Pinctada martensii) mantle type V collagen and tilapia ( Oreochromis niloticus) scale type I collagen

NASA Astrophysics Data System (ADS)

Xia, Guanghua; Zhang, Xueying; Dong, Zhenghua; Shen, Xuanri

2017-12-01

In this study, Pearl oyster mantle type V collagen (POMC) and tilapia scale type I collagen (TSC) were extracted and hydrolyzed by various proteases in order to obtain peptides. The antioxidant activity of the peptides was investigated by DPPH, hydroxyl radical scavenging experiments and a dynamic digestion model in vitro. The results show that there are significant differences in amino acid composition between POMC and TSC. The collagen peptides obtained from pearl oyster mantle (POMCP) by treating with alkaline protease exhibited higher antioxidant activity than that from tilapia scale (TSCP) treated with papaya protease, and both of them showed greater DPPH and hydroxyl radical scavenging activity than other peptides. After being separated via Sephadex G-25 chromatography, the M1 fraction isolated from POMCP, and the S1 fraction from TSCP with which both had higher molecular weights showed the strongest antioxidant activity than other fractions, and the M1 fraction exhibited stronger antioxidant activity than the S1 fraction in scavenging free-radicals and protecting cells from the oxidation damage. Furthermore, after treating the dynamic digestion system model in vitro, the DPPH and hydroxyl radical scavenging activity of the M1 fraction increased slightly. These results suggest that POMCP exhibits stronger antioxidant activity than TSCP, which means that PMOP may be a good candidate to be a potential natural antioxidant in the food-processing industry.

An evaluation of extracts of five traditional medicinal plants from Iran on the inhibition of mushroom tyrosinase activity and scavenging of free radicals.

PubMed

Khazaeli, P; Goldoozian, R; Sharififar, F

2009-10-01

This study aimed to evaluate the free radical scavenging and inhibition properties of five medicinal plants, including Quercus infectoria Olive., Terminalia chebula Retz., Lavendula stoechas L., Mentha longifolia L., Rheum palmatum L., toward the activity of mushroom tyrosinase using L-tyrosine and L-3,4-dihydroxyphenylalanine (L-DOPA) as the substrate.The methanol extracts of Q. infectoria and T. chebula showed strong radical scavenging effect in 2,2'-dipheny L-1-picrylhydrazyl (DPPH) assay(IC50 = 15.3 and 82.2 microg mL)1 respectively).These plants also showed inhibitory effects against the activity of mushroom tyrosinase in hydroxylation of L-tyrosine (85.9% and 82.2% inhibition,respectively). These two plants also inhibited the oxidation of l-DOPA similar to kojic acid as positive control (IC50 = 102.8 and 192.6 microg mL)1 respectively). In general Q. infectoria and T. chebula significantly inhibited tyrosinase activity and DPPH radical. Both activities were concentration dependant but not in linear manner. It is needed to study the cytotoxicity of these plant extracts in pigment cell culture before further evaluation and moving to in vivo conditions.

Methanolic extract of leaves of Jasminum grandiflorum Linn modulates oxidative stress and inflammatory mediators.

PubMed

Chaturvedi, Adya Prasad; Tripathi, Yamini Bhusan

2011-10-01

The leaves of Jasminum grandiflorum (JG) are in clinical use in Ayurveda for wound management. Since, oxidative stress and inflammation are the primary causes in delayed wound healing, so here its antioxidant and anti-inflammatory activities have been investigated using in vitro as well as in vivo models. The solvent-free methanolic extract of dried leaves of JG were tested for its trapping capacity toward pre-generated ABTS•+ radicals, instantly generated superoxide and hydroxyl radicals, along with metal chelation property, reducing power and total phenolic content. Further, it was tested on LPS-induced nitric oxide and cell viability, on primary culture of rat peritoneal macrophages. Its anti-inflammatory property was also tested on carrageenan-induced paw edema in rats. This extract significantly inhibited iron-induced lipid peroxidation and trapped ABTS•+, superoxide and OH radicals. It significantly inhibited nitric oxide (NO) release, without affecting the cell viability at 800 μg/ml concentration and reduced the formation of paw edema in rats. Thus, it could be suggested that the aforesaid anti-inflammatory properties of JG leaves are associated to its high phenolic content (2.25±0.105 mg/l of gallic acid equivalent), reducing power and its free radical-scavenging property.