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Sample records for acid oxidation rate

  1. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  2. Measurement of the rates of oxindole-3-acetic acid turnover, and indole-3-acetic acid oxidation in Zea mays seedlings

    Science.gov (United States)

    Nonhebel, H. M.; Bandurski, R. S. (Principal Investigator)

    1986-01-01

    Oxindole-3-acetic acid is the principal catabolite of indole-3-acetic acid in Zea mays seedlings. In this paper measurements of the turnover of oxindole-3-acetic acid are presented and used to calculate the rate of indole-3-acetic acid oxidation. [3H]Oxindole-3-acetic acid was applied to the endosperm of Zea mays seedlings and allowed to equilibrate for 24 h before the start of the experiment. The subsequent decrease in its specific activity was used to calculate the turnover rate. The average half-life of oxindole-3-acetic acid in the shoots was found to be 30 h while that in the kernels had an average half-life of 35h. Using previously published values of the pool sizes of oxindole-3-acetic acid in shoots and kernels from seedlings of the same age and variety, and grown under the same conditions, the rate of indole-3-acetic acid oxidation was calculated to be 1.1 pmol plant-1 h-1 in the shoots and 7.1 pmol plant-1 h-1 in the kernels.

  3. Vitamin E supplementation in elderly lowers the oxidation rate of linoleic acid in LDL.

    NARCIS (Netherlands)

    Waart, de F.; Moser, U.; Kok, F.J.

    1997-01-01

    .Oxidation of LDL–linoleic acid (LDL–LA), a major substrate for lipid peroxidation, may be counteracted by the antioxidant vitamin E. In a 3-month randomized double-blind placebo-controlled trial in 83 apparently healthy Dutch elderly, aged 67–85 years, the direct protective effect of 100 IU vitamin

  4. Lipotoxic Palmitate Impairs the Rate of β-Oxidation and Citric Acid Cycle Flux in Rat Neonatal Cardiomyocytes.

    Science.gov (United States)

    Haffar, Taha; Akoumi, Ali; Bousette, Nicolas

    2016-01-01

    Diabetic hearts exhibit intracellular lipid accumulation. This suggests that the degree of fatty acid oxidation (FAO) in these hearts is insufficient to handle the elevated lipid uptake. We previously showed that palmitate impaired the rate of FAO in primary rat neonatal cardiomyocytes. Here we were interested in characterizing the site of FAO impairment induced by palmitate since it may shed light on the metabolic dysfunction that leads to lipid accumulation in diabetic hearts. We measured fatty acid oxidation, acetyl-CoA oxidation, and carnitine palmitoyl transferase (Cpt1b) activity. We measured both forward and reverse aconitase activity, as well as NAD+ dependent isocitrate dehydrogenase activity. We also measured reactive oxygen species using the 2', 7'-Dichlorofluorescin Diacetate (DCFDA) assay. Finally we used thin layer chromatography to assess diacylglycerol (DAG) levels. We found that palmitate significantly impaired mitochondrial β-oxidation as well as citric acid cycle flux, but not Cpt1b activity. Palmitate negatively affected net aconitase activity and isocitrate dehydrogenase activity. The impaired enzyme activities were not due to oxidative stress but may be due to DAG mediated PKC activation. This work demonstrates that palmitate, a highly abundant fatty acid in human diets, causes impaired β-oxidation and citric acid cycle flux in primary neonatal cardiomyocytes. This metabolic defect occurs prior to cell death suggesting that it is a cause, rather than a consequence of palmitate mediated lipotoxicity. This impaired mitochondrial metabolism can have important implications for metabolic diseases such as diabetes and obesity. © 2016 The Author(s) Published by S. Karger AG, Basel.

  5. Lipotoxic Palmitate Impairs the Rate of β-Oxidation and Citric Acid Cycle Flux in Rat Neonatal Cardiomyocytes

    Directory of Open Access Journals (Sweden)

    Taha Haffar

    2016-12-01

    Full Text Available Background/Aims: Diabetic hearts exhibit intracellular lipid accumulation. This suggests that the degree of fatty acid oxidation (FAO in these hearts is insufficient to handle the elevated lipid uptake. We previously showed that palmitate impaired the rate of FAO in primary rat neonatal cardiomyocytes. Here we were interested in characterizing the site of FAO impairment induced by palmitate since it may shed light on the metabolic dysfunction that leads to lipid accumulation in diabetic hearts. Methods: We measured fatty acid oxidation, acetyl-CoA oxidation, and carnitine palmitoyl transferase (Cpt1b activity. We measured both forward and reverse aconitase activity, as well as NAD+ dependent isocitrate dehydrogenase activity. We also measured reactive oxygen species using the 2', 7'-Dichlorofluorescin Diacetate (DCFDA assay. Finally we used thin layer chromatography to assess diacylglycerol (DAG levels. Results: We found that palmitate significantly impaired mitochondrial β-oxidation as well as citric acid cycle flux, but not Cpt1b activity. Palmitate negatively affected net aconitase activity and isocitrate dehydrogenase activity. The impaired enzyme activities were not due to oxidative stress but may be due to DAG mediated PKC activation. Conclusion: This work demonstrates that palmitate, a highly abundant fatty acid in human diets, causes impaired β-oxidation and citric acid cycle flux in primary neonatal cardiomyocytes. This metabolic defect occurs prior to cell death suggesting that it is a cause, rather than a consequence of palmitate mediated lipotoxicity. This impaired mitochondrial metabolism can have important implications for metabolic diseases such as diabetes and obesity.

  6. High-intensity interval training increases intrinsic rates of mitochondrial fatty acid oxidation in rat red and white skeletal muscle.

    Science.gov (United States)

    Hoshino, Daisuke; Yoshida, Yuko; Kitaoka, Yu; Hatta, Hideo; Bonen, Arend

    2013-03-01

    High-intensity interval training (HIIT) can increase mitochondrial volume in skeletal muscle. However, it is unclear whether HIIT alters the intrinsic capacity of mitochondrial fatty acid oxidation, or whether such changes are associated with changes in mitochondrial FAT/CD36, a regulator of fatty acid oxidation, or with reciprocal changes in the nuclear receptor coactivator (peroxisome proliferator-activated receptor gamma coactivator-1alpha (PGC-1α)) and the corepressor (receptor-interacting protein 140 (RIP140)). We examined whether HIIT alters fatty acid oxidation rates in the isolated subsarcolemmal (SS) and intermyofibrillar (IMF) mitochondria of red and white skeletal muscle and (or) induces changes in muscle PGC-1α and RIP140 proteins and mitochondrial FAT/CD36 protein content. Rats were divided into untrained or HIIT-trained groups. HIIT animals performed 10 bouts of 1-min high-intensity treadmill running (30-55 m·min(-1)), separated by 2 min of rest, for 5 days a week for 4 weeks. As expected, after the training period, HIIT increased mitochondrial enzymes (citrate synthase, COXIV, and β-hydroxyacyl CoA dehydrogenase) in red and white muscle, indicating that muscle mitochondrial volume had increased. HIIT also increased the rates of palmitate oxidation in mitochondria of red (37% for SS and 19% for IMF) and white (36% for SS and 12% for IMF) muscle. No changes occurred in SS and IMF mitochondrial FAT/CD36 proteins, despite increasing FAT/CD36 at the whole-muscle level (27% for red and 22% for white). Concurrently, muscle PGC-1α protein was increased in red (22%) and white (16%) muscle, but RIP140 was not altered. These results indicate that increases in SS and IMF mitochondrial fatty acid oxidation induced by HIIT are accompanied by an increase in PGC-1α, but not RIP140 or FAT/CD36.

  7. Carnitine palmitoyl transferase activity and whole muscle oxidation rates vary with fatty acid substrate in avian flight muscles.

    Science.gov (United States)

    Price, Edwin R; Staples, James F; Milligan, C Louise; Guglielmo, Christopher G

    2011-05-01

    Birds primarily fuel migratory flights with fat, and the composition of that fat has the potential to affect overall lipid oxidation rates. We measured the whole muscle lipid oxidation rates in extensor digitorum communis muscles from white-throated sparrows (Zonotrichia albicollis Gmelin) incubated for 20 min at 20°C with radiolabeled stearate (18:0), oleate (18:1ω9), or linoleate (18:2ω6). Lipid oxidation rates were ~40% higher with linoleate than oleate (oleate: 36 ± 8.54 μmol CO(2) g(-1) h(-1)), and ~75% lower with stearate compared with oleate, indicating that maximal lipid oxidation rates can indeed be affected by the type of fatty acid supplied to the muscle. Additionally, we investigated the activity of the mitochondrial fatty acid transport-associated enzyme carnitine palmitoyl transferase (CPT) in pectoralis muscles of 5 bird species (Zonotrichia albicollis, Philomachus pugnax, Sturnus vulgaris, Taeniopygia guttata, Passer domesticus). Activity was measured in homogenized samples using various fatty acyl-CoA substrates (16:0, 16:1, 18:0, 18:1ω9, 18:2ω6, 18:3ω3, 18:3ω6, 20:0, 20:4ω6, 22:6ω3) in a spectrophotometric assay. CPT activity increased with the degree of unsaturation and decreased with chain length. CPT activity did not differ between ω3 and ω6 isomers of 18:3, nor was the pattern of CPT substrate preference different between captive white-throated sparrows in a migratory (i.e., displaying Zugunruhe) or non-migratory state. These findings can explain previously observed differences in peak performance induced by dietary fat composition and suggest that lipid supply is limiting to maximal exercise performance in birds.

  8. Fatty Acid Oxidation Disorders

    Science.gov (United States)

    ... acid oxidation disorders are tested for in newborn screening? The March of Dimes recommends that all babies ... in behavior Diarrhea, nausea (feeling sick to your stomach) and throwing up Drowsiness Fever Fussiness Little appetite ...

  9. Kinetics of wet oxidation of formic acid and acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Mahajani, V.V. [Univ. of Mumbai (India). Dept. of Chemical Technology

    1997-11-01

    Oxidation of lower molecular weight carboxylic acids such as formic, acetic, glyoxalic, and oxalic acids is often the rate-controlling step during wet oxidation (WO) of an aqueous waste stream exhibiting very high chemical oxygen demand (COD). The kinetics of WO of formic acid was studied in the absence and presence of a cupric sulfate as catalyst in the temperature range 150--240 C and oxygen partial pressure range 0.345--1.380 MPa. Wet oxidation of acetic acid was carried out in the presence of cupric sulfate in the temperature range 215--235 C. Homogeneous copper sulfate was found to be a very good catalyst for oxidation of formic acid and acetic acid.

  10. Oxidation of phenolic acids by soil iron and manganese oxides

    Energy Technology Data Exchange (ETDEWEB)

    Lehmann, R.G.; Cheng, H.H.; Harsh, J.B.

    Phenolic acids are intermediary metabolites of many aromatic chemicals and may be involved in humus formation, allelopathy, and nutrient availability. Depending on their structures, six phenolic acids were shown to react at different rates with oxidized forms of Fe and Mn in a Palouse soil (fine-silty, mixed, mesic Pachic Ultic Haploxeroll). Increasing methoxy substitution on the aromatic ring of phenolic acids increased the reaction rate. Reaction rate was also increased for longer carboxyl-containing side chains. After 4 h reaction, little of the applied (10 mg kg/sup -1/ soil) p-hydroxybenzoic or p-coumaric acids had reacted, while 0 to 5, 70, 90, and 100% of the vanillic, ferulic, syringic, and sinapic acids, respectively, had reacted. After 72 h under conditions limiting microbial growth, none of the p-hydroxybenzoic, 30% of the p-coumaric, and 50% of the vanillic acids had reacted. The reaction was shown to be predominantly chemical, and not biological, since phenolic acid extractabilities were similar for Palouse soil and for Palouse soil pretreated with LiOBr to remove organic matter. When the Palouse soil was pretreated with a sodium dithionite-citrate solution to remove Fe and Mn oxides, none of the phenolic acids reacted after 1 h. The reaction of sinapic acid with Palouse soil was shown to produce Fe(II) and soluble Mn as reaction products. The reaction of phenolic acids with soil was thus shown to be an oxidation of the phenolic acids, coupled with a reduction of soil Fe and Mn oxides.

  11. Improving the cycle life of lead-acid batteries using three-dimensional reduced graphene oxide under the high-rate partial-state-of-charge condition

    Science.gov (United States)

    Long, Qunying; Ma, Guozheng; Xu, Qiqin; Ma, Cheng; Nan, Junmin; Li, Aiju; Chen, Hongyu

    2017-03-01

    A three-dimensional reduced graphene oxide (3D-RGO) material has been successfully prepared by a facile hydrothermal method and is employed as the negative additive to curb the sulfation of lead-acid battery. When added with 1.0 wt% 3D-RGO, the initial discharge capacity (0.05 C, 185.36 mAh g-1) delivered by the battery is 14.46% higher than that of the control cell (161.94 mAh g-1); and the cycle life under the high-rate partial-state-of-charge (HRPSoC) condition is significantly improved by more than 224% from 8142 to 26,425 cycles. In comparison to the conventional carbon additions like the activated carbon and acetylene black, the 3D-RGO also exhibits the highest initial discharge capacity, the best rate capabilities and the longest HRPSoC cycling life. Finally, we propose a possible mechanism for 3D-RGO to suppress lead-acid battery sulfation, where the abundant pore structure and excellent conductivity of 3D-RGO may have a synergistic effect on facilitating the charge and discharge process of negative plate.

  12. Identification of a novel malonyl-CoA IC(50) for CPT-I: implications for predicting in vivo fatty acid oxidation rates.

    Science.gov (United States)

    Smith, Brennan K; Perry, Christopher G R; Koves, Timothy R; Wright, David C; Smith, Jeffrey C; Neufer, P Darrell; Muoio, Deborah M; Holloway, Graham P

    2012-11-15

    Published values regarding the sensitivity (IC(50)) of CPT-I (carnitine palmitoyltransferase I) to M-CoA (malonyl-CoA) inhibition in isolated mitochondria are inconsistent with predicted in vivo rates of fatty acid oxidation. Therefore we have re-examined M-CoA inhibition kinetics under various P-CoA (palmitoyl-CoA) concentrations in both isolated mitochondria and PMFs (permeabilized muscle fibres). PMFs have an 18-fold higher IC(50) (0.61 compared with 0.034 μM) in the presence of 25 μM P-CoA and a 13-fold higher IC(50) (6.3 compared with 0.49 μM) in the presence of 150 μM P-CoA compared with isolated mitochondria. M-CoA inhibition kinetics determined in PMFs predicts that CPT-I activity is inhibited by 33% in resting muscle compared with >95% in isolated mitochondria. Additionally, the ability of M-CoA to inhibit CPT-I appears to be dependent on P-CoA concentration, as the relative inhibitory capacity of M-CoA is decreased with increasing P-CoA concentrations. Altogether, the use of PMFs appears to provide an M-CoA IC(50) that better reflects the predicted in vivo rates of fatty acid oxidation. These findings also demonstrate that the ratio of [P-CoA]/[M-CoA] is critical for regulating CPT-I activity and may partially rectify the in vivo disconnect between M-CoA content and CPT-I flux within the context of exercise and Type 2 diabetes.

  13. Identification of a novel malonyl-CoA IC50 for CPT-1: implications for predicting in vivo fatty acid oxidation rates

    Science.gov (United States)

    Smith, Brennan K.; Perry, Christopher G.R.; Koves, Timothy R.; Wright, David C.; Smith, Jeffrey C.; Neufer, P. Darrell; Muoio, Deborah M.; Holloway, Graham P.

    2013-01-01

    Synopsis Published values regarding the sensitivity (IC50) of carnitine palmitoyl transferase I (CPT-I) to malonyl-CoA (M-CoA) inhibition in isolated mitochondria are inconsistent with predicted in vivo rates of fatty acid oxidation. Therefore, we have re-examined M-CoA inhibition kinetics under varying palmitoyl-CoA (P-CoA) concentrations in both isolated mitochondria and permeabilized muscle fibres (PMF). PMF have an 18-fold higher IC50 (0.61 vs 0.034 μM) in the presence of 25 μM P-CoA and a 13-fold higher IC50 (6.3 vs 0.49 μM) in the presence of 150 μM P-CoA compared to isolated mitochondria. M-CoA inhibition kinetics determined in PMF predicts that CPT-I activity is inhibited by 33% in resting muscle compared to >95% in isolated mitochondria. Additionally, the ability of M-CoA to inhibit CPT-I appears to be dependent on P-CoA concentration, as the relative inhibitory capacity of M-CoA is decreased with increasing P-CoA concentrations. Altogether, the use of PMF appears to provide a M-CoA IC50 that better reflects the predicted in vivo rates of fatty acid oxidation. These findings also demonstrate the ratio of [P-CoA]/[M-CoA] is critical for regulating CPT-I activity and may partially rectify the in vivo disconnect between M-CoA content and CPT-I flux within the context of exercise and type II diabetes. PMID:22928974

  14. Ultrasound assisted reduction of graphene oxide to graphene in L-ascorbic acid aqueous solutions: kinetics and effects of various factors on the rate of graphene formation.

    Science.gov (United States)

    Abulizi, Abulikemu; Okitsu, Kenji; Zhu, Jun-Jie

    2014-05-01

    The reduction of graphene oxide (GO) to graphene (rGO) was achieved by using 20 kHz ultrasound in L-ascorbic acid (L-AA, reducing agent) aqueous solutions under various experimental conditions. The effects of ultrasound power, ultrasound pulse mode, reaction temperature, pH value and L-AA amount on the rates of rGO formation from GO reduction were investigated. The rates of rGO formation were found to be enhanced under the following conditions: high ultrasound power, long pulse mode, high temperature, high pH value and large amount of L-AA. It was also found that the rGO formation under ultrasound treatment was accelerated in comparison with a conventional mechanical mixing treatment. The pseudo rate and pseudo activation energy (Ea) of rGO formation were determined to discuss the reaction kinetics under both treatment. The Ea value of rGO formation under ultrasound treatment was clearly lower than that obtained under mechanical mixing treatment at the same condition. We proposed that physical effects such as shear forces, microjets and shock waves during acoustic cavitation enhanced the mass transfer and reaction of L-AA with GO to form rGO as well as the change in the surface morphology of GO. In addition, the rates of rGO formation were suggested to be affected by local high temperatures of cavitation bubbles.

  15. Assessing Oxidative Stress in Tumors by Measuring the Rate of Hyperpolarized [1-13C]Dehydroascorbic Acid Reduction Using 13C Magnetic Resonance Spectroscopy*

    Science.gov (United States)

    Timm, Kerstin N.; Hu, De-En; Williams, Michael; Wright, Alan J.; Kettunen, Mikko I.; Kennedy, Brett W. C.; Larkin, Timothy J.; Dzien, Piotr; Marco-Rius, Irene; Bohndiek, Sarah E.; Brindle, Kevin M.

    2017-01-01

    Rapid cancer cell proliferation promotes the production of reducing equivalents, which counteract the effects of relatively high levels of reactive oxygen species. Reactive oxygen species levels increase in response to chemotherapy and cell death, whereas an increase in antioxidant capacity can confer resistance to chemotherapy and is associated with an aggressive tumor phenotype. The pentose phosphate pathway is a major site of NADPH production in the cell, which is used to maintain the main intracellular antioxidant, glutathione, in its reduced state. Previous studies have shown that the rate of hyperpolarized [1-13C]dehydroascorbic acid (DHA) reduction, which can be measured in vivo using non-invasive 13C magnetic resonance spectroscopic imaging, is increased in tumors and that this is correlated with the levels of reduced glutathione. We show here that the rate of hyperpolarized [1-13C]DHA reduction is increased in tumors that have been oxidatively prestressed by depleting the glutathione pool by buthionine sulfoximine treatment. This increase was associated with a corresponding increase in pentose phosphate pathway flux, assessed using 13C-labeled glucose, and an increase in glutaredoxin activity, which catalyzes the glutathione-dependent reduction of DHA. These results show that the rate of DHA reduction depends not only on the level of reduced glutathione, but also on the rate of NADPH production, contradicting the conclusions of some previous studies. Hyperpolarized [1-13C]DHA can be used, therefore, to assess the capacity of tumor cells to resist oxidative stress in vivo. However, DHA administration resulted in transient respiratory arrest and cardiac depression, which may prevent translation to the clinic. PMID:27994059

  16. Wet oxidation of salicylic acid solutions.

    Science.gov (United States)

    Collado, Sergio; Garrido, Laura; Laca, Adriana; Diaz, Mario

    2010-11-15

    Salicylic acid is a frequent pollutant in several industrial wastewaters. Uncatalyzed wet air oxidation, which is a promising technique for the treatment of phenolic effluents, has not been analyzed yet for the removal of salicylic acid. The effect of different conditions of pH (1.3-12.3), pressure (1.0-4.1 MPa), temperature (413-443 K), and initial concentrations (1.45-14.50 mM) on the wet oxidation of salicylate/salicylic acid solutions have here been investigated. The pH value of the reaction media was found to be a key parameter for the rate of the oxidation process with an optimum at pH 3.1, when the concentrations of salicylic acid and salicylate were similar. The oxidation reaction followed pseudofirst-order kinetics with respect to salicylic acid and 0.82 order with respect to dissolved oxygen. Additionally, the evolution of the color during the wet oxidation was analyzed and discussed in relation with the formation of intermediate compounds. Then, a reaction pathway for the noncatalytic wet oxidation of the salicylic acid was proposed.

  17. Kinetics of wet air oxidation of glyoxalic acid and oxalic acid

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Mahajani, V.V. (Univ. of Bombay (India). Dept. of Chemical Technology)

    1994-12-01

    Oxidation of lower molecular weight monobasic and dibasic acids such as formic acid, acetic acid, glyoxalic acid, and oxalic acid is often the rate-controlling step during wet air oxidation (WAO) of an aqueous waste stream exhibiting very high chemical oxygen demand (COD). The kinetics of WAO of glyoxalic acid and oxalic acid was studied in absence and presence of a cupric sulfate catalyst in the temperature range of 120--245 C and oxygen partial pressure of 0.345--1.380 MPa. The wet oxidation of oxalic acid was found to require more severe conditions as compared to glyoxalic acid. The reaction mechanism and kinetic model have been discussed.

  18. Fe{sup 2+} oxidation rate drastically affect the formation and phase of secondary iron hydroxysulfate mineral occurred in acid mine drainage

    Energy Technology Data Exchange (ETDEWEB)

    Huang Shan; Zhou Lixiang, E-mail: lxzhou@njau.edu.cn

    2012-05-01

    During the processes of secondary iron hydroxysulfate mineral formation, Fe{sup 2+} ion was oxidized by the following three methods: (1) biooxidation treatment by Acidithiobacillus ferrooxidans (A. ferrooxidans); (2) rapid abiotic oxidation of Fe{sup 2+} with H{sub 2}O{sub 2} (rapid oxidation treatment); (3) slow abiotic oxidation of Fe{sup 2+} with H{sub 2}O{sub 2} (slow oxidation treatment). X-ray diffraction (XRD) patterns, element composition, precipitate weight and total Fe removal efficiency were analyzed. The XRD patterns and element composition of precipitates synthesized through the biooxidation and the slow oxidation treatments well coincide with those of potassium jarosite, while precipitates formed at the initial stage of incubation in the rapid oxidation treatment showed a similar XRD pattern to schwertmannite. With the ongoing incubation, XRD patterns and element composition of the precipitates that occurred in the rapid oxidation treatment were gradually close to those in the biooxidation and the slow oxidation treatments. Due to the inhibition of A. ferrooxidans itself and its extracellular polymeric substances (EPS) in aggregation of precipitates, the amount of precipitates and soluble Fe removal efficiency were lower in the biooxidation treatment than in the slow oxidation treatment. Therefore, it is concluded that Fe{sup 2+} oxidation rate can greatly affect the mineral phase of precipitates, and slow oxidation of Fe{sup 2+} is helpful in improving jarosite formation. - Highlights: Black-Right-Pointing-Pointer Slow oxidation of Fe{sup 2+} is helpful in jarosite formation. Black-Right-Pointing-Pointer The already-formed schwertmannite can be gradually transformed to jarosite. Black-Right-Pointing-Pointer Precipitates formation can be inhibited probably by EPS from A. ferrooxidans.

  19. Tabulated Neutron Emission Rates for Plutonium Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Shores, Erik Frederick [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-07-24

    This work tabulates neutron emission rates for 80 plutonium oxide samples as reported in the literature. Plutonium-­238 and plutonium-­239 oxides are included and such emission rates are useful for scaling tallies from Monte Carlo simulations and estimating dose rates for health physics applications.

  20. Kinetics of Oxidation of 3-Benzoylpropionic Acid by N-Chlorobenzamide in Aqueous Acetic Acid Medium

    Directory of Open Access Journals (Sweden)

    N. A. Mohamed Farook

    2011-01-01

    Full Text Available The kinetics of oxidation of 3-benzoylpropionic acid (KA by N-chlorobenzamide (NCB in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order dependence each in [KA], [NCB] and [H+]. The main product of the oxidation is the corresponding carboxylic acid. The rate decreases with the addition of benzamide, one of the products of the reaction. Variation in ionic strength of the reaction medium has no significant effect on the rate of oxidation. But the rate of the reaction is enhanced by lowering the dielectric constant of the reaction medium. Hypochlorous acidium ion (H2O+Cl, has been postulated as the reactive oxidizing species. A mechanism consistent with observed results have been proposed and the related rate law deduced. The activation parameters have been computed with respect to slow step of the mechanism.

  1. Selenium dioxide catalysed oxidation of acetic acid hydrazide by bromate in aqueous hydrochloric acid medium

    Indian Academy of Sciences (India)

    R S Yalgudre; G S Gokavi

    2012-07-01

    Selenium dioxide catalysed acetic acid hydrazide oxidation by bromate was studied in hydrochloric acid medium. The order in oxidant concentration, substrate and catalyst were found to be unity. Increasing hydrogen ion concentration increases the rate of the reaction due to protonation equilibria of the oxidant. The mechanism of the reaction involves prior complex formation between the catalyst and substrate, hydrazide, followed by its oxidation by diprotonated bromate in a slow step. Acetic acid was found to be the oxidation product. Other kinetic data like effect of solvent polarity and ionic strength on the reaction support the proposed mechanism.

  2. Aspirin increases mitochondrial fatty acid oxidation.

    Science.gov (United States)

    Uppala, Radha; Dudiak, Brianne; Beck, Megan E; Bharathi, Sivakama S; Zhang, Yuxun; Stolz, Donna B; Goetzman, Eric S

    2017-01-08

    The metabolic effects of salicylates are poorly understood. This study investigated the effects of aspirin on fatty acid oxidation. Aspirin increased mitochondrial long-chain fatty acid oxidation, but inhibited peroxisomal fatty acid oxidation, in two different cell lines. Aspirin increased mitochondrial protein acetylation and was found to be a stronger acetylating agent in vitro than acetyl-CoA. However, aspirin-induced acetylation did not alter the activity of fatty acid oxidation proteins, and knocking out the mitochondrial deacetylase SIRT3 did not affect the induction of long-chain fatty acid oxidation by aspirin. Aspirin did not change oxidation of medium-chain fatty acids, which can freely traverse the mitochondrial membrane. Together, these data indicate that aspirin does not directly alter mitochondrial matrix fatty acid oxidation enzymes, but most likely exerts its effects at the level of long-chain fatty acid transport into mitochondria. The drive on mitochondrial fatty acid oxidation may be a compensatory response to altered mitochondrial morphology and inhibited electron transport chain function, both of which were observed after 24 h incubation of cells with aspirin. These studies provide insight into the pathophysiology of Reye Syndrome, which is known to be triggered by aspirin ingestion in patients with fatty acid oxidation disorders. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Kinetics of wet oxidation of propionic and 3-hydroxypropionic acids

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    Shende, R.V.; Levec, J. [National Inst. of Chemistry, Ljubljana (Slovenia). Lab. for Catalysis and Chemical Reaction Engineering]|[Univ. of Ljubljana (Slovenia). Dept. of Chemical Engineering

    1999-07-01

    Oxidation of aqueous solutions of 3-hydroxypropionic (3-HPA) and propionic acids (PA) was studied in a titanium high-pressure reactor at 280--310 C using oxygen partial pressures between 10 and 45 bar. Oxidation of both acids was found to obey first-order kinetic with respect to their concentrations as well as to their lumped TOC concentrations. Oxidation rate revealed a half order dependence with respect to oxygen for oxidation of both acids. In the case of 3-HPA oxidation, the activation energy was found to be 135 kJ/mol, and it was 140 kJ/mol when lumped concentration TOC was used. The activation energy for PA oxidation is 150 kJ/mol, and it is slightly higher, 158 kJ/mol, for TOC reduction. Almost complete conversion of 3-HPA was achieved at 300 C after 1 h, whereas 95% conversion of PA acid was obtained at 310 C after 3 h. During oxidation of 3-HPA, 3-oxopropionic and acetic acids were identified as intermediate products. Oxidation of PA yielded acetic and formic acids as intermediates; at oxygen partial pressures above 25 bar and 310 C, the formation of acetic acid was appreciably reduced. In both cases, however, direct oxidation to carbon dioxide and water was found to be the main reaction route.

  4. Macrokinetics of magnesium sulfite oxidation inhibited by ascorbic acid

    Energy Technology Data Exchange (ETDEWEB)

    Lidong, Wang, E-mail: wld@tsinghua.edu.cn [School of Environmental Science and Engineering, North China Electric Power University, Baoding 071003 (China); Department of Environmental Science and Engineering, Tsinghua University, Beijing 100054 (China); Yongliang, Ma, E-mail: liang@tsinghua.edu.cn [Department of Environmental Science and Engineering, Tsinghua University, Beijing 100054 (China); Wendi, Zhang; Qiangwei, Li; Yi, Zhao [School of Environmental Science and Engineering, North China Electric Power University, Baoding 071003 (China); Zhanchao, Zhang [Jinan Environmental Monitoring Center, Jinan 250014 (China)

    2013-08-15

    Graphical abstract: Ascorbic acid is used as an inhibitor to retard the oxidation rate of magnesium sulfite. It shows that the oxidation rate would decrease greatly with the rise of initial ascorbic acid concentration, which provides a useful reference for sulfite recovery in magnesia desulfurization. -- Highlights: • We studied the kinetics of magnesium sulfite oxidation inhibited by ascorbic acid. • The oxidation process was simulated by a three-phase model and proved by HPLC–MS. • We calculated the kinetic parameters of intrinsic oxidation of magnesium sulfite. -- Abstract: Magnesia flue gas desulfurization is a promising process for small to medium scale industrial coal-fired boilers in order to reduce sulfur dioxide emissions, in which oxidation control of magnesium sulfite is of great importance for the recycling of products. Effects of four inhibitors were compared by kinetic experiments indicating that ascorbic acid is the best additive, which retards the oxidation process of magnesium sulfite in trace presence. The macrokinetics of magnesium sulfite oxidation inhibited by ascorbic acid were studied. Effects of the factors, including ascorbic acid concentration, magnesium sulfite concentration, oxygen partial pressure, pH, and temperature, were investigated in a stirred reactor with bubbling. The results show that the reaction rate is −0.55 order in ascorbic acid, 0.77 in oxygen partial pressure, and zero in magnesium sulfite concentration, respectively. The apparent activation energy is 88.0 kJ mol{sup −1}. Integrated with the kinetic model, it is concluded that the oxidation rate of magnesium sulfite inhibited by ascorbic acid is controlled by the intrinsic chemical reaction. The result provides a useful reference for sulfite recovery in magnesia desulfurization.

  5. Wet oxidation kinetics of refractory low molecular mass carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Levec, J.

    1999-10-01

    Wet oxidation kinetics of aqueous solutions of formic, acetic, oxalic, and glyoxalic acids was studied in a titanium autoclave at a temperature range of 150--320 C and oxygen partial pressures between 8 and 60 bar. Oxidation reactions obeyed a first-order kinetics with respect to concentration of all substrates. On the basis of acid concentration decay, the activation energy for acetic, oxalic, and glyoxalic acid oxidation was 178, 137, and 97 kJ/mol, respectively; whereas on the total organic carbon (TOC) conversion basis, these values were slightly higher, namely 182, 141, and 104 kJ/mol. The activation energy for formic acid took a unique value of 149 kJ/mol regardless of the type of concentration used. The rate of oxidation was proportional to a square root of oxygen concentration (partial pressure) for acetic, formic, and oxalic acids, whereas it was linearly proportional for glyoxalic acid. When sufficiently high oxygen partial pressure was applied ({ge}22 bar), the individual acid conversion in a mixture of these acids was well predicted by the rate expression derived for that acid. The lumped TOC concentration of mixtures did not obey a first-order kinetic behavior, although underlying TOC kinetics for each individual acid was linear. The oxidation results are also discussed in a view of speculated reaction pathways and the reactor material.

  6. Kinetics of Oxidation of Some Amino Acids by N-Chlorosaccharin in Aqueous Acetic Acid Medium

    Directory of Open Access Journals (Sweden)

    N. A. Mohamed Farook

    2004-01-01

    Full Text Available The kinetics of oxidation of some amino acids namely, glycine, alanine, aspartic acid, arginine, and histidine, (AA by N-chlorosaccharin (NCSA in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order in [AA], [NCSA] and of inverse fractional order in [H+]. The main product of the oxidation is the corresponding aldehyde. The ionic strength on the reaction rate has no significant effect. The effect of changing the dielectric constant of the medium on the rate indicates the reaction to be of dipole-dipole type. Hypochlorous acid has been postulated as the reactive oxidizing species. The reaction constants involved in the mechanism are derived. The activation parameters are computed with respect to slow step of the mechanism.

  7. AMPK-independent pathways regulate skeletal muscle fatty acid oxidation

    DEFF Research Database (Denmark)

    Dzamko, Nicolas; Schertzer, Jonathan D.; Ryall, James G.

    2008-01-01

    , malonyl-CoA levels were reduced and rates of fatty acid oxidation were comparable between genotypes. During treadmill exercise both KD and WT mice had similar values of respiratory exchange ratio. These studies suggested the presence of an alternative ACC2 kinase(s). Using a phosphoproteomics......The activation of AMP-activated protein kinase (AMPK) and phosphorylation/inhibition of acetyl-CoA carboxylase 2 (ACC2) is believed to be the principal pathway regulating fatty acid oxidation. However, during exercise AMPK activity and ACC Ser-221 phosphorylation does not always correlate...... with rates of fatty acid oxidation. To address this issue we have investigated the requirement for skeletal muscle AMPK in controlling aminoimidazole-4-carboxymide-1-beta-d-ribofuranoside (AICAR) and contraction-stimulated fatty acid oxidation utilizing transgenic mice expressing a muscle-specific kinase...

  8. Nickel inhibits mitochondrial fatty acid oxidation.

    Science.gov (United States)

    Uppala, Radha; McKinney, Richard W; Brant, Kelly A; Fabisiak, James P; Goetzman, Eric S

    2015-08-07

    Nickel exposure is associated with changes in cellular energy metabolism which may contribute to its carcinogenic properties. Here, we demonstrate that nickel strongly represses mitochondrial fatty acid oxidation-the pathway by which fatty acids are catabolized for energy-in both primary human lung fibroblasts and mouse embryonic fibroblasts. At the concentrations used, nickel suppresses fatty acid oxidation without globally suppressing mitochondrial function as evidenced by increased glucose oxidation to CO2. Pre-treatment with l-carnitine, previously shown to prevent nickel-induced mitochondrial dysfunction in neuroblastoma cells, did not prevent the inhibition of fatty acid oxidation. The effect of nickel on fatty acid oxidation occurred only with prolonged exposure (>5 h), suggesting that direct inhibition of the active sites of metabolic enzymes is not the mechanism of action. Nickel is a known hypoxia-mimetic that activates hypoxia inducible factor-1α (HIF1α). Nickel-induced inhibition of fatty acid oxidation was blunted in HIF1α knockout fibroblasts, implicating HIF1α as one contributor to the mechanism. Additionally, nickel down-regulated the protein levels of the key fatty acid oxidation enzyme very long-chain acyl-CoA dehydrogenase (VLCAD) in a dose-dependent fashion. In conclusion, inhibition of fatty acid oxidation by nickel, concurrent with increased glucose metabolism, represents a form of metabolic reprogramming that may contribute to nickel-induced carcinogenesis.

  9. Sildenafil reduces signs of oxidative stress in pulmonary arterial hypertension: Evaluation by fatty acid composition, level of hydroxynonenal and heart rate variability

    Directory of Open Access Journals (Sweden)

    Khrystyna Semen

    2016-04-01

    Full Text Available Pulmonary arterial hypertension (PAH is a rare multifactorial disease with an unfavorable prognosis. Sildenafil therapy can improve functional capacity and pulmonary hemodynamics in PAH patients. Nowadays, it is increasingly recognized that the effects of sildenafil are pleiotropic and may also involve changes of the pro-/antioxidant balance, lipid peroxidation and autonomic control. In present study we aimed to assess the effects of sildenafil on the fatty acids (FAs status, level of hydroxynonenal (HNE and heart rate variability (HRV in PAH patients. Patients with PAH were characterized by an increase in HNE and changes in the FAs composition with elevation of linoleic, oleic, docosahexanoic acids in phospholipids as well as reduced HRV with sympathetic predominance. Sildenafil therapy improved exercise capacity and pulmonary hemodynamics and reduced NT-proBNP level in PAH. Antioxidant and anti-inflammatory effects of sildenafil were noted from the significant lowering of HNE level and reduction of the phopholipid derived oleic, linoleic, docosahexanoic, docosapentanoic FAs. That was also associated with some improvement of HRV on account of the activation of the neurohumoral regulatory component. Incomplete recovery of the functional metabolic disorders in PAH patients may be assumed from the persistent increase in free FAs, reduced HRV with the sympathetic predominance in the spectral structure after treatment comparing to control group. The possibilities to improve PAH treatment efficacy through mild stimulation of free radical reactions and formation of hormetic reaction in the context of improved NO signaling are discussed.

  10. Candida cloacae oxidation of long-chain fatty acids to dioic acids.

    Science.gov (United States)

    Green; Turner; Woodley

    2000-08-01

    Candida cloacae cells oxidize long-chain fatty acids to their corresponding dicarboxylic acids (dioic acids) at rates dependent on their chain length and degree of saturation. This is despite the well-known toxicity of the fatty acids. Among the saturated substrates, the oxidation is limited to lauric acid (C12). The addition of pristane (5% v/v), which acts as an inert carrier for the poorly water-soluble substrate, boosts the oxidation of lauric acid to a rate that is comparable to that of dodecane. When dissolved in pristane, myristic (C14) and palmitic (C16) acids are effective carbon sources for C. cloacae, but dioic acid production is very low. Media glucose concentration and pH also influence cell growth and productivity. After the glucose is depleted, oxidation is optimal at a low pH. A two-phase (pristane/water) reaction was tested in a 2-l stirred tank bioreactor in which growth and oxidation were separated. A 50% w/w conversion of lauric acid (10 g/l) to dodecanedioic acid was achieved. The bioreactor also alleviated poor mass transfer characteristics experienced in shake flasks.

  11. Free acetate production by rat hepatocytes during peroxisomal fatty acid and dicarboxylic acid oxidation.

    Science.gov (United States)

    Leighton, F; Bergseth, S; Rørtveit, T; Christiansen, E N; Bremer, J

    1989-06-25

    The fate of the acetyl-CoA units released during peroxisomal fatty acid oxidation was studied in isolated hepatocytes from normal and peroxisome-proliferated rats. Ketogenesis and hydrogen peroxide generation were employed as indicators of mitochondrial and peroxisomal fatty acid oxidation, respectively. Butyric and hexanoic acids were employed as mitochondrial substrates, 1, omega-dicarboxylic acids as predominantly peroxisomal substrates, and lauric acid as a substrate for both mitochondria and peroxisomes. Ketogenesis from dicarboxylic acids was either absent or very low in normal and peroxisome-proliferated hepatocytes, but free acetate release was detected at rates that could account for all the acetyl-CoA produced in peroxisomes by dicarboxylic and also by monocarboxylic acids. Mitochondrial fatty acid oxidation also led to free acetate generation but at low rates relative to ketogenesis. The origin of the acetate released was confirmed employing [1-14C]dodecanedioic acid. Thus, the activity of peroxisomes might contribute significantly to the free acetate generation known to occur during fatty acid oxidation in rats and possibly also in humans.

  12. Acid monolayer functionalized iron oxide nanoparticle catalysts

    Science.gov (United States)

    Ikenberry, Myles

    Superparamagnetic iron oxide nanoparticle functionalization is an area of intensely active research, with applications across disciplines such as biomedical science and heterogeneous catalysis. This work demonstrates the functionalization of iron oxide nanoparticles with a quasi-monolayer of 11-sulfoundecanoic acid, 10-phosphono-1-decanesulfonic acid, and 11-aminoundecanoic acid. The carboxylic and phosphonic moieties form bonds to the iron oxide particle core, while the sulfonic acid groups face outward where they are available for catalysis. The particles were characterized by thermogravimetric analysis (TGA), transmission electron microscopy (TEM), potentiometric titration, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectrometry (XPS), and dynamic light scattering (DLS). The sulfonic acid functionalized particles were used to catalyze the hydrolysis of sucrose at 80° and starch at 130°, showing a higher activity per acid site than the traditional solid acid catalyst Amberlyst-15, and comparing well against results reported in the literature for sulfonic acid functionalized mesoporous silicas. In sucrose catalysis reactions, the phosphonic-sulfonic nanoparticles (PSNPs) were seen to be incompletely recovered by an external magnetic field, while the carboxylic-sulfonic nanoparticles (CSNPs) showed a trend of increasing activity over the first four recycle runs. Between the two sulfonic ligands, the phosphonates produced a more tightly packed monolayer, which corresponded to a higher sulfonic acid loading, lower agglomeration, lower recoverability through application of an external magnetic field, and higher activity per acid site for the hydrolysis of starch. Functionalizations with 11-aminoundecanoic acid resulted in some amine groups binding to the surfaces of iron oxide nanoparticles. This amine binding is commonly ignored in iron oxide

  13. Direct Oxidation of Ethene to Acetic Acid

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Direct oxidation of ethene to acetic acid over Pd-SiW12/SiO2 catalysts prepared by several methods was studied. A better method for reducing palladium composition of the catalysts was found. Acetic acid was obtained with selectivity of 82.7% and once-through space time yield (STY) of 257.4 g/h×L.

  14. Kinetics of Oxidation of 3-Benzoylpropionic Acid by N-Bromoacetamide in Aqueous Acetic Acid Medium

    Directory of Open Access Journals (Sweden)

    N. A. Mohamed Farook

    2011-01-01

    Full Text Available The kinetics of oxidation of 3-benzoylpropionic acid (KA with N-bromoacetamide (NBA have been studied potentiometrically in 50:50 (v/v aqueous acetic acid medium at 298 K The reaction was first order each with respect to [KA], [NBA] and [H+]. The main product of the oxidation is the corresponding carboxylic acid. The rate decreases with the addition of acetamide, one of the products of the reaction. Variation in ionic strength of the reaction medium has no significant effect on the rate of oxidation. But the rate of the reaction is enhanced by lowering the dielectric constant of the reaction medium. A mechanism consistent with observed results have been proposed and the related rate law was deduced.

  15. The kinetics of oxidation of bilirubin and ascorbic acid in solution

    Science.gov (United States)

    Solomonov, A. V.; Rumyantsev, E. V.; Kochergin, B. A.; Antina, E. V.

    2012-07-01

    The results of a comparative study of the oxidation of bilirubin, ascorbic acid, and their mixture in aqueous solutions under the action of air oxygen and hydrogen peroxide are presented. The observed and true rate constants for the oxidation reactions were determined. It was shown that the oxidation of tetrapyrrole pigment occurred under these conditions bypassing the stage of biliverdin formation to monopyrrole products. Simultaneous oxidation of bilirubin and ascorbic acid was shown to be accompanied by the inhibition of ascorbic acid oxidation by bilirubin, whereas ascorbic acid itself activated the oxidation of bilirubin.

  16. Fatty acid oxidation and ketogenesis in astrocytes

    Energy Technology Data Exchange (ETDEWEB)

    Auestad, N.

    1988-01-01

    Astrocytes were derived from cortex of two-day-old rat brain and grown in primary culture to confluence. The metabolism of the fatty acids, octanoate and palmitate, to CO{sub 2} in oxidative respiration and to the formation of ketone bodies was examined by radiolabeled tracer methodology. The net production of acetoacetate was also determined by measurement of its mass. The enzymes in the ketogenic pathway were examined by measuring enzymic activity and/or by immunoblot analyses. Labeled CO{sub 2} and labeled ketone bodies were produced from the oxidation of fatty acids labeled at carboxy- and {omega}-terminal carbons, indicating that fatty acids were oxidized by {beta}-oxidation. The results from the radiolabeled tracer studies also indicated that a substantial proportion of the {omega}-terminal 4-carbon unit of the fatty acids bypassed the {beta}-ketothiolase step of the {beta}-oxidation pathway. The ({sup 14}C)acetoacetate formed from the (1-{sup 14}C)labeled fatty acids, obligated to pass through the acetyl-CoA pool, contained 50% of the label at carbon 3 and 50% at carbon 1. In contrast, the ({sup 14}C)acetoacetate formed from the ({omega}-1)labeled fatty acids contained 90% of the label at carbon 3 and 10% at carbon 1.

  17. Kinetics and mechanism of the oxidation of some neutral and acidic -amino acids by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; Kalyan K Banerji

    2004-03-01

    The oxidation of eleven amino acids by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid results in the formation of the corresponding carbonyl compounds and ammonia. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with some of the amino acids while others exhibit second-order dependence. It failed to induce polymerization of acrylonitrile. The effect of solvent composition indicate that the rate of reaction increases with increase in the polarity of the medium. Addition of tetrabutylammonium chloride has no effect on the rate of oxidation. Addition of bromide ion causes decrease in the oxidation rate but only to a limiting value. The reaction is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

  18. Cyanide-insensitive and clofibrate enhanced beta-oxidation of dodecanedioic acid in rat liver. An indication of peroxisomal beta-oxidation of N-dicarboxylic acids.

    Science.gov (United States)

    Mortensen, P B; Kølvraa, S; Gregersen, N; Rasmussen, K

    1982-11-12

    The beta-oxidation rate of dodecanedioic acid in rat liver homogenates (600 X g supernatant fraction) was determined by simultaneous measurements of the C6-C12-dicarboxylic acids, i.e., adipic, suberic, sebacic and dodecanedioic acids, in relation to time in assays incubated with dodecanedioic acid. Measurements were performed by a combined gas chromatographic-mass spectrometric technique, i.e., selected ion-monitoring. The beta-oxidation rate was registered as the consumption rate of dodecanedioic acid and as the initial rise in the concentrations of C6-C10-dicarboxylic acids. The beta-oxidation rate of C8-C12-dicarboxylic acids was increased many times in homogenates from clofibrate-treated rats. Moreover, it was unexpectedly found that 2.0 mM cyanide was unable to inhibit the beta-oxidation rate of the dicarboxylic acids in vitro, but in fact caused a minor increase in the rate of beta-oxidation in homogenates from both normal and clofibrate-treated rats. It was concluded that the present results strongly indicate the existence of a peroxisomal beta-oxidation of dicarboxylic acids.

  19. Control of food intake by fatty acid oxidation and ketogenesis.

    Science.gov (United States)

    Scharrer, E

    1999-09-01

    in response to decreased fatty acid oxidation. As ketones are products of hepatic fatty acid oxidation that are released into the circulation and peripheral (and central) administration of 3-hydroxybutyrate reduced voluntary food intake in rats, ketones being utilized as fuels by the peripheral and central nervous system might contribute to control of eating by fatty acid oxidation, especially when high levels of circulating ketones occur. Whether a modulation of the hepatic membrane potential resulting from changes in the rate of fatty acid oxidation and/or ketogenesis represent a signal for control of eating transmitted to the brain by vagal afferents remains to be established. Recent in vivo studies investigating the effects of mercaptoacetate on the hepatic membrane potential and on afferent activity of the hepatic vagus branch are consistent with this notion. Further investigations are necessary to delineate the coding mechanisms by which fatty acid oxidation and/or ketogenesis modulate vagal afferent activity.

  20. Kinetics and Mechanism of Oxidation of Glutamic Acid by N-Bromophthalimide in Aqueous Acidic Medium

    OpenAIRE

    2011-01-01

    The kinetics of oxidation of glutamic acid (Glu) with N-bromophthalimide (NBP) was studied in perchloric acid medium at 30 °C by potentiometric method. The reaction is first order each in NBP and glutamic acid and is negative fractional order in [H+]. Addition of KBr or the reaction product, phthalimide had no effect on the rate. Similarly variation of ionic strength of the medium did not affect the rate of the reaction. Also the rate increased with decrease in dielectric constant of the reac...

  1. Prevalent mutations in fatty acid oxidation disorders

    DEFF Research Database (Denmark)

    Gregersen, N; Andresen, B S; Bross, P

    2000-01-01

    UNLABELLED: The mutational spectrum in a given disease-associated gene is often comprised of a large number of different mutations, of which a single or a few are present in a large proportion of diseased individuals. Such prevalent mutations are known in four genes of the fatty acid oxidation: t...... of the disease in question and determination of the carrier frequency in the general population may help in elucidating the penetrance of the genotype. This is exemplified in disorders of mitochondrial fatty acid oxidation....

  2. Oxidation of cumene in an aprotic medium in the presence of ascorbic acid

    Science.gov (United States)

    Smirnova, O. V.; Efimova, I. V.; Opeida, I. A.

    2015-06-01

    The process of the initiated oxidation of cumene (IPB) with oxygen under homophase conditions in the presence of ascorbic acid (AA) used over a wide range of concentrations is studied. It is shown that in this system, ascorbic acid is consumed in two ways: the auto-oxidation and the inhibition of the oxidation of cumene. The amount of ascorbic acid that participates in inhibiting the oxidation of cumene falls from 28.5 to 16.6% with a rise in the concentration of ascorbic acid in the range of 0.003-0.3 mol/L. The contribution from the rate of the oxidation of ascorbic acid to the total rate of the oxidation of the IPB-AA-DMSO-AIBN system grows from 67.2 to 92.5% with a rise in the concentration of ascorbic acid in the range of 0.01-0.3 mol/L. It is established that the most effective inhibition of the oxidation of cumene with ascorbic acid in aprotic media occurs at concentrations of ascorbic acid of up to 0.01 mol/L. A scheme for the initiated radical-chain oxidation of cumene with ascorbic acid in the aprotic medium that considers the inhibition of the oxidation of cumene with ascorbic acid and the auto-oxidation of ascorbic acid is proposed.

  3. Kinetics and mechanism of the oxidation of some -hydroxy acids by hexamethylenetetramine-bromine

    Indian Academy of Sciences (India)

    Dimple Garg; Seema Kothari

    2004-11-01

    The oxidation of lactic acid, mandelic acid and ten monosubstituted mandelic acids by hexamethylenetetramine-bromine (HABR) in glacial acetic acid, leads to the formation of the corresponding oxoacid. The reaction is first order with respect to each of the hydroxy acids and HABR. It is proposed that HABR itself is the reactive oxidizing species. The oxidation of -deuteriomandelic acid exhibits the presence of a substantial kinetic isotope effect (/ = 5.91 at 298 K). The rates of oxidation of the substituted mandelic acids show excellent correlation with Brown’s + values. The reaction constants are negative. The oxidation exhibits an extensive cross conjugation between the electron-donating substituent and the reaction centre in the transition state. A mechanism involving transfer of a hydride ion from the acid to the oxidant is postulated.

  4. Ab initio and kinetic modeling studies of formic acid oxidation

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... as the fate of HOCO, determines the oxidation rate of formic acid. At lower temperatures HO2, formed from HOCO + O2, is an important chain carrier and modeling predictions become sensitive to the HOCHO + HO2 reaction. © 2014 The Combustion Institute....... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...

  5. Kinetics and mechanism of the oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate

    Indian Academy of Sciences (India)

    Poonam Gupta; Seema Kothari

    2001-04-01

    The oxidation of formic and oxalic acids by benzyltrimethylammonium dichloroiodate (BTMACI), in the presence of zinc chloride, leads to the formation of carbon dioxide. The reaction is first order with respect to BTMACI, zinc chloride and organic acid. Oxidation of deuteriated formic acid indicates the presence of a kinetic isotope effect. Addition of benzyltrimethylammonium chloride enhances the rate. It is proposed that the reactive oxidizing species is [(PhCH2Me3N)+ (IZn2Cl6)−]. Suitablemechanisms have been proposed.

  6. Mitochondrial fatty acid oxidation alterations in heart failure, ischaemic heart disease and diabetic cardiomyopathy.

    Science.gov (United States)

    Fillmore, N; Mori, J; Lopaschuk, G D

    2014-04-01

    Heart disease is a leading cause of death worldwide. In many forms of heart disease, including heart failure, ischaemic heart disease and diabetic cardiomyopathies, changes in cardiac mitochondrial energy metabolism contribute to contractile dysfunction and to a decrease in cardiac efficiency. Specific metabolic changes include a relative increase in cardiac fatty acid oxidation rates and an uncoupling of glycolysis from glucose oxidation. In heart failure, overall mitochondrial oxidative metabolism can be impaired while, in ischaemic heart disease, energy production is impaired due to a limitation of oxygen supply. In both of these conditions, residual mitochondrial fatty acid oxidation dominates over mitochondrial glucose oxidation. In diabetes, the ratio of cardiac fatty acid oxidation to glucose oxidation also increases, although primarily due to an increase in fatty acid oxidation and an inhibition of glucose oxidation. Recent evidence suggests that therapeutically regulating cardiac energy metabolism by reducing fatty acid oxidation and/or increasing glucose oxidation can improve cardiac function of the ischaemic heart, the failing heart and in diabetic cardiomyopathies. In this article, we review the cardiac mitochondrial energy metabolic changes that occur in these forms of heart disease, what role alterations in mitochondrial fatty acid oxidation have in contributing to cardiac dysfunction and the potential for targeting fatty acid oxidation to treat these forms of heart disease.

  7. Bond energies in polyunsaturated acids and kinetics of co-oxidation of protiated and deuterated acids

    Science.gov (United States)

    Andrianova, Z. S.; Breslavskaya, N. N.; Pliss, E. M.; Buchachenko, A. L.

    2016-10-01

    A computational program specially designed to analyze co-oxidation of substances in mixtures is suggested. The rigorous kinetic scheme of 32 reactions describing co-oxidation of isotope differing polyunsaturated fatty acids was computed to enlighten experimentally detected enormously large H/D isotope effects. The latter were shown to depend on the kinetic chain length and exhibit two extreme regimes of short and long chains which characterize isotope effects on the initiation and propagation chain reactions of hydrogen (deuterium) atom abstraction. No protective effect of deuterated polyunsaturated acids on the oxidation of protiated acids was detected. Protective effect of the deuterated compounds on the biologically important processes seems to be induced by the low yield of products formed in the chain termination reactions due to the low rate of initiation by deuterated compounds.

  8. Effect of sulfonylureas on hepatic fatty acid oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Patel, T.B.

    1986-08-01

    In isolated rat livers perfused with oleic acid (0.1 mM), infusion of tolbutamide or glyburide decreased the rate of ketogenesis in a dose-dependent manner. The inhibition of fatty acid oxidation was maximal at 2.0 mM and 10 M concentrations of tolbutamide and glyburide, respectively. Neither tolbutamide nor glyburide inhibited ketogenesis in livers perfused with octanoate. The inhibition of hepatic ketogenesis by sulfonylureas was independent of perfusate oleic acid concentration. Additionally, in rat livers perfused with oleic acid in the presence of L-(-)-carnitine (10 mM), submaximal concentrations of tolbutamide and glyburide did not inhibit hepatic ketogenesis. Finally, glyburide infusion into livers perfused with (U- $C)oleic acid (0.1 mM) increased the rate of UC label incorporation into hepatic triglycerides by 2.5-fold. These data suggest that both tolbutamide and glyburide inhibit long-chain fatty acid oxidation by inhibition the key regulatory enzyme, carnitine palmitoyltransferase I, most probably by competing with L-(-)-carnitine.

  9. Chloramines and hypochlorous acid oxidize erythrocyte peroxiredoxin 2.

    Science.gov (United States)

    Stacey, Melissa M; Peskin, Alexander V; Vissers, Margreet C; Winterbourn, Christine C

    2009-11-15

    Peroxiredoxin 2 (Prx2) is an abundant thiol protein that is readily oxidized in erythrocytes exposed to hydrogen peroxide. We investigated its reactivity in human erythrocytes with hypochlorous acid (HOCl) and chloramines, relevant oxidants in inflammation. Prx2 was oxidized to a disulfide-linked dimer by HOCl, glycine chloramine (GlyCl), and monochloramine (NH(2)Cl) in a dose-dependent manner. In the absence of added glucose, Prx2 and GSH showed similar sensitivities. Second-order rate constants for the reactions of Prx2 with NH(2)Cl and GlyCl were 1.5 x 10(4) and 8 M(-1) s(-1), respectively. The NH(2)Cl value is approximately 10 times higher than that for GSH, whereas Prx2 is approximately 30 times less sensitive than GSH to GlyCl. Thus, the relative sensitivity of Prx2 to GlyCl is greater in the erythrocyte. Oxidation of erythrocyte Prx2 and GSH was less in the presence of glucose, probably because of recycling. High doses of NH(2)Cl resulted in incomplete regeneration of reduced Prx2, suggesting impairment of the recycling mechanism. Our results show that, although HOCl and chloramines are less selective than H(2)O(2), they nevertheless oxidize Prx2. Exposure to these inflammatory oxidants will result in Prx2 oxidation and could compromise the erythrocyte's ability to resist damaging oxidative insult.

  10. Hypochlorous and peracetic acid induced oxidation of dairy proteins.

    Science.gov (United States)

    Kerkaert, Barbara; Mestdagh, Frédéric; Cucu, Tatiana; Aedo, Philip Roger; Ling, Shen Yan; De Meulenaer, Bruno

    2011-02-09

    Hypochlorous and peracetic acids, both known disinfectants in the food industry, were compared for their oxidative capacity toward dairy proteins. Whey proteins and caseins were oxidized under well controlled conditions at pH 8 as a function of the sanitizing concentration. Different markers for protein oxidation were monitored. The results established that the protein carbonyl content was a rather unspecific marker for protein oxidation, which did not allow one to differentiate the oxidant used especially at the lower concentrations. Cysteine, tryptophan, and methionine were proven to be the most vulnerable amino acids for degradation upon hypochlorous and peracetic acid treatment, while tyrosine was only prone to degradation in the presence of hypochlorous acid. Hypochlorous acid induced oxidation gave rise to protein aggregation, while during peracetic acid induced oxidation, no high molecular weight aggregates were observed. Protein aggregation upon hypochlorous acid oxidation could primarily be linked to tryptophan and tyrosine degradation.

  11. Kinetic study of formic acid oxidation on carbon supported Pd electrocatalyst

    Science.gov (United States)

    Wang, Yujiao; Wu, Bing; Gao, Ying; Tang, Yawen; Lu, Tianhong; Xing, Wei; Liu, Changpeng

    The oxidation of formic acid at the Pd/C catalyst electrode is a completely irreversible kinetic process with the reaction order of 1.0. The oxidation rate of formic acid is increased with increasing the concentration of formic acid and is decreased with increasing H + concentration. The apparent negative reaction order with respect to H + is about -0.18 or -0.04 in H 2SO 4 or HClO 4 solution respectively, because bisulfate anions would inhibit formic acid oxidation at some extent. The kinetic parameters, charge transfer coefficient and the diffusion coefficient of formic acid were obtained under the quasi steady-state conditions.

  12. Implications of impaired ketogenesis in fatty acid oxidation disorders.

    Science.gov (United States)

    Olpin, Simon Edward

    2004-03-01

    Long-chain fatty acids are important sources of respiratory fuel for many tissues and during fasting the rate of hepatic production of ketone bodies is markedly increased. Many extra hepatic tissues utilize ketone bodies in the fasted state with the advantage that glucose is "spared" for more vital tissues like the brain. This glucose sparing effect of ketones is especially important in infants where there is a high proportional glucose utilization in cerebral tissue. The first reported inherited defect affecting fatty acid oxidation was described in 1973 and to date about 15 separate disorders have been described. Although individually rare, cumulatively fatty acid oxidation defects are relatively common, have major consequences for affected individuals and their families, and carry significant health care implications. The major biochemical consequence of fatty acid oxidation defects is an inability of extra hepatic tissues to utilize fatty acids as an energy source with absent or limited hepatic capacity to generate ketones. Clinically patients usually present in infancy with acute life-threatening hypoketotic hypoglycaemia, liver disease, hyperammonaemia and cerebral oedema, with or without cardiac involvement, usually following a period of catabolic stress. Chronically there may be muscle involvement with hypotonia or exercise intolerance with or without cardiomyopathy. Treatment is generally by the avoidance of fasting, frequent carbohydrate rich feeds and for long-chain defects, the replacement of long-chain dietary fats with medium-chain formulae. Novel approaches to treatment include the use of d,l-3-hydoxybutyrate or heptanoate as an alternative energy source.

  13. Electrochemical degradation of clofibric acid in water by anodic oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Sires, Ignasi [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Cabot, Pere Lluis [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Centellas, Francesc [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Garrido, Jose Antonio [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Rodriguez, Rosa Maria [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Arias, Conchita [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Brillas, Enric [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)]. E-mail: brillas@ub.edu

    2006-10-05

    Aqueous solutions containing the metabolite clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid) up to close to saturation in the pH range 2.0-12.0 have been degraded by anodic oxidation with Pt and boron-doped diamond (BDD) as anodes. The use of BDD leads to total mineralization in all media due to the efficient production of oxidant hydroxyl radical ({center_dot}OH). This procedure is then viable for the treatment of wastewaters containing this compound. The effect of pH, apparent current density, temperature and metabolite concentration on the degradation rate, consumed specific charge and mineralization current efficiency has been investigated. Comparative treatment with Pt yields poor decontamination with complete release of stable chloride ion. When BDD is used, this ion is oxidized to Cl{sub 2}. Clofibric acid is more rapidly destroyed on Pt than on BDD, indicating that it is more strongly adsorbed on the Pt surface enhancing its reaction with {center_dot}OH. Its decay kinetics always follows a pseudo-first-order reaction and the rate constant for each anode increases with increasing apparent current density, being practically independent of pH and metabolite concentration. Aromatic products such as 4-chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol are detected by gas chromatography-mass spectrometry (GC-MS) and reversed-phase chromatography. Tartronic, maleic, fumaric, formic, 2-hydroxyisobutyric, pyruvic and oxalic acids are identified as generated carboxylic acids by ion-exclusion chromatography. These acids remain stable in solution using Pt, but they are completely converted into CO{sub 2} with BDD. A reaction pathway for clofibric acid degradation involving all these intermediates is proposed.

  14. CATALYTIC HYDROGENATION AND OXIDATION OF BIOMASS-DERIVED LEVULINIC ACID

    Directory of Open Access Journals (Sweden)

    Yan Gong

    2011-02-01

    Full Text Available Levulinic acid (LA, 4-oxo-pentanoic acid, is a new platform chemical with various potential uses. In this paper, catalytic hydrogenation and oxidation of levulinic acid were studied. It was shown from experiments that levulinic acid can be hydrogenated to γ-valerolactone (GVL over transition metal catalysts and oxidative-decarboxylated to 2-butanone (methyl-ethyl-ketone, MEK and methyl-vinyl-ketone (MVK by cupric oxide (CuO, cupric oxide/cerium oxide (CuO/CeO2, cupric oxide/ alumina (CuO/ Al2O3, and silver(I/ peroxydisulfate (Ag(I/S2O82-.

  15. ω-Alkynyl lipid surrogates for polyunsaturated fatty acids: free radical and enzymatic oxidations.

    Science.gov (United States)

    Beavers, William N; Serwa, Remigiusz; Shimozu, Yuki; Tallman, Keri A; Vaught, Melissa; Dalvie, Esha D; Marnett, Lawrence J; Porter, Ned A

    2014-08-13

    Lipid and lipid metabolite profiling are important parameters in understanding the pathogenesis of many diseases. Alkynylated polyunsaturated fatty acids are potentially useful probes for tracking the fate of fatty acid metabolites. The nonenzymatic and enzymatic oxidations of ω-alkynyl linoleic acid and ω-alkynyl arachidonic acid were compared to that of linoleic and arachidonic acid. There was no detectable difference in the primary products of nonenzymatic oxidation, which comprised cis,trans-hydroxy fatty acids. Similar hydroxy fatty acid products were formed when ω-alkynyl linoleic acid and ω-alkynyl arachidonic acid were reacted with lipoxygenase enzymes that introduce oxygen at different positions in the carbon chains. The rates of oxidation of ω-alkynylated fatty acids were reduced compared to those of the natural fatty acids. Cyclooxygenase-1 and -2 did not oxidize alkynyl linoleic but efficiently oxidized alkynyl arachidonic acid. The products were identified as alkynyl 11-hydroxy-eicosatetraenoic acid, alkynyl 11-hydroxy-8,9-epoxy-eicosatrienoic acid, and alkynyl prostaglandins. This deviation from the metabolic profile of arachidonic acid may limit the utility of alkynyl arachidonic acid in the tracking of cyclooxygenase-based lipid oxidation. The formation of alkynyl 11-hydroxy-8,9-epoxy-eicosatrienoic acid compared to alkynyl prostaglandins suggests that the ω-alkyne group causes a conformational change in the fatty acid bound to the enzyme, which reduces the efficiency of cyclization of dioxalanyl intermediates to endoperoxide intermediates. Overall, ω-alkynyl linoleic acid and ω-alkynyl arachidonic acid appear to be metabolically competent surrogates for tracking the fate of polyunsaturated fatty acids when looking at models involving autoxidation and oxidation by lipoxygenases.

  16. Regulation and limitations to fatty acid oxidation during exercise

    DEFF Research Database (Denmark)

    Jeppesen, Jacob; Kiens, Bente

    2012-01-01

    Fatty acids (FA) as fuel for energy utilization during exercise originate from different sources: FA transported in the circulation either bound to albumin or as triacylglycerol (TG) carried by very low density lipoproteins (VLDL) and FA from lipolysis of muscle TG stores (IMTG). Despite a high...... rate of energy expenditure during high intensity exercise the total fatty acid oxidation is suppressed to below that observed during moderate intensity exercise. Although this has been known for many years, the mechanisms behind this phenomenon are still not fully elucidated. A failure of adipose...... tissue to deliver sufficient fatty acids to exercising muscle has been proposed, but evidence is emerging that factors within the muscle might be of more importance. The high rate of glycolysis during high intensity exercise might be the "driving force" via the increased production of acetyl CoA which...

  17. Kinetics of oxidation of acidic amino acids by sodium N-bromobenzenesulphonamide in acid medium: A mechanistic approach

    Indian Academy of Sciences (India)

    Puttaswamy; Nirmala Vaz

    2001-08-01

    Kinetics of oxidation of acidic amino acids (glutamic acid (Glu) and aspartic acid (Asp)) by sodium N-bromobenzenesulphonamide (bromamine-B or BAB) has been carried out in aqueous HClO4 medium at 30°C. The rate shows firstorder dependence each on [BAB]o and [amino acid]o and inverse first-order on [H+]. At [H+] > 0 60 mol dm-3, the rate levelled off indicating zero-order dependence on [H+] and, under these conditions, the rate has fractional order dependence on [amino acid]. Succinic and malonic acids have been identified as the products. Variation of ionic strength and addition of the reaction product benzenesulphonamide or halide ions had no significant effect on the reaction rate. There is positive effect of dielectric constant of the solvent. Proton inventory studies in H2O-D2O mixtures showed the involvement of a single exchangeable proton of the OH- ion in the transition state. Kinetic investigations have revealed that the order of reactivity is Asp > Glu. The rate laws proposed and derived in agreement with experimental results are discussed.

  18. Inhibition of oxidative metabolism by propionic acid and its reversal by carnitine in isolated rat hepatocytes.

    Science.gov (United States)

    Brass, E P; Fennessey, P V; Miller, L V

    1986-01-01

    The present study was designed to study the interaction of propionic acid and carnitine on oxidative metabolism by isolated rat hepatocytes. Propionic acid (10 mM) inhibited hepatocyte oxidation of [1-14C]-pyruvate (10 mM) by 60%. This inhibition was not the result of substrate competition, as butyric acid had minimal effects on pyruvate oxidation. Carnitine had a small inhibitory effect on pyruvate oxidation in the hepatocyte system (210 +/- 19 and 184 +/- 18 nmol of pyruvate/60 min per mg of protein in the absence and presence of 10 mM-carnitine respectively; means +/- S.E.M., n = 10). However, in the presence of propionic acid (10 mM), carnitine (10 mM) increased the rate of pyruvate oxidation by 19%. Under conditions where carnitine partially reversed the inhibitory effect of propionic acid on pyruvate oxidation, formation of propionylcarnitine was documented by using fast-atom-bombardment mass spectroscopy. Propionic acid also inhibited oxidation of [1-14C]palmitic acid (0.8 mM) by hepatocytes isolated from fed rats. The degree of inhibition caused by propionic acid was decreased in the presence of 10 mM-carnitine (41% inhibition in the absence of carnitine, 22% inhibition in the presence of carnitine). Propionic acid did not inhibit [1-14C]palmitic acid oxidation by hepatocytes isolated from 48 h-starved rats. These results demonstrate that propionic acid interferes with oxidative metabolism in intact hepatocytes. Carnitine partially reverses the inhibition of pyruvate and palmitic acid oxidation by propionic acid, and this reversal is associated with increased propionylcarnitine formation. The present study provides a metabolic basis for the efficacy of carnitine in patients with abnormal organic acid accumulation, and the observation that such patients appear to have increased carnitine requirements ('carnitine insufficiency'). PMID:3790065

  19. Electrocatalysis by nanoparticles: Oxidation of formic acid at manganese oxide nanorods-modified Pt planar and nanohole-arrays

    Directory of Open Access Journals (Sweden)

    Mohamed S. El-Deab

    2010-01-01

    Full Text Available The electro-oxidation of formic acid (an essential reaction in direct formic acid fuel cells is a challenging process because of the deactivation of anodes by the adsorption of the poisoning intermediate carbon monoxide (CO. Pt electrodes in two geometries (planar and nanohole-array were modified by the electrodeposition of manganese oxide nanorods (nano-MnOx. The modified Pt electrodes were then tested for their electrocatalytic activity through the electro-oxidation of formic acid in a solution of pH 3.45. Two oxidation peaks (Ipd and Ipind were observed at 0.2 and 0.55 V, respectively; these were assigned to the direct and indirect oxidative pathways. A significant enhancement of the direct oxidation of formic acid to CO2 was observed at the modified electrodes, while the formation of the poisoning intermediate CO was suppressed. Ipd increases with surface coverage (θ of nano-MnOx with a concurrent depression of Ipind. An increase in the ratio Ipd/ν1/2 with decreasing potential scan rate (ν indicates that the oxidation process proceeds via a catalytic mechanism. The modification of Pt anodes with manganese oxide nanorods results in a significant improvement of the electrocatalytic activity along with a higher tolerance to CO. Thus nano-MnOx plays a crucial role as a catalytic mediator which facilitates the charge transfer during the direct oxidation of formic acid to CO2.

  20. Oxidation of nonplasma fatty acids during exercise is increased in women with abdominal obesity.

    Science.gov (United States)

    Horowitz, J F; Klein, S

    2000-12-01

    We evaluated plasma fatty acid availability and plasma and whole body fatty acid oxidation during exercise in five lean and five abdominally obese women (body mass index = 21 +/- 1 vs. 38 +/- 1 kg/m(2)), who were matched on aerobic fitness, to test the hypothesis that obesity alters the relative contribution of plasma and nonplasma fatty acids to total energy production during exercise. Subjects exercised on a recumbent cycle ergometer for 90 min at 54% of their peak oxygen consumption. Stable isotope tracer methods ([(13)C]palmitate) were used to measure fatty acid rate of appearance in plasma and the rate of plasma fatty acid oxidation, and indirect calorimetry was used to measure whole body substrate oxidation. During exercise, palmitate rate of appearance increased progressively and was similar in obese and lean groups between 60 and 90 min of exercise [3.9 +/- 0.4 vs. 4.0 +/- 0.3 micromol. kg fat free mass (FFM)(-1). min(-1)]. The rate of plasma fatty acid oxidation was also similar in obese and lean subjects (12.8 +/- 1.7 vs. 14.5 +/- 1.8 micromol. kg FFM(-1). min(-1); P = not significant). However, whole body fatty acid oxidation during exercise was 25% greater in obese than in lean subjects (21.9 +/- 1.2 vs. 17.5 +/- 1.6 micromol. kg FFM(-1). min(-1); P obese women, women with abdominal obesity use more fat as a fuel by oxidizing more nonplasma fatty acids.

  1. Comparison of the Oxidation Rates of Some New Copper Alloys

    Science.gov (United States)

    Ogbuji, Linus U. J. Thomas; Humphrey, Donald L.

    2002-01-01

    Copper alloys were studied for oxidation resistance and mechanisms between 550 and 700 C, in reduced-oxygen environments expected in rocket engines, and their oxidation behaviors compared to that of pure copper. They included two dispersion-strengthened alloys (precipitation-strengthened and oxide-dispersion strengthened, respectively) and one solution-strengthened alloy. In all cases the main reaction was oxidation of Cu into Cu2O and CuO. The dispersion-strengthened alloys were superior to both Cu and the solution-strengthened alloy in oxidation resistance. However, factors retarding oxidation rates seemed to be different for the two dispersion-strengthened alloys.

  2. Modulating fatty acid oxidation in heart failure.

    Science.gov (United States)

    Lionetti, Vincenzo; Stanley, William C; Recchia, Fabio A

    2011-05-01

    In the advanced stages of heart failure, many key enzymes involved in myocardial energy substrate metabolism display various degrees of down-regulation. The net effect of the altered metabolic phenotype consists of reduced cardiac fatty oxidation, increased glycolysis and glucose oxidation, and rigidity of the metabolic response to changes in workload. Is this metabolic shift an adaptive mechanism that protects the heart or a maladaptive process that accelerates structural and functional derangement? The question remains open; however, the metabolic remodelling of the failing heart has induced a number of investigators to test the hypothesis that pharmacological modulation of myocardial substrate utilization might prove therapeutically advantageous. The present review addresses the effects of indirect and direct modulators of fatty acid (FA) oxidation, which are the best pharmacological agents available to date for 'metabolic therapy' of failing hearts. Evidence for the efficacy of therapeutic strategies based on modulators of FA metabolism is mixed, pointing to the possibility that the molecular/biochemical alterations induced by these pharmacological agents are more complex than originally thought. Much remains to be understood; however, the beneficial effects of molecules such as perhexiline and trimetazidine in small clinical trials indicate that this promising therapeutic strategy is worthy of further pursuit.

  3. Stimulation of polyunsaturated fatty acid oxidation in myocytes by regulating its cellular uptake

    Energy Technology Data Exchange (ETDEWEB)

    Abdel-aleem, S.; Frangakis, C. (Glaxo Inc., Research Triangle Park, NC (USA)); Badr, M. (Univ. of Missouri-Kansas City, MO (USA))

    1991-01-01

    In order to investigate the regulation of polyunsaturated fatty acid oxidation in the heart, the effect of the phosphodiesterase inhibitor enoximone on the oxidation of (1-{sup 14}C) arachidonic acid, and (1-{sup 14}C) arachidonyl-CoA, were studied in adult rat myocytes, and isolated rat heart mitochondria. Enoximone stimulated arachidonate oxidation by 94%, at a concentration of 0.25 mM. The apparent Vmax value of archidonate oxidation in the presence of enoximone was approximately 75% higher than the value observed with the control in isolated myocytes. Also, enoximone stimulated arachidonate uptake by 27% at a concentration of 0.25 mM. On the other hand, enoximone had no effect on the oxidation of (1-{sup 14}C) arachidonyl-CoA in isolated rat heart mitochondria. These results suggest that the oxidation of polyunsaturated fatty acids in myocytes is regulated by the rate of uptake of these acids across sarcolemmal membranes.

  4. Physiological effects of γ-linolenic acid and sesamin on hepatic fatty acid synthesis and oxidation.

    Science.gov (United States)

    Ide, Takashi; Iwase, Haruka; Amano, Saaya; Sunahara, Saki; Tachihara, Ayuka; Yagi, Minako; Watanabe, Tsuyoshi

    2017-03-01

    Interrelated effects of γ-linolenic acid (GLA) and sesamin, a sesame lignan, on hepatic fatty acid synthesis and oxidation were examined. Rats were fed experimental diets supplemented with 0 or 2 g/kg sesamin (1:1 mixture of sesamin and episesamin) and containing 100 g/kg of palm oil (saturated fat), safflower oil rich in linoleic acid, or oil of evening primrose origin containing 43% GLA (GLA oil) for 18 days. In rats fed sesamin-free diets, GLA oil, compared with other oils, increased the activity and mRNA levels of various enzymes involved in fatty acid oxidation, except for some instances. Sesamin greatly increased these parameters, and the enhancing effects of sesamin on peroxisomal fatty acid oxidation rate and acyl-CoA oxidase, enoyl-CoA hydratase and acyl-CoA thioesterase activities were more exaggerated in rats fed GLA oil than in the animals fed other oils. The combination of sesamin and GLA oil also synergistically increased the mRNA levels of some peroxisomal fatty acid oxidation enzymes and of several enzymes involved in fatty acid metabolism located in other cell organelles. In the groups fed sesamin-free diets, GLA oil, compared with other oils, markedly reduced the activity and mRNA levels of various lipogenic enzymes. Sesamin reduced all these parameters, except for malic enzyme, in rats fed palm and safflower oils, but the effects were attenuated in the animals fed GLA oil. These changes by sesamin and fat type accompanied profound alterations in serum lipid levels. This may be ascribable to the changes in apolipoprotein-B-containing lipoproteins.

  5. wet oxidation of maleic acid by a pumice supported copper

    African Journals Online (AJOL)

    Mgina

    materials were tested in a wet oxidation of maleic acid using air or hydrogen peroxide as an oxidant. Results ... textile, pharmaceuticals, paper and pulp .... Fourier Transform Infrared (FTIR). The ... to analysis and then run at room temperature.

  6. Advanced oxidation processes of decomposing dichloroacetic acid and trichloroacetic acid in water

    Institute of Scientific and Technical Information of China (English)

    WANG Kun-ping; GUO Jin-song; YANG Min; JUNJI Hirotsuji; DENG Rong-sen; LIU Wei

    2008-01-01

    We studied the decomposition of two haloacetic acids (HAAs), dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA), in water by single oxidants ozone (O3) and ultraviolet radiation (UV) and the advanced oxidation processes (AOPs) constituted by the combinations of O3/UV, H2O2/UV, O3 /H2O2, and O3/H2O2/UV. The concentrations of HAAs were analyzed at specified time intervals to track their decomposition. Except for O3 and UV, the four combined oxidation processes remarkably enhance the decomposition of DCAA and TCAA owing to the generated very reactive hydroxyl radicals. The fastest decomposition process is O3/H2O2/UV, closely followed by O3/UV. DCAA is much easier to decompose than TCAA. The kinetics of HAA decomposition by O3/UV can be described well by a pseudo first-order reaction model under a constant initial dissolved O3 concentration and fixed UV radiation. Humic acids and HCO3- in the reaction system both decrease the decomposition rate constants for DCAA and TCAA. The amount of H2O2 accumulates in the presence of humic acids in the O3/UV process.

  7. Effects of Fe oxide on N transformations in subtropical acid soils

    Science.gov (United States)

    Jiang, Xianjun; Xin, Xiaoping; Li, Shiwei; Zhou, Junchao; Zhu, Tongbin; Müller, Christopher; Cai, Zucong; Wright, Alan L.

    2015-02-01

    Subtropical ecosystems are often characterized by high N cycling rates, but net nitrification rates are often low in subtropical acid soils. NO3--N immobilization into organic N may be a contributing factor to understand the observed low net nitrification rates in these acid soils. The effects of Fe oxide and organic matter on soil N transformations were evaluated using a 15N tracing study. Soil net nitrification was low for highly acidic yellow soil (Ferralsols), but gross ammonia oxidation was 7 times higher than net nitrification. In weakly acidic purple soil (Cambisols), net nitrification was 8 times higher than in Ferralsols. The addition of 5% Fe oxide to Cambisols, reduced the net nitrification rate to a negative rate, while NO3--N immobilization rate increased 8 fold. NO3--N immobilization was also observed in Ferralsols which contained high Fe oxides levels. A possible mechanism for these reactions could be stimulation of NO3--N immobilization by Fe oxide which promoted the abiotic formation of nitrogenous polymers, suggesting that the absence of net nitrification in some highly acid soils may be due to high rates of NO3--N immobilization caused by high Fe oxide content rather than a low pH.

  8. Advanced oxidation of acid and reactive dyes

    DEFF Research Database (Denmark)

    Arslan-Alaton, I.; Gursoy, B.H.; Schmidt, Jens Ejbye

    2008-01-01

    M) for 10:hsp sp="0.25" min Fenton treatment at pH 3, resulting in reduced chemical oxygen demand and dissolved organic carbon removal efficiencies; only acetate was detected as a stable dye oxidation end product. During anaerobic digestion, 100, 29% and no inhibition in methane production was observed...... for the untreated blue, red and orange dyes, respectively. The inhibitory effect of the blue reactive dye on methane production was ∼21% after Fenton treatment. Neither untreated nor treated dyes exhibited an inhibitory effect on denitrification. Aerobic glucose degradation was inhibited by 23-29% by untreated dyes......The effect of untreated and Fenton-treated acid dyes (C.I. Acid Red 183 and C.I. Acid Orange 51) and a reactive dye (C.I. Reactive Blue 4) on aerobic, anoxic and anaerobic processes was investigated. The optimum Fe2+:H2O2 molar ratio was selected as 1:5 (4:hsp sp="0.25" mM:20:hsp sp="0.25"m...

  9. Anodic oxidation of oxytetracycline: Influence of the experimental conditions on the degradation rate and mechanism

    Directory of Open Access Journals (Sweden)

    Annabel Fernandes

    2014-12-01

    Full Text Available The anodic oxidation of oxytetracycline was performed with success using as anode a boron-doped diamond electrode. The experiments were conducted in batch mode, using two different electrochemical cells: an up-flow cell, with recirculation, that was used to evaluate the influence of recirculation flow rate; and a stirred cell, used to determine the influence of the applied current density. Besides oxytetracyclin electrodegradation rate and mineralization extent, oxidation by-products were also assessed. Both the flow rate and the applied current density have shown positive influence on the oxytetracycline oxidation rate. On the other hand, the mineralization degree presented the highest values at the lowest flow rate and the lowest current density tested. The main oxidation by-products detected were oxalic, oxamic and maleic acids.

  10. Mitochondrial fatty acid oxidation defects--remaining challenges

    DEFF Research Database (Denmark)

    Gregersen, Niels; Andresen, Brage S; Pedersen, Christina B;

    2008-01-01

    Mitochondrial fatty acid oxidation defects have been recognized since the early 1970s. The discovery rate has been rather constant, with 3-4 'new' disorders identified every decade and with the most recent example, ACAD9 deficiency, reported in 2007. In this presentation we will focus on three...... of different mitochondrial dehydrogenases as well as deficiency of FAD and coenzyme Q(10). With SCAD deficiency, the challenge is to elucidate whether ACADS gene variations are disease-associated, especially when combined with other genetic/cellular/environmental factors, which may act synergistically....

  11. Mitochondrial free fatty acid β-oxidation supports oxidative phosphorylation and proliferation in cancer cells.

    Science.gov (United States)

    Rodríguez-Enríquez, Sara; Hernández-Esquivel, Luz; Marín-Hernández, Alvaro; El Hafidi, Mohammed; Gallardo-Pérez, Juan Carlos; Hernández-Reséndiz, Ileana; Rodríguez-Zavala, José S; Pacheco-Velázquez, Silvia C; Moreno-Sánchez, Rafael

    2015-08-01

    Oxidative phosphorylation (OxPhos) is functional and sustains tumor proliferation in several cancer cell types. To establish whether mitochondrial β-oxidation of free fatty acids (FFAs) contributes to cancer OxPhos functioning, its protein contents and enzyme activities, as well as respiratory rates and electrical membrane potential (ΔΨm) driven by FFA oxidation were assessed in rat AS-30D hepatoma and liver (RLM) mitochondria. Higher protein contents (1.4-3 times) of β-oxidation (CPT1, SCAD) as well as proteins and enzyme activities (1.7-13-times) of Krebs cycle (KC: ICD, 2OGDH, PDH, ME, GA), and respiratory chain (RC: COX) were determined in hepatoma mitochondria vs. RLM. Although increased cholesterol content (9-times vs. RLM) was determined in the hepatoma mitochondrial membranes, FFAs and other NAD-linked substrates were oxidized faster (1.6-6.6 times) by hepatoma mitochondria than RLM, maintaining similar ΔΨm values. The contents of β-oxidation, KC and RC enzymes were also assessed in cells. The mitochondrial enzyme levels in human cervix cancer HeLa and AS-30D cells were higher than those observed in rat hepatocytes whereas in human breast cancer biopsies, CPT1 and SCAD contents were lower than in human breast normal tissue. The presence of CPT1 and SCAD in AS-30D mitochondria and HeLa cells correlated with an active FFA utilization in HeLa cells. Furthermore, the β-oxidation inhibitor perhexiline blocked FFA utilization, OxPhos and proliferation in HeLa and other cancer cells. In conclusion, functional mitochondria supported by FFA β-oxidation are essential for the accelerated cancer cell proliferation and hence anti-β-oxidation therapeutics appears as an alternative promising approach to deter malignant tumor growth.

  12. Ascorbic acid protects lipids in human plasma and low-density lipoprotein against oxidative damage

    Energy Technology Data Exchange (ETDEWEB)

    Frei, B. (Department of Nutrition, Harvard School of Public Health, Boston, MA (Unites States))

    1991-12-01

    The authors exposed human blood plasma and low-density lipoprotein (LDL) to many different oxidative challenges and followed the temporal consumption of endogenous antioxidants in relation to the initiation of oxidative damage. Under all types of oxidizing conditions, ascorbic acid completely protects lipids in plasma and LDL against detectable peroxidative damage as assessed by a specific and highly sensitive assay for lipid peroxidation. Ascorbic acid proved to be superior to the other water-soluble plasma antioxidants bilirubin, uric acid, and protein thiols as well as to the lipoprotein-associated antioxidants alpha-tocopherol, ubiquinol-10, lycopene, and beta-carotene. Although these antioxidants can lower the rate of detectable lipid peroxidation, they are not able to prevent its initiation. Only ascorbic acid is reactive enough to effectively intercept oxidants in the aqueous phase before they can attack and cause detectable oxidative damage to lipids.

  13. Influence of Fluorine on the Conductivity and Oxidation of Silicon Nanomembranes after Hydrofluoric Acid Treatment

    Institute of Scientific and Technical Information of China (English)

    ZHAO Xiang-Fu; HAN Ping; ZHANG Rong; ZHENG You-Dou

    2011-01-01

    @@ After immersion in hydrofluoric acid, the sheet resistance of a 220-nm-thick silicon nanomembrane, measured in dry air by van der Pauw method, drops around two orders of magnitude initially, then increases and reaches the level of a sample with a native oxide surface in about one month.The surface component and oxidation rate are also characterized by x-ray photo electronic spectroscopy measurement.Fluorine is found to play a significant role in improving conductivity and has no apparent influence on the oxidation rate after hydrofluoric acid treatment.

  14. Kinetics and Mechanism of Oxidation of Phenyl Acetic Acid and Dl-Mandelic Acid by Permanganate in Acid Medium

    Directory of Open Access Journals (Sweden)

    B.Syama Sundar

    2014-06-01

    Full Text Available Kinetics of oxidation of phenyl acetic acid and DL- Mandelic acid by potassium permanganate in aqueous acetic acid and perchloric acid mixture reveals that the kinetic orders are first order in oxidant, first order in H+ and zero order in substrate for phenyl acetic acid. DL-Mandelic acid exhibits first order in oxidant and zero order in substrate. The results are rationalised by a mechanism involving intermediate formation of mandelic acid in case of Phenyl acetic acid and ester formation with Mn (VII in case of DL-Mandelic acid. The following order of reactivity is observed: DL-Mandelic acid > Phenyl acetic acid. The high reactivity of DL-Mandelic acid over phenyl acetic acid may be due to different mechanisms operating with the two substrates and benzaldehyde is the final product in both the cases.

  15. Refsum disease: a defect in the alpha-oxidation of phytanic acid in peroxisomes.

    Science.gov (United States)

    Singh, I; Pahan, K; Singh, A K; Barbosa, E

    1993-10-01

    The oxidation of phytanic acid to pristanic acid was previously demonstrated to be deficient in monolayer cultures of skin fibroblasts (Herndon et al. 1969. J. Clin. Invest. 48: 1017-1032). However, identification of subcellular organelle with deficient enzyme activity has not been established. To define the subcellular organelle with deficient enzyme activity in the catabolism of phytanic acid, we measured the oxidation of [1-14C] phytanic acid to 14CO2 and pristanic acid in different subcellular organelles isolated from cultured skin fibroblasts from control and Refsum patients. The rates of oxidation of phytanic acid in peroxisomes, mitochondria, and endoplasmic reticulum were 37.1 +/- 2.65, 1.9 +/- 0.3, and 0.4 +/- 0.07 pmol/h per mg protein, respectively, from control fibroblasts. The phytanic acid oxidation activity in mitochondria (2.04 +/- 0.7 pmol/h per mg protein) and endoplasmic reticulum (0.43 +/- 0.2 pmol/h per mg protein) from Refsum fibroblasts was similar to control fibroblasts. However, phytanic acid oxidation in peroxisomes from Refsum fibroblasts was not detected at all the protein concentrations tested. On the other hand, the peroxisomes from Refsum fibroblasts had normal rates of activation and oxidation of palmitic and lignoceric acids, suggesting that the peroxisomes isolated from Refsum fibroblasts were metabolically active. The phytanoyl-CoA ligase, the first enzyme in the alpha-oxidation pathway, had activity similar to that in peroxisomes from control (9.86 +/- 0.09 nmol/h per mg protein) and Refsum (10.25 +/- 0.31 nmol/h per mg protein) fibroblasts. The data described here clearly demonstrate that pathognomonic accumulation of phytanic acid in patients with Refsum disease is due to the deficient activity of peroxisomal alpha-oxidation enzyme system.

  16. Effects of rapeseed oil on fatty acid oxidation and lipid levels in rat heart and liver.

    Science.gov (United States)

    Kienle, M G; Cighetti, G; Spagnuolo, C; Galli, C

    1976-09-01

    The comparative rates of oxidation of erucic and oleic acids and of their CoA esters were studied in heart and liver mitochondria of rats fed a standard diet or semisynthetic diets containing 25% of the calories as either rapeseed oil (46.6% erucic and 10.4% eicosenoic acid) or olive oil, for a period of 5 months. The long exposure to the diet containing 25% rapeseed oil did not alter the oxidative activity of mitochondria and did not induce morphological changes in the heart. It is confirmed that erucic acid is oxidized in mitochondria at lower rates than other long chain fatty acids and that its activation as CoA derivative may be one of the rate limiting steps of the overall oxidationprocess. Total lipids and triglycerides do not significantly change in the heart whereas they increase in the liver of rats fed the diet containing rapeseed oil.

  17. Fasting rapidly increases fatty acid oxidation in white adipose tissue of young broiler chickens.

    Science.gov (United States)

    Torchon, Emmanuelle; Ray, Rodney; Hulver, Matthew W; McMillan, Ryan P; Voy, Brynn H

    2017-01-02

    Upregulating the fatty acid oxidation capacity of white adipose tissue in mice protects against diet-induced obesity, inflammation and insulin resistance. Part of this capacity results from induction of brown-like adipocytes within classical white depots, making it difficult to determine the oxidative contribution of the more abundant white adipocytes. Avian genomes lack a gene for uncoupling protein 1 and are devoid of brown adipose cells, making them a useful model in which to study white adipocyte metabolism in vivo. We recently reported that a brief (5 hour) period of fasting significantly upregulated many genes involved in mitochondrial and peroxisomal fatty acid oxidation pathways in white adipose tissue of young broiler chickens. The objective of this study was to determine if the effects on gene expression manifested in increased rates of fatty acid oxidation. Abdominal adipose tissue was collected from 21 day-old broiler chicks that were fasted for 3, 5 or 7 hours or fed ad libitum (controls). Fatty acid oxidation was determined by measuring and summing (14)CO2 production and (14)C-labeled acid-soluble metabolites from the oxidation of [1-(14)C] palmitic acid. Fasting induced a progressive increase in complete fatty acid oxidation and citrate synthase activity relative to controls. These results confirm that fatty acid oxidation in white adipose tissue is dynamically controlled by nutritional status. Identifying the underlying mechanism may provide new therapeutic targets through which to increase fatty acid oxidation in situ and protect against the detrimental effects of excess free fatty acids on adipocyte insulin sensitivity.

  18. Calcite crystal growth rate inhibition by polycarboxylic acids

    Science.gov (United States)

    Reddy, M.M.; Hoch, A.R.

    2001-01-01

    Calcite crystal growth rates measured in the presence of several polycarboxyclic acids show that tetrahydrofurantetracarboxylic acid (THFTCA) and cyclopentanetetracarboxylic acid (CPTCA) are effective growth rate inhibitors at low solution concentrations (0.01 to 1 mg/L). In contrast, linear polycarbocylic acids (citric acid and tricarballylic acid) had no inhibiting effect on calcite growth rates at concentrations up to 10 mg/L. Calcite crystal growth rate inhibition by cyclic polycarboxyclic acids appears to involve blockage of crystal growth sites on the mineral surface by several carboxylate groups. Growth morphology varied for growth in the absence and in the presence of both THFTCA and CPTCA. More effective growth rate reduction by CPTCA relative to THFTCA suggests that inhibitor carboxylate stereochemical orientation controls calcite surface interaction with carboxylate inhibitors. ?? 20O1 Academic Press.

  19. Oxidative stress and nucleic acid oxidation in patients with chronic kidney disease.

    Science.gov (United States)

    Sung, Chih-Chien; Hsu, Yu-Chuan; Chen, Chun-Chi; Lin, Yuh-Feng; Wu, Chia-Chao

    2013-01-01

    Patients with chronic kidney disease (CKD) have high cardiovascular mortality and morbidity and a high risk for developing malignancy. Excessive oxidative stress is thought to play a major role in elevating these risks by increasing oxidative nucleic acid damage. Oxidative stress results from an imbalance between reactive oxygen/nitrogen species (RONS) production and antioxidant defense mechanisms and can cause vascular and tissue injuries as well as nucleic acid damage in CKD patients. The increased production of RONS, impaired nonenzymatic or enzymatic antioxidant defense mechanisms, and other risk factors including gene polymorphisms, uremic toxins (indoxyl sulfate), deficiency of arylesterase/paraoxonase, hyperhomocysteinemia, dialysis-associated membrane bioincompatibility, and endotoxin in patients with CKD can inhibit normal cell function by damaging cell lipids, arachidonic acid derivatives, carbohydrates, proteins, amino acids, and nucleic acids. Several clinical biomarkers and techniques have been used to detect the antioxidant status and oxidative stress/oxidative nucleic acid damage associated with long-term complications such as inflammation, atherosclerosis, amyloidosis, and malignancy in CKD patients. Antioxidant therapies have been studied to reduce the oxidative stress and nucleic acid oxidation in patients with CKD, including alpha-tocopherol, N-acetylcysteine, ascorbic acid, glutathione, folic acid, bardoxolone methyl, angiotensin-converting enzyme inhibitor, and providing better dialysis strategies. This paper provides an overview of radical production, antioxidant defence, pathogenesis and biomarkers of oxidative stress in patients with CKD, and possible antioxidant therapies.

  20. Oxidative Stress and Nucleic Acid Oxidation in Patients with Chronic Kidney Disease

    Directory of Open Access Journals (Sweden)

    Chih-Chien Sung

    2013-01-01

    Full Text Available Patients with chronic kidney disease (CKD have high cardiovascular mortality and morbidity and a high risk for developing malignancy. Excessive oxidative stress is thought to play a major role in elevating these risks by increasing oxidative nucleic acid damage. Oxidative stress results from an imbalance between reactive oxygen/nitrogen species (RONS production and antioxidant defense mechanisms and can cause vascular and tissue injuries as well as nucleic acid damage in CKD patients. The increased production of RONS, impaired nonenzymatic or enzymatic antioxidant defense mechanisms, and other risk factors including gene polymorphisms, uremic toxins (indoxyl sulfate, deficiency of arylesterase/paraoxonase, hyperhomocysteinemia, dialysis-associated membrane bioincompatibility, and endotoxin in patients with CKD can inhibit normal cell function by damaging cell lipids, arachidonic acid derivatives, carbohydrates, proteins, amino acids, and nucleic acids. Several clinical biomarkers and techniques have been used to detect the antioxidant status and oxidative stress/oxidative nucleic acid damage associated with long-term complications such as inflammation, atherosclerosis, amyloidosis, and malignancy in CKD patients. Antioxidant therapies have been studied to reduce the oxidative stress and nucleic acid oxidation in patients with CKD, including alpha-tocopherol, N-acetylcysteine, ascorbic acid, glutathione, folic acid, bardoxolone methyl, angiotensin-converting enzyme inhibitor, and providing better dialysis strategies. This paper provides an overview of radical production, antioxidant defence, pathogenesis and biomarkers of oxidative stress in patients with CKD, and possible antioxidant therapies.

  1. Acetic Acid bacteria: physiology and carbon sources oxidation.

    Science.gov (United States)

    Mamlouk, Dhouha; Gullo, Maria

    2013-12-01

    Acetic acid bacteria (AAB) are obligately aerobic bacteria within the family Acetobacteraceae, widespread in sugary, acidic and alcoholic niches. They are known for their ability to partially oxidise a variety of carbohydrates and to release the corresponding metabolites (aldehydes, ketones and organic acids) into the media. Since a long time they are used to perform specific oxidation reactions through processes called "oxidative fermentations", especially in vinegar production. In the last decades physiology of AAB have been widely studied because of their role in food production, where they act as beneficial or spoiling organisms, and in biotechnological industry, where their oxidation machinery is exploited to produce a number of compounds such as l-ascorbic acid, dihydroxyacetone, gluconic acid and cellulose. The present review aims to provide an overview of AAB physiology focusing carbon sources oxidation and main products of their metabolism.

  2. In vitro studies on the oxidation of medium-chain dicarboxylic acids in rat liver.

    Science.gov (United States)

    Kølvraa, S; Gregersen, N

    1986-05-21

    The degradation of medium-chained dicarboxylic (DC) acids was investigated on purified mitochondria and peroxisomes. Intact organelles were incubated with dodecanedioic acid (DC12), suberic acid (DC8) and adipic acid (DC6), and the production of lower-chained DC-acids and of acetyl-CoA + acetyl-carnitine was monitored. It was shown, that intact peroxisomes could beta-oxidize DC12, DC10, and DC8 at least as far as DC6, while intact mitochondria readily beta-oxidized DC12, and DC10 as far as succinic acid. DC8 and DC6 were not oxidized by intact mitochondria when these two acids were presented externally to the intact organelle. When they were formed intramitochondrially from DC12 and DC10, both DC8 and DC6 were, however, to a great extent beta-oxidized as far as succinic acid. The major reason for this difference between mitochondrial oxidation of externally and internally located DC8 and DC6 seems to be an inability to transport these two acids through the mitochondrial membrane. For DC12 and DC10, the mitochondrial transport systems, which were indicated to be identical to the systems used by the corresponding monocarboxylic acids, were found to be rate-limiting in the beta-oxidation of these acids. A contributing factor to the undetectable beta-oxidation of externally located DC8 and DC6 may also be, that the Km values of DC8-CoA (460 +/- 70 mumol/l) and DC6-CoA (980 +/- 90 mumol/l) towards the acyl-CoA dehydrogenases are very high. These results imply that very high concentrations of intermediates are created intramitochondrially during beta-oxidation, concentrations which are probably only formed through formation of DC8-CoA and DC6-CoA from longer DC-acids and not by transport from outside the mitochondria. The data presented thus for the first time give evidence to a pathway for medium-chained monocarboxylic acids (especially lauric acid and decanoic acid) through cytosolic omega-oxidation followed by activation, transport over the mitochondrial membrane and

  3. Integrated iron(II) oxidation and limestone neutralisation of acid mine water

    CSIR Research Space (South Africa)

    Maree, JP

    1999-01-01

    Full Text Available Volumetric iron (II) oxidation rates exceeding 100 g/(l.d) were achieved by dosing powdered limestone to a bio-reactor treating artificial acid mine water. Neutralisation and partial sulphate removal were achieved as well. The rate is highly...

  4. Polyaniline: Aniline oxidation with strong and weak oxidants under various acidity

    Energy Technology Data Exchange (ETDEWEB)

    Bláha, Michal, E-mail: blaha@imc.cas.cz [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Trchová, Miroslava; Bober, Patrycja; Morávková, Zuzana [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic); Prokeš, Jan [Charles University, Faculty of Mathematics and Physics, 180 00 Prague 8 (Czech Republic); Stejskal, Jaroslav [Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 162 06 Prague 6 (Czech Republic)

    2017-06-15

    Aniline was oxidized with three strong inorganic oxidants (ammonium peroxydisulfate, cerium(IV) sulfate, potassium dichromate), two weak inorganic oxidants (iron(III) chloride, silver nitrate), and one organic oxidant (p-benzoquinone) in aqueous solutions of methanesulfonic acid (MSA) of various concentration. Whereas oxidation of aniline with ammonium peroxydisulfate yielded high-molecular-weight conducting polyaniline (PANI) in the whole acidity range, the oxidation with cerium(IV) sulfate led also to a single product close to PANI with considerably lower molecular weight and lower conductivity. Potassium dichromate gave PANI only at high concentration of MSA. The use of iron(III) chloride yielded composite mixtures of PANI and low-molecular-weight aniline oligomers. The oxidation of aniline with silver nitrate led to composites of silver and an organic part, which was constituted either by aniline oligomers or conducting polyaniline or both. p-Benzoquinone as oxidant produced mainly aniline oligomers with poor conductivity and 2,5-dianilino-p-benzoquinone-like structure detected in FTIR and Raman spectra when oxidation proceeded with weak oxidants. A general model of oxidation with strong and weak oxidants was formulated. - Highlights: • Comparison of aniline oxidation with oxidants of different redox potential. • UV–vis, FTIR and Raman spectroscopies combined with size-exclusion chromatography. • The contents of polymer and oligomers were analyzed and discussed. • General model of aniline oxidation with strong and weak oxidants was formulated.

  5. Oxidation of resin acids in colophony (rosin) and its implications for patch testing.

    Science.gov (United States)

    Sadhra, S; Foulds, I S; Gray, C N

    1998-08-01

    Commercial preparations of colophony (rosin) used for patch testing are made from unmodified rosin in pet. and may be stored for some considerable time before being used. This would be satisfactory if the composition and dermatological activity of the preparations were both reproducible and stable, but investigations by the authors have shown that the resin acids undergo progressive and substantial oxidation and that the dermatological activity of the preparations increases significantly with time. This may be a cause of inconsistent patch test results unless the composition can be stabilized. Gas liquid chromatography (GLC) analysis of a raw rosin sample and its commercial patch test preparation has shown that they both contained the same resin acids, but the concentration of the abietic type resin acids was found to be lower in the patch test preparations. The degradation of resin acids is due to their atmospheric oxidation, which may occur during the preparation and storage of the commercial rosin patch test preparation. The susceptibility of individual resin acids to atmospheric oxidation was demonstrated by analysing a sample of raw Portuguese gum rosin, which was then left exposed to air and light. Most of the resin acids were found to undergo oxidation at a rate which gradually diminished. More importantly, it is presumed that the concentration of oxidized resin acids increased correspondingly, and these have been shown to be more dermatologically active than the unoxidised resin acids. The rate of decrease of resin acid concentration was found to be in the following order: neoabietic>levopimaric and palustric>abietic>dehydroabetic acid. The pimaric type resin acids were found to be relatively inert to atmospheric oxidation when compared with the abietic type resin acids. Patch testing with the resulting partly oxidized Portuguese rosin produced positive reactions at a 35% higher frequency than the raw Portuguese rosin. The study demonstrates that the

  6. Cardiac fatty acid oxidation in heart failure associated with obesity and diabetes.

    Science.gov (United States)

    Fukushima, Arata; Lopaschuk, Gary D

    2016-10-01

    Obesity and diabetes are major public health problems, and are linked to the development of heart failure. Emerging data highlight the importance of alterations in cardiac energy metabolism as a major contributor to cardiac dysfunction related to obesity and diabetes. Increased rates of fatty acid oxidation and decreased rates of glucose utilization are two prominent changes in cardiac energy metabolism that occur in obesity and diabetes. This metabolic profile is probably both a cause and consequence of a prominent cardiac insulin resistance, which is accompanied by a decrease in both cardiac function and efficiency, and by the accumulation of potentially toxic lipid metabolites in the heart that can further exaggerate insulin resistance and cardiac dysfunction. The high cardiac fatty acid oxidation rates seen in obesity and diabetes are attributable to several factors, including: 1) increased fatty acid supply and uptake into the cardiomyocyte, 2) increased transcription of fatty acid metabolic enzymes, 3) decreased allosteric control of mitochondrial fatty acid uptake and fatty acid oxidation, and 4) increased post-translational acetylation control of various fatty acid oxidative enzymes. Emerging evidence suggests that therapeutic approaches aimed at switching the balance of cardiac energy substrate preference from fatty acid oxidation to glucose use can prevent cardiac dysfunction associated with obesity and diabetes. Modulating acetylation control of fatty acid oxidative enzymes is also a potentially attractive strategy, although presently this is limited to precursors of nicotinamide adenine or nonspecific activators of deacetylation such as resveratrol. This review will focus on the metabolic alterations in the heart that occur in obesity and diabetes, as well as on the molecular mechanisms controlling these metabolic changes. This article is part of a Special Issue entitled: Heart Lipid Metabolism edited by G.D. Lopaschuk.

  7. Targets for modulation of fatty acid oxidation in the heart.

    Science.gov (United States)

    Lopaschuk, Gary D

    2004-03-01

    Fatty acids are a major source of fuel used by the heart to provide large amounts of energy necessary to sustain contractile function. In the healthy heart, a balance between fatty acid and carbohydrate use ensures that energy supply to the heart matches demand. However, myocardial ischemia causes profound changes in metabolism, including alterations in glucose and fatty acid metabolism that can lead to excessive myocardial fatty acid oxidation, which occurs at the expense of glucose oxidation. This contributes to cellular acidosis, a decrease in cardiac efficiency and contractile dysfunction in the ischemic heart. Inhibition of fatty acid oxidation has recently emerged as a promising approach to the prevention of these adverse effects of fatty acids. As a result, a number of key enzymes involved in the metabolism of fatty acids are potential targets for therapeutic intervention in myocardial ischemia. This includes inhibition of fatty acid uptake into the myocyte, inhibition of mitochondrial fatty acid uptake and direct inhibition of fatty acid beta-oxidation. This review describes these potential targets for modulation of energy metabolism in the heart.

  8. Formic acid oxidation at platinum-bismuth catalysts

    National Research Council Canada - National Science Library

    Popović Ksenija Đ; Lović Jelena D

    2015-01-01

    ..., activity, and stability. The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small organic molecules and because of its technical relevance...

  9. Sodium Picosulfate, Magnesium Oxide, and Anhydrous Citric Acid

    Science.gov (United States)

    Sodium picosulfate, magnesium oxide, and anhydrous citric acid combination powder is used to empty the colon (large ... clear view of the walls of the colon. Sodium picosulfate is in a class of medications called ...

  10. On the mechanism of the direct pathway for formic acid oxidation at a Pt(111) electrode.

    Science.gov (United States)

    Xu, Jie; Yuan, Daofu; Yang, Fan; Mei, Dong; Zhang, Zunbiao; Chen, Yan-Xia

    2013-03-28

    In order determine whether formate is a reaction intermediate of the direct pathway for formic acid oxidation at a Pt electrode, formic acid (HCOOH) oxidation at a Pt(111) electrode has been studied by normal and fast scan voltammetry in 0.1 M HClO4 solutions with different HCOOH concentrations. The relationship between the HCOOH oxidation current density (j(ox)) and formate coverage (θ(formate)) is quantitatively analyzed. The kinetic simulation reveals that the previously proposed formate pathway, with decomposition of the bridge-bonded formate (HCOO(B)) as a rate determining step (rds), cannot be the main pathway responsible for the majority of the current for HCOOH oxidation. Instead, a kinetic model based on a mechanism with formic acid adsorption [structure: see text], along with simultaneous C-H bond activation as the rds for the direct pathway, explains the measured data well. It was found for the relatively slow rate of formic acid oxidation, that adsorption-desorption of the formate is faster, which competes for the surface sites for formic acid oxidation.

  11. Remediation of TCE-contaminated groundwater using acid/BOF slag enhanced chemical oxidation.

    Science.gov (United States)

    Tsai, T T; Kao, C M; Wang, J Y

    2011-04-01

    The objective of this study was to evaluate the potential of applying acid/H(2)O(2)/basic oxygen furnace slag (BOF slag) and acid/S(2)O(8)(2-)/BOF slag systems to enhance the chemical oxidation of trichloroethylene (TCE)-contaminated groundwater. Results from the bench-scale study indicate that TCE oxidation via the Fenton-like oxidation process can be enhanced with the addition of BOF slag at low pH (pH=2-5.2) and neutral (pH=7.1) conditions. Because the BOF slag has iron abundant properties (14% of FeO and 6% of Fe(2)O(3)), it can be sustainably reused for the supplement of iron minerals during the Fenton-like or persulfate oxidation processes. Results indicate that higher TCE removal efficiency (84%) was obtained with the addition of inorganic acid for the activation of Fenton-like reaction compared with the experiments with organic acids addition (with efficiency of 10-15% lower) (BOF slag=10gL(-1); initial pH=5.2). This could be due to the fact that organic acids would compete with TCE for available oxidants. Results also indicate that the pH value had a linear correlation with the observed first-order decay constant of TCE, and thus, lower pH caused a higher TCE oxidation rate.

  12. Measurement of fatty acid oxidation: validation of isotopic equilibrium extrapolation

    Energy Technology Data Exchange (ETDEWEB)

    Robin, A.P.; Jeevanandam, M.; Elwyn, D.H.; Askanazi, J.; Kinney, J.M.

    1989-01-01

    Measurement of whole body substrate oxidation requires prolonged isotope infusion to attain plateau specific activity (SA) of expired CO/sub 2/. We have investigated in 13 hospitalized patients a technique whereby plateau /sup 14/CO/sub 2/ SA is extrapolated using computer curve fitting based upon the early exponential rise. A primed-constant infusion of albumin-bound 1-/sup 14/C-palmitate was continued for 260 minutes with isotope priming of the secondary bicarbonate pool at 70 minutes. Plasma free fatty acid (FFA) SA reached steady state by 40 minutes and was 91% +/- 4% (SE) of values obtained at 190 to 260 minutes. At 70 minutes /sup 14/CO/sub 2/ SA reached only 44% +/- 1% of the 190 to 260 minute values, which were consistently at plateau. The predicted steady state /sup 14/CO/sub 2/ SA from the 40 to 70 minute curves and the FFA oxidation rates calculated from those values were 94% +/- 2% and 102% +/- 4%, respectively, of values measured at steady state (190 to 260 minutes). The relationship between predicted and measured values approximated the line of identity for /sup 14/CO/sub 2/ SA (y = 0.90x + 0.14, r = .98, P less than .001) and FFA oxidation (y = 1.02x, r = .98, P less than .001). The results suggest that FFA oxidation can be accurately calculated using a short infusion of labeled FFA without bicarbonate pool priming, thus avoiding overpriming or underpriming and possibly allowing multiple studies and diminished radioisotope exposure.

  13. Induction of omega-oxidation of monocarboxylic acids in rats by acetylsalicylic acid.

    Science.gov (United States)

    Kundu, R K; Tonsgard, J H; Getz, G S

    1991-12-01

    The accumulation of dicarboxylic acids, particularly long chain, is a prominent feature of Reye's syndrome and diseases of peroxisomal metabolism. We assessed the omega-oxidation of a spectrum of fatty acids in rats and asked whether pretreatment of rats with aspirin, which is known to predispose children to Reye's syndrome, would affect omega-oxidation of long chain fatty acids. We found that aspirin increased liver free fatty acids and increased the capacity for omega-oxidation three- to sevenfold. Omega-oxidation of long chain substrate was stimulated to a greater degree than medium chain substrate and was apparent within one day of treatment, at serum aspirin concentrations below the therapeutic range in humans. The apparent Km for lauric acid was 0.9 microM and 12 microM for palmitate. We also found a difference in the storage stability of activity toward medium and long chain substrate. Saturating concentrations of palmitate had no effect on the formation of dodecanedioic acid, whereas laurate decreased but never eliminated the omega-oxidation of palmitate. 97% of the total laurate omega-oxidative activity recovered was found in the microsomes, but 32% of palmitate omega-oxidative activity was present in the cytosol. These results demonstrate that aspirin is a potent stimulator of omega-oxidation and suggest that there may be multiple enzymes for omega-oxidation with overlapping substrate specificity.

  14. The Oxidation of Hydrazine by Nitric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Karraker, D.G.

    2001-07-02

    Hydrazine nitrate-nitric acid solutions are used in the ion exchange process for separating Pu-238 and Np-237 and have been found to dissolve plutonium metal in a manner advantageous to SRP metal recovery operations. Laboratory tests on the stability of hydrazine in nitric acid solutions were performed to obtain accurate data, and the results of these tests are reported here. These tests provide sufficient information to specify temperature control for hydrazine-nitric acid solutions in plant processes.

  15. Platinum nanoparticles–manganese oxide nanorods as novel binary catalysts for formic acid oxidation

    Directory of Open Access Journals (Sweden)

    Mohamed S. El-Deab

    2012-01-01

    Full Text Available The current study proposes a novel binary catalyst system (composed of metal/metal oxide nanoparticles as a promising electrocatalyst in formic acid oxidation. The electro-catalytic oxidation of formic acid is carried out with binary catalysts of Pt nanoparticles (nano-Pt and manganese oxide nanorods (nano-MnOx electrodeposited onto glassy carbon (GC electrodes. Cyclic voltammetric (CV measurements showed that unmodified GC and nano-MnOx/GC electrodes have no catalytic activity. While two oxidation peaks were observed at nano-Pt/GC electrode at ca. 0.2 and 0.55 V (corresponding to the direct oxidation of formic acid and the oxidation of the poisoning CO intermediate, respectively. The combined use of nano-MnOx and nano-Pt results in superb enhancement of the direct oxidation pathway. Nano-MnOx is shown to facilitate the oxidation of CO (to CO2 by providing oxygen at low over-potential. This leads to retrieval of Pt active sites necessary for the direct oxidation of formic acid. The higher catalytic activity of nano-MnOx/nano-Pt/GC electrode (with Pt firstly deposited compared to its mirror image electrode (i.e., with MnOx firstly deposited, nano-Pt/nano-MnOx/GC reveals that the order of the electrodeposition is an essential parameter.

  16. Isoniazid cocrystals with anti-oxidant hydroxy benzoic acids

    Science.gov (United States)

    Mashhadi, Syed Muddassir Ali; Yunus, Uzma; Bhatti, Moazzam Hussain; Tahir, Muhammad Nawaz

    2014-11-01

    Isoniazid is the primary constituent of “triple therapy” used to effectively treat tuberculosis. In tuberculosis and other diseases, tissue inflammation and free radical burst from macrophages results in oxidative stress. These free radicals cause pulmonary inflammation if not countered by anti-oxidants. Therefore, in the present study cocrystals of isoniazid with four anti-oxidant hydroxy benzoic acids have been reported. Gallic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and 3-hydroxybenzoic acid resulted in the formation of cocrystals when reacted with isoniazid. Cocrystal structure analysis confirmed the existence of pyridine-carboxylic acid synthon in the cocrystals of isoniazid with Gallic acid, 2,3-dihydroxybenzoic acid and 3-hydroxybenzoic acid. While cocrystal of 3,5-dihydroxybenzoic acid formed the pyridine-hydroxy group synthon. Other synthons of different graph sets are formed between hydrazide group of isoniazid and coformers involving Nsbnd H⋯O and Osbnd H⋯N bonds. All the cocrystals were in 1:1 stoichiometric ratio.

  17. Photocatalytic Oxidation of Sulfurous Acid in an Aqueous Medium

    Science.gov (United States)

    Romero, Alicia; Hernandez, Willie; Suarez, Marco F.

    2005-01-01

    The effect of some parameters on sulfurous acid and sulfur oxidation kinetics such as initial concentration of sulfurous acid, oxygen, TiO[2] crystalline concentration, the power of black light, and quantity of TiO[2] is investigated. The experiments can be performed in an undergraduate physical chemistry laboratory with an inexpensive…

  18. Photocatalytic Oxidation of Sulfurous Acid in an Aqueous Medium

    Science.gov (United States)

    Romero, Alicia; Hernandez, Willie; Suarez, Marco F.

    2005-01-01

    The effect of some parameters on sulfurous acid and sulfur oxidation kinetics such as initial concentration of sulfurous acid, oxygen, TiO[2] crystalline concentration, the power of black light, and quantity of TiO[2] is investigated. The experiments can be performed in an undergraduate physical chemistry laboratory with an inexpensive…

  19. Abiotic reduction of nitroaromatic compounds by Fe(II) associated with iron oxides and humic acid.

    Science.gov (United States)

    Luan, Fubo; Xie, Li; Li, Jun; Zhou, Qi

    2013-05-01

    Experiments were conducted to examine the reduction of nitroaromatic compounds (NACs) by Fe(II) associated with iron oxides (goethite, hematite and magnetite) and humic acid. The reduction rate of nitrobenzene decreased in the order of Fe(II) associated with magnetite>Fe(II) associated with goethite>Fe(II) associated with hematite. We proposed a four-step model (adsorption, electron transfer to conduction band, electron transfer to nitrobenzene and electron transfer to crystal lattice) for nitrobenzene reduction by Fe(II) associated with iron oxides. Fe(II)-humic acid complexes did not present reduction capability of nitrobenzene. Furthermore, Humic acid significantly inhibited nitrobenzene reduction by Fe(II) associated with iron oxides. The inhibitory effect of humic acid toward the reduction of nitrobenzene decreased in the order of magnetite>goethite>hematite. Copyright © 2013 Elsevier Ltd. All rights reserved.

  20. Kinetics and mechanism of the oxidation of formic and oxalic acids by quinolinium fluorochromate

    Indian Academy of Sciences (India)

    Madhu Khurana; Pradeep K Sharma; Kalyan K Banerji

    2000-04-01

    Kinetics and mechanism of oxidation of formic and oxalic acids by quinolinium fluorochromate (QFC) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first-order with respect to QFC. Michaelis-Menten type of kinetics were observed with respect to the reductants. The reaction is acid-catalysed and the acid dependence has the form: obs = + [H+]. The oxidation of -deuterioformic acid exhibits a substantial primary kinetic isotope effect (H/D = 6.01 at 303 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft’s and Swain’s multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical cyclic transition state in the rate-determining step. Suitable mechanisms have been proposed

  1. Vitamin C fails to protect amino acids and lipids from oxidation during acute inflammation.

    Science.gov (United States)

    Gaut, Joseph P; Belaaouaj, Abderrazzaq; Byun, Jaeman; Roberts, L Jackson; Maeda, Nobuyo; Frei, Balz; Heinecke, Jay W

    2006-05-01

    The observation that antioxidant vitamins fail to confer protective benefits in large, well-designed randomized clinical trials has led many to question the role of oxidative stress in the pathogenesis of disease. However, there is little evidence that proposed antioxidants actually scavenge reactive intermediates in vivo. Ascorbate reacts rapidly with oxidants produced by activated neutrophils in vitro, and neutrophils markedly increase their oxidant production when mice are infected intraperitoneally with the gram-negative bacterium Klebsiella pneumoniae. To explore the antioxidant properties of ascorbate in vivo, we therefore used K. pneumoniae infection as a model of oxidative stress. When mice deficient in L-gulono-gamma-lactone oxidase (Gulo(-/-)), the rate-limiting enzyme in ascorbate synthesis, were depleted of ascorbate and infected with K. pneumoniae, they were three times as likely as ascorbate-replete Gulo(-/-)mice to die from infection. Mass spectrometric analysis of peritoneal lavage fluid revealed a marked increase in the levels of oxidized amino acids and of F2-isoprostanes (sensitive and specific markers of lipid oxidation) in infected animals. Surprisingly, there were no significant differences in the levels of the oxidation products in the ascorbate-deficient and -replete Gulo(-/-)mice. Our observations suggest that ascorbate plays a previously unappreciated role in host defense mechanisms against invading pathogens but that the vitamin does not protect amino acids and lipids from oxidative damage during acute inflammation. To examine the oxidation hypothesis of disease, optimal antioxidant regimens that block oxidative reactions in animals and humans need to be identified.

  2. Evaluation of antioxidants using oxidation reaction rate constants

    Institute of Scientific and Technical Information of China (English)

    SHI Yan; ZHAN Xiancheng; MA Lie; LI Linli; LI Chengrong

    2007-01-01

    An evaluation method for the capacity of antioxidants to protect drugs against oxidation is presented.As a new viewpoint,to determine the priority of the competitive oxidations between the antioxidant and the protected drug,and to compare the drug-protection capacity of antioxidants,it is important to determine their oxidation rate constants using chemical kinetics instead of standard oxidation (or reduction) potentials.Sodium sulfite,sodium bisulfite and sodium pyrosulfite were used as models for the determination of oxidation reaction rate constants in aqueous solutions.In the experiments,sufficient air was continually infused into the solution to keep the concentration of dissolved oxygen constant.The residual concentrations of the antioxidants were determined by iodimetry,and the concentration of dissolved oxygen by oxygen electrode.The data were fitted by linear regressions to obtain the reaction rate constants.It was found that the degradation of sodium sulfite,sodium bisulfite or sodium pyrosulfite obeyed pseudo zero-order kinetics in the buffer solutions.Because of the ionization equilibrium,these three antioxidants have the same ion form in solutions at a definite pH value and therefore their apparent rate constants were essentially the same.The average apparent rate constants of the three antioxidants at 25~C are (1.34±0.03)×10-3 at pH 6.8,(1.20±0.02) x 10-3 at pH 4.0 and (6.58±0.02)×10-3 mol.L-1.h-1 at pH 9.2,respectively.

  3. Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of Butanone and Uncatalyzed Oxidation of Cychlohexanone by Cerium(IV) in Acid Sulphate Medium

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Priyamvada; Hemkar, Shalini; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

    2012-02-15

    The kinetics of ruthenium(III) chloride catalyzed oxidation of butanone and uncatalyzed oxidation of cyclohexanone by cerium(IV) in sulphuric acid medium have been studied. The kinetic rate law(I) in case of butanone conforms to the proposed mechanism. Kinetics and activation parameters have been evaluated conventionally. Kinetically preferred mode of reaction is via ketonic and not the enolic forms.

  4. Formation rates, stability and reactivity of sulfuric acid - amine clusters predicted by computational chemistry

    Science.gov (United States)

    Kurtén, Theo; Ortega, Ismael; Kupiainen, Oona; Olenius, Tinja; Loukonen, Ville; Reiman, Heidi; McGrath, Matthew; Vehkamäki, Hanna

    2013-04-01

    Despite the importance of atmospheric particle formation for both climate and air quality, both experiments and non-empirical models using e.g. sulfuric acid, ammonia and water as condensing vapors have so far been unable to reproduce atmospheric observations using realistic trace gas concentrations. Recent experimental and theoretical evidence has shown that this mystery is likely resolved by amines. Combining first-principles evaporation rates for sulfuric acid - dimethylamine clusters with cluster kinetic modeling, we show that even sub-ppt concentrations of amines, together with atmospherically realistic concentrations of sulfuric acid, result in formation rates close to those observed in the atmosphere. Our simulated cluster formation rates are also close to, though somewhat larger than, those measured at the CLOUD experiment in CERN for both sulfuric acid - ammonia and sulfuric acid - dimethylamine systems. A sensitivity analysis indicates that the remaining discrepancy for the sulfuric acid - amine particle formation rates is likely caused by steric hindrances to cluster formation (due to alkyl groups of the amine molecules) rather than by significant errors in the evaporation rates. First-principles molecular dynamic and reaction kinetic modeling shed further light on the microscopic physics and chemistry of sulfuric acid - amine clusters. For example, while the number and type of hydrogen bonds in the clusters typically reach their equilibrium values on a picosecond timescale, and the overall bonding patterns predicted by traditional "static" quantum chemical calculations seem to be stable, the individual atoms participating in the hydrogen bonds continuously change at atmospherically realistic temperatures. From a chemical reactivity perspective, we have also discovered a surprising phenomenon: clustering with sulfuric acid molecules slightly increases the activation energy required for the abstraction of alkyl hydrogens from amine molecules. This implies

  5. Malonyl CoA control of fatty acid oxidation in the ischemic heart.

    Science.gov (United States)

    Dyck, Jason R B; Lopaschuk, Gary D

    2002-09-01

    Abnormally high rates of fatty acid metabolism is an important contributor to the severity of ischemic heart disease. During and following myocardial ischemia a number of alterations in fatty acid oxidation occur that result in an excessive amount of fatty acids being used as a fuel source by the heart. This contributes to a decrease in cardiac efficiency both during and following the ischemic episode. Central to the regulation of fatty acid oxidation in the heart is malonyl CoA, which is a potent endogenous inhibitor of mitochondrial fatty acid uptake. The levels of malonyl CoA are regulated both by its synthesis by acetyl CoA carboxylase (ACC) and its degradation by malonyl CoA decarboxylase (MCD). ACC is in turn controlled by AMP-activated protein kinase (AMPK), which acts as a fuel gauge in the heart. The control of these enzymes are altered during ischemia, such that malonyl CoA levels in the heart decrease, resulting in an increased relative contribution of fatty acids to oxidative metabolism. Activation of AMPK during and following ischemia appears to be centrally involved in this decrease in malonyl CoA. Clinical evidence is now accumulating that show that inhibition of fatty acid oxidation is an effective approach to treating ischemic heart disease. As a result, modulation of fatty acid oxidation by targeting the enzymes controlling malonyl CoA may be a novel approach to treating angina pectoris and acute myocardial infarction. This paper will discuss some of the molecular changes that occur in fatty acid oxidation in the ischemic heart and will include a discussion of the important role of malonyl CoA in this process.

  6. Formic Acid Oxidation at Platinum-Bismuth Clusters

    DEFF Research Database (Denmark)

    Lovic, J. D.; Stevanovic, S. I.; Tripkovic, D. V.

    2014-01-01

    Formic acid oxidation was studied on platinum-bismuth deposits on glassy carbon (GC) substrate. The catalysts of equimolar ratio were prepared by potentiostatic deposition using chronocoulometry. Bimetallic structures obtained by two-step process, comprising deposition of Bi followed by deposition...... of Pt, were characterized by AFM spectroscopy which indicated that Pt crystallizes preferentially onto previously formed Bi particles. The issue of Bi leaching (dissolution) from PtBi catalysts, and their catalytic effect alongside the HCOOH oxidation is rather unresolved. In order to control Bi...... dissolution, deposits were subjected to electrochemical oxidation, in the relevant potential range and supporting electrolyte, prior to use as catalysts for HCOOH oxidation. Anodic striping charges indicated that along oxidation procedure most of deposited Bi was oxidized. ICP mass spectroscopy analysis...

  7. Supercritical water oxidation of acrylic acid production wastewater.

    Science.gov (United States)

    Gong, Y M; Wang, S Z; Tang, X Y; Xu, D H; Ma, H H

    2014-01-01

    Supercritical water oxidation (SCWO) of wastewater from an acrylic acid manufacturing plant has been studied on a continuous flow experimental system, whose reactor was made of Hastelloy C-276. Experimental conditions included a reaction temperature (T) ranging from 673 to 773K, a residence time (t) ranging from 72.7 to 339s, a constant pressure (P) of 25 MPa and a fixed oxidation coefficient (alpha) of 2.0. Experimental results indicated that reaction temperature and residence time had significant influences on the oxidation reaction, and increasing the two operation parameters could improve both degradation of chemical oxygen demand (COD) and ammonia nitrogen (NH3-N). The COD removal efficiency could reach up to 98.73% at 25 MPa, 773 K and 180.1 s, whereas the destruction efficiency of NH3-N was only 43.71%. We further carried out a kinetic analysis considering the induction period through free radical chain mechanism. It confirms that the power-law rate equation for COD removal was 345 exp(-52200/RT)[COD]1.98[O2]0.17 and for NH3-N removal was 500 exp(-64492.19/RT)[NH3-N]1.87 [O2]0.03. Moreover, the induction time formulations for COD and NH3-N were suspected to be exp(38250/RT)/173 and exp(55690/RT)/15231, respectively. Correspondingly, induction time changed from 2.22 to 5.38 s for COD and 0.38 to 1.38 s for NH3-N. Owing to the catalysis of reactor inner wall surface, more than 97% COD removal was achieved in all samples.

  8. Comparison of the methane oxidation rate in four media

    Directory of Open Access Journals (Sweden)

    Juliana Lundgren Rose

    2012-06-01

    Full Text Available Landfill gas emissions are one of the main sources of anthropogenic methane (CH4, a major greenhouse gas. In this paper, an economically attractive alternative to minimize greenhouse gas emissions from municipal solid waste landfills was sought. This alternative consists in special biofilters as landfill covers with oxidative capacity in the presence of CH4. To improve the quality/cost ratio of the project, compost was chosen as one of the cover substrates and soil (Typic red yellow-silt-clay Podzolic as the other. The performance of four substrates was studied in laboratory experiments: municipal solid waste (MSW compost, soil, and two soil-compost at different proportions. This study aimed to evaluate the suitability and environmental compatibility as a means of CH4 oxidation in biofilters. Four biofilters were constructed in 60 cm PVC tubes with an internal diameter of 10 cm. Each filter contained 2.3 L of oxidizing substrate at the beginning of the experiment. The gas used was a mixture of CH4 and air introduced at the bottom of each biofilter, at a flow of 150 mL min-1, by a flow meter. One hundred days after the beginning of the experiment, the best biofilter was the MSW compost with an oxidation rate of 990 g m-3 day-1 , corresponding to an efficiency of 44 %. It can be concluded that the four substrates studied have satisfactory oxidative capacity, and the substrates can be used advantageously as cover substrate of MSW landfills.

  9. A method for measuring fatty acid oxidation in C. elegans

    DEFF Research Database (Denmark)

    Elle, Ida Coordt; Rødkær, Steven Vestergaard; Fredens, Julius;

    2012-01-01

    The nematode C. elegans has during the past decade proven to be a valuable model organism to identify and examine molecular mechanisms regulating lipid storage and metabolism. While the primary approach has been to identify genes and pathways conferring alterations in lipid accumulation, only a few...... recent studies have recognized the central role of fatty acid degradation in cellular lipid homeostasis. In the present study, we show how complete oxidation of fatty acids can be determined in live C. elegans by examining oxidation of tritium-labeled fatty acids to tritiated H2O that can be measured......, the present methodology can be used to delineate the role of specific genes and pathways in the regulation of β-oxidation in C. elegans....

  10. Impact of Fluorescent Lighting on Oxidation of Model Wine Solutions Containing Organic Acids and Iron.

    Science.gov (United States)

    Grant-Preece, Paris; Barril, Celia; Schmidtke, Leigh M; Clark, Andrew C

    2017-03-22

    Previous studies have provided evidence that light exposure can increase oxygen consumption in wine and that the photodegradation of iron(III) tartrate could contribute to this process. In the present study, model wine solutions containing iron(III) and various organic acids, either alone or combined, were stored in sealed clear glass wine bottles and exposed to light from fluorescent lamps. Dissolved oxygen was monitored, and afterward the organic acid degradation products were determined and the capacity of the solutions to bind sulfur dioxide, the main wine preservative, was assessed. In the dark controls, little or no dissolved oxygen was consumed and the organic acids were stable. In the irradiated solutions, dissolved oxygen was consumed at a rate that was dependent on the specific organic acid present, and the latter were oxidized to various carbonyl compounds. For the solutions containing tartaric acid, malic acid, and/or citric acid, irradiation increased their sulfur dioxide-binding capacity.

  11. The relationship between uric acid and its oxidative product allantoin: a potential indicator for the evaluation of oxidative stress in birds.

    Science.gov (United States)

    Tsahar, Ella; Arad, Zeev; Izhaki, Ido; Guglielmo, Christopher G

    2006-09-01

    Uric acid is the main nitrogenous waste product in birds but it is also known to be a potent antioxidant. Hominoid primates and birds lack the enzyme urate oxidase, which oxidizes uric acid to allantoin. Consequently, the presence of allantoin in their plasma results from non-enzymatic oxidation. In humans, the allantoin to uric acid ratio in plasma increases during oxidative stress, thus this ratio has been suggested to be an in vivo marker for oxidative stress in humans. We measured the concentrations of uric acid and allantoin in the plasma and ureteral urine of white-crowned sparrows (Zonotrichia leucophrys gambelii) at rest, immediately after 30 min of exercise in a hop/hover wheel, and after 1 h of recovery. The plasma allantoin concentration and the allantoin to uric acid ratio did not increase during exercise but we found a positive relationship between the concentrations of uric acid and allantoin in the plasma and in the ureteral urine in the three activity phases. In the plasma, the slope of the regression describing the above positive relationships was significantly higher immediately after activity. We suggest that the slope indicates the rate of uric acid oxidation and that during activity this rate increases as a result of higher production of free radicals. The present study demonstrates that allantoin is present in the plasma and in the ureteral urine of white-crowned sparrows and therefore might be useful as an indicator of oxidative stress in birds.

  12. Prolonged maternal amino acid infusion in late-gestation pregnant sheep increases fetal amino acid oxidation.

    Science.gov (United States)

    Rozance, Paul J; Crispo, Michelle M; Barry, James S; O'Meara, Meghan C; Frost, Mackenzie S; Hansen, Kent C; Hay, William W; Brown, Laura D

    2009-09-01

    Protein supplementation during human pregnancy does not improve fetal growth and may increase small-for-gestational-age birth rates and mortality. To define possible mechanisms, sheep with twin pregnancies were infused with amino acids (AA group, n = 7) or saline (C group, n = 4) for 4 days during late gestation. In the AA group, fetal plasma leucine, isoleucine, valine, and lysine concentrations were increased (P < 0.05), and threonine was decreased (P < 0.05). In the AA group, fetal arterial pH (7.365 +/- 0.007 day 0 vs. 7.336 +/- 0.012 day 4, P < 0.005), hemoglobin-oxygen saturation (46.2 +/- 2.6 vs. 37.8 +/- 3.6%, P < 0.005), and total oxygen content (3.17 +/- 0.17 vs. 2.49 +/- 0.20 mmol/l, P < 0.0001) were decreased on day 4 compared with day 0. Fetal leucine disposal did not change (9.22 +/- 0.73 vs. 8.09 +/- 0.63 micromol x min(-1) x kg(-1), AA vs. C), but the rate of leucine oxidation increased 43% in the AA group (2.63 +/- 0.16 vs. 1.84 +/- 0.24 micromol x min(-1) x kg(-1), P < 0.05). Fetal oxygen utilization tended to be increased in the AA group (327 +/- 23 vs. 250 +/- 29 micromol x min(-1) x kg(-1), P = 0.06). Rates of leucine incorporation into fetal protein (5.19 +/- 0.97 vs. 5.47 +/- 0.89 micromol x min(-1) x kg(-1), AA vs. C), release from protein breakdown (4.20 +/- 0.95 vs. 4.62 +/- 0.74 micromol x min(-1) x kg(-1)), and protein accretion (1.00 +/- 0.30 vs. 0.85 +/- 0.25 micromol x min(-1) x kg(-1)) did not change. Consistent with these data, there was no change in the fetal skeletal muscle ubiquitin ligases MaFBx1 or MuRF1 or in the protein synthesis regulators 4E-BP1, eEF2, eIF2alpha, and p70(S6K). Decreased concentrations of certain essential amino acids, increased amino acid oxidation, fetal acidosis, and fetal hypoxia are possible mechanisms to explain fetal toxicity during maternal amino acid supplementation.

  13. Role of tartaric and malic acids in wine oxidation.

    Science.gov (United States)

    Danilewicz, John C

    2014-06-04

    Tartaric acid determines the reduction potential of the Fe(III)/Fe(II) redox couple. Therefore, it is proposed that it determines the ability of Fe to catalyze wine oxidation. The importance of tartaric acid was demonstrated by comparing the aerial oxidation of 4-methylcatechol (4-MeC) in model wine made up with tartaric and acetic acids at pH 3.6. Acetic acid, as a weaker Fe(III) ligand, should raise the reduction potential of the Fe couple. 4-MeC was oxidized in both systems, but the mechanisms were found to differ. Fe(II) readily reduced oxygen in tartrate model wine, but Fe(III) alone failed to oxidize the catechol, requiring sulfite assistance. In acetate model wine the reverse was found to operate. These observations should have broad application to model systems designed to study the oxidative process in foods and other beverages. Consideration should be given to the reduction potential of metal couples by the inclusion of appropriate ligands.

  14. Assembly and Succession of Iron Oxide Microbial Mat Communities in Acidic Geothermal Springs

    Directory of Open Access Journals (Sweden)

    Jacob P. Beam

    2016-02-01

    Full Text Available Biomineralized ferric oxide microbial mats are ubiquitous features on Earth, are common in hot springs of Yellowstone National Park (YNP, WY, USA, and form due to direct interaction between microbial and physicochemical processes. The overall goal of this study was to determine the contribution of different community members to the assembly and succession of acidic high-temperature Fe(III-oxide mat ecosystems. Spatial and temporal changes in Fe(III-oxide accretion and the abundance of relevant community members were monitored over 70 days using sterile glass microscope slides incubated in the outflow channels of two acidic geothermal springs (pH = 3 - 3.5; temperature = 68 - 75 °C in YNP. Hydrogenobaculum spp. were the most abundant taxon identified during early successional stages (4 - 40 d, and have been shown to oxidize arsenite, sulfide, and hydrogen coupled to oxygen reduction. Iron-oxidizing populations of Metallosphaera yellowstonensis were detected within 4 d, and reached steady-state levels within 14 - 30 d, corresponding to visible Fe(III-oxide accretion. Heterotrophic archaea colonized near 30 d, and emerged as the dominant functional guild after 70 d and in mature Fe(III-oxide mats (1 - 2 cm thick. First-order rate constants of Fe(III-oxide accretion ranged from 0.046 - 0.05 d-1, and in situ microelectrode measurements showed that the oxidation of Fe(II is limited by the diffusion of O2 into the Fe(III-oxide mat. The formation of microterracettes also implicated O2 as a major variable controlling microbial growth and subsequent mat morphology. The assembly and succession of Fe(III-oxide mat communities follows a repeatable pattern of colonization by lithoautotrophic organisms, and the subsequent growth of diverse organoheterotrophs. The unique geochemical signatures and micromorphology of extant biomineralized Fe(III-oxide mats are useful for understanding other Fe(II-oxidizing systems.

  15. All-trans retinoic acid increases oxidative metabolism in mature adipocytes

    DEFF Research Database (Denmark)

    Mercader, Josep; Madsen, Lise; Felipe, Francisco;

    2007-01-01

    BACKGROUND/AIMS: In rodents, retinoic acid (RA) treatment favors loss of body fat mass and the acquisition of brown fat features in white fat depots. In this work, we sought to examine to what extent these RA effects are cell autonomous or dependent on systemic factors. METHODS: Parameters of lipid...... metabolism and related gene expression were analyzed in differentiated 3T3-L1 adipocytes after exposure to RA or vehicle. RESULTS: Treatment with RA resulted in decreased cellular triacylglycerol content and increased basal lipolysis and fatty acid oxidation rate. At the mRNA level, RA treatment led......), and to an increased expression of proteins favoring fat oxidation (peroxisome proliferator-activated receptor gamma coactivator-1alpha, uncoupling protein 2, fasting-induced adipose factor, enzymes of mitochondrial fatty acid oxidation). These changes paralleled inactivation of the retinoblastoma protein and were...

  16. Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

    Science.gov (United States)

    Verplanck, P.L.; Nordstrom, D.K.; Taylor, H.E.; Kimball, B.A.

    2004-01-01

    Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

  17. Oxidation in fish oil enriched mayonnaise: ascorbic acid and low pH increase oxidative deterioration.

    Science.gov (United States)

    Jacobsen, C; Timm, M; Meyer, A S

    2001-08-01

    The effect of ascorbic acid (0-4000 ppm) and pH (3.8-6.2) on oxidation and levels of iron and copper in various fractions of mayonnaise enriched with 16% fish oil was investigated. Ascorbic acid induced release of iron from the assumed oil-water interface into the aqueous phase at all pH levels, but this effect of ascorbic acid was strongest at low pH (pH 3.8-4.2). Ascorbic acid generally promoted formation of volatile oxidation compounds and reduced the peroxide value in mayonnaises. Peroxide values and total volatiles generally increased with decreasing pH values, suggesting that low pH promoted oxidation. It is proposed that iron bridges between the egg yolk proteins low-density lipoproteins, lipovitellin, and phosvitin at the oil-water interface are broken at low pH values, whereby iron ions become accessible as oxidation initiators. In the presence of ascorbic acid, oxidation is further enhanced due to the reduction of Fe(3+) to Fe(2+) that rapidly catalyzes lipid oxidation via lipid hydroperoxide decomposition at the oil-water interface in mayonnaise.

  18. alpha-Lipoic acid and ascorbate prevent LDL oxidation and oxidant stress in endothelial cells.

    Science.gov (United States)

    Sabharwal, Anup K; May, James M

    2008-02-01

    Both alpha-lipoic acid (LA) and ascorbic acid (vitamin C) have been shown to improve endothelial dysfunction, a precursor of atherosclerosis. Since oxidant stress can cause endothelial dysfunction, we tested the interaction and efficacy of these antioxidants in preventing oxidant damage to lipids due to both intra- and extracellular oxidant stresses in EA.hy926 endothelial cells. LA spared intracellular ascorbate in culture and in response to an intracellular oxidant stress induced by the redox cycling agent menadione. Extracellular oxidant stress generated by incubating cells for 2 h in with 0.2 mg/ml LDL and 5 muM Cu2+ caused a time-dependent increase of the lipid peroxidation product malondialdehyde in both cells and LDL, preceded by rapid disappearance of; alpha-tocopherol in LDL. alpha-Lipoic acid at concentrations of 40-80 microM blunted these effects. Similarly, intracellular ascorbate concentrations of 1-2 mM also prevented Cu2+-induced lipid peroxidation in LDL and cells. Cu2+-dependent oxidation of LDL in the presence of ascorbate-loaded cells decreased intracellular ascorbate by 20%, but this decrease was not reversed by LA. Both LA and ascorbate protect endothelial cells and LDL from either intra- or extracellular oxidant stress, but that LA does not spare ascorbate in oxidatively stressed cells.

  19. Acetylsalicylic acid and acetaminophen protect against oxidative neurotoxicity.

    Science.gov (United States)

    Maharaj, H; Maharaj, D S; Daya, S

    2006-09-01

    Due to the implication of oxidative stress in neurodegenerative disorders we decided to investigate the antioxidant properties of acetylsalicylic acid and acetaminophen either alone or in combination. The thiobarbituric acid assay (TBA) and the nitroblue tetrazolium (NBT) assay were used to investigate quinolinic acid (QA)-induced: lipid peroxidation and superoxide anion generation in the rat hippocampus, in vivo. The study also shows, using cresyl violet staining, the preservation of structural integrity of neuronal cells following treatment with acetylsalicylic acid and acetaminophen in QA-lesioned rat hippocampus. Furthermore the study sought to determine whether these agents have any effect on endogenous (QA) formation. This study shows that acetylsalicylic acid and acetaminophen inhibit QA-induced superoxide anion generation, lipid peroxidation and cell damage, in vivo, in the rat hippocampus. In addition these agents inhibit the enzyme, 3-hydroxyanthranilic acid oxygenase (3-HAO), responsible for the synthesis of endogenous QA.

  20. Oxidation in fish oil enriched mayonnaise : Ascorbic acid and low pH increase oxidative deterioration

    DEFF Research Database (Denmark)

    Jacobsen, Charlotte; Timm Heinrich, Maike; Meyer, Anne S.

    2001-01-01

    The effect of ascorbic acid (0-4000 ppm) and pH (3.8-6.2) on oxidation and levels of iron and copper in various fractions of mayonnaise enriched with 16% fish oil was investigated. Ascorbic acid induced release of iron from the assumed oil- water interface into the aqueous phase at all pH levels......, but this effect of ascorbic acid was strongest at low pH (pH 3.8- 4.2). Ascorbic acid generally promoted formation of volatile oxidation compounds and reduced the peroxide value in mayonnaises. Peroxide values and total volatiles generally increased with decreasing pH values, suggesting that low pH promoted...... due to the reduction of Fe3+ to Fe2+ that rapidly catalyzes lipid oxidation via lipid hydroperoxide decomposition at the oil-water interface in mayonnaise...

  1. Effect of chelating agent on oxidation rate of aniline in ferrous ion activated persulfate system at neutral pH

    Institute of Scientific and Technical Information of China (English)

    张永清; 谢晓芳; 黄少斌; 梁海云

    2014-01-01

    In the interest of accelerating aniline degradation, Fe2+and chelated Fe2+activated persulfate oxidations were investigated in neutral pH condition. Three kinds of chelating agents were selected including citric acid, oxalic acid and ethylenediamine tetraaceatate (EDTA) to maintain available Fe2+. The results indicate that the concentration of chelating agent and ferrous ion didn’t follow a linear relationship with the degradation rate of aniline. A 1/1 ratio of chelating agent/Fe2+results in a higher degradation rate compared to the results by other ratios. The oxidation enhancement factor using oxalic acid was found to be relatively low. In contrast, citric acid is more suitable chelating agent in the ferrous iron activated persulfate system and aniline exhibits a highest degradation with a persulfate/Fe2+/citric acid/aniline molar ratio of 50/25/25/1 compared to other molar ratios.

  2. Oxidative cleavage of erucic acid for the synthesis of brassylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Mohammed J. Nasrullah; Pooja Thapliyal; Erica N. Pfarr; Nicholas S. Dusek; Kristofer L. Schiele; James A. Bahr

    2010-10-29

    The main focus of this work is to synthesize Brassylic Acid (BA) using oxidative cleavage of Erucic Acid (EA). Crambe (Crambe abyssinica) is an industrial oilseed grown in North Dakota. Crambe has potential as an industrial fatty acid feedstock as a source of Erucic acid (EA). It has approximately 50-60 % of EA, a C{sub 22} monounsaturated fatty acid. Oxidative cleavage of unsaturated fatty acids derived from oilseeds produces long chain (9, 11, and 13 carbon atoms) dibasic and monobasic acids. These acids are known commercial feedstocks for the preparation of nylons, polyesters, waxes, surfactants, and perfumes. Other sources of EA are Rapeseed seed oil which 50-60 % of EA. Rapeseed is grown outside USA. The oxidative cleavage of EA was done using a high throughput parallel pressure reactor system. Kinetics of the reaction shows that BA yields reach a saturation at 12 hours. H{sub 2}WO{sub 4} was found to be the best catalyst for the oxidative cleavage of EA. High yields of BA were obtained at 80 C with bubbling of O{sub 2} or 10 bar of O{sub 2} for 12 hours.

  3. Characterization of Humic Acid in the Chemical Oxidation Technology (II) - Characteristics by Ozonation -

    Energy Technology Data Exchange (ETDEWEB)

    Lee, D.S.; Jung, Y.R. [Kangwon National University, Chunchon (Korea)

    2000-04-01

    In this paper, ozonation of humic acid in water was characterized using UV{sub 254} absorbance, TOC, Ultra Filtration and {sup 13}C-NMR. Also, carbonyl compounds in ozonated water were analyzed by GC/MS using PFBOA method. Ozonation by-products of water containing humic acid were determined as formaldehyde, acetaldehyde, acetone, glyoxal and methylglyoxal. Results of UV{sub 254} absorbance and TOC with ozonation time at humic acid 20, 100 ppm represent that decrease rate of 80% within ozonation time is 20 min and TOC removal rate of 40-50% within ozonation time is 30 min. Results for {sup 13}C-NMR and Ultra Filtration, humic acid of high molecular weight by ozonation are oxidated and decomposed so that it was conversed low molecular weight such as aldehydes, carboxylic acid. (author). 7 refs., 3 tabs., 9 figs.

  4. Structure and friction of stearic acid and oleic acid films adsorbed on iron oxide surfaces in squalane.

    Science.gov (United States)

    Doig, Michael; Warrens, Chris P; Camp, Philip J

    2014-01-14

    The structure and friction of fatty acid surfactant films adsorbed on iron oxide surfaces lubricated by squalane are examined using large-scale molecular dynamics simulations. The structures of stearic acid and oleic acid films under static and shear conditions, and at various surface coverages, are described in detail, and the effects of unsaturation in the tail group are highlighted. At high surface coverage, the measured properties of stearic acid and oleic acid films are seen to be very similar. At low and intermediate surface coverages, the presence of a double bond, as in oleic acid, is seen to give rise to less penetration of lubricant in to the surfactant film and less layering of the lubricant near to the film. The kinetic friction coefficient is measured as a function of shear rate within the hydrodynamic (high shear rate) lubrication regime. Lubricant penetration and layering are observed to be correlated with friction coefficient. The friction coefficient with oleic acid depends only weakly on surface coverage, while stearic acid admits more lubricant penetration, and its friction coefficient increases significantly with decreasing surface coverage. Connections between film structure and friction are discussed.

  5. Dissolution study of thorium-uranium oxides in aqueous triflic acid solutions

    Energy Technology Data Exchange (ETDEWEB)

    Bulemela, E.; Bergeron, A.; Stoddard, T. [Canadian Nuclear Laboratories - CNL, 286 Plant Rd., Chalk River, Ontario, K0J 1J0 (Canada)

    2016-07-01

    The dissolution of sintered mixed oxides of thorium with uranium in various concentrations of trifluoromethanesulfonic (triflic) acid solutions was investigated under reflux conditions to evaluate the suitability of the method. Various fragment sizes (1.00 mm < x < 7.30 mm) of sintered (Th,U)O{sub 2} and simulated high-burnup nuclear fuel (SIMFUEL) were almost completely dissolved in a few hours, which implies that triflic acid could be used as an alternative to the common dissolution method, involving nitric acid-hydrofluoric acid mixture. The influence of acid concentration, composition of the solids, and reaction time on the dissolution yield of Th and U ions was studied using Inductively Coupled Plasma - Mass Spectrometry (ICP-MS). The dissolution rate was found to depend upon the triflic acid concentration and size of the solid fragments, with near complete dissolution for the smallest fragments occurring in boiling 87% w/w triflic acid. The formation of Th and U ions in solution appears to occur at the same rate as the triflic acid simultaneously reacts with the constituent oxides as evidenced by the results of a constant U/Th concentration ratio with the progress of the dissolution. (authors)

  6. Application of normal pulse voltammetry to the kinetic study of formic acid oxidation on a carbon supported Pd electrocatalyst

    Science.gov (United States)

    Wang, Yujiao; Wu, Xiaochen; Wu, Bing; Gao, Ying

    The kinetic parameters of formic acid oxidation on a carbon supported Pd electrode, such as the charge transfer coefficient (α) and apparent diffusion coefficient (D) are obtained by applying the technique of normal pulse voltammetry. The standard rate constant (k 0) of formic acid oxidation on a Pd/C electrode is estimated. The results show that formic acid oxidation is more sensitive to temperature at relatively high potential because the activation energy is significantly increased as the potential rose above 0.6 V.

  7. Human placenta metabolizes fatty acids: implications for fetal fatty acid oxidation disorders and maternal liver diseases.

    Science.gov (United States)

    Shekhawat, Prem; Bennett, Michael J; Sadovsky, Yoel; Nelson, D Michael; Rakheja, Dinesh; Strauss, Arnold W

    2003-06-01

    The role of fat metabolism during human pregnancy and in placental growth and function is poorly understood. Mitochondrial fatty acid oxidation disorders in an affected fetus are associated with maternal diseases of pregnancy, including preeclampsia, acute fatty liver of pregnancy, and the hemolysis, elevated liver enzymes, and low platelets syndrome called HELLP. We have investigated the developmental expression and activity of six fatty acid beta-oxidation enzymes at various gestational-age human placentas. Placental specimens exhibited abundant expression of all six enzymes, as assessed by immunohistochemical and immunoblot analyses, with greater staining in syncytiotrophoblasts compared with other placental cell types. beta-Oxidation enzyme activities in placental tissues were higher early in gestation and lower near term. Trophoblast cells in culture oxidized tritium-labeled palmitate and myristate in substantial amounts, indicating that the human placenta utilizes fatty acids as a significant metabolic fuel. Thus human placenta derives energy from fatty acid oxidation, providing a potential explanation for the association of fetal fatty acid oxidation disorders with maternal liver diseases in pregnancy.

  8. Lewis acidity enhancement of triarylborane by appended phosphine oxide groups.

    Science.gov (United States)

    Kwak, Jaewoo; Nghia, Nguyen Van; Lee, Junseong; Kim, Hyoseok; Park, Myung Hwan; Lee, Min Hyung

    2015-03-14

    A series of mono-, di-, and tri-phosphine oxide substituted triarylboranes, Mes2BAr (1), MesBAr2 (2), and BAr3 (3) (Ar = 4-(Ph2PO)-2,6-Me2-C6H2) were prepared to investigate the effect of a phosphine oxide group (Ph2PO) on Lewis acidity enhancement of triarylboranes. The X-ray crystal structure of 3 revealed peripheral decoration of Ph2PO groups with a C3-axis perpendicular to the trigonal boron center. UV/Vis absorption and PL spectra indicated a significant contribution of π(Mes or phenylene) → pπ(B) charge transfer in the lower-energy electronic transition. The reduction potential measured by cyclic voltammetry showed apparent LUMO stabilization by introduction of phosphine oxide groups, the extent of which gradually increased with the increasing number of phosphine oxide groups. Lewis acidity enhancement was also supported by the gradual increase in fluoride ion affinity in the order 3 > 2 > 1. Theoretical calculations suggest that introduction of a Ph2PO group into a triarylborane significantly enhances the Lewis acidity of the boron center via an inductive electron-withdrawing effect and this effect is additive for multiple phosphine oxide groups.

  9. Assays for urinary biomarkers of oxidatively damaged nucleic acids

    DEFF Research Database (Denmark)

    Weimann, Allan; Broedbaek, Kasper; Henriksen, Trine;

    2012-01-01

    and skills requirement. The available ELISA methods present considerable specificity problems and cannot be recommended at present. The oxidized nucleic acid metabolites in urine are assumed to originate from the DNA and RNA. However, direct evidence is not available. A possible contribution from...

  10. Oxidation in fish oil enriched mayonnaise : Ascorbic acid and low pH increase oxidative deterioration

    DEFF Research Database (Denmark)

    Jacobsen, Charlotte; Timm Heinrich, Maike; Meyer, Anne S.

    2001-01-01

    oxidation. It is proposed that iron bridges between the egg yolk proteins low-density lipoproteins, lipovitellin, and phosvitin at the oil-water interface are broken at low pH values, whereby iron ions become accessible as oxidation initiators. In the presence of ascorbic acid, oxidation is further enhanced......The effect of ascorbic acid (0-4000 ppm) and pH (3.8-6.2) on oxidation and levels of iron and copper in various fractions of mayonnaise enriched with 16% fish oil was investigated. Ascorbic acid induced release of iron from the assumed oil- water interface into the aqueous phase at all pH levels......, but this effect of ascorbic acid was strongest at low pH (pH 3.8- 4.2). Ascorbic acid generally promoted formation of volatile oxidation compounds and reduced the peroxide value in mayonnaises. Peroxide values and total volatiles generally increased with decreasing pH values, suggesting that low pH promoted...

  11. Oxidation of [1,12-14C]dodecanedioic acid by rat pancreatic islets.

    Science.gov (United States)

    Malaisse, W J; Greco, A V; Mingrone, G

    2000-10-01

    Several aliphatic dioic acids were recently reported to stimulate insulin release in isolated rat pancreatic islets incubated at close-to-physiological D-glucose concentrations. In order to gain insight into the mode of action of these acids in pancreatic islet B-cells, the oxidation of [1,12-14C]dodecanedioic acid (5.0 mM) was now measured in rat islets. Expressed as pmol of [1, 12-14C]dodecanedioic acid equivalent, the production of 14CO2 was close to 1.0 pmol/islet per 120 min, representing about 8% of that attributable to the oxidation of D-[U-14C]-glucose (8.3 mM). The dioic acid and the hexose failed to exert any significant reciprocal effect upon their respective oxidation rate. These findings support the view that the insulinotropic action of dodecanedioic acid, and presumably other aliphatic dioic acids, is causally linked to their capacity to act as nutrients in pancreatic islet cells.

  12. Heterogeneous Reactions of Acetic Acid with Oxide Surfaces: Effects of Mineralogy and Relative Humidity.

    Science.gov (United States)

    Tang, Mingjin; Larish, Whitney A; Fang, Yuan; Gankanda, Aruni; Grassian, Vicki H

    2016-07-21

    We have investigated the heterogeneous uptake of gaseous acetic acid on different oxides including γ-Al2O3, SiO2, and CaO under a range of relative humidity conditions. Under dry conditions, the uptake of acetic acid leads to the formation of both acetate and molecularly adsorbed acetic acid on γ-Al2O3 and CaO and only molecularly adsorbed acetic acid on SiO2. More importantly, under the conditions of this study, dimers are the major form for molecularly adsorbed acetic acid on all three particle surfaces investigated, even at low acetic acid pressures under which monomers are the dominant species in the gas phase. We have also determined saturation surface coverages for acetic acid adsorption on these three oxides under dry conditions as well as Langmuir adsorption constants in some cases. Kinetic analysis shows that the reaction rate of acetic acid increases by a factor of 3-5 for γ-Al2O3 when relative humidity increases from 0% to 15%, whereas for SiO2 particles, acetic acid and water are found to compete for surface adsorption sites.

  13. Hydrogen oxidation on gold electrode in perchloric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Sustersic, M.G.; Almeida, N.V.; Von Mengershausen, A.E. [Facultad de Ingenieria y Ciencias Economico Sociales, Universidad Nacional de San Luis, 25 de Mayo N 384, 5730 Villa Mercedes, San Luis (Argentina)

    2010-06-15

    The aim of this research is to study the interface gold/perchloric acid solution in presence of hydrogen. The reactive is generated by H{sup +} ion reduction and by saturating the electrolyte with the gaseous H{sub 2}. No evidence of H{sub 2} dissociative adsorption is found. In special conditions, a strongly adsorbed layer is formed from the atoms diffusing from inside of the metal. The mass transport occurs in three ways: the diffusion of H atoms inwards, the diffusion of H atoms back to the surface and the dissolved H{sub 2} diffusion from the bulk electrolyte to the surface. When dissolved H{sub 2} reacts, the reaction is kinetically controlled when the H{sub 2} partial pressure is high, and it is diffusionally controlled when the reactive partial pressure is low. Above 0.7 V, (measured vs. RHE), the (100) plane surface reconstruction lifts, and the rate determining step is the H diffusion towards inside of the metal, and the current suddenly falls. The Hydrogen redox reaction on gold shows reversibility with respect to the potential when the reactives are the H diffusing outwards of the metal and the H{sup +} ion present in the electrolyte. However, the absolute current values of oxidation and reduction are different because the reactive sources are different. (author)

  14. Mechanistic chemistry of oxidation of balsalazide with acidic chloramine-T and bromamine-T: A comparative spectrophotometric kinetic study

    Indian Academy of Sciences (India)

    Puttaswamy; S Dakshayani

    2014-11-01

    Balsalazide (BSZ) belongs to a class of non-steroidal anti-inflammatory drugs. Kinetics and mechanism of oxidation of BSZ with sodium N-halo-p-toluenesulfonamides viz., chloramine-T(CAT) and bromamine-T(BAT) in HClO4 medium have been spectrophotometrically investigated (max =357nm) at 303 K. Under comparable experimental conditions, reactions with both the oxidants follow a first-order dependence of rate on [BSZ] and fractional-order dependence on each [oxidant] and [HClO4]. Activation parameters and reaction constants have been computed. 2-hydroxy-5-nitroso-benzoic acid and 3-(4-nitroso-benzoylamino)-propionic acid are identified as the oxidation products of BSZ with both CAT and BAT. The rate of oxidation of BSZ is about five-fold faster with BAT than with CAT. Plausible mechanism and related rate law have been deduced for the observed kinetics.

  15. Enhanced Rates of Hydrogen Absorption Resulting from Oxidation of Pd and Internal Oxidation of Pd-Al Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Shanahan, K.L.

    1999-08-20

    The goal of this research was the determination of the relative rates before and after internal oxidation of Pd--Al alloys and oxidation (Pd) and this is independent of whether heat transfer is the rate-limiting step for the internally oxidized Pd--Al alloys rather than a more fundamental step.

  16. Pd oxides/hydrous oxides as highly efficient catalyst for formic acid electrooxidation

    Science.gov (United States)

    Yan, Liang; Yao, Shikui; Chang, Jinfa; Liu, Changpeng; Xing, Wei

    2014-03-01

    A novel Pd-based catalyst for formic acid electrooxidation (FAEO) was prepared by annealing commercial Pd/C catalyst under the O2 atmosphere at 100 °C, which exhibits excellent catalytic activity and stability for FAEO due to introduction of Pd oxides/hydrous oxides (POHOs). The catalytic activity of the as-prepared catalyst towards FAEO is 1.86 times of the commercial Pd/C catalyst in 0.5 M H2SO4 + 0.5 M HCOOH solution. Chronoamperometric curves show obvious improvement of the as-prepared catalyst electrocatalytic stability for FAEO. It is confirmed that POHOs can provide the required oxygen species for intermediate CO oxidation during the oxidation process of formic acid.

  17. Comparison of degradation reactions of Acid Yellow 61 in both oxidation processes of H202/UV and 03

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The comparison of degradation of Acid Yellow 61 as a model dye compound in both oxidation processes of H2 O2/UV and O3 has been studied. When the decolorization rate of Acid Yellow 61 in both reactions presented similar, it was found there are some differences from the results of AOX removal and production of inorganic ions and organic acids. The results reveal that the H2O2/UV has beneficial effect on mineralization than O3 only for degradation of Acid Yellow 61 solution and it is possible for enhancement of method efficiency by taking longer reaction time and addition of high concentration of oxidants.

  18. Mechanistic study of electrocatalytic oxidation of formic acid at platinum in acidic solution by time-resolved surface-enhanced infrared absorption spectroscopy.

    Science.gov (United States)

    Samjeské, Gabor; Miki, Atsushi; Ye, Shen; Osawa, Masatoshi

    2006-08-24

    Surface-enhanced infrared absorption spectroscopy (SEIRAS) combined with cyclic voltammetry or chronoamperometry has been utilized to examine kinetic and mechanistic aspects of the electrocatalytic oxidation of formic acid on a polycrystalline Pt surface at the molecular scale. Formate is adsorbed on the electrode in a bridge configuration in parallel to the adsorption of linear and bridge CO produced by dehydration of formic acid. A solution-exchange experiment using isotope-labeled formic acids (H(12)COOH and H(13)COOH) reveals that formic acid is oxidized to CO(2) via adsorbed formate and the decomposition (oxidation) of formate to CO(2) is the rate-determining step of the reaction. The adsorption/oxidation of CO and the oxidation/reduction of the electrode surface strongly affect the formic acid oxidation by blocking active sites for formate adsorption and also by retarding the decomposition of adsorbed formate. The interplay of the involved processes also affects the kinetics and complicates the cyclic voltammograms of formic acid oxidation. The complex voltammetric behavior is comprehensively explained at the molecular scale by taking all these effects into account.

  19. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid

    Science.gov (United States)

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

    2014-10-01

    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (Ep, 1.10 ≤ Ep ≤ 1.50 V), polarization time (tp, 100 ≤ tp ≤ 104 s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (dox). Because X1 > dox for the entire range of Ep, tp, and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Ptδ+-Oδ- surface dipole (μPtO), and the potential drop (Vox) and electric field (Eox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

  20. Microbial Methane Oxidation Rates in Guandu Wetland of northern Taiwan

    Science.gov (United States)

    Yu, Zih-Huei; Wang, Pei-Ling; Lin, Li-Hung

    2016-04-01

    Wetland is one of the major sources of atmospheric methane. The exact magnitude of methane emission is essentially controlled by microbial processes. Besides of methanogenesis, methanotrophy oxidizes methane with the reduction of various electron acceptors under oxic or anoxic conditions. The interplay of these microbial activities determines the final methane flux under different circumstances. In a tidal wetland, the cyclic flooding and recession of tide render oxygen and sulfate the dominant electron acceptors for methane oxidation. However, the details have not been fully examined, especially for the linkage between potential methane oxidation rates and in situ condition. In this study, a sub-tropical wetland in northern Taiwan, Guandu, was chosen to examine the tidal effect on microbial methane regulation. Several sediment cores were retrieved during high tide and low tide period and their geochemical profiles were characterized to demonstrate in situ microbial activities. Incubation experiments were conducted to estimate potential aerobic and anaerobic methane oxidation rates in surface and core sediments. Sediment cores collected in high tide and low tide period showed different geochemical characteristics, owning to tidal inundation. Chloride and sulfate concentration were lower during low tide period. A spike of enhanced sulfate at middle depth intervals was sandwiched by two sulfate depleted zones above and underneath. Methane was accumulated significantly with two methane depletion zones nearly mirroring the sulfate spike zone identified. During the high tide period, sulfate decreased slightly with depth with methane production inhibited at shallow depths. However, a methane consumption zone still occurred near the surface. Potential aerobic methane oxidation rates were estimated between 0.7 to 1.1 μmole/g/d, showing no difference between the samples collected at high tide or low tide period. However, a lag phase was widely observed and the lag phase

  1. Ascorbate and dehydroascorbic acid as reliable biomarkers of oxidative stress

    DEFF Research Database (Denmark)

    Lykkesfeldt, Jens

    2007-01-01

    Lack of post-sampling stability of ascorbate and dehydroascorbic acid and failure to block their in vivo equilibrium have lowered their value as biomarkers of oxidative stress and limited the ability to further investigate their possible role in disease prevention. In the present paper, the analy......Lack of post-sampling stability of ascorbate and dehydroascorbic acid and failure to block their in vivo equilibrium have lowered their value as biomarkers of oxidative stress and limited the ability to further investigate their possible role in disease prevention. In the present paper......, the analytical reproducibility was tested by repeated analysis of plasma aliquots from one individual over four years. The plasma was subjected to acidic deproteinization with an equal volume of 10% meta-phosphoric acid containing 2 mM EDTA and analyzed for ascorbate and dehydroascorbic acid by high......-performance liquid chromatography with coulometric detection. In a parallel experiment, stability of human plasma samples treated as above and stored at -80°C for five years was tested in a cohort of 131 individuals. No degradation or shift in the equilibrium between ascorbate and dehydroascorbic acid was observed...

  2. Tissue-specific changes in fatty acid oxidation in hypoxic heart and skeletal muscle.

    Science.gov (United States)

    Morash, Andrea J; Kotwica, Aleksandra O; Murray, Andrew J

    2013-09-01

    Exposure to hypobaric hypoxia is sufficient to decrease cardiac PCr/ATP and alters skeletal muscle energetics in humans. Cellular mechanisms underlying the different metabolic responses of these tissues and the time-dependent nature of these changes are currently unknown, but altered substrate utilization and mitochondrial function may be a contributory factor. We therefore sought to investigate the effects of acute (1 day) and more sustained (7 days) hypoxia (13% O₂) on the transcription factor peroxisome proliferator-activated receptor α (PPARα) and its targets in mouse cardiac and skeletal muscle. In the heart, PPARα expression was 40% higher than in normoxia after 1 and 7 days of hypoxia. Activities of carnitine palmitoyltransferase (CPT) I and β-hydroxyacyl-CoA dehydrogenase (HOAD) were 75% and 35% lower, respectively, after 1 day of hypoxia, returning to normoxic levels after 7 days. Oxidative phosphorylation respiration rates using palmitoyl-carnitine followed a similar pattern, while respiration using pyruvate decreased. In skeletal muscle, PPARα expression and CPT I activity were 20% and 65% lower, respectively, after 1 day of hypoxia, remaining at this level after 7 days with no change in HOAD activity. Oxidative phosphorylation respiration rates using palmitoyl-carnitine were lower in skeletal muscle throughout hypoxia, while respiration using pyruvate remained unchanged. The rate of CO₂ production from palmitate oxidation was significantly lower in both tissues throughout hypoxia. Thus cardiac muscle may remain reliant on fatty acids during sustained hypoxia, while skeletal muscle decreases fatty acid oxidation and maintains pyruvate oxidation.

  3. Selective oxidation of propane to acrylic acid over mixed metal oxide catalysts

    Institute of Scientific and Technical Information of China (English)

    Wei Zheng; Zhenxing Yu; Ping Zhang; Yuhang Zhang; Hongying Fu; Xiaoli Zhang; Qiquan Sun; Xinguo Hu

    2008-01-01

    The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic perfor-mances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 ℃ showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio (Mo1 V0.31Te0.23Nb0.12). The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H81 :O2 : H2O : N1 = 4.4 : 12.8 : 15.3 : 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.

  4. Hepatic Fatty Acid Oxidation Restrains Systemic Catabolism during Starvation

    Directory of Open Access Journals (Sweden)

    Jieun Lee

    2016-06-01

    Full Text Available The liver is critical for maintaining systemic energy balance during starvation. To understand the role of hepatic fatty acid β-oxidation on this process, we generated mice with a liver-specific knockout of carnitine palmitoyltransferase 2 (Cpt2L−/−, an obligate step in mitochondrial long-chain fatty acid β-oxidation. Fasting induced hepatic steatosis and serum dyslipidemia with an absence of circulating ketones, while blood glucose remained normal. Systemic energy homeostasis was largely maintained in fasting Cpt2L−/− mice by adaptations in hepatic and systemic oxidative gene expression mediated in part by Pparα target genes including procatabolic hepatokines Fgf21, Gdf15, and Igfbp1. Feeding a ketogenic diet to Cpt2L−/− mice resulted in severe hepatomegaly, liver damage, and death with a complete absence of adipose triglyceride stores. These data show that hepatic fatty acid oxidation is not required for survival during acute food deprivation but essential for constraining adipocyte lipolysis and regulating systemic catabolism when glucose is limiting.

  5. Impaired fatty acid oxidation as a cause for lipotoxicity in cardiomyocytes

    Energy Technology Data Exchange (ETDEWEB)

    Haffar, T. [Université de Montreal (Canada); Montreal Heart Institute (Canada); Bérubé-Simard, F. [Montreal Heart Institute (Canada); Bousette, N., E-mail: nicolas.bousette@umontreal.ca [Université de Montreal (Canada); Montreal Heart Institute (Canada)

    2015-12-04

    A major cause for diabetic cardiomyopathy is excess lipid accumulation. To elucidate mechanisms of lipotoxicity mediated diabetic heart disease we need to further our understanding of how lipid metabolism is altered in the diabetic heart. Here we investigated the role of lipid clearance by oxidation as a regulator of lipid-mediated toxicity (lipotoxicity). We evaluated the effect of pre-treating rat neonatal cardiomyocytes (NCMs) with either oleate (mono-unsaturated fatty acid) or palmitate (saturated fatty acid) on fatty acid oxidation (FAO) by measuring {sup 14}C–CO{sub 2} production. We evaluated carnitine palmitoyltransferase (Cpt1b) expression by western blotting and mitochondrial membrane potential by quantitative and qualitative fluorescence analyses using the JC-1 dye. We inhibited the Cpt1b pharmacologically using etomoxir and genetically by knocking down its expression using LentiVector mediated transduction of siRNAs targeting the Cpt1b gene. We found that palmitate had a slower clearance rate from NCMs than oleate, and this was associated with a significant decrease in FAO. This impairment in FAO was not the result of either loss of Cpt1b protein or mitochondrial integrity. Enhancing FAO with either oleate or carnitine was associated with a significant attenuation of palmitate mediated lipotoxicity. In contrast impairing FAO in oleate treated NCMs caused lipotoxicity. Here we demonstrate that a major difference between non-toxic unsaturated fatty acids and toxic saturated fatty acids is there ability to stimulate or inhibit fatty acid oxidation, respectively. This has important implications for diabetic cardiomyopathy since diabetic hearts consistently exhibit elevated lipid accumulation. - Highlights: • Palmitate had a slower clearance rate from NCMs than oleate. • Palmitate caused a significant decrease in fatty acid oxidation in cardiomyocytes. • Impaired FAO was not due to loss of Cpt1b protein or mitochondrial integrity. • Enhancing FAO

  6. Acid Separation, Catalytic Oxidation and Coagulation for ATC Waste Liquid Treatment

    Institute of Scientific and Technical Information of China (English)

    DING Xiaoling; JIA Chunning

    2005-01-01

    It is difficult to treat 2-amino-thiazoline-4-carboxylic acid (ATC) waste liquid effectively at present for its characteristics of high chemical oxygen demand (COD), high salinity and low biodegradability. In order to solve this problem, this paper presents several kinds of physical-chemical treatment unit techniques, including acid separation, catalytic oxidation and coagulation. First of all, acid separation was adopted to precipitate relevant organics at isoelectric point. When the temperature and pH value of acid separation were controlled at about 5 ℃ and 2.2 respectively, the COD removal rate could reach 27.6%. Secondly, oxidation was used to break chemical constitution of refractory organics. The optimal reaction parameters of catalytic oxidation should be 20 ℃, pH adjusted to 5.0 and [Fe2+] 300 mg/L. Then with 5% H 2O 2 added and after one-hour reaction, the COD removal rate could achieve about 52%. Finally, coagulation was adopted to remove a portion of refractory organics, and 15% polymeric molysite flocculant was the best for the coagulation, and the COD removal rate could reach about 15%. Therefore, the proposed feasible process of physical-chemical pretreatment for ATC waste liquid could have about 70% COD removed in total.

  7. The inborn errors of mitochondrial fatty acid oxidation.

    Science.gov (United States)

    Vianey-Liaud, C; Divry, P; Gregersen, N; Mathieu, M

    1987-01-01

    To date, seven inborn errors of mitochondrial fatty acid oxidation have been identified. A total of about 100 patients in the world have been reported. Clinically the beta-oxidation defects are more often characterized by episodic hypoglycaemia leading to a coma mimicking Reye's syndrome. The hypoglycaemia is non-ketotic since the synthesis of ketone bodies is deficient. Periods of decompensation occur when carbohydrate supply is poor, e.g. prolonged fasting, vomiting, or increased caloric requirements, as and when lipid stores are used. Defects in beta-oxidation have also been reported to be one cause of sudden infant death syndrome. The diagnosis of these inborn errors is by biochemical investigation since where symptoms suggest such a defect, the precise aetiology cannot be assessed. The biochemical diagnosis is based firstly on identification of abnormal plasma and of urinary metabolites during acute attacks. Derivatives of the omega-oxidation and omega-1-oxidation of medium chain fatty acids have been identified, as well as acylglycine and acylcarnitine conjugates. These metabolites are nearly always absent when patients are in good clinical condition. Secondly, the diagnosis must be based on the identification of the enzymatic defects: this involves global assays which allow a localization of the 'level' of the defect (i.e. the oxidation of long, medium or short chain fatty acids) and specific measurement of enzyme activities (acyl-CoA dehydrogenases and electron carriers: ETF and ETF-DH). The diagnosis of these disorders is of prime importance because of the severity of the clinical symptoms. These can be prevented, in some cases, by an appropriate diet (a high carbohydrate, low fat diet, sometimes supplemented with L-carnitine). In other cases, genetic counselling can be offered.

  8. Dietary sesamin and docosahexaenoic and eicosapentaenoic acids synergistically increase the gene expression of enzymes involved in hepatic peroxisomal fatty acid oxidation in rats.

    Science.gov (United States)

    Arachchige, Premakumara G; Takahashi, Yoko; Ide, Takashi

    2006-03-01

    The interaction of sesamin, one of the most abundant lignans in sesame seed, and highly purified docosahexaenoic acid (DHA) or eicosapentaenoic acid (EPA) in the form of ethyl ester in affecting hepatic fatty acid oxidation was examined in rats. In the first experiment, 3 groups of rats were fed with purified experimental diets free of n-3 fatty acid ethyl ester and containing 0%, 0.2%, and 0.4% sesamin (1:1 mixture of sesamin and episesamin), and 2 groups of animals were fed with a 2% DHA ethyl ester diet containing either 0% or 0.2% sesamin. In the second trial, 4 groups of rats were fed with either a 0% or a 2% EPA ethyl ester diet containing 0% or 0.2% sesamin. After 15 days of feeding, DHA and EPA ethyl esters added to a sesamin-free diet little affected the activity and messenger RNA (mRNA) levels of various enzymes involved in fatty acid oxidation. Sesamin increased the activity levels of various hepatic enzymes involved in fatty acid oxidation irrespective of the presence or absence of n-3 fatty acid ethyl ester in diets. However, the diet containing sesamin and DHA or EPA ethyl ester in combination increased many of these parameters synergistically. In particular, the peroxisomal palmitoyl-coenzyme A oxidation rate and acyl-coenzyme A oxidase activity level were much higher in rats fed with sesamin and DHA or EPA in combination than in animals fed with a diet free of n-3 fatty acid ethyl ester and containing sesamin. Analyses of mRNA levels revealed that a diet simultaneously containing sesamin and n-3 fatty acid ethyl ester increased the gene expression of various enzymes involved in peroxisomal fatty acid oxidation in a synergistic manner. However, the combination of sesamin and n-3 fatty acid ethyl esters was ineffective in causing a synergistic increase in mRNA levels of enzymes of mitochondrial fatty acid oxidation, microsomal cytochrome P-450 IV A1, and cytosolic liver-type fatty acid-binding protein. It was concluded that sesamin and DHA or EPA

  9. Formic acid oxidation at platinum-bismuth catalysts

    Directory of Open Access Journals (Sweden)

    Popović Ksenija Đ.

    2015-01-01

    Full Text Available The field of heterogeneous catalysis, specifically catalysis on bimetallic surfaces, has seen many advances over the past few decades. Bimetallic catalysts, which often show electronic and chemical properties that are distinct from those of their parent metals, offer the opportunity to obtain new catalysts with enhanced selectivity, activity, and stability. The oxidation of formic acid is of permanent interest as a model reaction for the mechanistic understanding of the electrooxidation of small organic molecules and because of its technical relevance for fuel cell applications. Platinum is one of the most commonly used catalysts for this reaction, despite the fact that it shows a few significant disadvantages: high cost and extreme susceptibility to poisoning by CO. To solve this problem, several approaches have been used, but generally, they all consist in the modification of platinum with a second element. Especially, bismuth has received significant attention as Pt modifier. According to the results presented in this survey dealing with the effects influencing the formic acid oxidation it was found that two types of Pt-Bi bimetallic catalysts (bulk and low loading deposits on GC showed superior catalytic activity in terms of the lower onset potential and oxidation current density, as well as exceptional stability compared to Pt. The findings in this report are important for the understanding of mechanism of formic acid electrooxidation on a bulk alloy and decorated surface, for the development of advanced anode catalysts for direct formic acid fuel cells, as well as for the synthesis of novel low-loading bimetallic catalysts. The use of bimetallic compounds as the anode catalysts is an effective solution to overcoming the problems of the formic acid oxidation current stability for long term applications. In the future, the tolerance of both CO poisoning and electrochemical leaching should be considered as the key factors in the development

  10. Significant enhancement of formic acid oxidation using rhodium nanostructures.

    Science.gov (United States)

    Balan, Beena K; Sathe, Bhaskar R

    2012-12-01

    The electrocatalytic activity of as-synthesized shape selective Rh nanostructures has been demonstrated using cyclic voltammetry, revealing unique shape-dependant performance towards HCOOH oxidation. Interestingly, the enhancement factor (R) for different shapes of Rh with respect to that of commercial Rh towards formic acid oxidation ranges up to 20,000% for cubes as compared to 17,500% for pyramids and 11,000% for hexagons respectively. Mechanistic pathway for comparatively better sensitivity of cubes as compared to other shapes has been correlated with the results of X-ray diffraction.

  11. Efficiency of mitochondrially targeted gallic acid in reducing brain mitochondrial oxidative damage.

    Science.gov (United States)

    Parihar, P; Jat, D; Ghafourifar, P; Parihar, M S

    2014-07-03

    Oxidative stress is associated with mitochondrial impairments. Supplying mitochondria with potent antioxidants can reduce oxidative stress—induced mitochondrial impairment. Gallic acid can be used to reduce oxidative burden in mitochondria. In order to increase the bioavailability of gallic acid inside the mitochondria we synthesized mitochondrially targeted gallic acid and explored its preventive effects against sodium nitroprusside induced oxidative stress in isolated mitochondria. Our observations revealed an increase in oxidative stress,decrease in reduced glutathione in mitochondria and increase in the mitochondrial permeability pore transition due to sodium nitroprusside treatment. Pre—treatment of gallic acid and mitochondrially targeted gallic acid to sodium nitroprusside treated mitochondria not only significantly reduced the oxidative stress but also prevented mitochondrial permeability pore transition to a significant difference. Mitochondrially targeted gallic acid was found more effective in reducing oxidative stress and mitochondrial permeability pore transition than gallic acid. We conclude that mitochondrially targeted gallic acid can be used for preventing mitochondrial impairment caused by oxidative stress.

  12. Oxidative stability of Liposomes composed of docosahexaenoic acid-containing phospholipids

    DEFF Research Database (Denmark)

    Vikbjerg, Anders Falk; Andresen, Thomas Lars; Jørgensen, Kent

    2007-01-01

    Oxidative stability of liposomes made of (Docosahexaenoic acid) DHA-containing phosphatidylcholine (PC) was examined during preparation and storage. After preparation of the liposomes, the concentration of primary (conjugated dienes) and secondary oxidation products (Thiobarbituric acid...

  13. Refsum disease, peroxisomes and phytanic acid oxidation: a review.

    Science.gov (United States)

    Wanders, R J; Jansen, G A; Skjeldal, O H

    2001-11-01

    Refsum disease was first recognized as a distinct disease entity by Sigvald Refsum in the 1940s. The discovery of markedly elevated levels of the branched-chain fatty acid phytanic acid in certain patients marked Refsum disease as a disorder of lipid metabolism. Although it was immediately recognized that the accumulation of phytanic acid is due to its deficient breakdown in Refsum disease patients, the true enzymatic defect remained mysterious until recently. A major breakthrough in this respect was the resolution of the mechanism of phytanic acid alpha-oxidation in humans. In this review we describe the many aspects of Refsum disease from the clinical signs and symptoms to the enzyme and molecular defect plus the recent identification of genetic heterogeneity in Refsum disease.

  14. Amino Acid and Peptide Immobilization on Oxidized Nanocellulose: Spectroscopic Characterization

    Directory of Open Access Journals (Sweden)

    Claude Daneault

    2012-06-01

    Full Text Available In this work, oxidized nanocellulose (ONC was synthesized and chemically coupled with amino acids and peptides using a two step coupling method at room temperature. First, ONC was activated by N-ethyl-N’-(3-dimethylaminopropyl carbodiimide hydrochloride, forming a stable active ester in the presence of N-hydroxysuccinimide. Second, the active ester was reacted with the amino group of the amino acid or peptide, forming an amide bond between ONC and the grafted molecule. Using this method, the intermolecular interaction of amino acids and peptides was avoided and uniform coupling of these molecules on ONC was achieved. The coupling reaction was very fast in mild conditions and without alteration of the polysaccharide. The coupling products (ONC-amino acids and ONC-peptides were characterized by transmission electron microscopy and by the absorption, emission, Fourier transform infrared spectroscopy (FTIR and X-ray photoelectron spectroscopy (XPS spectroscopic techniques.

  15. Exogenous amino acids suppress glucose oxidation and potentiate hepatic glucose production in late gestation fetal sheep.

    Science.gov (United States)

    Brown, Laura D; Kohn, Jaden R; Rozance, Paul J; Hay, William W; Wesolowski, Stephanie R

    2017-02-08

    Acute amino acid (AA) infusion increases AA oxidation rates in normal late gestation fetal sheep. Because fetal oxygen consumption rate does not change with increased AA oxidation, we hypothesized that AA infusion would suppress glucose oxidation pathways and that the additional carbon supply from AA would activate hepatic glucose production. To test this, late gestation fetal sheep were infused intravenously for 3h with saline or exogenous AA (AA). Glucose tracer metabolic studies were performed and skeletal muscle and liver tissues samples were collected. AA infusion increased fetal arterial plasma branched chain AA, cortisol, and glucagon concentrations. Fetal glucose utilization rates were similar between basal and AA periods, yet the fraction of glucose oxidized and glucose oxidation rate were decreased by 40% in the AA period. AA infusion increased expression of PDK4, an inhibitor of glucose oxidation, nearly 2-fold in muscle and liver. In liver, AA infusion tended to increase PCK1 gluconeogenic gene and PCK1 correlated with plasma cortisol concentrations. AA infusion also increased liver mRNA expression of lactate transporter gene (MCT1), protein expression of GLUT2 and LDHA, and phosphorylation of AMPK, 4EBP1, and S6 proteins. In isolated fetal hepatocytes, AA supplementation increased glucose production and PCK1, LDHA, and MCT1 gene expression. These results demonstrate that AA infusion into fetal sheep competitively suppresses glucose oxidation and potentiates hepatic glucose production. These metabolic patterns support flexibility in fetal metabolism in response to increased nutrient substrate supply while maintaining a relatively stable rate of oxidative metabolism.

  16. The Oxidation of Ascorbic Acid by Hexacyanoferrate(III) Ion in Acidic Aqueous Media.

    Science.gov (United States)

    Martins, Luis J. A.; da Costa, J. Barbosa

    1988-01-01

    Describes a kinetic and mechanistic investigation of ascorbic acid by a substitution-inert complex in acidic medium suitable for the undergraduate level. Discusses obtaining the second order rate constant for the rate determining step at a given temperature and comparison with the value predicted on the basis of the Marcus cross-relation. (CW)

  17. Assembly and Succession of Iron Oxide Microbial Mat Communities in Acidic Geothermal Springs

    Energy Technology Data Exchange (ETDEWEB)

    Beam, Jake; Bernstein, Hans C.; Jay, Z.; Kozubal, Mark; Jennings, Ryan; Tringe, Susannah G.; Inskeep, William P.

    2016-02-15

    Iron oxide microbial mats are ubiquitous geobiological features on Earth and occur in extant acidic hot springs of Yellowstone National Park (YNP), WY, USA, and form as a result of microbial processes. The relative contribution of different organisms to the development of these mat ecosystems is of specific interest. We hypothesized that chemolithoautotrophic organisms contribute to the early development and production of Fe(III)-oxide mats, which could support later-colonizing heterotrophic microorganisms. Sterile glass slides were incubated in the outflow channels of two acidic geothermal springs in YNP, and spatiotemporal changes in Fe(III)-oxide accretion and abundance of relevant community members were measured. Lithoautotrophic Hydrogenobaculum spp. were first colonizers and the most abundant taxa identified during early successional stages (7 – 40 days). Populations of M. yellowstonensis colonized after ~ 7 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized after 30 days, and emerge as the dominant functional guild in mature iron oxide mats (1 – 2 cm thick) that form after 70 – 120 days. First-order rate constants of iron oxide accretion ranged from 0.05 – 0.046 day-1, and reflected the absolute amount of iron accreted. Micro- and macroscale microterracettes were identified during iron oxide mat development, and suggest that the mass transfer of oxygen limits microbial growth. This was also demonstrated using microelectrode measurements of oxygen as a function of mat depth, which showed steep gradients in oxygen from the aqueous mat interface to ~ 1 mm. The formation and succession of amorphous Fe(III)-oxide mat communities follows a predictable pattern of distinct stages and growth. The successional stages and microbial signatures observed in these extant Fe(III)-oxide mat communities may be relevant to other past or present Fe(III)-oxide mineralizing systems.

  18. Dynamic simulations on the mitochondrial fatty acid Beta-oxidation network

    Directory of Open Access Journals (Sweden)

    Weinberger Klaus M

    2009-01-01

    Full Text Available Abstract Background The oxidation of fatty acids in mitochondria plays an important role in energy metabolism and genetic disorders of this pathway may cause metabolic diseases. Enzyme deficiencies can block the metabolism at defined reactions in the mitochondrion and lead to accumulation of specific substrates causing severe clinical manifestations. Ten of the disorders directly affecting mitochondrial fatty acid oxidation have been well-defined, implicating episodic hypoketotic hypoglycemia provoked by catabolic stress, multiple organ failure, muscle weakness, or hypertrophic cardiomyopathy. Additionally, syndromes of severe maternal illness (HELLP syndrome and AFLP have been associated with pregnancies carrying a fetus affected by fatty acid oxidation deficiencies. However, little is known about fatty acids kinetics, especially during fasting or exercise when the demand for fatty acid oxidation is increased (catabolic stress. Results A computational kinetic network of 64 reactions with 91 compounds and 301 parameters was constructed to study dynamic properties of mitochondrial fatty acid β-oxidation. Various deficiencies of acyl-CoA dehydrogenase were simulated and verified with measured concentrations of indicative metabolites of screened newborns in Middle Europe and South Australia. The simulated accumulation of specific acyl-CoAs according to the investigated enzyme deficiencies are in agreement with experimental data and findings in literature. Investigation of the dynamic properties of the fatty acid β-oxidation reveals that the formation of acetyl-CoA – substrate for energy production – is highly impaired within the first hours of fasting corresponding to the rapid progress to coma within 1–2 hours. LCAD deficiency exhibits the highest accumulation of fatty acids along with marked increase of these substrates during catabolic stress and the lowest production rate of acetyl-CoA. These findings might confirm gestational loss to

  19. Effects of intravenous methyl palmoxirate on the turnover and oxidation of fatty acids in conscious dogs

    Energy Technology Data Exchange (ETDEWEB)

    Bailey, J.W.; Jensen, M.D.; Miles, J.M. (Mayo Medical School, Rochester, MN (USA))

    1991-04-01

    Methyl palmoxirate (MP) is a member of a class of hypoglycemic agents that inhibit fatty acid oxidation in vitro. The studies presented here were undertaken to determine the effects of intravenous (IV) MP on tracer-determined rates of fatty acid oxidation and systemic adipose tissue lipolysis in dogs. MP (40 mg/kg) was administered IV to five mongrel dogs using a primed continuous infusion of (1-{sup 14}C)palmitate to determine palmitate kinetics. Palmitate concentration and rate of appearance decreased rapidly (from 155 +/- 25 to 47 +/- 6 mumol/L and 2.9 +/- 0.5 to 0.9 +/- 0.2 mumol.kg-1.min-1, respectively, at 15 minutes, both P less than .05). Palmitate oxidation also decreased, from 1.5 +/- 0.4 to 0.3 +/- 0.1 mumol.kg-1.min-1, P less than .05. Oxidative clearance decreased by approximately 50% 90 minutes after MP administration (P less than .05). Fractional oxidation of palmitate also decreased by approximately 40% (P less than .05). Plasma insulin increased from 45 +/- 6 to 240 +/- 93 pmol/L at 15 minutes (P less than .05). Plasma glucose decreased over the course of study by approximately 20% (P less than .05). In summary, MP has a specific inhibitory effect on plasma free fatty acid (FFA) oxidation in dogs, confirming previous in vitro observations in an in vivo model. In addition, it has a potent antilipolytic effect when administered IV, an effect likely mediated by stimulation of insulin secretion. The observation that systemic FFA oxidation was only partially suppressed at this relatively high dose of MP is consistent with previous studies suggesting that MP may exert its major effect in the liver, and may be less potent in extrahepatic tissues.

  20. KINETIC AND MECHANISTIC STUDY OF OXIDATION OF ATENOLOL BY CERIUM (IV IN SULPHURIC ACIDIC MEDIUM

    Directory of Open Access Journals (Sweden)

    Fadnis G Anand

    2012-03-01

    Full Text Available The kinetics of oxidation of antihypertensive drug, atenolol by cerium (IV in sulphuric acidic medium has been studied spectrophotometrically at 360 nm. The reaction between cerium (IV and atenolol in acidic medium has exhibited 2:1 stoichiometry. The order of the reaction with respect to atenolol has been found to be one. The observed pseudo first order rate constants kobs increased with sulphuric acid and hydrogen ion concentrations where as decreased bisulphate ion concentration indicating the formation bisulphato reactive species of cerium (IV in the present reaction. The thermodynamic parameters have been evaluated from the temperature variation kinetic data. A possible mechanism is proposed which has been validated by derived rate law. An attempt has been made to use rate data for kinetic estimation of atenolol.KEYWORDS:

  1. Downscaled anodic oxidation process for aluminium in oxalic acid

    Science.gov (United States)

    Sieber, M.; Morgenstern, R.; Kuhn, D.; Hackert-Oschätzchen, M.; Schubert, A.; Lampke, T.

    2017-03-01

    The increasing multi-functionality of parts and assemblies in several fields of engineering demands, amongst others, highly functionalised surfaces. For the different applications, on the one hand, there is a need to scale up surface modification processes originating in the nano- and micro-scale. On the other hand, conventional macro-scale surface refinement methods offer a huge potential for application in the said nano- and micro-scale. The anodic oxidation process, which is established especially for aluminium and its alloys, allows the formation of oxide ceramic layers on the surface. The build-up of an oxide ceramic coating comes along with altered chemical, tribological and electrical surface properties. As a basis for further investigations regarding the use of the anodic oxidation process for micro-scale-manufacturing, the scale effects of oxalic acid anodising on commercially pure aluminium as well as on the AlZn5.5MgCu alloy are addressed in the present work. The focus is on the amount of oxide formed during a potentiostatic process in relation to the exchanged amount of charge. Further, the hardness of the coating as an integral measure to assess the porous oxide structure is approached by nano-indentation technique.

  2. Oxidized fatty acids as inter-kingdom signaling molecules.

    Science.gov (United States)

    Pohl, Carolina H; Kock, Johan L F

    2014-01-20

    Oxylipins or oxidized fatty acids are a group of molecules found to play a role in signaling in many different cell types. These fatty acid derivatives have ancient evolutionary origins as signaling molecules and are ideal candidates for inter-kingdom communication. This review discusses examples of the ability of organisms from different kingdoms to "listen" and respond to oxylipin signals during interactions. The interactions that will be looked at are signaling between animals and plants; between animals and fungi; between animals and bacteria and between plants and fungi. This will aid in understanding these interactions, which often have implications in ecology, agriculture as well as human and animal health.

  3. Enhanced formic acid oxidation on Cu-Pd nanoparticles

    Science.gov (United States)

    Dai, Lin; Zou, Shouzhong

    Developing catalysts with high activity and high resistance to surface poisoning remains a challenge in direct formic acid fuel cell research. In this work, copper-palladium nanoparticles were formed through a galvanic replacement process. After electrochemically selective dissolution of surface Cu, Pd-enriched Cu-Pd nanoparticles were formed. These particles exhibit much higher formic acid oxidation activities than that on pure Pd nanoparticles, and they are much more resistant to the surface poisoning. Possible mechanisms of catalytic activity enhancement are briefly discussed.

  4. Synthesis of docosahexaenoic acid from eicosapentaenoic acid in retina neurons protects photoreceptors from oxidative stress.

    Science.gov (United States)

    Simón, María Victoria; Agnolazza, Daniela L; German, Olga Lorena; Garelli, Andrés; Politi, Luis E; Agbaga, Martin-Paul; Anderson, Robert E; Rotstein, Nora P

    2016-03-01

    Oxidative stress is involved in activating photoreceptor death in several retinal degenerations. Docosahexaenoic acid (DHA), the major polyunsaturated fatty acid in the retina, protects cultured retina photoreceptors from apoptosis induced by oxidative stress and promotes photoreceptor differentiation. Here, we investigated whether eicosapentaenoic acid (EPA), a metabolic precursor to DHA, had similar effects and whether retinal neurons could metabolize EPA to DHA. Adding EPA to rat retina neuronal cultures increased opsin expression and protected photoreceptors from apoptosis induced by the oxidants paraquat and hydrogen peroxide (H2 O2 ). Palmitic, oleic, and arachidonic acids had no protective effect, showing the specificity for DHA. We found that EPA supplementation significantly increased DHA percentage in retinal neurons, but not EPA percentage. Photoreceptors and glial cells expressed Δ6 desaturase (FADS2), which introduces the last double bond in DHA biosynthetic pathway. Pre-treatment of neuronal cultures with CP-24879 hydrochloride, a Δ5/Δ6 desaturase inhibitor, prevented EPA-induced increase in DHA percentage and completely blocked EPA protection and its effect on photoreceptor differentiation. These results suggest that EPA promoted photoreceptor differentiation and rescued photoreceptors from oxidative stress-induced apoptosis through its elongation and desaturation to DHA. Our data show, for the first time, that isolated retinal neurons can synthesize DHA in culture. Docosahexaenoic acid (DHA), the major polyunsaturated fatty acid in retina photoreceptors, and its precursor, eicosapentaenoic acid (EPA) have multiple beneficial effects. Here, we show that retina neurons in vitro express the desaturase FADS2 and can synthesize DHA from EPA. Moreover, addition of EPA to these cultures protects photoreceptors from oxidative stress and promotes their differentiation through its metabolization to DHA.

  5. The Aerobic Oxidation of Bromide to Dibromine Catalyzed by Homogeneous Oxidation Catalysts and Initiated by Nitrate in Acetic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.; Pham, Van Thai; Chen, Yongsheng

    2014-06-01

    A small amount of nitrate, ~0.002 molal, initiates the Co/Mn catalyzed aerobic oxidation of bromide compounds (HBr,NaBr,LiBr) to dibromine in acetic acid at room temperature. At temperatures 40oC or less , the reaction is autocatalytic. Co(II) and Mn(II) themselves and mixed with ionic bromide are known homogeneous oxidation catalysts. The reaction was discovered serendipitously when a Co/Br and Co/Mn/Br catalyst solution was prepared for the aerobic oxidation of methyaromatic compounds and the Co acetate contained a small amount of impurity i.e. nitrate. The reaction was characterized by IR, UV-VIS, MALDI and EXAFS spectroscopies and the coordination chemistry is described. The reaction is inhibited by water and its rate changed by pH. The change in these variables, as well as others, are identical to those observed during homogeneous, aerobic oxidation of akylaromatics. A mechanism is proposed. Accidental addition of a small amount of nitrate compound into a Co/Mn/Br/acetic acid mixture in a large, commercial feedtank is potentially dangerous.

  6. Cellulose acetate layer effect toward aluminium corrosion rate in hydrochloric acid media

    Science.gov (United States)

    Andarany, K. S.; Sagir, A.; Ahmad, A.; Deni, S. K.; Gunawan, W.

    2017-09-01

    Corrosion occurs due to the oxidation and reduction reactions between the material and its environment. The oxidation reaction defined as reactions that produce electrons and reduction is between two elements that bind the electrons. Corrosion cannot be inevitable in life both within the industry and household. Corrosion cannot eliminate but can be control. According to the voltaic table, Aluminum is a metal that easily corroded. This study attempts to characterize the type of corrosion by using a strong acid media (HCl). Experiment using a strong acid (HCl), at a low concentration that occurs is pitting corrosion, whereas at high concentrations that occurs is corrosion erosion. One of prevention method is by using a coating method. An efforts are made to slow the rate of corrosion is by coating the metal with “cellulose acetate” (CA). cellulose acetate consisted of cellulose powder dissolved in 99% acetic acid, and then applied to the aluminum metal. Soaking experiments using hydrochloric acid, cellulose acetate is able to slow down the corrosion rate of 47 479%.

  7. Hypochlorous acid-mediated protein oxidation: how important are chloramine transfer reactions and protein tertiary structure?

    Science.gov (United States)

    Pattison, David I; Hawkins, Clare L; Davies, Michael J

    2007-08-28

    Hypochlorous acid (HOCl) is a powerful oxidant generated from H2O2 and Cl- by the heme enzyme myeloperoxidase, which is released from activated leukocytes. HOCl possesses potent antibacterial properties, but excessive production can lead to host tissue damage that occurs in numerous human pathologies. As proteins and amino acids are highly abundant in vivo and react rapidly with HOCl, they are likely to be major targets for HOCl. In this study, two small globular proteins, lysozyme and insulin, have been oxidized with increasing excesses of HOCl to determine whether the pattern of HOCl-mediated amino acid consumption is consistent with reported kinetic data for isolated amino acids and model compounds. Identical experiments have been carried out with mixtures of N-acetyl amino acids (to prevent reaction at the alpha-amino groups) that mimic the protein composition to examine the role of protein structure on reactivity. The results indicate that tertiary structure facilitates secondary chlorine transfer reactions of chloramines formed on His and Lys side chains. In light of these data, second-order rate constants for reactions of Lys side chain and Gly chloramines with Trp side chains and disulfide bonds have been determined, together with those for further oxidation of Met sulfoxide by HOCl and His side chain chloramines. Computational kinetic models incorporating these additional rate constants closely predict the experimentally observed amino acid consumption. These studies provide insight into the roles of chloramine formation and three-dimensional structure on the reactions of HOCl with isolated proteins and demonstrate that kinetic models can predict the outcome of HOCl-mediated protein oxidation.

  8. Anodic oxidation of salicylic acid on BDD electrode: Variable effects and mechanisms of degradation

    Energy Technology Data Exchange (ETDEWEB)

    Rabaaoui, Nejmeddine, E-mail: chimie_tunisie@yahoo.fr [Faculte des Sciences de Sfax, Departement de Chimie, 3038 Sfax (Tunisia); Allagui, Mohamed Salah [Faculte des Sciences de Gafsa, Campus Universitaire Sidi Ahmed Zarrouk, 2112 Gafsa (Tunisia)

    2012-12-15

    Highlights: Black-Right-Pointing-Pointer Oxidation with BDD is a powerful electrochemical method able to mineralize. Black-Right-Pointing-Pointer SA is oxidized to aromatic compounds then CO{sub 2} and H{sub 2}O. Black-Right-Pointing-Pointer Polymeric intermediate products were formed. - Abstract: The degradation of 100 mL of solution with salicylic acid (SA) in the pH range 3.0-10.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 3 cm{sup 2} area, by applying a current of 100, 300 and 450 mA at 25 Degree-Sign C. Completed mineralization is always achieved due to the great concentration of hydroxyl radical ({center_dot}OH) generated at the BDD surface. The mineralization rate increases with increasing applied current, but decreases when drug concentration rises from 200 mg L{sup -1}. Nevertheless, the pH effect was not significant. During oxidation it was observed that catechol, 2,5-dihydroxylated benzoic acid, 2,3-dihydroxylated benzoic acid and hydroquinone were formed as aromatic intermediates. In addition, ion-exclusion chromatography allowed the detection of fumaric, maleic, oxalic and formic as the ultimate carboxylic acid.

  9. Free fatty acid oxidation in insulin resistance and obesity

    OpenAIRE

    Abel, E. Dale

    2010-01-01

    The growing worldwide epidemic of obesity and diabetes portends a significant increase in cardiovascular disease. Obesity is associated with insulin resistance, and there is growing evidence that these conditions independently increase the risk of heart failure. Changes in myocardial substrate utilization develop in obesity and insulin resistance, and are characterized by increased fatty acid oxidation and utilization, and decreased glucose utilization. This paper will review the evidence for...

  10. Glycolic acid production using ethylene glycol-oxidizing microorganisms.

    Science.gov (United States)

    Kataoka, M; Sasaki, M; Hidalgo, A R; Nakano, M; Shimizu, S

    2001-10-01

    Screening for microorganisms oxidizing ethylene glycol to glycolic acid was carried out. Among stock cultures, several yeasts and acetic acid bacteria showed high glycolic acid producing activity. Pichia naganishii AKU 4267 formed the highest concentration of glycolic acid, 35.3 g/l, from 10% (v/v) ethylene glycol (molar conversion yield, 26.0%). Among soil isolates, Rhodotorula sp. 3Pr-126, isolated using propylene glycol as a sole carbon source, formed the highest concentration of glycolic acid, 25.1 g/l, from 10% (v/v) ethylene glycol (molar conversion yield, 18.5%). Rhodotorula sp. 3Pr-126 showed higher activity toward 20% (v/v) ethylene glycol than P. naganishii AKU 4267. Optimization of the conditions for glycolic acid production was investigated using P. naganishii AKU 4267 and Rhodotorula sp. 3Pr-126. Under the optimized conditions, P. naganishii AKU 4267 and Rhodotorula sp. 3Pr-126 formed 105 and 110 g/l of glycolic acid (corrected molar conversion yields, 88.0 and 92.2%) during 120 h of reaction, respectively.

  11. Roles of Fatty Acid oversupply and impaired oxidation in lipid accumulation in tissues of obese rats.

    Science.gov (United States)

    Oakes, Nicholas D; Kjellstedt, Ann; Thalén, Pia; Ljung, Bengt; Turner, Nigel

    2013-01-01

    To test the roles of lipid oversupply versus oxidation in causing tissue lipid accumulation associated with insulin resistance/obesity, we studied in vivo fatty acid (FA) metabolism in obese (Obese) and lean (Lean) Zucker rats. Indices of local FA utilization and storage were calculated using the partially metabolizable [9,10-(3)H]-(R)-2-bromopalmitate ((3)H-R-BrP) and [U-(14)C]-palmitate ((14)C-P) FA tracers, respectively. Whole-body FA appearance (R a ) was estimated from plasma (14)C-P kinetics. Whole-body FA oxidation rate (R ox) was assessed using (3)H2O production from (3)H-palmitate infusion, and tissue FA oxidative capacity was evaluated ex vivo. In the basal fasting state Obese had markedly elevated FA levels and R a , associated with elevated FA utilization and storage in most tissues. Estimated rates of muscle FA oxidation were not lower in obese rats and were similarly enhanced by contraction in both lean and obese groups. At comparable levels of FA availability, achieved by nicotinic acid, R ox was lower in Obese than Lean. In Obese rats, FA oxidative capacity was 35% higher than that in Lean in skeletal muscle, 67% lower in brown fat and comparable in other organs. In conclusion, lipid accumulation in non-adipose tissues of obese Zucker rats appears to result largely from systemic FA oversupply.

  12. Roles of Fatty Acid Oversupply and Impaired Oxidation in Lipid Accumulation in Tissues of Obese Rats

    Directory of Open Access Journals (Sweden)

    Nicholas D. Oakes

    2013-01-01

    Full Text Available To test the roles of lipid oversupply versus oxidation in causing tissue lipid accumulation associated with insulin resistance/obesity, we studied in vivo fatty acid (FA metabolism in obese (Obese and lean (Lean Zucker rats. Indices of local FA utilization and storage were calculated using the partially metabolizable [9,10-3H]-(R-2-bromopalmitate (3H-R-BrP and [U-14C]-palmitate (14C-P FA tracers, respectively. Whole-body FA appearance (Ra was estimated from plasma 14C-P kinetics. Whole-body FA oxidation rate (Rox was assessed using 3H2O production from 3H-palmitate infusion, and tissue FA oxidative capacity was evaluated ex vivo. In the basal fasting state Obese had markedly elevated FA levels and Ra, associated with elevated FA utilization and storage in most tissues. Estimated rates of muscle FA oxidation were not lower in obese rats and were similarly enhanced by contraction in both lean and obese groups. At comparable levels of FA availability, achieved by nicotinic acid, Rox was lower in Obese than Lean. In Obese rats, FA oxidative capacity was 35% higher than that in Lean in skeletal muscle, 67% lower in brown fat and comparable in other organs. In conclusion, lipid accumulation in non-adipose tissues of obese Zucker rats appears to result largely from systemic FA oversupply.

  13. Stearic acid protects primary cultured cortical neurons against oxidative stress

    Institute of Scientific and Technical Information of China (English)

    Ze-jian WANG; Cui-ling LIANG; Guang-mei LI; Cai-yi YU; Ming YIN

    2007-01-01

    Aim: To observe the effects of stearic acid against oxidative stress in primary cultured cortical neurons. Methods: Cortical neurons were exposed to glutamate,hydrogen peroxide (H202), or NaN3 insult in the presence or absence of stearic acid. Cell viability of cortical neurons was determined by MTT assay and LDH release. Endogenous antioxidant enzymes activity[superoxide dismutases (SOD),glutathione peroxidase (GSH-Px), and catalase (CAT)] and lipid peroxidation in cultured cortical neurons were evaluated using commercial kits. {3-[1(p-chloro-benzyl)-5-(isopropyl)-3-t-butylthiondol-2-yl]-2,2-dimethylpropanoic acid, Na}[MK886; 5 pmol/L; a noncompetitive inhibitor of proliferator-activated receptor(PPAR)α], bisphenol A diglycidyl ether (BADGE; 100 μmol/L; an antagonist of PPARγ), and cycloheximide (CHX; 30 μmol/L, an inhibitor of protein synthesis)were tested for their effects on the neuroprotection afforded by stearic acid.Western blotting was used to determine the PPARγ protein level in cortical neurons.Results: Stearic acid dose-dependently protected cortical neurons against glutamate or H202 injury and increased glutamate uptake in cultured neurons.This protection was concomitant to the inhibition of lipid peroxidation and to the promotion activity of Cu/Zn SOD and CAT in cultured cortical neurons. Its neuroprotective effects were completely blocked by BADGE and CHX. After incubation with H2O2 for 24 h, the expression of the PPARγ protein decreased significantly (P<0.05), and the inhibitory effect of H2O2 on the expression of PPARγ can be attenuated by stearic acid. Conclusion: Stearic acid can protect cortical neurons against oxidative stress by boosting the internal antioxidant enzymes.Its neuroprotective effect may be mainly mediated by the activation of PPARγ and new protein synthesis in cortical neurons.

  14. Electrochemical destruction of trans-cinnamic acid by advanced oxidation processes: kinetics, mineralization, and degradation route.

    Science.gov (United States)

    Flores, Nelly; Thiam, Abdoulaye; Rodríguez, Rosa María; Centellas, Francesc; Cabot, Pere Lluís; Garrido, José Antonio; Brillas, Enric; Sirés, Ignasi

    2017-03-01

    Acidic solutions of trans-cinnamic acid at pH 3.0 have been comparatively treated by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), and photoelectro-Fenton (PEF). The electrolytic experiments were carried out with a boron-doped diamond (BDD)/air-diffusion cell. The substrate was very slowly abated by AO-H2O2 because of its low reaction rate with oxidizing (•)OH produced from water discharge at the BDD anode. In contrast, its removal was very rapid and at similar rate by EF and PEF due to the additional oxidation by (•)OH in the bulk, formed from Fenton's reaction between cathodically generated H2O2 and added Fe(2+). The AO-H2O2 treatment yielded the lowest mineralization. The EF process led to persistent final products like Fe(III) complexes, which were quickly photolyzed upon UVA irradiation in PEF to give an almost total mineralization with 98 % total organic carbon removal. The effect of current density and substrate concentration on all the mineralization processes was examined. Gas chromatography-mass spectrometry (GC-MS) analysis of electrolyzed solutions allowed identifying five primary aromatics and one heteroaromatic molecule, whereas final carboxylic acids like fumaric, acetic, and oxalic were quantified by ion exclusion high-performance liquid chromatography (HPLC). From all the products detected, a degradation route for trans-cinnamic acid is proposed.

  15. On the activation energy of the formic acid oxidation reaction on platinum electrodes

    OpenAIRE

    Perales-Rondón, Juan V.; Herrero, Enrique; Feliu, Juan M

    2015-01-01

    A temperature dependent study on the formic acid oxidation reaction has been carried out in order to determine the activation energy of this reaction on different platinum single crystal electrodes, namely Pt(1 0 0), Pt(1 1 1), Pt(5 5 4) and Pt(5 4 4) surfaces. The chronoamperometric transients obtained with pulsed voltammetry have been analyzed to determine the current densities through the active intermediate and the CO formation rate. From the temperature dependency of those parameters, th...

  16. Proteomics-Based Metabolic Modeling Reveals That Fatty Acid Oxidation (FAO) Controls Endothelial Cell (EC) Permeability*

    Science.gov (United States)

    Patella, Francesca; Schug, Zachary T.; Persi, Erez; Neilson, Lisa J.; Erami, Zahra; Avanzato, Daniele; Maione, Federica; Hernandez-Fernaud, Juan R.; Mackay, Gillian; Zheng, Liang; Reid, Steven; Frezza, Christian; Giraudo, Enrico; Fiorio Pla, Alessandra; Anderson, Kurt; Ruppin, Eytan; Gottlieb, Eyal; Zanivan, Sara

    2015-01-01

    Endothelial cells (ECs) play a key role to maintain the functionality of blood vessels. Altered EC permeability causes severe impairment in vessel stability and is a hallmark of pathologies such as cancer and thrombosis. Integrating label-free quantitative proteomics data into genome-wide metabolic modeling, we built up a model that predicts the metabolic fluxes in ECs when cultured on a tridimensional matrix and organize into a vascular-like network. We discovered how fatty acid oxidation increases when ECs are assembled into a fully formed network that can be disrupted by inhibiting CPT1A, the fatty acid oxidation rate-limiting enzyme. Acute CPT1A inhibition reduces cellular ATP levels and oxygen consumption, which are restored by replenishing the tricarboxylic acid cycle. Remarkably, global phosphoproteomic changes measured upon acute CPT1A inhibition pinpointed altered calcium signaling. Indeed, CPT1A inhibition increases intracellular calcium oscillations. Finally, inhibiting CPT1A induces hyperpermeability in vitro and leakage of blood vessel in vivo, which were restored blocking calcium influx or replenishing the tricarboxylic acid cycle. Fatty acid oxidation emerges as central regulator of endothelial functions and blood vessel stability and druggable pathway to control pathological vascular permeability. PMID:25573745

  17. Proteomics-based metabolic modeling reveals that fatty acid oxidation (FAO) controls endothelial cell (EC) permeability.

    Science.gov (United States)

    Patella, Francesca; Schug, Zachary T; Persi, Erez; Neilson, Lisa J; Erami, Zahra; Avanzato, Daniele; Maione, Federica; Hernandez-Fernaud, Juan R; Mackay, Gillian; Zheng, Liang; Reid, Steven; Frezza, Christian; Giraudo, Enrico; Fiorio Pla, Alessandra; Anderson, Kurt; Ruppin, Eytan; Gottlieb, Eyal; Zanivan, Sara

    2015-03-01

    Endothelial cells (ECs) play a key role to maintain the functionality of blood vessels. Altered EC permeability causes severe impairment in vessel stability and is a hallmark of pathologies such as cancer and thrombosis. Integrating label-free quantitative proteomics data into genome-wide metabolic modeling, we built up a model that predicts the metabolic fluxes in ECs when cultured on a tridimensional matrix and organize into a vascular-like network. We discovered how fatty acid oxidation increases when ECs are assembled into a fully formed network that can be disrupted by inhibiting CPT1A, the fatty acid oxidation rate-limiting enzyme. Acute CPT1A inhibition reduces cellular ATP levels and oxygen consumption, which are restored by replenishing the tricarboxylic acid cycle. Remarkably, global phosphoproteomic changes measured upon acute CPT1A inhibition pinpointed altered calcium signaling. Indeed, CPT1A inhibition increases intracellular calcium oscillations. Finally, inhibiting CPT1A induces hyperpermeability in vitro and leakage of blood vessel in vivo, which were restored blocking calcium influx or replenishing the tricarboxylic acid cycle. Fatty acid oxidation emerges as central regulator of endothelial functions and blood vessel stability and druggable pathway to control pathological vascular permeability.

  18. Dependence of reaction rate of pyrite oxidation on temperature, pH and oxidant concentration

    Institute of Scientific and Technical Information of China (English)

    LU; Long; WANG; Rucheng; XUE; Jiyue; CHEN; Fanrong; CHEN; J

    2005-01-01

    The kinetic sstudy of pyrite oxidation was performed in a series of experiments by a mixed flow reactor. The release rates of Fe(II) are in the order of 3.22×10-9-5.51×10-7 mol·m-2·s-1 at temperature (T ) 25 to 44℃, initial pH (pH )1.4 to 2.7, and initial Fe(III) concentration ([Fe(III)]I) 10-5 to 5×10-3 mol·kg-1. The release rate of Fe(II) increased with increasing T or/and pH or/and [Fe(III)]I in the above range. The rate law and activation energy of pyrite oxidation were derived by statistical analyses of Rfe(II) vs. [Fe(III)]I, Rfe(II) vs. pH and Rfe(II) vs. T, and are given as (1) Rate law: Rfe(II)=104.65e-64.54×103/8.31T[Fe(III)]i0.6./[H+]0.45 ; (2) activation energy: 64.54 ( 8.07 kJ·mol-1. The expression can be applied to more cases (e.g., quantifying the pollutant released from sulfide-rich mining waste and assessing reliable performance of underground repository sites where pyrite acts as an engineered barrier material). Using the rate law derived from this study, the magnitude of the pollutants transferred to secondary phases, soil and water from oxidized pyrite during Jiguanshan mine waste weathering was preliminarily estimated. The estimated magnitude is very high, suggesting that the pile has possibly posed significant impact on the water quality in this region.

  19. Neutral fat hydrolysis and long-chain fatty acid oxidation during anaerobic digestion of slaughterhouse wastewater.

    Science.gov (United States)

    Masse, L; Massé, D I; Kennedy, K J; Chou, S P

    2002-07-05

    Neutral fat hydrolysis and long-chain fatty acid (LCFA) oxidation rates were determined during the digestion of slaughterhouse wastewater in anaerobic sequencing batch reactors operated at 25 degrees C. The experimental substrate consisted of filtered slaughterhouse wastewater supplemented with pork fat particles at various average initial sizes (D(in)) ranging from 60 to 450 microm. At the D(in) tested, there was no significant particle size effect on the first-order hydrolysis rate. The neutral fat hydrolysis rate averaged 0.63 +/- 0.07 d(-1). LCFA oxidation rate was modelled using a Monod-type equation. The maximum substrate utilization rate (kmax) and the half-saturation concentration (Ks) averaged 164 +/- 37 mg LCFA/L/d and 35 +/- 31 mg LCFA/L, respectively. Pork fat particle degradation was mainly controlled by LCFA oxidation rate and, to a lesser extent, by neutral fat hydrolysis rate. Hydrolysis pretreatment of fat-containing wastewaters and sludges should not substantially accelerate their anaerobic treatment. At a D(in) of 450 microm, fat particles were found to inhibit methane production during the initial 20 h of digestion. Inhibition of methane production in the early phase of digestion was the only significant effect of fat particle size on anaerobic digestion of pork slaughterhouse wastewater. Soluble COD could not be used to determine the rate of lipid hydrolysis due to LCFA adsorption on the biomass.

  20. Study of photo-oxidative reactivity of sunscreening agents based on photo-oxidation of uric acid by kinetic Monte Carlo simulation

    Energy Technology Data Exchange (ETDEWEB)

    Moradmand Jalali, Hamed; Bashiri, Hadis, E-mail: hbashiri@kashanu.ac.ir; Rasa, Hossein

    2015-05-01

    In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO{sub 2}, ZnO and ZrO{sub 2}) was obtained by applying kinetic Monte Carlo simulation. The values of the rate constants for each step of the suggested mechanism have been obtained by simulation. The effect of the initial concentration of mineral oxides and uric acid on the rate of uric acid photo-oxidation by irradiation of some sun care agents has been studied. The kinetic Monte Carlo simulation results agree qualitatively with the existing experimental data for the production of free radicals by sun care agents. - Highlights: • The mechanism and kinetics of uric acid photo-oxidation by irradiation of sun care agents has been obtained by simulation. • The mechanism has been used for free radical production of TiO{sub 2} (rutile and anatase), ZnO and ZrO{sub 2}. • The ratios of photo-activity of ZnO to anastase, rutile and ZrO have been obtained. • By doubling the initial concentrations of mineral oxide, the rate of reaction was doubled. • The optimum ratio of initial concentration of mineral oxides to uric acid has been obtained.

  1. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)] anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25—40 ℃. The order of the redox reaction of lactic acid and DDA was found to be first-order. The rates increased with the increase in [OH-] and decreased with the increase in [tellurate]. No free radical was detected. In the view of this the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species. A plausible mechanism involving a two-electron transfer is proposed, and the rate equation derived from the mechanism can be used to explain all the experimental results. The activation parameters(25 ℃) and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  2. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ)in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHANJin-huan; WANGLi; LIUBao-sheng; SHENShi-gang

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)]anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25-40℃.The order of the redox reaction of lactic acid and DDA was found to be first-order.The rates increased with the increase in [OH-]and decreased with the increase in [tellurate].No free radical was detected.In the view of this the dihydroxymonotelluratoargentate(Ⅲ)species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can be used to explain all the experimenttal results.The activation parameters(25℃)and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  3. Oxidation of dietary stearic, oleic, and linoleic acids in growing pigs follows a biphasic pattern.

    Science.gov (United States)

    Bruininx, Erik; van den Borne, Joost; van Heugten, Eric; van Milgen, Jaap; Verstegen, Martin; Gerrits, Walter

    2011-09-01

    We used the pig as a model to assess the effects of dietary fat content and composition on nutrient oxidation and energy partitioning in positive energy balance. Pigs weighing 25 kg were assigned to either: 1) a low fat-high starch diet, or 2) a high saturated-fat diet, or 3) a high unsaturated-fat diet. In the high-fat treatments, 20% starch was iso-energetically replaced by 10.8% lard or 10.2% soybean oil, respectively. For 7 d, pigs were fed twice daily at a rate of 1200 kJ digestible energy · kg(-0.75) · d(-1). Oral bolus doses of [U-(13)C] glucose, [U-(13)C] α-linoleate, [U-(13)C] stearate, and [U-(13)C] oleate were administered on d 1, 2, 4, and 6, respectively, and (13)CO(2) production was measured. Protein and fat deposition were measured for 7 d. Fractional oxidation of fatty acids from the low-fat diet was lower than from the high-fat diets. Within diets, the saturated [U-(13)C] stearate was oxidized less than the unsaturated [U-(13)C] oleate and [U-(13)C] linoleate. For the high unsaturated-fat diet, oxidation of [U-(13)C] oleate was higher than that of [U-(13)C] linoleate. In general, recovery of (13)CO(2) from labeled fatty acids rose within 2 h after ingestion but peaked around the next meal. This peak was induced by an increased energy expenditure that was likely related to increased eating activity. In conclusion, oxidation of dietary fatty acids in growing pigs depends on the inclusion level and composition of dietary fat. Moreover, our data suggest that the most recently ingested fatty acids are preferred substrates for oxidation when the direct supply of dietary nutrients has decreased and ATP requirements increase.

  4. Oxidation and etching behaviors of the InAs surface in various acidic and basic chemical solutions

    Science.gov (United States)

    Na, Jihoon; Lee, Seunghyo; Lim, Sangwoo

    2017-04-01

    Indium arsenide (InAs) is the candidate of choice as a new channel material for application in future technologies beyond the Si-based electronic devices because it has a much higher electron mobility than silicon. In this study, the oxidation and etching behaviors of InAs (100) in various acidic and basic solutions, such as HF, HCl, H2SO4, NaOH, KOH, and NH4OH, were investigated. In addition, the effect of pH on the oxidation and etching reactions taking place on the InAs surface was studied using solutions with a pH ranging from 1 to 13. It was observed that the oxidation of the InAs surface was hindered in acidic solutions, which was attributed to the dissolution of the oxidized surface layer. In particular, the treatment of the InAs surface using a strongly acidic solution with a pH of less than 3 produced an oxide-free surface due to the predominant etching of the InAs surface. The addition of H2O2 to the acidic solutions greatly increased the etching rate of the InAs surface, which suggests that the oxidation process is the rate-limiting step in the sequence of reactions that occur during the etching of the InAs surface in acidic solutions. The etching of InAs was suppressed in neutral solutions, which resulted in the formation of a relatively thicker oxide layer on the surface, and mild etching of the InAs surface took place in basic solutions. However, in basic solutions, the addition of H2O2 did not significantly contribute to the increase of the oxidation state of the InAs surface; thus, its effect on the etching rate of InAs was smaller than in acidic solutions.

  5. Acetic acid enhances endurance capacity of exercise-trained mice by increasing skeletal muscle oxidative properties.

    Science.gov (United States)

    Pan, Jeong Hoon; Kim, Jun Ho; Kim, Hyung Min; Lee, Eui Seop; Shin, Dong-Hoon; Kim, Seongpil; Shin, Minkyeong; Kim, Sang Ho; Lee, Jin Hyup; Kim, Young Jun

    2015-01-01

    Acetic acid has been shown to promote glycogen replenishment in skeletal muscle during exercise training. In this study, we investigated the effects of acetic acid on endurance capacity and muscle oxidative metabolism in the exercise training using in vivo mice model. In exercised mice, acetic acid induced a significant increase in endurance capacity accompanying a reduction in visceral adipose depots. Serum levels of non-esterified fatty acid and urea nitrogen were significantly lower in acetic acid-fed mice in the exercised mice. Importantly, in the mice, acetic acid significantly increased the muscle expression of key enzymes involved in fatty acid oxidation and glycolytic-to-oxidative fiber-type transformation. Taken together, these findings suggest that acetic acid improves endurance exercise capacity by promoting muscle oxidative properties, in part through the AMPK-mediated fatty acid oxidation and provide an important basis for the application of acetic acid as a major component of novel ergogenic aids.

  6. Importance of acid-base equilibrium in electrocatalytic oxidation of formic acid on platinum.

    Science.gov (United States)

    Joo, Jiyong; Uchida, Taro; Cuesta, Angel; Koper, Marc T M; Osawa, Masatoshi

    2013-07-10

    Electro-oxidation of formic acid on Pt in acid is one of the most fundamental model reactions in electrocatalysis. However, its reaction mechanism is still a matter of strong debate. Two different mechanisms, bridge-bonded adsorbed formate mechanism and direct HCOOH oxidation mechanism, have been proposed by assuming a priori that formic acid is the major reactant. Through systematic examination of the reaction over a wide pH range (0-12) by cyclic voltammetry and surface-enhanced infrared spectroscopy, we show that the formate ion is the major reactant over the whole pH range examined, even in strong acid. The performance of the reaction is maximal at a pH close to the pKa of formic acid. The experimental results are reasonably explained by a new mechanism in which formate ion is directly oxidized via a weakly adsorbed formate precursor. The reaction serves as a generic example illustrating the importance of pH variation in catalytic proton-coupled electron-transfer reactions.

  7. 'Low-acid' sulfide oxidation using nitrate-enriched groundwater

    Science.gov (United States)

    Donn, Michael; Boxall, Naomi; Reid, Nathan; Meakin, Rebecca; Gray, David; Kaksonen, Anna; Robson, Thomas; Shiers, Denis

    2016-04-01

    Acid drainage (AMD/ARD) is undoubtedly one of the largest environmental, legislative and economic challenges facing the mining industry. In Australia alone, at least 60m is spent on AMD related issues annually, and the global cost is estimated to be in the order of tens of billions US. Furthermore, the challenge of safely and economically storing or treating sulfidic wastes will likely intensify because of the trend towards larger mines that process increasingly higher volumes of lower grade ores and the associated sulfidic wastes and lower profit margins. While the challenge of managing potentially acid forming (PAF) wastes will likely intensify, the industrial approaches to preventing acid production or ameliorating the effects has stagnated for decades. Conventionally, PAF waste is segregated and encapsulated in non-PAF tips to limit access to atmospheric oxygen. Two key limitations of the 'cap and cover' approach are: 1) the hazard (PAF) is not actually removed; only the pollutant linkage is severed; and, 2) these engineered structures are susceptible to physical failure in short-to-medium term, potentially re-establishing that pollutant linkage. In an effort to address these concerns, CSIRO is investigating a passive, 'low-acid' oxidation mechanism for sulfide treatment, which can potentially produce one quarter as much acidity compared with pyrite oxidation under atmospheric oxygen. This 'low-acid' mechanism relies on nitrate, rather than oxygen, as the primary electron accepter and the activity of specifically cultured chemolithoautotrophic bacteria and archaea communities. This research was prompted by the observation that, in deeply weathered terrains of Australia, shallow (oxic to sub-oxic) groundwater contacting weathering sulfides are commonly inconsistent with the geochemical conditions produced by ARD. One key characteristic of these aquifers is the natural abundance of nitrate on a regional scale, which becomes depleted around the sulfide bodies, and

  8. A preliminary study of the electro-oxidation of L-ascorbic acid on polycrystalline silver in alkaline solution

    Science.gov (United States)

    Majari Kasmaee, L.; Gobal, F.

    Electrochemical oxidation of L-ascorbic acid on polycrystalline silver in alkaline aqueous solutions is studied by cyclic voltammetry (CV), chronoamperometry (CA) and impedance spectroscopy (IS). The anodic electro-oxidation starts at -500 mV versus SCE and shows continued anodic oxidation in the cathodic half cycle in the CV regime signifying slowly oxidizing adsorbates. Diffusion coefficient of ascorbate ion measured under both voltammetric regimes is around 1.4 × 10 -5 cm 2 s -1. Impedance spectroscopy measures the capacitances associated with double layer and adsorption around 50 μF cm -2 and 4 mF cm -2 as well as the adsorption and decomposition resistances (rates).

  9. Oxidation of Tetracaine Hydrochloride by Chloramine-B in Acid Medium: Kinetic Modeling

    Directory of Open Access Journals (Sweden)

    Jayachamarajapura Pranesh Shubha

    2014-01-01

    Full Text Available Tetracaine hydrochloride (TCH is one of the potent local anaesthetics. A kinetic study of oxidation of tetracaine hydrochloride by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB has been carried in HClO4 medium at 303 K. The rate shows first-order dependence on [CAB]o, shows fractional–order dependence on [substrate]o, and is self-governing on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increased the rate. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction was found to be 1 : 5 and the oxidation products were identified by spectral analysis. The conjugate free acid C6H5SO2NHCl of CAB is postulated as the reactive oxidizing species. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

  10. Anisotropic interpolation method of silicon carbide oxidation growth rates for three-dimensional simulation

    Science.gov (United States)

    Šimonka, Vito; Nawratil, Georg; Hössinger, Andreas; Weinbub, Josef; Selberherr, Siegfried

    2017-02-01

    We investigate anisotropical and geometrical aspects of hexagonal structures of Silicon Carbide and propose a direction dependent interpolation method for oxidation growth rates. We compute three-dimensional oxidation rates and perform one-, two-, and three-dimensional simulations for 4H- and 6H-Silicon Carbide thermal oxidation. The rates of oxidation are computed according to the four known growth rate values for the Si- (0 0 0 1) , a- (1 1 2 bar 0) , m- (1 1 bar 0 0) , and C-face (0 0 0 1 bar) . The simulations are based on the proposed interpolation method together with available thermal oxidation models. We additionally analyze the temperature dependence of Silicon Carbide oxidation rates for different crystal faces using Arrhenius plots. The proposed interpolation method is an essential step towards highly accurate three-dimensional oxide growth simulations which help to better understand the anisotropic nature and oxidation mechanism of Silicon Carbide.

  11. Kinetic investigation of the oxidation of N-alkyl anilines by peroxomonophosphoric acid in anionic surfactant sodium lauryl sulphate

    Indian Academy of Sciences (India)

    G P Panigrahi; Jagannath Panda

    2000-12-01

    Kinetics of oxidation of N-methyl and N-ethyl aniline by peroxomono-phosphoric acid (PMPA) in aqueous and 5% (v/v) acetonitrile medium respectively have been studied in presence of anionic micelles of sodium lauryl sulphate (SLS) at different H. Oxidation rate of both the substrates increases up to a certain [SLS] much below the critical micellar concentration (cmc) after which the rate is retarded. Kinetic data have been used to compute the binding constants of both substrate and oxidant with the micelle. A scheme explaining the kinetic data has been proposed.

  12. Quinolinic acid induces oxidative stress in rat brain synaptosomes.

    Science.gov (United States)

    Santamaría, A; Galván-Arzate, S; Lisý, V; Ali, S F; Duhart, H M; Osorio-Rico, L; Ríos, C; St'astný, F

    2001-03-26

    The oxidative action of quinolinic acid (QUIN), and the protective effects of glutathione (GSH), and 2-amino-5-phosphonovaleric acid (APV), were tested in rat brain synaptosomes, Reactive oxygen species (ROS) formation was quantified after the exposure of synaptosomes to increasing concentrations of QUIN (25-500 microM). The potency of QUIN to induce lipid peroxidation (LP) was tested as a regional index of thiobarbituric acid-reactive substances (TBARS) production, and the antioxidant actions of both GSH (50 microM) and APV (250 microM) on QUIN-induced LP were evaluated in synaptosomes prepared from different brain regions. QUIN induced concentration-dependent increases in ROS formation and TBARS in all regions analyzed, but increased production of fluorescent peroxidized lipids only in the striatum and the hippocampus, whereas both GSH and APV decreased this index. These results suggest that the excitotoxic action of QUIN involves regional selectivity in the oxidative status of brain synaptosomes, and may be prevented by substances exhibiting antagonism at the NMDA receptor.

  13. Oxidation of hydrogen peroxide by [NiIII(cyclam)]3+ in aqueous acidic media

    Indian Academy of Sciences (India)

    Sankaran Anuradha; Venkatapuram Ramanujam Vijayaraghavan

    2013-09-01

    The kinetics of oxidation of H2O2 by [NiIII(cyclam)]3+, [NiIIIL1], was studied in aqueous acidic media at 25°C and I = 0.5M (NaClO4). The [NiIIIL1] to [NiIIL1] reduction was found to be fast in the presence of Cu(II) ion than the oxidation of the cyclam ligand by ·OH. The rate constant showed an inverse acid dependence on H+ ion at the pH range 1-1.5. The presence of sulphate retards the reaction. Macrocylic ligand oxidation was followed spectrophotometrically by examining the oxidation of nickel(II) complexes of macrocyclic ligands such as 1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane (L2), -5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L3), rac-Me6[14]-4,11-dieneN4 (L4) by reaction with hydrogen peroxide. The rate constant for the cross reaction is discussed in terms of Marcus relationship.

  14. Acrylic acid polymerization and its graft copolymerization to poly(ethylene oxide) by gamma rays

    Energy Technology Data Exchange (ETDEWEB)

    Hochberg, A.

    1984-01-01

    Free radical initiated polymerization of acrylic acid was investigated in methanol-water solutions with and without poly(ethylene oxide) (PEO). The formation of poly(acrylic acid) (PAA) initiated both by gamma irradiation and water soluble azo initiators was found to follow classical free radical kinetics. A significant increase in the rate of the propagation step (together with the degree of polymerization) was observed as the water fraction of the medium increased. During homogeneous polymerization of acrylic acid in methanol-water solutions containing poly(ethylene oxide), PAA grafting efficiency was found to be 67% and independent of initiation rate and yield. A mechanism of grafting to poly(ethylene oxide) was proposed. Chain transfer to PEO (K/sub tr/ = 6.5 x 10/sup -5/) was found to be the dominant mechanism for graft formation. Drag reduction characteristics of these PEO-PAA graft copolymers were measured in dilute aqueous solutions as a function of Reynolds number and solution pH. PEO graft copolymers containing 45% by mole PAA graft had, in neutral and basic solutions, drag reduction characteristics equivalent on a mass basis to the initial PEO. However at low pH, drag reduction characteristics disappeared as the PEO-PAA coacervate formed.

  15. Fatty acids and oxidative stress in psychiatric disorders

    Directory of Open Access Journals (Sweden)

    Tonello Lucio

    2008-04-01

    Full Text Available Abstract Background The aim of this study was to determine whether there is published evidence for increased oxidative stress in neuropsychiatric disorders. Methods A PubMed search was carried out using the MeSH search term 'oxidative stress' in conjunction with each of the DSM-IV-TR diagnostic categories of the American Psychiatric Association in order to identify potential studies. Results There was published evidence of increased oxidative stress in the following DSM-IV-TR diagnostic categories: mental retardation; autistic disorder; Rett's disorder; attention-deficit hyperactivity disorder; delirium; dementia; amnestic disorders; alcohol-related disorders; amphetamine (or amphetamine-like-related disorders; hallucinogen-related disorders; nicotine-related disorders; opioid-related disorders; schizophrenia and other psychotic disorders; mood disorders; anxiety disorders; sexual dysfunctions; eating disorders; and sleep disorders. Conclusion Most psychiatric disorders are associated with increased oxidative stress. Patients suffering from that subgroup of these psychiatric disorders in which there is increased lipid peroxidation might therefore benefit from fatty acid supplementation (preferably with the inclusion of an antioxidant-rich diet while patients suffering from all these psychiatric disorders might benefit from a change to a whole-food plant-based diet devoid of refined carbohydrate products.

  16. Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides

    KAUST Repository

    Paniagua, Sergio A.

    2016-05-26

    Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic-organic interface - the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology - significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientation on TCOs. The next sections discuss TCO work-function modification using PAs, tuning of TCO surface energy using PAs, and initiation of polymerizations from TCO-tethered PAs. Finally, studies that examine the use of PA-modified TCOs in organic light-emitting diodes and organic photovoltaics are compared. © 2016 American Chemical Society.

  17. Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

    Science.gov (United States)

    Khan, Sameera Razi; Ashfaq, Maria; Mubashir; Masood, Summyia

    2016-05-01

    The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298-318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy ( E a), enthalpy change (Δ H*), free energy change (Δ G*), and entropy change (Δ S*) have also been evaluated.

  18. Oleic acid-grafted chitosan/graphene oxide composite coating for corrosion protection of carbon steel.

    Science.gov (United States)

    Fayyad, Eman M; Sadasivuni, Kishor Kumar; Ponnamma, Deepalekshmi; Al-Maadeed, Mariam Al Ali

    2016-10-20

    An anticorrosion coating film based on the formation of nanocomposite coating is reported in this study. The composite consisted of chitosan (green matrix), oleic acid, and graphene oxide (nano filler). The nanocomposite coating was arranged on the surface of carbon steel, and the corrosion resistance was monitored using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PP). Compared to the pure chitosan (CS) coating, the corrosion resistance of oleic acid-modified chitosan/graphene oxide film (CS/GO-OA) is increased by 100 folds. Since the well-dispersed smart grafted nanolayers delayed the penetration rate of corrosive species and thus maintained long term anticorrosive stability which is correlated with hydrophobicity and permeability.

  19. Single-crystalline Pd square nanoplates enclosed by {100} facets on reduced graphene oxide for formic acid electro-oxidation.

    Science.gov (United States)

    Jiang, Yi; Yan, Yucong; Chen, Wenlong; Khan, Yousaf; Wu, Jianbo; Zhang, Hui; Yang, Deren

    2016-12-06

    Single-crystalline Pd square nanoplates enclosed by {100} facets were generated on reduced graphene oxide and exhibited the substantially enhanced properties for the formic acid oxidation reaction. The combination of carbonyl groups formed on the surface of annealed graphene oxide and Br(-) ions played important roles in this synthesis.

  20. Oxidation of phenyl alanine by pyridinium chlorochromate in acidic DMF–water medium: A kinetic study

    Directory of Open Access Journals (Sweden)

    B.L. Hiran

    2016-11-01

    Full Text Available The kinetics of oxidation of phenyl alanine by pyridinium chlorochromate in DMF–water (70:30% mixture in presence of perchloric acid leads to the formation of corresponding aldehyde. The reaction is of first order each in [PCC], [HClO4] and [AA]. Michaelis–Menten type kinetics was observed with phenyl alanine. The reaction rates were determined at different temperatures [25, 30, 35, 40, 45, 50 °C] and the activation parameters were calculated. The reaction does not induce polymerization of acrylonitrile. With an increase in the amount of DMF in its aqueous mixture, the rate increases. A suitable mechanism for the reaction was postulated.

  1. Oxidation of glycylglycine by ferricyanide in acid medium: Kinetics and mechanism

    Directory of Open Access Journals (Sweden)

    Krishna K. Yerneni

    2015-12-01

    Full Text Available The oxidative degradation of glycylglycine (GlyGly to formic acid, ammonium ion, and carbon dioxide occurs when it reacts with ferricyanide in acid medium, which has been studied spectrophotometrically at 303 nm at constant temperature. Kinetic runs have been performed under a pseudo-first-order condition of [GlyGly]0 >> [ferricyanide]0. The experimental rate law obtained for the redox reaction is: rate = kı [$ \\text{Fe(CN}^{3 - }_{6} $] [GlyGly]x [H+]y[Pd(II]0, where x and y are fractional orders. Effects of ionic strength and dielectric constant are also investigated. Activation parameters have been evaluated using Arrhenius and Eyring plots. A probable mechanism has been proposed and the derived rate law is consistent with the kinetic data.

  2. Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

    CERN Document Server

    Kürten, Andreas; Almeida, Joao; Kupiainen-Määttä, Oona; Dunne, Eimear M.; Duplissy, Jonathan; Williamson, Christina; Barmet, Peter; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M.; Flagan, Richard C.; Franchin, Alessandro; Gordon, Hamish; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Ickes, Luisa; Jokinen, Tuija; Kangasluoma, Juha; Kim, Jaeseok; Kirkby, Jasper; Kupc, Agnieszka; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Onnela, Antti; Ortega, Ismael K.; Petäjä, Tuukka; Praplan, Arnaud P.; Riccobono, Francesco; Rissanen, Matti P.; Rondo, Linda; Schnitzhofer, Ralf; Schobesberger, Siegfried; Smith, James N.; Steiner, Gerhard; Stozhkov, Yuri; Tomé, António; Tröstl, Jasmin; Tsagkogeorgas, Georgios; Wagner, Paul E.; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Ken; Kulmala, Markku; Curtius, Joachim

    2016-01-01

    Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia arethought to be the dominant processes responsible for new particle formation (NPF) in the cold temperaturesof the middle and upper troposphere. Ions are also thought to be important for particle nucleation inthese regions. However, global models presently lack experimentally measured NPF rates under controlledlaboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here withdata obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets)chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. Theconditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrationsbet ween 5 × 105and 1 × 109cm3, and ammonia mixing ratios from zero added ammonia, i.e., nominally purebinary, to a maximum of ~1400 parts per trillion by volume (pptv). We performed nucleation s...

  3. Electro-oxidation of methanol and formic acid on platinum nanoparticles with different oxidation levels

    Energy Technology Data Exchange (ETDEWEB)

    Hsieh, Chien-Te, E-mail: cthsieh@saturn.yzu.edu.tw [Department of Chemical Engineering and Materials Science, Yuan Ze University, Taoyuan 320, Taiwan (China); Hsiao, Han-Tsung; Tzou, Dong-Ying; Yu, Po-Yuan [Department of Chemical Engineering and Materials Science, Yuan Ze University, Taoyuan 320, Taiwan (China); Chen, Po-Yen; Jang, Bi-Sheng [Materials and Electro-Optics Research Division, National Chung-Shan Institute of Science and Technology, Taoyuan 325, Taiwan (China)

    2015-01-15

    Herein reported is an atomic layer deposition (ALD) process of platinum (Pt) from (methylcyclopentadienyl) trimethylplatinum (MeCpPtMe{sub 3}) and oxygen (O{sub 2}) for synthesizing the Pt electrocatalysts toward methanol and formic acid oxidation. The as-synthesized Pt catalysts are thermally reduced in 5 vol% H{sub 2} within temperature window of 150–450 °C. The reduction treatment induces a decrease in amount of Pt oxide (Pt–O) species, e.g., PtO and PtO{sub 2}. The presence of Pt–O species not only enhances catalytic activity but also improves anti-poisoning ability toward the oxidation of methanol and formic acid. The improved activity originates from the fact that the Pt–O species, formed by the ALD route, creates a large number of active sites (e.g., Pt–O{sub ads} and Pt–(OH){sub ads}) to strip the CO-adsorbed sites, leading to a high-level of CO tolerance. This work also proposes a stepwise reaction steps to shed some lights on how the Pt–O species promote the catalytic activity. - Highlights: • This study adopts atomic layer deposition (ALD) to grow metallic Pt nanoparticles. • The Pt catalysts show catalytic activity toward methanol and formic acid oxidation. • The reduction treatment induces a decrease in amount of Pt oxide (Pt–O) species. • The Pt–O species creates a number of active sites to strip the CO-adsorbed sites. • A stepwise reaction step concerning the promoted catalytic activity is proposed.

  4. Omega-3 Polyunsaturated Fatty Acids and Heart Rate Variability

    OpenAIRE

    Jeppe Hagstrup Christensen

    2011-01-01

    Omega-3 polyunsaturated fatty acids (PUFA) may modulate autonomic control of the heart because omega-3 PUFA is abundant in the brain and other nervous tissue as well as in cardiac tissue. This might partly explain why omega-3 PUFA offer some protection against sudden cardiac death (SCD). The autonomic nervous system is involved in the pathogenesis of SCD. Heart rate variability (HRV) can be used as a non-invasive marker of cardiac autonomic control and a low HRV is a predictor for SCD and arr...

  5. Field rates for natural attenuation of arsenic in Tinto Santa Rosa acid mine drainage (SW Spain).

    Science.gov (United States)

    Asta, Maria P; Ayora, Carlos; Acero, Patricia; Cama, Jordi

    2010-05-15

    Reactive transport modelling of the main processes related to the arsenic natural attenuation observed in the acid mine drainage (AMD) impacted stream of Tinto Santa Rosa (SW Spain) was performed. Despite the simplicity of the kinetic expressions used to deal with arsenic attenuation processes, the model reproduced successfully the major chemical trends observed along the acid discharge. Results indicated that the rate of ferrous iron oxidation was similar to the one obtained in earlier field studies in which microbial catalysis is reported to occur. With regard to the scaled arsenic oxidation rate, it is one order of magnitude faster than the values obtained under laboratory conditions suggesting the existence of a catalytic agent in the natural system. Schwertmannite precipitation rate, which was represented by a simple kinetic expression relying on Fe(III) and pH, was in the range calculated for other AMD impacted sites. Finally, the obtained distribution coefficients used for representing arsenic sorption onto Fe(III) precipitates were lower than those deduced from reported laboratory data. This discrepancy is attributed to a decrease in the schwertmannite arsenate sorption capacity as sulphate increases in the solution.

  6. Bacterial Oxidation and Reduction of Iron in the Processes of Creation and Treatment of Acid Mining Waters

    Directory of Open Access Journals (Sweden)

    Daniel Kupka

    2004-12-01

    Full Text Available Acid mine drainages (AMDs arise at the weathering of sulphidic minerals. The occurrence of acidic streams is commonly associated with the human mining activities. Due to the disruption and excavation of sulphide deposits, the oxidation processes have initiated. Acidic products of sulphide oxidation accelerate the degradation of accompanying minerals. AMDs typically contain high concentrations of sulfuric acid and soluble metals and cause serious ecological problems due to the water pollution and the devastation of adjacent country. Microbial life in these extremely acidic environments may be considerably diverse. AMDs are abundant in bacteria capable to oxidize and/or to reduce iron. The rate of bacterial oxidation of ferrous iron released from pyrite surfaces is up to one million times faster than the chemical oxidation rate at low pH. Bacterial regeneration of ferric iron maintains the continuity of pyrite oxidation and the production of AMDs. Another group of microorganisms living in these environments are acidophilic ferric iron reducing bacteria. This group of microorganisms has been discovered only relatively recently. Acidophilic heterotrophic bacteria reduce ferric iron in either soluble or solid forms to ferrous iron. The reductive dissolution of ferric iron minerals brings about a mobilization of iron as well as associated heavy metals. The Bacterial oxidation and reduction of iron play an important role in the transformation of either crystalline or amorphous iron-containing minerals, including sulphides, oxides, hydroxysulfates, carbonates and silicates. This work discusses the role of acidophilic bacteria in the natural iron cycling and the genesis of acidic effluents. The possibilities of application of iron bacteria in the remediation of AMDs are also considered.

  7. Iron photoreduction and oxidation in an acidic mountain stream.

    Science.gov (United States)

    McKnight, D M; Kimball, B A; Bencala, K E

    1988-04-29

    In a small mountain stream in Colorado that receives acidic mine drainage, photoreduction of ferric iron results in a well-defined increase in dissolved ferrous iron during the day. To quantify this process, an instream injection of a conservative tracer was used to measure discharge at the time that each sample was collected. Daytime production of ferrous iron by photoreduction was almost four times as great as nighttime oxidation of ferrous iron. The photoreduction process probably involves dissolved or colloidal ferric iron species and limited interaction with organic species because concentrations of organic carbon are low in this stream.

  8. Aerobic oxidation of aqueous ethanol using heterogeneous gold catalysts: Efficient routes to acetic acid and ethyl acetate

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Christiansen, Sofie Egholm; Thomsen, M.L.D.

    2007-01-01

    The aerobic oxidation of aqueous ethanol to produce acetic acid and ethyl acetate was studied using heterogeneous gold catalysts. Comparing the performance of Au/MgAl2O4 and Au/TiO2 showed that these two catalysts exhibited similar performance in the reaction. By proper selection of the reaction...... conditions, yields of 90-95% of acetic acid could be achieved at moderate temperatures and pressures. Based on our findings, a reaction pathway for the catalytic oxidation of ethanol via acetaldehyde to acetic acid is proposed, and the rate-determining step (RDS) in the mechanism is found to be the (possibly......, the possibilities for producing ethyl acetate by the aerobic oxidation of ethanol is also studied. At low ethanol concentrations, the main product is acetic acid; at concentrations >60 wt%, it is ethyl acetate....

  9. Effects of phenformin and alpha-bromopalmitate on fatty acid and glucose oxidation in muscle.

    Science.gov (United States)

    Tutwiler, G F

    1978-03-01

    Hemidiaphragms removed from fasted rats which were treated with the fatty acid oxidation inhibitor, alpha-bromopalmitate (125-250 mg/kg, i.p.) oxidized less glucose to CO2 than vehicle-treated rats. Hypoglycemia was noted and was preceded by reduction of muscle palmitate oxidation and by increased plasma free fatty acids (FFA). However, phenformin (100 mg/kg, i.p.) lowered plasma FFA and diaphragm oxidation of both palmitic acid and glucose, without altering glucose levels. These results fail to support the hypothesis that phenformin lowers blood glucose secondary to inhibiton of fatty acid oxidation.

  10. La2O3 Promoted Pd/rGO Electro-catalysts for Formic Acid Oxidation.

    Science.gov (United States)

    Ali, Hassan; Kanodarwala, Fehmida K; Majeed, Imran; Stride, John Arron; Nadeem, Muhammad Arif

    2016-11-30

    High activity, a low rate of CO poisoning, and long-term stability of Pd electro-catalysts are necessary for practical use as an anode material in direct formic acid fuel cells. Achieving a high degree of Pd nanoparticle dispersion on a carbon support, without agglomeration, while maintaining a facile electron transfer through the catalyst surface are two challenging tasks to be overcome in fulfilling this aim. Herein, we report the effect of addition of La/La-oxides on the efficiency of Pd nanoparticles supported on reduced graphene oxide (rGO) for formic acid electro-oxidation reaction. A series of electro-catalysts with different Pd-La molar ratios were successfully synthesized and characterized using a range of techniques including PXRD, XPS, TEM, FTIR, and Raman spectroscopy and then tested as anode materials for direct formic acid fuel cells. We explore that the lanthanum species (La/La-oxide) significantly promote the activity and stability of Pd catalyst toward electrocatalytic oxidation of formic acid. The metallic ratio is found to be critical, and the activity order of various catalysts is observed as follows; Pd30La70/rGO > Pd80La20/rGO > Pd70La30 rGO. The obtained mass specific activity for Pd30La70/rGO (986.42 A/g) is 2.18 times higher than that for Pd/rGO (451 A/g) and 16 times higher than that for Pd/C (61.5 A/g) at given onset peak potentials. The high activity and stability of the electro-catalysts are attributed to the uniform dispersion of Pd nanoparticles over the rGO support, as evidenced from TEM images. It is believed that the role of La species in promoting the catalyst activity is to disperse the catalyst particles during synthesis and to facilitate the electron transfer via providing a suitable pathway during electrochemical testing.

  11. Fatty acid oxidation is required for the respiration and proliferation of malignant glioma cells.

    Science.gov (United States)

    Lin, Hua; Patel, Shaan; Affleck, Valerie S; Wilson, Ian; Turnbull, Douglass M; Joshi, Abhijit R; Maxwell, Ross; Stoll, Elizabeth A

    2017-01-01

    Glioma is the most common form of primary malignant brain tumor in adults, with approximately 4 cases per 100 000 people each year. Gliomas, like many tumors, are thought to primarily metabolize glucose for energy production; however, the reliance upon glycolysis has recently been called into question. In this study, we aimed to identify the metabolic fuel requirements of human glioma cells. We used database searches and tissue culture resources to evaluate genotype and protein expression, tracked oxygen consumption rates to study metabolic responses to various substrates, performed histochemical techniques and fluorescence-activated cell sorting-based mitotic profiling to study cellular proliferation rates, and employed an animal model of malignant glioma to evaluate a new therapeutic intervention. We observed the presence of enzymes required for fatty acid oxidation within human glioma tissues. In addition, we demonstrated that this metabolic pathway is a major contributor to aerobic respiration in primary-cultured cells isolated from human glioma and grown under serum-free conditions. Moreover, inhibiting fatty acid oxidation reduces proliferative activity in these primary-cultured cells and prolongs survival in a syngeneic mouse model of malignant glioma. Fatty acid oxidation enzymes are present and active within glioma tissues. Targeting this metabolic pathway reduces energy production and cellular proliferation in glioma cells. The drug etomoxir may provide therapeutic benefit to patients with malignant glioma. In addition, the expression of fatty acid oxidation enzymes may provide prognostic indicators for clinical practice. © The Author(s) 2016. Published by Oxford University Press on behalf of the Society for Neuro-Oncology.

  12. Oxidized Fatty Acids as Inter-Kingdom Signaling Molecules

    Directory of Open Access Journals (Sweden)

    Carolina H. Pohl

    2014-01-01

    Full Text Available Oxylipins or oxidized fatty acids are a group of molecules found to play a role in signaling in many different cell types. These fatty acid derivatives have ancient evolutionary origins as signaling molecules and are ideal candidates for inter-kingdom communication. This review discusses examples of the ability of organisms from different kingdoms to “listen” and respond to oxylipin signals during interactions. The interactions that will be looked at are signaling between animals and plants; between animals and fungi; between animals and bacteria and between plants and fungi. This will aid in understanding these interactions, which often have implications in ecology, agriculture as well as human and animal health.

  13. Hepatic fatty acid oxidation : activity, localization and function of some enzymes involved

    NARCIS (Netherlands)

    A. van Tol (Arie)

    1971-01-01

    textabstractFatty acid oxidation is an important pathway for energy production in mammals and birds. In animal tissues the enzymes of fatty acid oxidation are located in the mitochondrion. Recent reports suggest that this is not the case in Castor bean endosperm. In this tissue the enzymes of B-oxid

  14. Hepatic fatty acid oxidation : activity, localization and function of some enzymes involved

    NARCIS (Netherlands)

    A. van Tol (Arie)

    1971-01-01

    textabstractFatty acid oxidation is an important pathway for energy production in mammals and birds. In animal tissues the enzymes of fatty acid oxidation are located in the mitochondrion. Recent reports suggest that this is not the case in Castor bean endosperm. In this tissue the enzymes of B-oxid

  15. Soot Nanostructure And Its Impact Upon The O2 Oxidation Rate

    Science.gov (United States)

    Wal, Randy L. Vander; Tomasek, Aaron J.

    2003-01-01

    Studies of soot oxidation have ranged from in situ flame studies to shock tubes to flow reactors. Each of these systems possesses particular advantages and limitations related to temperature, time and chemical environments. Despite the aforementioned differences, these soot oxidation investigations share three striking features. First and foremost is the wide variation in the rates of oxidation. Reported oxidation rates vary by factors of +6 to - 20 relative to the Nagle Strickland-Constable (NSC) rate for graphite oxidation [3]. Rate variations are not surprising, as the temperatures, residence times, types of oxidants and methods of oxidation differ from study to study. Nevertheless, a valid explanation for rate differences of this magnitude has yet to be presented.

  16. Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

    Directory of Open Access Journals (Sweden)

    F. Riccobono

    2012-05-01

    Full Text Available Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to formation and to the early growth of nucleated particles, respectively. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two Chemical Ionization Mass Spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene.

    New analysis methods were applied to the data collected with a Condensation Particle Counter battery and a Scanning Mobility Particle Sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ, defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is dominated by organic compounds already at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particles growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. The size resolved growth analysis finally indicates that both condensation of oxidized organic compounds and reactive uptake contribute to

  17. Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

    Directory of Open Access Journals (Sweden)

    F. Riccobono

    2012-10-01

    Full Text Available Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to the formation and early growth of nucleated particles. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two chemical ionization mass spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene.

    New analysis methods were applied to the data collected with a condensation particle counter battery and a scanning mobility particle sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ, defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is already dominated by organic compounds at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size, supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particle growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. Finally, the size resolved growth analysis indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

  18. beta-oxidation modulates metabolic competition between eicosapentaenoic acid and arachidonic acid regulating prostaglandin E(2) synthesis in rat hepatocytes-Kupffer cells

    DEFF Research Database (Denmark)

    Du, Zhen-Yu; Ma, Tao; Winterthun, Synnøve

    2010-01-01

    and eicosapentaenoic acid (EPA) for PGE(2) synthesis in a rat hepatocyte-Kupffer cell (HPC/KC) co-culture system when the cellular oxidation capacity was enhanced by exogenous l-carnitine. We demonstrate that in the absence of l-carnitine, 1) beta-oxidation rates of EPA and AA were comparable in HPCs and in KCs; 2) AA...... and not EPA was preferentially incorporated into glycerolipids; and 3) addition of EPA significantly decreased AA-dependent PGE(2) synthesis in HPCs and cyclooxygenase-2 (COX-2) expression in co-cultured HPCs/KCs. However, enhancing the cellular oxidation capacity by the addition of l-carnitine 1...

  19. ANTIOXIDANT AND PRO-OXIDANT EFFECT OF ASCORBIC ACID

    Directory of Open Access Journals (Sweden)

    Goran Rankovic

    2005-01-01

    Full Text Available Free radicals attack proteins, lipids, enzymes and DNA causing pathological changes in organism. There are many mechanisms that organism uses to fight against free radicals. Ascorbic acid is one of the strongest reducers and eliminators of free radicals. It reduces stable oxygenic, azoth and thyol radicals and acts as a primary defense against water radicals in blood. When radicals are dissolved in water suspensions of erythrocytes and low density lipoproteins (LDL, ascorbic acid catches and eliminates free radicals before they arrive to the membrane and LDL molecules. Even though ascorbic acid is not capable of eliminating free radicals out of fluid medium, it acts as synergist to alpha-tocopherol in lipid section, contributes to the lessening of lipid tocoperoxil radicals, and above all, regenerates alpha-tocopherol. Ascorbic acid may act as pro-oxidant under in vitro conditions in the presence of metals; however, this effect is probably not important under in vivo conditions where metal ions, being sequestered, become second reducers.

  20. Ammonia-oxidizing archaea have more important role than ammonia-oxidizing bacteria in ammonia oxidation of strongly acidic soils.

    Science.gov (United States)

    Zhang, Li-Mei; Hu, Hang-Wei; Shen, Ju-Pei; He, Ji-Zheng

    2012-05-01

    Increasing evidence demonstrated the involvement of ammonia-oxidizing archaea (AOA) in the global nitrogen cycle, but the relative contributions of AOA and ammonia-oxidizing bacteria (AOB) to ammonia oxidation are still in debate. Previous studies suggest that AOA would be more adapted to ammonia-limited oligotrophic conditions, which seems to be favored by protonation of ammonia, turning into ammonium in low-pH environments. Here, we investigated the autotrophic nitrification activity of AOA and AOB in five strongly acidic soils (pHnitrification inhibitor dicyandiamide (DCD) completely inhibited the nitrification activity and CO(2) fixation by AOA, accompanied by decreasing thaumarchaeal amoA gene abundance. Bacterial amoA gene abundance decreased in all microcosms irrespective of DCD addition, and mostly showed no correlation with nitrate concentrations. Phylogenetic analysis of thaumarchaeal amoA gene and 16S rRNA gene revealed active (13)CO(2)-labeled AOA belonged to groups 1.1a-associated and 1.1b. Taken together, these results provided strong evidence that AOA have a more important role than AOB in autotrophic ammonia oxidation in strongly acidic soils.

  1. Calcination/acid-activation treatment of an anodic oxidation TiO2/Ti film catalyst

    Institute of Scientific and Technical Information of China (English)

    YAO Zhongping; JIANG Yanli; JIANG Zhaohua; ZHU Hongkui; BAI Xuefeng

    2009-01-01

    The aim of this work was to investigate the effects of calcination/acid-activation on the composition, structure, and photocatalytic (PC) re-duction property of an anodic oxidation TiO2/Ti film catalyst. The surface morphology and phase composition were examined by scanning electron microscopy and X-ray diffraction. The catalytic property of the film catalysts was evaluated through the removal rate of potassium chromate during the PC reduction process. The results showed that the film catalysts were composed of anatase and mtile TiO2 with a mi-cro-porous surface structure. The calcination treatment increased the content of TiO2 in the film, changed the relative ratio of anatase and rutile TiO2, and decreased the size of the micro pores of the film cat.a/ysts. The removal rate of potassium chromate was related to the tech-nique parameters of calcination/acid-activation treatment. When the anodic oxidation TiO2Ti film catalyst was calcined at 873 K for 30 min and then acid-activated in the concentrated H2SO4 for 60 min, it presented the highest catalytic property, with the removal rate of potassium chromate of 96.3% during the PC reduction process under the experimental conditions.

  2. Ruthenium-catalyzed aerobic oxidative decarboxylation of amino acids: a green, zero-waste route to biobased nitriles.

    Science.gov (United States)

    Claes, Laurens; Verduyckt, Jasper; Stassen, Ivo; Lagrain, Bert; De Vos, Dirk E

    2015-04-18

    Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent.

  3. Mechanism of Oxidation of (p-Substituted Phenylthioacetic Acids with N-Bromophthalimide

    Directory of Open Access Journals (Sweden)

    N. M. I. Alhaji

    2011-01-01

    Full Text Available The kinetics of oxidation of (phenylthioacetic acid (PTAA by N-Bromophthalimide (NBP in acetonitrile-water solvent mixture at 298 K in the presence of perchloric acid has been followed potentiometrically. The reaction is first-order each in NBP and PTAA and inverse fractional-order in H+. Also, it has been found that the reaction rate is not affected by changes in ionic strength of the reaction medium or by the addition of chemicals such as phthalimide, acrylonitrile and potassium bromide. However, an increase in the water content of the solvent mixture causes an increase in the rate of reaction. These observations have been well analyzed in favour of a SN2-type mechanism, involving NBP itself as the reactive species. Effect of substituents on the reaction rate has been analysed by employing various (p-sustituted phenylthioacetic acids. The electron-releasing substituent in the phenyl ring of PTAA accelerates the reaction rate while the electron-withdrawing substituent retards the rate. The excellently linear Hammett plot yields a large negative ρ value, supporting the involvement a bromosulphonium ion intermediate in the rate-determining step.

  4. Lewis acid catalysis and Green oxidations: sequential tandem oxidation processes induced by Mn-hyperaccumulating plants.

    Science.gov (United States)

    Escande, Vincent; Renard, Brice-Loïc; Grison, Claude

    2015-04-01

    Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines.

  5. Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex in perchloric acid medium

    Indian Academy of Sciences (India)

    T V N Partha Sarathi; A Kalyan Kumar; K Krishna Kishore; P Vani

    2005-07-01

    Kinetics and mechanism of oxidation of glycine by iron(III)-1,10-phenanthroline complex has been studied in perchloric acid medium. The reaction is first order with respect to iron(III) and glycine. An increase in (phenanthroline) increases the rate, while increase in [H+] decreases the rate. Hence it can be inferred that the reactive species of the substrate is the zwitterionic form and that of the oxidant is [Fe(phen)2(H2O)2]3+. The proposed mechanism leads to the rate law as elucidated.

  6. Novel texturing method for sputtered zinc oxide films prepared at high deposition rate from ceramic tube targets

    Directory of Open Access Journals (Sweden)

    Hüpkes J.

    2011-10-01

    Full Text Available Sputtered and wet-chemically texture etched zinc oxide (ZnO films on glass substrates are regularly applied as transparent front contact in silicon based thin film solar cells. In this study, chemical wet etching in diluted hydrofluoric acid (HF and subsequently in diluted hydrochloric acid (HCl on aluminum doped zinc oxide (ZnO:Al films deposited by magnetron sputtering from ceramic tube targets at high discharge power (~10 kW/m target length is investigated. Films with thickness of around 800 nm were etched in diluted HCl acid and HF acid to achieve rough surface textures. It is found that the etching of the films in both etchants leads to different surface textures. A two steps etching process, which is especially favorable for films prepared at high deposition rate, was systematically studied. By etching first in diluted hydrofluoric acid (HF and subsequently in diluted hydrochloric acid (HCl these films are furnished with a surface texture which is characterized by craters with typical diameter of around 500 − 1000 nm. The resulting surface structure is comparable to etched films sputtered at low deposition rate, which had been demonstrated to be able to achieve high efficiencies in silicon thin film solar cells.

  7. Activation of peroxisome proliferator-activated receptor-{alpha} enhances fatty acid oxidation in human adipocytes

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Joo-Young; Hashizaki, Hikari; Goto, Tsuyoshi; Sakamoto, Tomoya; Takahashi, Nobuyuki [Laboratory of Molecular Function of Food, Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Uji, Kyoto 611-0011 (Japan); Kawada, Teruo, E-mail: fat@kais.kyoto-u.ac.jp [Laboratory of Molecular Function of Food, Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Uji, Kyoto 611-0011 (Japan)

    2011-04-22

    Highlights: {yields} PPAR{alpha} activation increased mRNA expression levels of adipocyte differentiation marker genes and GPDH activity in human adipocytes. {yields} PPAR{alpha} activation also increased insulin-dependent glucose uptake in human adipocytes. {yields} PPAR{alpha} activation did not affect lipid accumulation in human adipocytes. {yields} PPAR{alpha} activation increased fatty acid oxidation through induction of fatty acid oxidation-related genes in human adipocytes. -- Abstract: Peroxisome proliferator-activated receptor-{alpha} (PPAR{alpha}) is a key regulator for maintaining whole-body energy balance. However, the physiological functions of PPAR{alpha} in adipocytes have been unclarified. We examined the functions of PPAR{alpha} using human multipotent adipose tissue-derived stem cells as a human adipocyte model. Activation of PPAR{alpha} by GW7647, a potent PPAR{alpha} agonist, increased the mRNA expression levels of adipocyte differentiation marker genes such as PPAR{gamma}, adipocyte-specific fatty acid-binding protein, and lipoprotein lipase and increased both GPDH activity and insulin-dependent glucose uptake level. The findings indicate that PPAR{alpha} activation stimulates adipocyte differentiation. However, lipid accumulation was not changed, which is usually observed when PPAR{gamma} is activated. On the other hand, PPAR{alpha} activation by GW7647 treatment induced the mRNA expression of fatty acid oxidation-related genes such as CPT-1B and AOX in a PPAR{alpha}-dependent manner. Moreover, PPAR{alpha} activation increased the production of CO{sub 2} and acid soluble metabolites, which are products of fatty acid oxidation, and increased oxygen consumption rate in human adipocytes. The data indicate that activation of PPAR{alpha} stimulates both adipocyte differentiation and fatty acid oxidation in human adipocytes, suggesting that PPAR{alpha} agonists could improve insulin resistance without lipid accumulation in adipocytes. The expected

  8. Oxidative aromatization of Hantzsch 1,4-dihydropyridines by aqueous hydrogen peroxide-acetic acid

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A simple method for the oxidative aromatization of Hantzsch 1,4-dihydropyridines to the corresponding pyridines is achieved by using hydrogen peroxide as green oxidant and acetic acid as catalyst in aqueous solution.

  9. The association between low-grade inflammation, iron status and nucleic acid oxidation in the elderly

    DEFF Research Database (Denmark)

    Broedbaek, Kasper; Siersma, Volkert Dirk; Andersen, Jon T

    2011-01-01

    This study applied a case-control approach to investigate the association between low-grade inflammation, defined by high values within the normal range of C-reactive protein (CRP) and interleukin-6 (IL-6), and urinary markers of nucleic acid oxidation. No differences in excretion of urinary...... markers of nucleic acid oxidation between cases and controls were found and multivariable linear regression analysis showed no association between urinary markers of nucleic acid oxidation and inflammatory markers. Post-hoc multivariable linear regression analysis showed significant associations between...... nucleic acid oxidation and various iron status markers and especially a close relationship between nucleic acid oxidation and ferritin. This study shows no association between low-grade inflammation and urinary markers of nucleic acid oxidation in a population of elderly Italian people. The results...

  10. BACE1 activity impairs neuronal glucose oxidation: rescue by beta-hydroxybutyrate and lipoic acid.

    Science.gov (United States)

    Findlay, John A; Hamilton, David L; Ashford, Michael L J

    2015-01-01

    Glucose hypometabolism and impaired mitochondrial function in neurons have been suggested to play early and perhaps causative roles in Alzheimer's disease (AD) pathogenesis. Activity of the aspartic acid protease, beta-site amyloid precursor protein (APP) cleaving enzyme 1 (BACE1), responsible for beta amyloid peptide generation, has recently been demonstrated to modify glucose metabolism. We therefore examined, using a human neuroblastoma (SH-SY5Y) cell line, whether increased BACE1 activity is responsible for a reduction in cellular glucose metabolism. Overexpression of active BACE1, but not a protease-dead mutant BACE1, protein in SH-SY5Y cells reduced glucose oxidation and the basal oxygen consumption rate, which was associated with a compensatory increase in glycolysis. Increased BACE1 activity had no effect on the mitochondrial electron transfer process but was found to diminish substrate delivery to the mitochondria by inhibition of key mitochondrial decarboxylation reaction enzymes. This BACE1 activity-dependent deficit in glucose oxidation was alleviated by the presence of beta hydroxybutyrate or α-lipoic acid. Consequently our data indicate that raised cellular BACE1 activity drives reduced glucose oxidation in a human neuronal cell line through impairments in the activity of specific tricarboxylic acid cycle enzymes. Because this bioenergetic deficit is recoverable by neutraceutical compounds we suggest that such agents, perhaps in conjunction with BACE1 inhibitors, may be an effective therapeutic strategy in the early-stage management or treatment of AD.

  11. Electrochemical oxidation of methanol and formic acid in fuel cell processes

    Energy Technology Data Exchange (ETDEWEB)

    Seland, Frode

    2005-07-01

    spectra with features in the corresponding d.c. voltammograms, and the ability to investigate conditions with partially covered surfaces that are inaccessible in steady-state measurements. A variety of spectral types were observed, and for methanol these showed only a single adsorption relaxation aside from the double-layer/charge-transfer relaxation, though some structure in the phase of the latter relaxation hints at another process. The charge-transfer resistance showed Tafel behaviour for potentials in the rising part of the oxidation peak. The rate limiting step was proposed to be the electrochemical reaction between adsorbed CO and OH at the edge of islands of OH, with competition between OH and CO adsorption for the released reaction sites. Only a single adsorption relaxation in methanol oxidation was observed, implying that only one single coverage is required to describe the state of the surface and the kinetics. It was assumed that this single coverage is that of OH, and all the surface not covered with OH is covered with CO so that the coverage of CO is not an independent variable. Inductive behaviour and negative relaxation times in the methanol oxidation were attributed to nucleation and growth behaviour. Linear voltammetry reversal and sweep-hold experiments also indicated nucleation-growth-collision behaviour in distinct potential regions, both in the forward and reverse potential scan for methanol oxidation on platinum. In both methanol oxidation and formic acid oxidation, a negative differential resistance (NDR) was observed in the potential regions that possess a negative d.c. polarization slope, and was attributed to the formation of surface oxide which inhibited the oxidation of methanol or formic acid. EIS spectra for formic acid clearly showed the presence of an additional low frequency relaxation at potentials where we expect adsorbed dissociated water or platinum oxide to be present, implying that more than one single coverage is required to

  12. Subcritical crack growth in oxide and non-oxide ceramics using the Constant Stress Rate Test

    Directory of Open Access Journals (Sweden)

    Agnieszka Wojteczko

    2015-12-01

    Full Text Available Fracture toughness is one of the most important parameters for ceramics description. In some cases, material failure occurs at lower stresses than described by KIc parameter. In these terms, determination of fracture toughness only, proves to be insufficient. This may be due to environmental factors, such as humidity, which might cause subcritical crack propagation in a material. Therefore, it is very important to estimate crack growth velocities to predict lifetime of ceramics used under specific conditions. Constant Stress Rate Test is an indirect method of subcritical crack growth parameters estimation. Calculations are made by using strength data, thus avoiding crack measurement. The expansion of flaws causes reduction of material strength. If subcritical crack growth phenomenon occurs, critical value of crack lengths increases with decreasing stress rate due to longer time for flaw to grow before the critical crack propagation at KIc takes place. Subcritical crack growth phenomenon is particularly dangerous for oxide ceramics due to chemical interactions occurring as a result of exposure to humidity. This paper presents results of Constant Stress Rate Test performed for alumina, zirconia, silicon carbide and silicon nitride in order to demonstrate the differences in subcritical crack propagation phenomenon course.

  13. Evaporation rates and vapor pressures of individual aerosol species formed in the atmospheric oxidation of alpha- and beta-pinene.

    Science.gov (United States)

    Bilde, M; Pandis, S N

    2001-08-15

    The semivolatile oxidation products (trans-norpinic acid, pinic acid, cis-pinonic acid, etc.) of the biogenic monoterpenes (alpha-pinene, beta-pinene, etc.) contribute to the atmospheric burden of particulate matter. Using the tandem differential mobility analysis (TDMA) technique evaporation rates of glutaric acid, trans-norpinic acid, and pinic acid particles were measured in a laminar flow reactor. The vapor pressure of glutaric acid was found to be log(p0 glutaric/Pa) = - 3,510 K/T + 8.647 over the temperature range 290-300 K in good agreement with the values previously reported by Tao and McMurry (1989). The measured vapor pressure of trans-norpinic acid over the temperature range 290-312 K is log(p0 norpinic/Pa) = - 2,196.9 K/T + 3.522, and the vapor pressure of pinic acid is log(p0 pinic/ Pa) = - 5,691.7 K/T + 14.73 over the temperature range 290-323 K. The uncertainty on the reported vapor pressures is estimated to be approximately +/- 50%. The vapor pressure of cis-pinonic acid is estimated to be of the order of 7 x 10(-5) Pa at 296 K.

  14. The rationale for preventing cancer cachexia: targeting excessive fatty acid oxidation

    OpenAIRE

    2016-01-01

    Cachexia commonly occurs at the terminal stage of cancer and has largely unclear molecular mechanisms. A recent study published in Nature Medicine, entitled “Excessive fatty acid oxidation induces muscle atrophy in cancer cachexia,” reveals that cachectic cancer cells can secrete multiple cytokines that induce excessive fatty acid oxidation, which is responsible for muscle loss in cancer cachexia. Inhibition of fatty acid oxidation using etomoxir can increase muscle mass and body weight in ca...

  15. THE INFLUENCE OF NIOBIUM ON THE ACIDITY AND STRUCTURE OF GAMMA-ALUMINA-SUPPORTED VANADIUM OXIDES

    Directory of Open Access Journals (Sweden)

    M.N.B. Sathler

    1998-06-01

    Full Text Available Gamma-alumina-supported niobium oxide was used as a support for vanadium oxides. The influence of the addition of niobium oxide was studied by looking for changes in the structure and acid-base character of superficial species. Vanadium oxide was deposited using the continuous adsorption method; niobium oxide was impregnated using the incipient wetness method. The catalysts were characterized by XPS, UV-visible and IR spectroscopy. Catalytic tests were performed using propane oxidation reaction at 400oC. For coverage below the monolayer, both vanadium and niobium oxides were observed in slightly condensed superficial species. The presence of vanadium oxide on the support was found to increase the Lewis acidity and create some Bronsted acidity. Higher catalytic activity and selectivity for propene were associated with vanadium oxides. The presence of niobium did not contribute to the modification of the chemical properties of superficial vanadium but did decrease the adsorption of vanadium on the alumina.

  16. CHLORINATION OF AMINO ACIDS: REACTION PATHWAYS AND REACTION RATES.

    Science.gov (United States)

    How, Zuo Tong; Linge, Kathryn; Busetti, Francesco; Joll, Cynthia A

    2017-03-15

    Chlorination of amino acids can result in the formation of organic monochloramines or organic dichloramines, depending on the chlorine to amino acid ratio (Cl:AA). After formation, organic chloramines degrade into aldehydes, nitriles and N-chloraldimines. In this paper, the formation of organic chloramines from chlorination of lysine, tyrosine and valine were investigated. Chlorination of tyrosine and lysine demonstrated that the presence of a reactive secondary group can increase the Cl:AA ratio required for the formation of N,N-dichloramines, and potentially alter the reaction pathways between chlorine and amino acids, resulting in the formation of unexpected by-products. In a detailed investigation, we report rate constants for all reactions in the chlorination of valine, for the first time, using experimental results and modelling. At Cl:AA = 2.8, the chlorine was found to first react quickly with valine (5.4x104 M-1 s-1) to form N-monochlorovaline, with a slower subsequent reaction with N-monochlorovaline to form N,N-dichlorovaline (4.9x102 M-1 s-1), although some N-monochlorovaline degraded into isobutyraldehyde (1.0x10-4 s-1). The N,N-dichlorovaline then competitively degraded into isobutyronitrile (1.3x10-4 s-1) and N-chloroisobutyraldimine (1.2x10-4 s-1). In conventional drinking water disinfection, N-chloroisobutyraldimine can potentially be formed in concentrations higher than its odour threshold concentration, resulting in aesthetic challenges and an unknown health risk.

  17. Prolonged infusion of amino acids increases leucine oxidation in fetal sheep

    Science.gov (United States)

    Maliszewski, Anne M.; Gadhia, Monika M.; O'Meara, Meghan C.; Thorn, Stephanie R.; Rozance, Paul J.

    2012-01-01

    Maternal high-protein supplements designed to increase birth weight have not been successful. We recently showed that maternal amino acid infusion into pregnant sheep resulted in competitive inhibition of amino acid transport across the placenta and did not increase fetal protein accretion rates. To bypass placental transport, singleton fetal sheep were intravenously infused with an amino acid mixture (AA, n = 8) or saline [control (Con), n = 10] for ∼12 days during late gestation. Fetal leucine oxidation rate increased in the AA group (3.1 ± 0.5 vs. 1.4 ± 0.6 μmol·min−1·kg−1, P Fetal protein accretion (2.6 ± 0.5 and 2.2 ± 0.6 μmol·min−1·kg−1 in AA and Con, respectively), synthesis (6.2 ± 0.8 and 7.0 ± 0.9 μmol·min−1·kg−1 in AA and Con, respectively), and degradation (3.6 ± 0.6 and 4.5 ± 1.0 μmol·min−1·kg−1 in AA and Con, respectively) rates were similar between groups. Net fetal glucose uptake decreased in the AA group (2.8 ± 0.4 vs. 3.9 ± 0.1 mg·kg−1·min−1, P Fetal insulin and IGF-I concentrations did not change. Fetal glucagon increased in the AA group (119 ± 24 vs. 59 ± 9 pg/ml, P fetal glucose uptake rates were inversely proportional to fetal glucagon (r2 = 0.38, P fetal skeletal muscle were similar between groups. In summary, prolonged infusion of amino acids directly into normally growing fetal sheep increased leucine oxidation. Amino acid-stimulated increases in fetal glucagon, cortisol, and NE may contribute to a shift in substrate oxidation by the fetus from glucose to amino acids. PMID:22454287

  18. IDH1 mutations alter citric acid cycle metabolism and increase dependence on oxidative mitochondrial metabolism

    National Research Council Canada - National Science Library

    Grassian, Alexandra R; Parker, Seth J; Davidson, Shawn M; Divakaruni, Ajit S; Green, Courtney R; Zhang, Xiamei; Slocum, Kelly L; Pu, Minying; Lin, Fallon; Vickers, Chad; Joud-Caldwell, Carol; Chung, Franklin; Yin, Hong; Handly, Erika D; Straub, Christopher; Growney, Joseph D; Vander Heiden, Matthew G; Murphy, Anne N; Pagliarini, Raymond; Metallo, Christian M

    2014-01-01

    .... We observed that under hypoxic conditions, IDH1-mutant cells exhibited increased oxidative tricarboxylic acid metabolism along with decreased reductive glutamine metabolism, but not IDH2-mutant cells...

  19. Oxidation states of molybdenum in oxide films formed in sulphuric acid and sodium hydroxide

    Energy Technology Data Exchange (ETDEWEB)

    Okonkwo, I.A.; Doff, J.; Baron-Wiechec, A. [Corrosion and Protection Centre, School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Jones, G. [Waters Corporation, Floats Rd, Roundthorn Ind. Est., Manchester M23 9LZ (United Kingdom); Koroleva, E.V. [Corrosion and Protection Centre, School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Skeldon, P., E-mail: p.skeldon@manchester.ac.uk [Corrosion and Protection Centre, School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Thompson, G.E. [Corrosion and Protection Centre, School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom)

    2012-07-31

    X-ray photoelectron spectroscopy is used to investigate the oxidation states of molybdenum in thin films formed potentiostatically, over a range of potentials, in either 1 mol dm{sup -3} H{sub 2}SO{sub 4} or 10 mol dm{sup -3} NaOH at 20 Degree-Sign C. Mo 3d spectra suggested that MoO{sub 2} and Mo(OH){sub 2} were the main components of the films, with smaller amounts of MoO{sub 3} and possibly Mo{sub 2}O{sub 5}. O 1s spectra indicated the presence of oxygen as oxide and hydroxide species and as bound water. Ion beam analysis revealed the formation of thin films at all potentials, with significant losses of oxidized molybdenum to the electrolyte. - Highlights: Black-Right-Pointing-Pointer Oxides are formed on molybdenum in sulphuric acid and sodium hydroxide solutions. Black-Right-Pointing-Pointer Molybdenum IV and VI are identified by XPS, with MoO2 species dominating. Black-Right-Pointing-Pointer Thicknesses of films are determined by ion beam analysis for a range of potentials. Black-Right-Pointing-Pointer Films form at low efficiency due to loss of molybdenum species to electrolyte.

  20. Omega-9 Oleic Acid Induces Fatty Acid Oxidation and Decreases Organ Dysfunction and Mortality in Experimental Sepsis

    Science.gov (United States)

    Oliveira, Flora Magno de Jesus; Burth, Patrícia; Bozza, Patrícia Torres; Castro Faria, Mauro Velho; Silva, Adriana Ribeiro; de Castro-Faria-Neto, Hugo Caire

    2016-01-01

    Sepsis is characterized by inflammatory and metabolic alterations, which lead to massive cytokine production, oxidative stress and organ dysfunction. In severe systemic inflammatory response syndrome, plasma non-esterified fatty acids (NEFA) are increased. Several NEFA are deleterious to cells, activate Toll-like receptors and inhibit Na+/K+-ATPase, causing lung injury. A Mediterranean diet rich in olive oil is beneficial. The main component of olive oil is omega-9 oleic acid (OA), a monounsaturated fatty acid (MUFA). We analyzed the effect of OA supplementation on sepsis. OA ameliorated clinical symptoms, increased the survival rate, prevented liver and kidney injury and decreased NEFA plasma levels in mice subjected to cecal ligation and puncture (CLP). OA did not alter food intake and weight gain but diminished reactive oxygen species (ROS) production and NEFA plasma levels. Carnitine palmitoyltransferase IA (CPT1A) mRNA levels were increased, while uncoupling protein 2 (UCP2) liver expression was enhanced in mice treated with OA. OA also inhibited the decrease in 5' AMP-activated protein kinase (AMPK) expression and increased the enzyme expression in the liver of OA-treated mice compared to septic animals. We showed that OA pretreatment decreased NEFA concentration and increased CPT1A and UCP2 and AMPK levels, decreasing ROS production. We suggest that OA has a beneficial role in sepsis by decreasing metabolic dysfunction, supporting the benefits of diets high in monounsaturated fatty acids (MUFA). PMID:27078880

  1. Anodic oxidation of salicylic acid on BDD electrode: variable effects and mechanisms of degradation.

    Science.gov (United States)

    Rabaaoui, Nejmeddine; Allagui, Mohamed Salah

    2012-12-01

    The degradation of 100mL of solution with salicylic acid (SA) in the pH range 3.0-10.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 3 cm(2) area, by applying a current of 100, 300 and 450 mA at 25°C. Completed mineralization is always achieved due to the great concentration of hydroxyl radical (OH) generated at the BDD surface. The mineralization rate increases with increasing applied current, but decreases when drug concentration rises from 200 mg L(-1). Nevertheless, the pH effect was not significant. During oxidation it was observed that catechol, 2,5-dihydroxylated benzoic acid, 2,3-dihydroxylated benzoic acid and hydroquinone were formed as aromatic intermediates. In addition, ion-exclusion chromatography allowed the detection of fumaric, maleic, oxalic and formic as the ultimate carboxylic acid. Copyright © 2012 Elsevier B.V. All rights reserved.

  2. Triiodothyronine activates lactate oxidation without impairing fatty acid oxidation and improves weaning from extracorporeal membrane oxygenation

    Energy Technology Data Exchange (ETDEWEB)

    Kajimoto, Masaki; Ledee, Dolena R.; Xu, Chun; Kajimoto, Hidemi; Isern, Nancy G.; Portman, Michael A.

    2014-01-01

    Background: Extracorporeal membrane oxygenation (ECMO) provides a rescue for children with severe cardiac failure. We previously showed that triiodothyronine (T3) improves cardiac function by modulating pyruvate oxidation during weaning. This study was focused on fatty acid (FA) metabolism modulated by T3 for weaning from ECMO after cardiac injury. Methods: Nineteen immature piglets (9.1-15.3 kg) were separated into 3 groups with ECMO (6.5 hours) and wean: normal circulation (Group-C);transient coronary occlusion (10 minutes) followed by ECMO (Group-IR); and IR with T3 supplementation (Group-IR-T3). 13-Carbon labeled lactate, medium-chain and long-chain FAs were infused as oxidative substrates. Substrate fractional contribution to the citric acid cycle (FC) was analyzed by 13-Carbon nuclear magnetic resonance. Results: ECMO depressed circulating T3 levels to 40% baseline at 4 hours and were restored in Group-IR-T3. Group-IR decreased cardiac power, which was not fully restorable and 2 pigs were lost because of weaning failure. Group-IR also depressed FC-lactate, while the excellent contractile function and energy efficiency in Group-IR-T3 occurred along with a marked FC-lactate increase and [ATP]/[ADP] without either decreasing FC-FAs or elevating myocardial oxygen consumption over Group-C or -IR. Conclusions: T3 releases inhibition of lactate oxidation following ischemia-reperfusion injury without impairing FA oxidation. These findings indicate that T3 depression during ECMO is maladaptive, and that restoring levels improves metabolic flux and enhances contractile function during weaning.

  3. Thermal-oxidation of biodiesel by pressurized-differential scanning calorimetry: Effects of heating ramp rate

    Science.gov (United States)

    Biodiesel, an alternative diesel fuel made from vegetable oils or animal fats with methanol or ethanol, is a mixture of relatively stable (saturated) and oxidatively unstable (unsaturated) long-chain fatty acid alkyl esters. During storage, oxidative degradation caused by contact with air is of utm...

  4. Magnetization and Specific Absorption Rate Studies of Ball-Milled Iron Oxide Nanoparticles for Biomedicine

    Directory of Open Access Journals (Sweden)

    P. Burnham

    2013-01-01

    Full Text Available Comparative studies are presented of iron oxide nanoparticles in the 7–15 nm average diameter range ball milled in hexane in the presence of oleic acid. Transmission electron microscopy identified spherical particles of decreasing size as milling time and/or surfactant concentration increased. Micromagnetic characterization via Mössbauer spectroscopy at room temperature yielded broadened magnetic spectroscopic signatures, while macromagnetic characterization via vibrating sample magnetometry of 7-8 nm diameter particles showed largely superparamagnetic behavior at room temperature and hysteretic at 2 K. Zero-field and field-cooled magnetization curves exhibited a broad maximum at ~215 K indicating the presence of strong interparticle magnetic interactions. The specific absorption rates of ferrofluids based on these nanoparticle preparations were measured in order to test their efficacies as hyperthermia agents.

  5. [The rate of free-radical oxidation in hereditary motor-sensor neuropathies and myotonic dystrophy].

    Science.gov (United States)

    Saĭfullina, E V; Magzhanov, R V; Farkhutdinov, R R

    2012-01-01

    The rate of free-radical oxidation in the blood of patients with hereditary motor-sensor neuropathies (HMSN) and myotonic dystrophy (MD) type I was evaluated by the generation of active oxygen forms, the content of the products of lipid peroxidation and the total blood antioxidant activity. The change in the generation of active oxygen forms was characterized by the increase in the spontaneous blood chemiluminescence in patients with HMSN compared to controls. In patients with MD, the concentration of the products reacted with thiobarbituric acid was identified. In most cases, no correlations between the parameters studied and clinical/genetic characteristics were found. This fact suggests that the changes are individual and the prescription of drugs with antioxidant activity to patients with HMSN and MD should be substantiated.

  6. Kinetics and Mechanism of Oxidation of Diethyl Ether by Chloramine-T in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Y. I. Hassan

    2012-01-01

    Full Text Available The kinetics of oxidation of diethyl ether (DE with sodium N-chloro-p-toluenesulphonamide (CAT in hydrochloric acid solution has been studied at (313°K.The reaction rate show a first order dependence on [CAT] and fractional order dependence on each [DE] and [H+] .The variation of ionic strength of the medium has no significant effect on the reaction rate , addition of p-toluenesulphonamide (p-TSA affects the reaction rate marginally the rate increased with decreasing dielectric constant of the medium , the stochiometry of the reaction was found to be 1:2 and oxidation products were identified , A Michaelis – Menten type mechanism has been suggested to explain the results.The equilibrium and the decomposition constants of CAT – diethyl ether complex have been evaluated. Thermodynamic parameters were computed by studying reaction at temperatures range ( 308 – 323°K for the rate limiting step and for the observed first order constants by the linear Arrhenius plot. The mechanism proposed and the derived rate law are consistent with observed kinetics.

  7. Enhanced charge trapping in bipolar spacer oxides during low-dose-rate irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Fleetwood, D.M.; Reber, R.A. Jr.; Winokur, P.S. [Sandia National Labs., Albuquerque, NM (United States); Kosier, S.L.; Schrimpf, R.D. [Arizona Univ., Tucson, AZ (United States). Dept. of Electrical and Computer Engineering; Nowlin, R.N. [Air Force Phillips Laboratory, Albuquerque, NM (United States); Pease, R.L. [RLP Research, Inc., Albuquerque, NM (United States); DeLaus, M. [Analog Devices, Wilmington, MA (United States)

    1994-03-01

    Thermally-stimulated-current and capacitance-voltage measurements reveal enhanced hole trapping in bipolar spacer-oxide capacitors irradiated at 0 V at low dose rates. Possible mechanisms and implications for bipolar low-rate response are discussed.

  8. Graphene Oxide-Gallic Acid Nanodelivery System for Cancer Therapy

    Science.gov (United States)

    Dorniani, Dena; Saifullah, Bullo; Barahuie, Farahnaz; Arulselvan, Palanisamy; Hussein, Mohd Zobir Bin; Fakurazi, Sharida; Twyman, Lance J.

    2016-11-01

    Despite the technological advancement in the biomedical science, cancer remains a life-threatening disease. In this study, we designed an anticancer nanodelivery system using graphene oxide (GO) as nanocarrier for an active anticancer agent gallic acid (GA). The successful formation nanocomposite (GOGA) was characterized using XRD, FTIR, HRTEM, Raman, and UV/Vis spectroscopy. The release study shows that the release of GA from the designed anticancer nanocomposite (GOGA) occurs in a sustained manner in phosphate-buffered saline (PBS) solution at pH 7.4. In in vitro biological studies, normal fibroblast (3T3) and liver cancer cells (HepG2) were treated with different concentrations of GO, GOGA, and GA for 72 h. The GOGA nanocomposite showed the inhibitory effect to cancer cell growth without affecting normal cell growth. The results of this research are highly encouraging to go further for in vivo studies.

  9. Degradation of trans-ferulic acid in acidic aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton.

    Science.gov (United States)

    Flores, Nelly; Sirés, Ignasi; Garrido, José Antonio; Centellas, Francesc; Rodríguez, Rosa María; Cabot, Pere Lluís; Brillas, Enric

    2016-12-01

    Solutions of pH 3.0 containing trans-ferulic acid, a phenolic compound in olive oil mill wastewater, have been comparatively degraded by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were performed with a BDD/air-diffusion cell, where oxidizing OH was produced from water discharge at the BDD anode and/or in the solution bulk from Fenton's reaction between cathodically generated H2O2 and added catalytic Fe(2+). The substrate was very slowly removed by AO-H2O2, whereas it was very rapidly abated by EF and PEF, at similar rate in both cases, due to its fast reaction with OH in the bulk. The AO-H2O2 process yielded a slightly lower mineralization than EF, which promoted the accumulation of barely oxidizable products like Fe(III) complexes. In contrast, the fast photolysis of these latter species under irradiation with UVA light in PEF led to an almost total mineralization with 98% total organic carbon decay. The effect of current density and substrate concentration on the performance of all treatments was examined. Several solar PEF (SPEF) trials showed its viability for the treatment of wastewater containing trans-ferulic acid at larger scale. Four primary aromatic products were identified by GC-MS analysis of electrolyzed solutions, and final carboxylic acids like fumaric, acetic and oxalic were detected by ion-exclusion HPLC. A reaction sequence for trans-ferulic acid mineralization involving all the detected products is finally proposed.

  10. Properties of nanocellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative and mechanical methods.

    Science.gov (United States)

    Liu, Chao; Li, Bin; Du, Haishun; Lv, Dong; Zhang, Yuedong; Yu, Guang; Mu, Xindong; Peng, Hui

    2016-10-20

    In this work, nanocellulose was extracted from bleached corncob residue (CCR), an underutilized lignocellulose waste from furfural industry, using four different methods (i.e. sulfuric acid hydrolysis, formic acid (FA) hydrolysis, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, and pulp refining, respectively). The self-assembled structure, morphology, dimension, crystallinity, chemical structure and thermal stability of prepared nanocellulose were investigated. FA hydrolysis produced longer cellulose nanocrystals (CNCs) than the one obtained by sulfuric acid hydrolysis, and resulted in high crystallinity and thermal stability due to its preferential degradation of amorphous cellulose and lignin. The cellulose nanofibrils (CNFs) with fine and individualized structure could be isolated by TEMPO-mediated oxidation. In comparison with other nanocellulose products, the intensive pulp refining led to the CNFs with the longest length and the thickest diameter. This comparative study can help to provide an insight into the utilization of CCR as a potential source for nanocellulose production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. RATES OF HYDROUS FERRIC OXIDE CRYSTALLIZATION AND THE INFLUENCE ON COPRECIPITATED ARSENATE

    Science.gov (United States)

    Arsenate coprecipitated with hydrous ferric oxide (HFO) was stabilized against dissolution during transformation of HFO to more crystalline iron (hydr)oxides. The rate of arsenate stabilization approximately coincided with the rate of HFO transformation at pH 6 and 40 ?C. Compa...

  12. Vanillic and syringic acids from biomass burning: Behaviour during Fenton-like oxidation in atmospheric aqueous phase and in the absence of light

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Gabriela T.A.D.; Santos, Patrícia S.M., E-mail: patricia.santos@ua.pt; Duarte, Armando C.

    2016-08-05

    Highlights: • The rate of oxidation of small aromatic acids increase with the pH decrease. • With the oxidation of aromatic acids are formed new small aromatic compounds. • The initial and formed compounds are not totally degraded during the night period. • The substituents and their positions in ring affect the oxidation of aromatic acids. • The OH radical attack to vanillic and syringic acids is different in atmospheric waters. - Abstract: Biomass combustion is a threat to the environment since it emits to the atmosphere organic compounds, which may react and originate others more aggressive. This work studied the behaviours of vanillic and syringic acids, small aromatic tracers of biomass burning, during Fenton-like oxidation in aqueous phase and absence of light. For both compounds, the extent of oxidation increased with pH decrease from neutral to acid in atmospheric waters, but for vanillic acid the neutral pH was not able of promoting the oxidation. With the oxidation of both acids were formed chromophoric compounds, and the formation rate increased with the degree of electron-donator substituents in benzene ring. The initial and produced compounds were not totally degraded up to 24 h of reaction at pH 4.5, suggesting that the night period may be not sufficient for their full degradation in atmospheric waters. The major compounds formed were the 3,4-dihydroxybenzoic acid for vanillic acid, and the 1,4-dihydroxy-2,6-dimethoxybenzene for syringic acid. These findings suggest the occurrence of an ipso attack by the hydroxyl radical preferential to the methoxy and carboxyl groups of vanillic and syringic acids, respectively. It is important to highlight that for both aromatic acids the main compounds produced are also small aromatic compounds.

  13. Palladium-catalyzed air-based oxidative coupling of arylboronic acids with H-phosphine oxides leading to aryl phosphine oxides.

    Science.gov (United States)

    Fu, Tingting; Qiao, Hongwei; Peng, Zhimin; Hu, Gaobo; Wu, Xueji; Gao, Yuxing; Zhao, Yufen

    2014-05-14

    We present a novel and highly efficient methodology that allows for the construction of C-P bonds via the palladium-catalyzed air-based oxidative coupling of various commercially available arylboronic acids with easily oxidized H-phosphine oxides leading to valuable aryl phosphine oxides, particularly triarylphosphine oxides, with the use of air as the green oxidant, broad substrate applicability and good to excellent yields. The described catalytic system should be an efficient complement to the Chan-Lam type reaction and be useful in synthetic programs.

  14. Photochemical oxidation of chloride ion by ozone in acid aqueous solution.

    Science.gov (United States)

    Levanov, Alexander V; Isaykina, Oksana Ya; Amirova, Nazrin K; Antipenko, Ewald E; Lunin, Valerii V

    2015-11-01

    The experimental investigation of chloride ion oxidation under the action of ozone and ultraviolet radiation with wavelength 254 nm in the bulk of acid aqueous solution at pH 0-2 has been performed. Processes of chloride oxidation in these conditions are the same as the chemical reactions in the system O3 - OH - Cl(-)(aq). Despite its importance in the environment and for ozone-based water treatment, this reaction system has not been previously investigated in the bulk solution. The end products are chlorate ion ClO3(-) and molecular chlorine Cl2. The ions of trivalent iron have been shown to be catalysts of Cl(-) oxidation. The dependencies of the products formation rates on the concentrations of O3 and H(+) have been studied. The chemical mechanism of Cl(-) oxidation and Cl2 emission and ClO3(-) formation has been proposed. According to the mechanism, the dominant primary process of chloride oxidation represents the complex interaction with hydroxyl radical OH with the formation of Cl2(-) anion-radical intermediate. OH radical is generated on ozone photolysis in aqueous solution. The key subsequent processes are the reactions Cl2(-) + O3 → ClO + O2 + Cl(-) and ClO + H2O2 → HOCl + HO2. Until the present time, they have not been taken into consideration on mechanistic description and modelling of Cl(-) oxidation. The final products are formed via the reactions 2ClO → Cl2O2, Cl2O2 + H2O → 2H(+) + Cl(-) + ClO3(-) and HOCl + H(+) + Cl(-) ⇄ H2O + Cl2. Some portion of chloride is oxidized directly by O3 molecule with the formation of molecular chlorine in the end.

  15. Mechanisms of Oxidative Damage in Multiple Sclerosis and Neurodegenerative Diseases: Therapeutic Modulation via Fumaric Acid Esters

    Directory of Open Access Journals (Sweden)

    Ralf Gold

    2012-09-01

    Full Text Available Oxidative stress plays a crucial role in many neurodegenerative conditions such as Alzheimer’s disease, amyotrophic lateral sclerosis and Parkinson’s as well as Huntington’s disease. Inflammation and oxidative stress are also thought to promote tissue damage in multiple sclerosis (MS. Recent data point at an important role of anti-oxidative pathways for tissue protection in chronic-progressive MS, particularly involving the transcription factor nuclear factor (erythroid-derived 2-related factor 2 (Nrf2. Thus, novel therapeutics enhancing cellular resistance to free radicals could prove useful for MS treatment. Here, fumaric acid esters (FAE are a new, orally available treatment option which had already been tested in phase II/III MS trials demonstrating beneficial effects on relapse rates and magnetic resonance imaging markers. In vitro, application of dimethylfumarate (DMF leads to stabilization of Nrf2, activation of Nrf2-dependent transcriptional activity and abundant synthesis of detoxifying proteins. Furthermore, application of FAE involves direct modification of the inhibitor of Nrf2, Kelch-like ECH-associated protein 1. On cellular levels, the application of FAE enhances neuronal survival and protects astrocytes against oxidative stress. Increased levels of Nrf2 are detected in the central nervous system of DMF treated mice suffering from experimental autoimmune encephalomyelitis (EAE, an animal model of MS. In EAE, DMF ameliorates the disease course and improves preservation of myelin, axons and neurons. Finally, Nrf2 is also up-regulated in the spinal cord of autopsy specimens from untreated patients with MS, probably as part of a naturally occurring anti-oxidative response. In summary, oxidative stress and anti-oxidative pathways are important players in MS pathophysiology and constitute a promising target for future MS therapies like FAE.

  16. Fatty Acid Incubation of Myotubues from Humans with Type 2 Diabetes Leads to Enhanced Release of Beta Oxidation Products Due to Impaired Fatty Acid Oxidation

    DEFF Research Database (Denmark)

    Wensaas, Andreas J; Rustan, Arild C; Just, Marlene

    2008-01-01

    Objective: Increased availability of fatty acids is important for accumulation of intracellular lipids and development of insulin resistance in human myotubes. It is unknown whether different types of fatty acids like eicosapentaenoic acid (EPA) or tetradecylthioacetic acid (TTA) influence...... these processes. Research Design and Methods: We examined fatty acid and glucose metabolism, and gene expression in cultured human skeletal muscle cells from control and T2D individuals after four days preincubation with EPA or TTA. Results: T2D myotubes exhibited reduced formation of CO(2) from palmitic acid (PA....... EPA markedly enhanced TAG accumulation in myotubes, more pronounced in T2D cells. TAG accumulation and fatty acid oxidation were inversely correlated only after EPA preincubation, and total level of acyl-CoA was reduced. Glucose oxidation (CO(2) formation) was enhanced and lactate production decreased...

  17. Intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid under different water quality and light conditions

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Oxidation of sulfite is an important process in wet flue gas desulfurization.Using highly purified water or distilled water as a reaction medium and a transparent or an opaque intermittent reaction apparatus,the intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid was investigated under four dif-ferent conditions.The reaction order of the reagents and the activation energy were obtained.The re-sults indicate that water quality and light have no obvious effects on the reaction order and activation energy,but have an influence on the reaction rate constant.The mechanism of the intrinsic reaction is proposed.The results derived with this mechanism are in good agreement with the experimental re-sults.

  18. Intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid under different water quality and light conditions

    Institute of Scientific and Technical Information of China (English)

    WANG LiDong; ZHAO Yi; LI QiangWei; CHEN ZhouYan; LIU SongTao; MA YongLiang; HAO JiMing

    2009-01-01

    Oxidation of sulfite is an important process in wet flue gas desulfurization. Using highly purified water or distilled water as a reaction medium and a transparent or an opaque intermittent reaction apparatus, the intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid was investigated under four dif-ferent conditions. The reaction order of the reagents and the activation energy were obtained. The re-sults indicate that water quality and light have no obvious effects on the reaction order and activation energy, but have an influence on the reaction rate constant. The mechanism of the intrinsic reaction is proposed. The results derived with this mechanism are in good agreement with the experimental re-sults.

  19. Oxidation of indole-3-acetic acid to oxindole-3-acetic acid by an enzyme preparation from Zea mays

    Science.gov (United States)

    Reinecke, D. M.; Bandurski, R. S.

    1988-01-01

    Indole-3-acetic acid is oxidized to oxindole-3-acetic acid by Zea mays tissue extracts. Shoot, root, and endosperm tissues have enzyme activities of 1 to 10 picomoles per hour per milligram protein. The enzyme is heat labile, is soluble, and requires oxygen for activity. Cofactors of mixed function oxygenase, peroxidase, and intermolecular dioxygenase are not stimulatory to enzymic activity. A heat-stable, detergent-extractable component from corn enhances enzyme activity 6- to 10-fold. This is the first demonstration of the in vitro enzymic oxidation of indole-3-acetic acid to oxindole-3-acetic acid in higher plants.

  20. Oxidation of indole-3-acetic acid to oxindole-3-acetic acid by an enzyme preparation from Zea mays

    Science.gov (United States)

    Reinecke, D. M.; Bandurski, R. S.

    1988-01-01

    Indole-3-acetic acid is oxidized to oxindole-3-acetic acid by Zea mays tissue extracts. Shoot, root, and endosperm tissues have enzyme activities of 1 to 10 picomoles per hour per milligram protein. The enzyme is heat labile, is soluble, and requires oxygen for activity. Cofactors of mixed function oxygenase, peroxidase, and intermolecular dioxygenase are not stimulatory to enzymic activity. A heat-stable, detergent-extractable component from corn enhances enzyme activity 6- to 10-fold. This is the first demonstration of the in vitro enzymic oxidation of indole-3-acetic acid to oxindole-3-acetic acid in higher plants.

  1. Solar thermal charging properties of graphene oxide embedded myristic acid composites phase change material

    Science.gov (United States)

    Yadav, Apurv; Barman, Bidyut; Kumar, Vivek; Kardam, Abhishek; Narayanan, S. Shankara; Verma, Abhishek; Madhwal, Devinder; Shukla, Prashant; Jain, V. K.

    2016-05-01

    The present paper reports the heat transfer characteristics of graphene oxide (GO) embedded myristic acid based phase change material (GO-PCM) composites. By varying concentrations of GO (0.1-0.5 wt%), different GO-PCM composites were preapred. Two different experimental setups were used for investigating the heat transfer characteristics of the prepared GO-PCM composites during the melting and solidification processes: (i) conventional heating and (ii) solar illumination. The experimental observations indicated a higher heat transfer rate in the GO-PCM composites as compared to pristine PCM for both experimental setups. From the experimental results of conventional heating setup, it was observed that the melting and solidification rate for GO-PCM composites, at 0.5 wt% of GO, increased by 48% and 70%, respectively in comparison to pristine PCM. The experimental results using solar illumination setup demonstrated an ultrafast heating rate for GO-PCM composites than the conventional heating based approach.

  2. Oxidation of hepatic carnitine palmitoyl transferase-I (CPT-I impairs fatty acid beta-oxidation in rats fed a methionine-choline deficient diet.

    Directory of Open Access Journals (Sweden)

    Gaetano Serviddio

    Full Text Available There is growing evidence that mitochondrial dysfunction, and more specifically fatty acid β-oxidation impairment, is involved in the pathophysiology of non-alcoholic steatohepatitis (NASH. The goal of the present study was to achieve more understanding on the modification/s of carnitinepalmitoyltransferase-I (CPT-I, the rate-limiting enzyme of the mitochondrial fatty acid β-oxidation, during steatohepatitis. A high fat/methionine-choline deficient (MCD diet, administered for 4 weeks, was used to induce NASH in rats.We demonstrated that CPT-I activity decreased, to the same extent, both in isolated liver mitochondria and in digitonin-permeabilized hepatocytes from MCD-diet fed rats.At the same time, the rate of total fatty acid oxidation to CO(2 and ketone bodies, measured in isolated hepatocytes, was significantly lowered in treated animals when compared to controls. Finally, an increase in CPT-I mRNA abundance and protein content, together with a high level of CPT-I protein oxidation was observed in treated rats. A posttranslational modification of rat CPT-I during steatohepatitis has been here discussed.

  3. Kinetics and mechanism of OsOsub(4) catalyzed oxidation of chalcones by Cesub(4) in aqueous acetic sulfuric acid media

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasulu, P.V.; Adinarayana, M.; Sethuram, B.; Rao, T.N. (Osmania Univ., Hyderabad (India). Dept. of Chemistry)

    1985-01-01

    Kinetics of OsOsub(4) catalyzed oxidation of chalcones by Cesup(4+) was studied in aqueous acetic-sulfuric acid medium in the temperature range 313 to 338 K. The order in oxidant is zero while the order with respect to substrate and catalyst are each fractional. The rate of the reaction decreased with increase in percentage of acetic acid while (Hsup(+)) had practically no effect on the rate. The rates of various substituted chalcones are given. A mechanism in which formation of a cyclic ester between chalcone and OsOsub(4) in a fast step followed by its decomposition in a rate-determining step is envisaged.

  4. Integrating nitric oxide into salicylic acid and jasmonic acid/ethylene plant defense pathways

    DEFF Research Database (Denmark)

    Mur, Luis A J; Prats, Elena; Pierre, Sandra

    2013-01-01

    Plant defence against pests and pathogens is known to be conferred by either salicylic acid (SA) or jasmonic acid (JA)/ethylene (ET) pathways, depending on infection or herbivore-grazing strategy. It is well attested that SA and JA/ET pathways are mutually antagonistic allowing defence responses...... to be tailored to particular biotic stresses. Nitric oxide (NO) has emerged as a major signal influencing resistance mediated by both signalling pathways but no attempt has been made to integrate NO into established SA/JA/ET interactions. NO has been shown to act as an inducer or suppressor of signalling along...... the cytoplasm to reduce TGA activation. In JA biosynthesis, NO will initiate the expression of JA biosynthetic enzymes, presumably to over-come any antagonistic effects of SA on JA-mediated transcription. NO will also initiate the expression of ET biosynthetic genes but a suppressive role is also observed...

  5. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event.

    Science.gov (United States)

    Konhauser, Kurt O; Lalonde, Stefan V; Planavsky, Noah J; Pecoits, Ernesto; Lyons, Timothy W; Mojzsis, Stephen J; Rouxel, Olivier J; Barley, Mark E; Rosìere, Carlos; Fralick, Phillip W; Kump, Lee R; Bekker, Andrey

    2011-10-19

    The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.

  6. Protein oxidation: an overview of metabolism of sulphur containing amino acid, cysteine.

    Science.gov (United States)

    Ahmad, Saheem; Khan, Hamda; Shahab, Uzma; Rehman, Shahnawaz; Rafi, Zeeshan; Khan, Mohd Yasir; Ansari, Ahsanullah; Siddiqui, Zeba; Ashraf, Jalaluddin Mohammad; Abdullah, Saleh M S; Habib, Safia; Uddin, Moin

    2017-01-01

    The available data suggest that among cellular constituents, proteins are the major target for oxidation primarily because of their quantity and high rate of interactions with ROS. Proteins are susceptible to ROS modifications of amino acid side chains which alter protein structure. Among the amino acids, Cysteine (Cys) is more prone to oxidation by ROS because of its high nucleophilic property. The reactivity of Cys with ROS is due to the presence of thiol group. In the oxidised form, Cys forms disulfide bond, which are primary covalent cross-link found in proteins, and which stabilize the native conformation of a protein. Indirect evidence suggests that thiol modifications by ROS may be involved in neurodegenerative disorders, but the significance and precise extent of the contributions are poorly understood. Here, we review the role of oxidized Cys in different pathological consequences and its biochemistry may increase the research in the discovery of new therapies. The purpose of this review is to re-examine the role and biochemistry of oxidised Cys residues.

  7. Long-chain fatty acid combustion rate is associated with unique metabolite profiles in skeletal muscle mitochondria.

    Directory of Open Access Journals (Sweden)

    Erin L Seifert

    Full Text Available BACKGROUND/AIM: Incomplete or limited long-chain fatty acid (LCFA combustion in skeletal muscle has been associated with insulin resistance. Signals that are responsive to shifts in LCFA beta-oxidation rate or degree of intramitochondrial catabolism are hypothesized to regulate second messenger systems downstream of the insulin receptor. Recent evidence supports a causal link between mitochondrial LCFA combustion in skeletal muscle and insulin resistance. We have used unbiased metabolite profiling of mouse muscle mitochondria with the aim of identifying candidate metabolites within or effluxed from mitochondria and that are shifted with LCFA combustion rate. METHODOLOGY/PRINCIPAL FINDINGS: Large-scale unbiased metabolomics analysis was performed using GC/TOF-MS on buffer and mitochondrial matrix fractions obtained prior to and after 20 min of palmitate catabolism (n = 7 mice/condition. Three palmitate concentrations (2, 9 and 19 microM; corresponding to low, intermediate and high oxidation rates and 9 microM palmitate plus tricarboxylic acid (TCA cycle and electron transport chain inhibitors were each tested and compared to zero palmitate control incubations. Paired comparisons of the 0 and 20 min samples were made by Student's t-test. False discovery rate were estimated and Type I error rates assigned. Major metabolite groups were organic acids, amines and amino acids, free fatty acids and sugar phosphates. Palmitate oxidation was associated with unique profiles of metabolites, a subset of which correlated to palmitate oxidation rate. In particular, palmitate oxidation rate was associated with distinct changes in the levels of TCA cycle intermediates within and effluxed from mitochondria. CONCLUSIONS/SIGNIFICANCE: This proof-of-principle study establishes that large-scale metabolomics methods can be applied to organelle-level models to discover metabolite patterns reflective of LCFA combustion, which may lead to identification of molecules

  8. 40 CFR 721.3680 - Ethylene oxide adduct of fatty acid ester with pentaerythritol.

    Science.gov (United States)

    2010-07-01

    ... ester with pentaerythritol. 721.3680 Section 721.3680 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3680 Ethylene oxide adduct of fatty acid ester with... identified generically as ethylene oxide adduct of fatty acid ester with pentaerythritol (PMN P-91-442)...

  9. Study of Oxidation of Glutathione Treated with Hypochlorous Acid by Capillary Electrophoresis

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Capillary electrophoresis (CE) method was developed for the separation and quantification of reduced glutathione (GSH), oxidized glutathione (GSSG) and glutathione sulphonic acid (GSO3H). Baseline separation was obtained within five minutes. The effects of reaction time and molar ratio of hypochlorous acid (HOCI) to GSH on the oxidation of GSH were investigated.

  10. Neuropsychological Outcomes in Fatty Acid Oxidation Disorders: 85 Cases Detected by Newborn Screening

    Science.gov (United States)

    Waisbren, Susan E.; Landau, Yuval; Wilson, Jenna; Vockley, Jerry

    2013-01-01

    Mitochondrial fatty acid oxidation disorders include conditions in which the transport of activated acyl-Coenzyme A (CoA) into the mitochondria or utilization of these substrates is disrupted or blocked. This results in a deficit in the conversion of fat into energy. Most patients with fatty acid oxidation defects are now identified through…

  11. Hepatic fatty acid oxidation : activity, localization and function of some enzymes involved

    NARCIS (Netherlands)

    A. van Tol (Arie)

    1971-01-01

    textabstractFatty acid oxidation is an important pathway for energy production in mammals and birds. In animal tissues the enzymes of fatty acid oxidation are located in the mitochondrion. Recent reports suggest that this is not the case in Castor bean endosperm. In this tissue the enzymes of

  12. Omega-3 Polyunsaturated Fatty Acids and Heart Rate Variability

    Directory of Open Access Journals (Sweden)

    Jeppe Hagstrup Christensen

    2011-11-01

    Full Text Available Omega-3 polyunsaturated fatty acids (PUFA may modulate autonomic control of the heart because omega-3 PUFA is abundant in the brain and other nervous tissue as well as in cardiac tissue. This might partly explain why omega-3 PUFA offer some protection against sudden cardiac death (SCD. The autonomic nervous system is involved in the pathogenesis of SCD. Heart rate variability (HRV can be used as a non-invasive marker of cardiac autonomic control and a low HRV is a predictor for SCD and arrhythmic events. Studies on HRV and omega-3 PUFA have been performed in several populations such as patients with ischemic heart disease, patients with diabetes mellitus, patients with chronic renal failure, and in healthy subjects as well as in children.. The studies have demonstrated a positive association between cellular content of omega-3 PUFA and HRV and supplementation with omega-3 PUFA seems to increase HRV which could be a possible explanation for decreased risk of arrhythmic events and SCD sometimes observed after omega-3 PUFA supplementation. However, the results are not consistent and further research is needed

  13. [Evaluation on contribution rate of each component total salvianolic acids and characterization of apparent oil/water partition coefficient].

    Science.gov (United States)

    Yan, Hong-mei; Chen, Xiao-yun; Xia, Hai-jian; Liu, Dan; Jia, Xiao-bin; Zhang, Zhen-hai

    2015-02-01

    The difference between three representative components of total salvianolic acids in pharmacodynamic activity were compared by three different pharmacological experiments: HUVECs oxidative damage experiment, 4 items of blood coagulation in vitro experiment in rabbits and experimental myocardial ischemia in rats. And the effects of contribution rate of each component were calculated by multi index comprehensive evaluation method based on CRITIC weights. The contribution rates of salvianolic acid B, rosmarinic acid and Danshensu were 28.85%, 30.11%, 41.04%. Apparent oil/water partition coefficient of each representative components of total salvianolic acids in n-octyl alcohol-buffer was tested and the total salvianolic acid components were characterized based on a combination of the approach of self-defined weighting coefficient with effects of contribution rate. Apparent oil/water partition coefficient of total salvianolic acids was 0.32, 1.06, 0.89, 0.98, 0.90, 0.13, 0.02, 0.20, 0.56 when in octanol-water/pH 1.2 dilute hydrochloric acid solution/ pH 2.0, 2.5, 5.0, 5.8, 6.8, 7.4, 7.8 phosphate buffer solution. It provides a certain reference for the characterization of components.

  14. Oxygen transfer rates and requirements in oxidative biocatalysis

    DEFF Research Database (Denmark)

    Pedersen, Asbjørn Toftgaard; Rehn, Gustav; Woodley, John M.

    2015-01-01

    Biocatalytic oxidation reactions offer several important benefits such as regio- and stereoselectivity, avoiding the use of toxic metal based catalysts and replacing oxidizing reagents by allowing the use of oxygen. In this contribution the oxygen requirements are analysed for different process s...... without oxygen supply being limiting. Also, membrane contactors can provide a feasible oxygen supply method when bubble-less aeration is desired. However, in order to support high productivity the oxygen flux using air may be insufficient, thus requiring the use of oxygen....... scenarios, considering different biocatalyst formats and variation of the desired productivity. Also, the applicability of two different oxygen supply methods (bubbling and membrane aeration) is considered. The results indicate that growing cells could be used to reach productivities up to 3.5 g L-1h-1...

  15. Degradation of trans-ferulic acid in acidic aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton

    Energy Technology Data Exchange (ETDEWEB)

    Flores, Nelly; Sirés, Ignasi; Garrido, José Antonio; Centellas, Francesc; Rodríguez, Rosa María; Cabot, Pere Lluís; Brillas, Enric, E-mail: brillas@ub.edu

    2016-12-05

    Highlights: • trans-Ferulic acid degradation by EAOPs using a stirred BDD/air-diffusion cell. • Slow substrate abatement and poor mineralization by AO-H{sub 2}O{sub 2}. • 98% Mineralization by PEF, but with rapid and similar substrate decay than by EF. • Quicker degradation by SPEF due to the more potent photolytic action of sunlight. • Reaction pathway with four primary aromatic products and three final carboxylic acids. - Abstract: Solutions of pH 3.0 containing trans-ferulic acid, a phenolic compound in olive oil mill wastewater, have been comparatively degraded by anodic oxidation with electrogenerated H{sub 2}O{sub 2} (AO-H{sub 2}O{sub 2}), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were performed with a BDD/air-diffusion cell, where oxidizing ·OH was produced from water discharge at the BDD anode and/or in the solution bulk from Fenton’s reaction between cathodically generated H{sub 2}O{sub 2} and added catalytic Fe{sup 2+}. The substrate was very slowly removed by AO-H{sub 2}O{sub 2}, whereas it was very rapidly abated by EF and PEF, at similar rate in both cases, due to its fast reaction with ·OH in the bulk. The AO-H{sub 2}O{sub 2} process yielded a slightly lower mineralization than EF, which promoted the accumulation of barely oxidizable products like Fe(III) complexes. In contrast, the fast photolysis of these latter species under irradiation with UVA light in PEF led to an almost total mineralization with 98% total organic carbon decay. The effect of current density and substrate concentration on the performance of all treatments was examined. Several solar PEF (SPEF) trials showed its viability for the treatment of wastewater containing trans-ferulic acid at larger scale. Four primary aromatic products were identified by GC–MS analysis of electrolyzed solutions, and final carboxylic acids like fumaric, acetic and oxalic were detected by ion-exclusion HPLC. A reaction sequence for trans-ferulic acid mineralization

  16. Wet oxidation of glycerol into fine organic acids: catalyst selection and kinetic evaluation

    Directory of Open Access Journals (Sweden)

    J. E. N. Brainer

    2014-12-01

    Full Text Available The liquid phase oxidation of glycerol was performed producing fine organic acids. Catalysts based on Pt, Pd and Bi supported on activated carbon were employed to perform the conversion of glycerol into organic acids at 313 K, 323 K and 333 K, under atmospheric pressure (1.0 bar, in a mechanically agitated slurry reactor (MASR. The experimental results indicated glycerol conversions of 98% with production of glyceric, tartronic and glycolic acids, and dihydroxyacetone. A yield of glyceric acid of 69.8%, and a selectivity of this compound of 70.6% were reached after 4 h of operation. Surface mechanisms were proposed and rate equations were formulated to represent the kinetic behavior of the process. Selective formation of glyceric acid was observed, and the kinetic parameter values indicated the lowest activation energy (38.5 kJ/mol for its production reaction step, and the highest value of the adsorption equilibrium constant of the reactant glycerol (10-4 dm³/mol.

  17. Water oxidation catalysis with nonheme iron complexes under acidic and basic conditions: homogeneous or heterogeneous?

    Science.gov (United States)

    Hong, Dachao; Mandal, Sukanta; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

    2013-08-19

    Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions.

  18. Electrophoretic deposition and electrochemical behavior of novel graphene oxide-hyaluronic acid-hydroxyapatite nanocomposite coatings

    Science.gov (United States)

    Li, Ming; Liu, Qian; Jia, Zhaojun; Xu, Xuchen; Shi, Yuying; Cheng, Yan; Zheng, Yufeng; Xi, Tingfei; Wei, Shicheng

    2013-11-01

    Novel ternary graphene oxide-hyaluronic acid-hydroxyapatite (GO-HY-HA) nanocomposite coatings were prepared on Ti substrate using anodic electrophoretic deposition (EPD). Hyaluronic acid was employed as charging additive and dispersion agent during EPD. The kinetics and mechanism of the deposition, and the microstructure of the coated samples were investigated using scanning electron microscopy, X-ray diffraction, Raman spectrum, thermo-gravimetric analysis, and microscopic Fourier transform infrared analysis. The results showed that the addition of GO sheets into the HY-HA suspensions could increase the deposition rate and inhibit cracks creation and propagation in the coatings. The corrosion resistant of the resulting samples were evaluated using potentiodynamic polarization method in simulated body fluid, and the GO-HY-HA coatings could effectively improve the anti-corrosion property of the Ti substrate.

  19. Enzymology of the branched-chain amino acid oxidation disorders: the valine pathway.

    Science.gov (United States)

    Wanders, Ronald J A; Duran, Marinus; Loupatty, Ference J

    2012-01-01

    Valine is one of the three branched-chain amino acids which undergoes oxidation within mitochondria. In this paper, we describe the current state of knowledge with respect to the enzymology of the valine oxidation pathway and the different disorders affecting oxidation.

  20. Reduction reaction analysis of nanoparticle copper oxide for copper direct bonding using formic acid

    Science.gov (United States)

    Fujino, Masahisa; Akaike, Masatake; Matsuoka, Naoya; Suga, Tadatomo

    2017-04-01

    Copper direct bonding is required for electronics devices, especially power devices, and copper direct bonding using formic acid is expected to lower the bonding temperature. In this research, we analyzed the reduction reaction of copper oxide using formic acid with a Pt catalyst by electron spin resonance analysis and thermal gravimetry analysis. It was found that formic acid was decomposed and radicals were generated under 200 °C. The amount of radicals generated was increased by adding the Pt catalyst. Because of these radicals, both copper(I) oxide and copper(II) oxide start to be decomposed below 200 °C, and the reduction of copper oxide is accelerated by reactants such as H2 and CO from the decomposition of formic acid above 200 °C. The Pt catalyst also accelerates the reaction of copper oxide reduction. Herewith, it is considered that the copper surface can be controlled more precisely by using formic acid to induce direct bonding.

  1. Lysine requirements of pre-lay broiler breeder pullets: determination by indicator amino acid oxidation.

    Science.gov (United States)

    Coleman, Russell A; Bertolo, Robert F; Moehn, Soenke; Leslie, Michael A; Ball, Ronald O; Korver, Doug R

    2003-09-01

    The indicator amino acid oxidation (IAAO) method allows the determination of amino acid requirements under conditions of low growth rate as found in pre-laying broiler breeder pullets. Cobb 500 breeder pullets (20 wk old; 2290 +/- 280 g, n = 4) were adapted (6 d) to a pelleted, purified control diet containing all nutrients at >or=110% of NRC recommendations. After recovery from surgery for implantation of a jugular catheter, each bird was fed, in random order, test diets containing one of nine levels of lysine (0.48, 0.96, 1.92, 2.88, 3.84, 4.80, 7.68, 9.60 and 14.40 g/kg of diet). Indicator oxidation was determined during 4-h primed (74 kBq/kg body), constant infusions (44 kBq x h(-1). kg body(-1)) of L-[1-(14)C]phenylalanine. Using the breakpoint of a one-slope broken-line model, the lysine requirement was determined to be 4.88 +/- 0.96 g/kg of diet or 366 +/- 72 mg x hen(-1) x d(-1) with an upper 95% CI of 6.40 g/kg of diet or 480 mg x hen(-1) x d(-1). IAAO allows determination of individual bird amino acid requirements for specific ages and types of birds over short periods of time and enables more accurate broiler breeder pullet diet formulation.

  2. Structural effects of electrochemical oxidation of formic acid on single crystal electrodes of palladium.

    Science.gov (United States)

    Hoshi, Nagahiro; Kida, Kaori; Nakamura, Masashi; Nakada, Miou; Osada, Kazuhito

    2006-06-29

    Structural effects on the rates of formic acid oxidation have been studied on Pd(111), Pd(100), Pd(110), and Pd(S)-[n(100) x (111)] (n = 2-9) electrodes in 0.1 M HClO4 containing 0.1 M formic acid with use of voltammetry. On the low index planes of Pd, the maximum current density of formic acid oxidation (jP) increases in the positive scan as follows: Pd(110) Pd(111) Pd(100). This order differs from that on the low index planes of Pt: Pt(111) Pd(S)-[n(100) x (111)] electrodes with terrace atomic rows n > or = 3 have almost the same jP as Pd(100), except Pd(911) n = 5. The value of jP on Pd(911) n = 5 is 20% higher than those of the other surfaces. Pd(311) n = 2, of which the first layer is composed of only step atoms, has the lowest jP in the Pd(S)-[n(100) x (111)] series. The adsorption geometry of the reaction intermediate (formate ion) is optimized by using density functional theory.

  3. Enhancing the crystalline degree of carbon nanotubes by acid treatment, air oxidization and heat treatment

    Institute of Scientific and Technical Information of China (English)

    Chensha Li; Baoyou Zhang; Xingjuan Chen; Xiaoqing Hu; Ji Liang

    2005-01-01

    Three approaches of treating carbon nanotubes (CNTs) including acid treatment, air oxidization and heat treatment at high temperature were studied to enhance the crystalline degree of carbon nanotubes. High temperature heat-treatment elevates the crystalline degree of carbon nanotubes. Acid treatment removes parts of amorphous carbonaceous matter through its oxidization effect.Air oxidization disperses carbon nanotubes and amorphous carbonaceous matter. The treatment of combining acid treatment with heat-treatment further elevates the crystalline degree of carbon nanotubes comparing with acid treatment or heat-treatment. The combination of the three treatments creates the thorough effects of enhancing the crystalline degree of carbon nanotubes.

  4. Manoyl oxide alpha-arabinopyranoside and grindelic acid diterpenoids from Grindelia integrifolia.

    Science.gov (United States)

    Ahmed, A A; Mahmoud, A A; Ahmed, U M; El-Bassuony, A A; Abd El-Razk, M H; Pare, P W; Karchesy, J

    2001-10-01

    Two new manoyl oxide-alpha-arabinopyranoside diterpenoids, 15-hydroxy-13-epi-manoyl oxide-14-O-alpha-L-arabinopyranoside (tarapacol-14-O-alpha-L-arabinopyranoside) (1) and 15-acetoxy-13-epi-manoyl oxide-14-O-alpha-L-arabinopyranoside (tarapacol-15-acetate-14-O-alpha-L-arabinopyranoside) (2), as well as a new grindelic acid derivative, 19-hydroxygrindelic acid (3), together with five known diterpenoids (tarapacol, tarapacanol A, grindelic acid, methyl grindeloate, 3beta-hydroxygrindelic acid, 4) were isolated from the aerial parts of Grindelia integrifolia. The structures of 1-3 were elucidated by spectral data analysis.

  5. Humic acids as electron acceptors for anaerobic microbial oxidation of vinyl chloride and dichloroethene

    Science.gov (United States)

    Bradley, P.M.; Chapelle, F.H.; Lovley, D.R.

    1998-01-01

    Anaerobic oxidation of [1,2-14C]vinyl chloride and [1,2- 14C]dichloroethene to 14CO2 under humic acid-reducing conditions was demonstrated. The results indicate that waterborne contaminants can be oxidized by using humic acid compounds as electron acceptors and suggest that natural aquatic systems have a much larger capacity for contaminant oxidation than previously thought.

  6. Study of wet etching thin films of indium tin oxide in oxalic acid by monitoring the resistance

    Energy Technology Data Exchange (ETDEWEB)

    Mammana, Suelene S., E-mail: ssmammana@abinfo.com.br [Brazilian Association for Informatics - ABINFO, Rua Deusdete Martins Gomes 163, CEP 13084-723, Campinas, SP (Brazil); Greatti, Alessandra; Luiz, Francis H.; Costa, Francisca I. da; Mammana, Alaide P. [Brazilian Association for Informatics - ABINFO, Rua Deusdete Martins Gomes 163, CEP 13084-723, Campinas, SP (Brazil); Calligaris, Guilherme A.; Cardoso, Lisandro P. [Institute of Physics Gleb Wataghin, State University of Campinas-UNICAMP, CEP 13083-859, Campinas, SP (Brazil); Mammana, Carlos I.Z.; Engelsen, Daniel den [Brazilian Association for Informatics - ABINFO, Rua Deusdete Martins Gomes 163, CEP 13084-723, Campinas, SP (Brazil)

    2014-09-30

    We describe a study on wet etching of thin films of indium tin oxide (ITO) using a simple method by monitoring the resistance of the thin film in aqueous solutions of oxalic acid and hydrochloric acid. Generally three different regimes can be distinguished during etching ITO in acids: (1) initial etching, which is slow, (2) a fast etching phase and (3) slow etching stage at the end. These regimes are explained in terms of a porosity–roughness model. This porosity model has been confirmed largely by X-ray reflection measurements at grazing incidence, roughness measurements and scanning electron microscopy (SEM). A reliable method for monitoring the resistance during etching has been developed. This method is based on a 2-strips measuring jig with a very low series contact resistance. The activation energy of the etch rate of ITO films was found to be 80 ± 5 kJ/mol for oxalic acid and 56 ± 5 kJ/mol for HCl. SEM analyses in the final stage of the etching process indicate an enrichment of Sn in the residual film material. These observations are explained in terms of preferential etching of In{sub 2}O{sub 3}. X-ray analyses showed that the density of the ITO film decreased by etching. By adding ferric chloride to the oxalic acid solution we could accelerate the etch rate substantially. - Highlights: • Etching of indium tin oxide thin films by monitoring the resistance. • Oxalic acid has 2–3 times lower etch rate than concentrated HCl. • The etch rate in oxalic acid can be accelerated substantially by adding FeCl{sub 3}. • The proposed etching model for indium tin oxide was confirmed by X-ray analysis and scanning electron microscopy. • Energy Dispersive X-ray Spectroscopy analyses showed preferential etching of In{sub 2}O{sub 3}, enriching the film with SnO{sub 2}.

  7. Kinetics of phosphotungstic acid catalyzed oxidation of propan-1,3-diol and butan-1,4-diol by N-chlorosaccharin

    Directory of Open Access Journals (Sweden)

    Sanjay Kumar Singh

    2011-09-01

    Full Text Available The kinetic studies of N-chlorosaccharin (NCSA oxidation of propan-1,3-diol and butan-1,4-diol have been reported in presence of phophotungstic acid and in aqueous acetic acid medium. The reactions follow first-order in NCSA and one to zero order with respect to substrate and phosphotungstic acid. Increase in the concentration of added perchloric acid increases the rate of oxidation. A negative effect on the oxidation rate is observed for solvent whereas the ionic strength does not influence the rate of reaction. Addition of the reaction product, saccharin, exhibited retarding effect. Various activation parameters have been evaluated. The products of the reactions were identified as the corresponding aldehydes. A suitable scheme of mechanism consistent with the experimental results has been proposed.

  8. Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

    DEFF Research Database (Denmark)

    Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

    2001-01-01

    the reaction stoichiometry and partitioning of gases between the solution and the gas phase. Pyrite oxidation with concurrent calcite dissolution was found to be consistent with the experimental data while organic carbon oxidation was not. The reaction involves changes in the total volume of the gas phase...

  9. Purification of carbon nanotubes from cathode deposit by means of different oxidation rates

    Energy Technology Data Exchange (ETDEWEB)

    Ikazaki, Fumikazu; Uchida, Kunio; Ohshima, Satoshi; Kuriki, Yasunori [National Inst. of Materials and Chemical Research, Ibaraki (Japan)] [and others

    1996-10-01

    Two purification methods of nanotubes from a cathode deposit by an arc plasma were conducted by means of different oxidation rates of various graphites. One was chemical and the other physical method. Both could purify nanotubes at their optimum conditions. In the former, the catalytic oxidation was used of graphitic materials by copper. Copper supported graphite was prepared by the intercalation of copper chloride and by the reduction to metal copper. The catalytic oxidation decomposed the graphite at 773 K. The temperature was 200 K lower than the oxidation temperature of graphite, which enabled purification. In the latter, dispersion, comminution and filtration of a cathode deposit in ethanol were used to separate coarse graphite. The rate of weight loss by oxidation increased with the decrease of size of the graphite. Nanotubes were more slowly oxidized from the edges than the graphite of the same size. This could purify nanotubes.

  10. Purification of carbon nanotubes from cathode deposit by means of different oxidation rates

    Energy Technology Data Exchange (ETDEWEB)

    Ikazaki, F.; Uchida, K.; Ohshima, S. [National Institute of Materials and Chemical Research, Tsukuba, Ibaraki (Japan)] [and others

    1996-12-31

    Two purification methods of nanotubes from a cathode deposit by an arc plasma were conducted by means of different oxidation rates of various graphites. One was chemical and the other physical method. Both could purify nanotubes at their optimum conditions. In the former, the catalytic oxidation was used of graphite materials by copper. Copper supported graphite was prepared by the intercalation of copper chloride and by the reduction to metal copper. The catalytic oxidation decomposed the graphite at 773 K and less. The temperature was significantly lower than the oxidation temperature former reported of graphite, which enabled purification. In the latter, dispersion, comminution and filtration of a cathode deposit in ethanol were used to separate coarse graphite. The rate of weight loss by oxidation increased with the decrease of size of the graphite. Nanotubes were more slowly oxidized from the edges than the graphite of the same size. This could purify nanotubes.

  11. Low Phytic Acid Barley Responses to Phosphorus Rates

    Science.gov (United States)

    Low phytic acid (LPA) barley (Hordeum vulgare L.) cultivars partition phosphorus in seed tissue differently than conventional barley cultivars through a reduction in seed phytic acid (myo-inositol-1,2,3,4,5,6-hexkisphosphate) coupled with an increase in inorganic phosphorus. The response of the LPA...

  12. Hepatic oleate regulates adipose tissue lipogenesis and fatty acid oxidation.

    Science.gov (United States)

    Burhans, Maggie S; Flowers, Matthew T; Harrington, Kristin R; Bond, Laura M; Guo, Chang-An; Anderson, Rozalyn M; Ntambi, James M

    2015-02-01

    Hepatic steatosis is associated with detrimental metabolic phenotypes including enhanced risk for diabetes. Stearoyl-CoA desaturases (SCDs) catalyze the synthesis of MUFAs. In mice, genetic ablation of SCDs reduces hepatic de novo lipogenesis (DNL) and protects against diet-induced hepatic steatosis and adiposity. To understand the mechanism by which hepatic MUFA production influences adipose tissue stores, we created two liver-specific transgenic mouse models in the SCD1 knockout that express either human SCD5 or mouse SCD3, that synthesize oleate and palmitoleate, respectively. We demonstrate that hepatic de novo synthesized oleate, but not palmitoleate, stimulate hepatic lipid accumulation and adiposity, reversing the protective effect of the global SCD1 knockout under lipogenic conditions. Unexpectedly, the accumulation of hepatic lipid occurred without induction of the hepatic DNL program. Changes in hepatic lipid composition were reflected in plasma and in adipose tissue. Importantly, endogenously synthesized hepatic oleate was associated with suppressed DNL and fatty acid oxidation in white adipose tissue. Regression analysis revealed a strong correlation between adipose tissue lipid fuel utilization and hepatic and adipose tissue lipid storage. These data suggest an extrahepatic mechanism where endogenous hepatic oleate regulates lipid homeostasis in adipose tissues.

  13. Modeling Low-Dose-Rate Effects in Irradiated Bipolar-Base Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Cirba, C.R.; Fleetwood, D.M.; Graves, R.J.; Michez, A.; Milanowski, R.J.; Saigne, F.; Schrimpf, R.D.; Witczak, S.C.

    1998-10-26

    A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in bipolar junction transistors. Multiple-trapping simulations show that space charge limited transport is partially responsible for low-dose-rate enhancement. At low dose rates, more holes are trapped near the silicon-oxide interface than at high dose rates, resulting in larger midgap voltage shifts at lower dose rates. The additional trapped charge near the interface may cause an exponential increase in excess base current, and a resultant decrease in current gain for some NPN bipolar technologies.

  14. The omega-hydroxlyation of lauric acid: oxidation of 12-hydroxlauric acid to dodecanedioic acid by a purified recombinant fusion protein containing P450 4A1 and NADPH-P450 reductase.

    Science.gov (United States)

    Shet, M s; Fisher, C W; Holmans, P L; Estabrook, R W

    1996-06-01

    The recombinant fusion protein rF450[mRat4Al/mRatOR]L1, containing the heme domain of P450 4A1 and the flavin domains of NADPH-P450 reductase, when incubated with dilaurylphosphatidylcholine (DLPC), Chaps, cytochrome b5, and a 20-fold excess of purified NADPH-P450 reductase, catalyzes the omega- oxidation of lauric acid at a rate of about 300 nmol/min/nmol P450. This is the first report of a mammalian P450 enzyme with such a high turnover number. The resultant 12-hydroxydodecanoic acid [12-hydroxylauric acid (12-OH LA)] is further oxidized by the P450 oxygenase reaction to dodecanedioic acid (decane-1,10-dicarboxylic acid) via 12,12-dihydroxydodecanoic acid. Spectral binding studies show that 12-OH LA inhibits the binding of lauric acid to the active site of P450 with a Ki of about 1.9 microM. The construction and expression of recombinant P450 4A1 containing a six-member polyhistidine domain at the carboxy-terminus of the protein is described. Reconstitution experiments with this purified recombinant P450 4A1, DLPC, Chaps, b5, and purified NADPH-P450 reductase show results similar to those obtained with the purified fusion protein, albeit at lower turnover rates. The requirement for normal-phase HPLC in resolving the metabolites formed during lauric acid metabolism is demonstrated.

  15. Imbalance of heterologous protein folding and disulfide bond formation rates yields runaway oxidative stress

    Directory of Open Access Journals (Sweden)

    Tyo Keith EJ

    2012-03-01

    Full Text Available Abstract Background The protein secretory pathway must process a wide assortment of native proteins for eukaryotic cells to function. As well, recombinant protein secretion is used extensively to produce many biologics and industrial enzymes. Therefore, secretory pathway dysfunction can be highly detrimental to the cell and can drastically inhibit product titers in biochemical production. Because the secretory pathway is a highly-integrated, multi-organelle system, dysfunction can happen at many levels and dissecting the root cause can be challenging. In this study, we apply a systems biology approach to analyze secretory pathway dysfunctions resulting from heterologous production of a small protein (insulin precursor or a larger protein (α-amylase. Results HAC1-dependent and independent dysfunctions and cellular responses were apparent across multiple datasets. In particular, processes involving (a degradation of protein/recycling amino acids, (b overall transcription/translation repression, and (c oxidative stress were broadly associated with secretory stress. Conclusions Apparent runaway oxidative stress due to radical production observed here and elsewhere can be explained by a futile cycle of disulfide formation and breaking that consumes reduced glutathione and produces reactive oxygen species. The futile cycle is dominating when protein folding rates are low relative to disulfide bond formation rates. While not strictly conclusive with the present data, this insight does provide a molecular interpretation to an, until now, largely empirical understanding of optimizing heterologous protein secretion. This molecular insight has direct implications on engineering a broad range of recombinant proteins for secretion and provides potential hypotheses for the root causes of several secretory-associated diseases.

  16. Reaction rate oscillations during catalytic CO oxidation: A brief overview

    Science.gov (United States)

    Tsotsis, T. T.; Sane, R. C.

    1987-04-01

    It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.

  17. Transformation of Unsaturated Fatty Acids/Esters to Corresponding Keto Fatty Acids/Esters by Aerobic Oxidation with Pd(II)/Lewis Acid Catalyst.

    Science.gov (United States)

    Senan, Ahmed M; Zhang, Sicheng; Zeng, Miao; Chen, Zhuqi; Yin, Guochuan

    2017-08-16

    Utilization of renewable biomass to partly replace the fossil resources in industrial applications has attracted attention due to the limited fossil feedstock with the increased environmental concerns. This work introduced a modified Wacker-type oxidation for transformation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, in which Cu(2+) cation was replaced with common nonredox metal ions, that is, a novel Pd(II)/Lewis acid (LA) catalyst. It was found that adding nonredox metal ions can effectively promote Pd(II)-catalyzed oxidation of unsaturated fatty acids/esters to the corresponding keto fatty acids/esters, even much better than Cu(2+), and the promotional effect is highly dependent on the Lewis acidity of added nonredox metal ions. The improved catalytic efficiency is attributed to the formation of heterobimetallic Pd(II)/LA species, and the oxidation mechanism of this Pd(II)/LA catalyst is also briefly discussed.

  18. Photocatalytic oxidation of humic acid and its effect on haloacetic acid formation potential: a fluorescence spectrometry study.

    Science.gov (United States)

    Xiaoju, Yan; Ruiling, Bao; Shuili, Yu; Qiongfang, Li; Wei, Chen

    2012-01-01

    By fluorescence spectrometry method, molecular conformation changes of humic acid (HA) during the photocatalytic oxidation process were studied. Haloacetic acids formation potential (HAAFP) changes during the oxidation process were also measured. The results indicated that aromatic rings of HA decreased and conjugated double bonds were destroyed at the beginning of the process. Meanwhile, organic matter with large molecular weight decomposed into intermediates with smaller molecular weight, such as tryptophan and tyrosine. HA can be degraded almost completely, but not be mineralized thoroughly. Structures of the intermediates were changing during the oxidation process. Molecular structure transformation of HA led to the fluctuation tendency of the HAAFP changes during the photocatalytic oxidation process. HAAFP increased to 1.22 times that in raw water after 30 min of ultraviolet (UV) radiation, and decreased to 0.66 times that in raw water after 60 min of photocatalytic oxidation.

  19. Micelle-assisted signaling of peracetic acid by the oxidation of pyreneboronic acid via monomer-excimer switching.

    Science.gov (United States)

    Choi, Jiyoung; Lee, Hyo Jin; Cho, Min Jeoung; Chang, Suk-Kyu

    2015-08-15

    A simple fluorescent probe for the industrial oxidant peracetic acid (PAA) was investigated. PAA-assisted oxidative conversion of pyrene-1-boronic acid into 1-hydroxypyrene was used as the signaling tool. Pyreneboronic acid was found to display selective signaling behavior, being more responsive to PAA than to other commonly used practical oxidants such as H2O2 and HOCl. The changes in pyrene monomer fluorescence to excimer were used in the quantitative analysis of PAA. When using the surfactant hexadecyltrimethylammonium bromide as a micellar additive, the signaling of PAA was markedly enhanced. Selective fluorescence signaling of PAA by pyrene-1-boronic acid with a detection limit of 1.5×10(-6)M in aqueous environment was successfully achieved.

  20. The Use of Ascorbate as an Oxidation Inhibitor in Prebiotic Amino Acid Synthesis: A Cautionary Note

    Science.gov (United States)

    Kuwahara, Hideharu; Eto, Midori; Kawamoto, Yukinori; Kurihara, Hironari; Kaneko, Takeo; Obayashi, Yumiko; Kobayashi, Kensei

    2012-12-01

    It is generally thought that the terrestrial atmosphere at the time of the origin of life was CO2-rich and that organic compounds such as amino acids would not have been efficiently formed abiotically under such conditions. It has been pointed out, however, that the previously reported low yields of amino acids may have been partially due to oxidation by nitrite/nitrate during acid hydrolysis. Specifically, the yield of amino acids was found to have increased significantly (by a factor of several hundred) after acid hydrolysis with ascorbic acid as an oxidation inhibitor. However, it has not been shown that CO2 was the carbon source for the formation of the amino acids detected after acid hydrolysis with ascorbic acid. We therefore reinvestigated the prebiotic synthesis of amino acids in a CO2-rich atmosphere using an isotope labeling experiment. Herein, we report that ascorbic acid does not behave as an appropriate oxidation inhibitor, because it contributes amino acid contaminants as a consequence of its reactions with the nitrogen containing species and formic acid produced during the spark discharge experiment. Thus, amino acids are not efficiently formed from a CO2-rich atmosphere under the conditions studied.

  1. The use of ascorbate as an oxidation inhibitor in prebiotic amino acid synthesis: a cautionary note.

    Science.gov (United States)

    Kuwahara, Hideharu; Eto, Midori; Kawamoto, Yukinori; Kurihara, Hironari; Kaneko, Takeo; Obayashi, Yumiko; Kobayashi, Kensei

    2012-12-01

    It is generally thought that the terrestrial atmosphere at the time of the origin of life was CO(2)-rich and that organic compounds such as amino acids would not have been efficiently formed abiotically under such conditions. It has been pointed out, however, that the previously reported low yields of amino acids may have been partially due to oxidation by nitrite/nitrate during acid hydrolysis. Specifically, the yield of amino acids was found to have increased significantly (by a factor of several hundred) after acid hydrolysis with ascorbic acid as an oxidation inhibitor. However, it has not been shown that CO(2) was the carbon source for the formation of the amino acids detected after acid hydrolysis with ascorbic acid. We therefore reinvestigated the prebiotic synthesis of amino acids in a CO(2)-rich atmosphere using an isotope labeling experiment. Herein, we report that ascorbic acid does not behave as an appropriate oxidation inhibitor, because it contributes amino acid contaminants as a consequence of its reactions with the nitrogen containing species and formic acid produced during the spark discharge experiment. Thus, amino acids are not efficiently formed from a CO(2)-rich atmosphere under the conditions studied.

  2. Kinetic analysis of the role of histidine chloramines in hypochlorous acid mediated protein oxidation.

    Science.gov (United States)

    Pattison, David I; Davies, Michael J

    2005-05-17

    Hypochlorous acid (HOCl) is a powerful oxidant generated from H(2)O(2) and chloride ions by the heme enzyme myeloperoxidase (MPO) released from activated leukocytes. In addition to its potent antibacterial effects, excessive HOCl production can lead to host tissue damage, with this implicated in human diseases such as atherosclerosis, cystic fibrosis, and arthritis. HOCl reacts rapidly with biological materials, with proteins being major targets. Chlorinated amines (chloramines) formed from Lys and His side chains and alpha-amino groups on proteins are major products of these reactions; these materials are however also oxidants and can undergo further reactions. In this study, the kinetics of reaction of His side-chain chloramines with other protein components have been investigated by UV/visible spectroscopy and stopped flow methods at pH 7.4 and 22 degrees C, using the chloramines of the model compound 4-imidazoleacetic acid and N-alpha-acetyl-histidine. The second-order rate constants decrease in a similar order (Cys > Met > disulfide bonds > Trp approximately alpha-amino > Lys > Tyr > backbone amides > Arg) to the corresponding reactions of HOCl, but are typically 5-25 times slower. These rate constants are consistent with His side-chain chloramines being important secondary oxidants in HOCl-mediated damage. These studies suggest that formation and subsequent reactions of His side-chain chloramines may be responsible for the targeted secondary modification of selected protein residues by HOCl that has previously been observed experimentally and highlight the importance of chloramine structure on their subsequent reactivity.

  3. The OH-initiated oxidation of atmospheric peroxyacetic acid: Experimental and model studies

    Science.gov (United States)

    Wu, Huihui; Wang, Yin; Li, Huan; Huang, Liubin; Huang, Dao; Shen, Hengqing; Xing, Yanan; Chen, Zhongming

    2017-09-01

    Peroxyacetic acid (PAA, CH3C(O)OOH) plays an important role in atmospheric chemistry, serving as reactive oxidant and affecting radical recycling. However, previous studies revealed an obvious gap between modelled and observed concentrations of atmospheric PAA, which may be partly ascribed to the uncertainty in the kinetics and mechanism of OH-oxidation. In this study, we measured the rate constant of OH radical reaction with PAA (kPAA+OH) and investigated the products in order to develop a more robust atmospheric PAA chemistry. Using the relative rates technique and employing toluene and meta-xylene as reference compounds, the kPAA+OH was determined to be (9.4-11.9) × 10-12 cm3 molecule-1 s-1 at 298 K and 1 atm, which is about (2.5-3.2) times larger than that parameter used in Master Chemical Mechanism v3.3.1 (MCM v3.3.1) (3.70 × 10-12 cm3 molecule-1 s-1). Incorporation of a box model and MCM v3.3.1 with revised PAA chemistry represented a better simulation of atmospheric PAA observed during Wangdu Campaign 2014, a rural site in North China Plain. It is found that OH-oxidation is an important sink of atmospheric PAA in this rural area, accounting for ∼30% of the total loss. Moreover, the major terminal products of PAA-OH reaction were identified as formaldehyde (HCHO) and formic acid (HC(O)OH). The modelled results show that both primary and secondary chemistry play an important role in the large HCHO and HC(O)OH formation under experimental conditions. There should exist the channel of methyl H-abstraction for PAA-OH reaction, which may also provide routes to HCHO and HC(O)OH formation.

  4. Overexpression of Fatty-Acid-β-Oxidation-Related Genes Extends the Lifespan of Drosophila melanogaster

    Directory of Open Access Journals (Sweden)

    Shin-Hae Lee

    2012-01-01

    Full Text Available A better understanding of the aging process is necessary to ensure that the healthcare needs of an aging population are met. With the trend toward increased human life expectancies, identification of candidate genes affecting the regulation of lifespan and its relationship to environmental factors is essential. Through misexpression screening of EP mutant lines, we previously isolated several genes extending lifespan when ubiquitously overexpressed, including the two genes encoding the fatty-acid-binding protein and dodecenoyl-CoA delta-isomerase involved in fatty-acid β-oxidation, which is the main energy resource pathway in eukaryotic cells. In this study, we analyzed flies overexpressing the two main components of fatty-acid β-oxidation, and found that overexpression of fatty-acid-β-oxidation-related genes extended the Drosophila lifespan. Furthermore, we found that the ability of dietary restriction to extend lifespan was reduced by the overexpression of fatty-acid-β-oxidation-related genes. Moreover, the overexpression of fatty-acid-β-oxidation-related genes enhanced stress tolerance to oxidative and starvation stresses and activated the dFOXO signal, indicating translocation to the nucleus and transcriptional activation of the dFOXO target genes. Overall, the results of this study suggest that overexpression of fatty-acid-β-oxidation-related genes extends lifespan in a dietary-restriction-related manner, and that the mechanism of this process may be related to FOXO activation.

  5. Catalytic ozonation of fenofibric acid over alumina-supported manganese oxide.

    Science.gov (United States)

    Rosal, Roberto; Gonzalo, María S; Rodríguez, Antonio; García-Calvo, Eloy

    2010-11-15

    The catalytic ozonation of fenofibric acid was studied using activated alumina and alumina-supported manganese oxide in a semicontinuous reactor. The rate constants at 20°C for the non-catalytic reaction of fenofibric acid with ozone and hydroxyl radicals were 3.43±0.20 M(-1) s(-1) and (6.55±0.33)×10(9) M(-1) s(-1), respectively. The kinetic constant for the catalytic reaction between fenofibric acid and hydroxyl radicals did not differ significantly from that of homogeneous ozonation, either using Al(2)O(3) or MnO(x)/Al(2)O(3). The results showed a considerable increase in the generation of hydroxyl radicals due to the use of catalysts even in the case of catalytic runs performed using a real wastewater matrix. Both catalysts promoted the decomposition of ozone in homogeneous phase, but the higher production of hydroxyl radicals corresponded to the catalyst with more activity in terms of ozone decomposition. We did not find evidence of the catalysts having any effect on rate constants, which suggests that the reaction may not involve the adsorption of organics on catalyst surface.

  6. Catalytic ozonation of fenofibric acid over alumina-supported manganese oxide

    Energy Technology Data Exchange (ETDEWEB)

    Rosal, Roberto, E-mail: roberto.rosal@uah.es [Departamento de Quimica Analitica e Ingenieria Quimica, Universidad de Alcala, E-28771 Alcala de Henares (Spain); Gonzalo, Maria S.; Rodriguez, Antonio; Garcia-Calvo, Eloy [Departamento de Quimica Analitica e Ingenieria Quimica, Universidad de Alcala, E-28771 Alcala de Henares (Spain)

    2010-11-15

    The catalytic ozonation of fenofibric acid was studied using activated alumina and alumina-supported manganese oxide in a semicontinuous reactor. The rate constants at 20 deg. C for the non-catalytic reaction of fenofibric acid with ozone and hydroxyl radicals were 3.43 {+-} 0.20 M{sup -1} s{sup -1} and (6.55 {+-} 0.33) x 10{sup 9} M{sup -1} s{sup -1}, respectively. The kinetic constant for the catalytic reaction between fenofibric acid and hydroxyl radicals did not differ significantly from that of homogeneous ozonation, either using Al{sub 2}O{sub 3} or MnO{sub x}/Al{sub 2}O{sub 3}. The results showed a considerable increase in the generation of hydroxyl radicals due to the use of catalysts even in the case of catalytic runs performed using a real wastewater matrix. Both catalysts promoted the decomposition of ozone in homogeneous phase, but the higher production of hydroxyl radicals corresponded to the catalyst with more activity in terms of ozone decomposition. We did not find evidence of the catalysts having any effect on rate constants, which suggests that the reaction may not involve the adsorption of organics on catalyst surface.

  7. Glycerol-3-phosphate Acyltransferase Isoform-4 (GPAT4) Limits Oxidation of Exogenous Fatty Acids in Brown Adipocytes.

    Science.gov (United States)

    Cooper, Daniel E; Grevengoed, Trisha J; Klett, Eric L; Coleman, Rosalind A

    2015-06-12

    Glycerol-3-phosphate acyltransferase-4 (GPAT4) null pups grew poorly during the suckling period and, as adults, were protected from high fat diet-induced obesity. To determine why Gpat4(-/-) mice failed to gain weight during these two periods of high fat feeding, we examined energy metabolism. Compared with controls, the metabolic rate of Gpat4(-/-) mice fed a 45% fat diet was 12% higher. Core body temperature was 1 ºC higher after high fat feeding. Food intake, fat absorption, and activity were similar in both genotypes. Impaired weight gain in Gpat4(-/-) mice did not result from increased heat loss, because both cold tolerance and response to a β3-adrenergic agonist were similar in both genotypes. Because GPAT4 comprises 65% of the total GPAT activity in brown adipose tissue (BAT), we characterized BAT function. A 45% fat diet increased the Gpat4(-/-) BAT expression of peroxisome proliferator-activated receptor α (PPAR) target genes, Cpt1α, Pgc1α, and Ucp1, and BAT mitochondria oxidized oleate and pyruvate at higher rates than controls, suggesting that fatty acid signaling and flux through the TCA cycle were enhanced. To assess the role of GPAT4 directly, neonatal BAT preadipocytes were differentiated to adipocytes. Compared with controls, Gpat4(-/-) brown adipocytes incorporated 33% less fatty acid into triacylglycerol and 46% more into the pathway of β-oxidation. The increased oxidation rate was due solely to an increase in the oxidation of exogenous fatty acids. These data suggest that in the absence of cold exposure, GPAT4 limits excessive fatty acid oxidation and the detrimental induction of a hypermetabolic state.

  8. Impact of acid and oxidative modifications, single or dual, of sorghum starch on biodegradable films.

    Science.gov (United States)

    Biduski, Bárbara; Silva, Francine Tavares da; Silva, Wyller Max da; Halal, Shanise Lisie de Mello El; Pinto, Vania Zanella; Dias, Alvaro Renato Guerra; Zavareze, Elessandra da Rosa

    2017-01-01

    The objective of this study was to evaluate the effects of acid and oxidation modifications on sorghum starch, as well as the effect of dual modification of starch on the physical, morphological, mechanical, and barrier properties of biodegradable films. The acid modification was performed with 3% lactic acid and the oxidation was performed with 1.5% active chlorine. For dual modification, the acid modification was performed first, followed by oxidation under the same conditions as above. Both films of the oxidized starches, single and dual, had increased stiffness, providing a higher tensile strength and lower elongation when compared to films based on native and single acid modified starches. However, the dual modification increased the water vapor permeability of the films without changing their solubility. The increase in sorghum starch concentration in the filmogenic solution increased the thickness, water vapor permeability, and elongation of the films.

  9. Inhibition of oxidative phosphorylation for enhancing citric acid production by Aspergillus niger.

    Science.gov (United States)

    Wang, Lu; Zhang, Jianhua; Cao, Zhanglei; Wang, Yajun; Gao, Qiang; Zhang, Jian; Wang, Depei

    2015-01-16

    The spore germination rate and growth characteristics were compared between the citric acid high-yield strain Aspergillus niger CGMCC 5751 and A. niger ATCC 1015 in media containing antimycin A or DNP. We inferred that differences in citric acid yield might be due to differences in energy metabolism between these strains. To explore the impact of energy metabolism on citric acid production, the changes in intracellular ATP, NADH and NADH/NAD+ were measured at various fermentation stages. In addition, the effects of antimycin A or DNP on energy metabolism and citric acid production was investigated by CGMCC 5751. By comparing the spore germination rate and the extent of growth on PDA plates containing antimycin A or DNP, CGMCC 5751 was shown to be more sensitive to antimycin A than ATCC 1015. The substrate-level phosphorylation of CGMCC 5751 was greater than that of ATCC 1015 on PDA plates with DNP. DNP at tested concentrations had no apparent effect on the growth of CGMCC 5751. There were no apparent effects on the mycelial morphology, the growth of mycelial pellets or the dry cell mass when 0.2 mg L(-1) antimycin A or 0.1 mg L(-1) DNP was added to medium at the 24-h time point. The concentrations of intracellular ATP, NADH and NADH/NAD+ of CGMCC 5751 were notably lower than those of ATCC 1015 at several fermentation stages. Moreover, at 96 h of fermentation, the citric acid production of CGMCC 5751 reached up to 151.67 g L(-1) and 135.78 g L(-1) by adding 0.2 mg L(-1) antimycin A or 0.1 mg L(-1) DNP, respectively, at the 24-h time point of fermentation. Thus, the citric acid production of CGMCC 5751 was increased by 19.89% and 7.32%, respectively. The concentrations of intracellular ATP, NADH and NADH/NAD+ of the citric acid high-yield strain CGMCC 5751 were notably lower than those of ATCC 1015. The excessive ATP has a strong inhibitory effect on citric acid accumulation by A. niger. Increasing NADH oxidation and appropriately reducing the concentration of

  10. Kinetics and mechanism of the oxidation of some substituted aldonitrones by quinolinium chlorochromate in aqueous DMF medium in the absence and presence of oxalic acid

    Directory of Open Access Journals (Sweden)

    GOVINDASAMY RAJARAJAN

    2009-02-01

    Full Text Available The kinetics of the oxidation of aldonitrones (nitrone by quinolinium chlorochromate (QCC was determined in 50 % DMF–water in the absence and presence of oxalic acid in order to study the effect of oxalic acid. It was considered worthwhile to investigate whether it undergoes co-oxidation or just functions as a catalyst in the reaction. The reaction was followed iodometrically. Under the employed experimental conditions, the reaction is first order each with respect to concentration of nitrone, QCC, and oxalic acid and fractional order with respect to H+ concentration. There was no discernible effect with increasing in ionic strength but the rate of oxidation decreased with decreasing dielectric constant of the medium. Addition of MnSO4 had a significant and acrylonitrile no effect on the reaction rate. A mechanism involving protonated nitrone and QCC as the reactive oxidant is proposed. The activation parameters were calculated and are presented.

  11. Increased hepatic fatty acids uptake and oxidation by LRPPRC-driven oxidative phosphorylation reduces blood lipid levels

    Directory of Open Access Journals (Sweden)

    Ping Zhou

    2016-07-01

    Full Text Available Hyperlipidemia is one of the major risk factors of atherosclerosis and other cardiovascular diseases. This study aimed to investigate the impact of leucine rich pentatricopeptide repeat containing protein (LRPPRC-driven hepatic oxidative phoshorylation on blood lipid levels. The hepatic LRPPRC level was modulated by liver-specific transgenic or adeno-associated virus 8 carried shRNA targeting Lrpprc (aav-shLrpprc. Mice were fed with a high fat diet to induce obesity. Gene expression was analyzed by quantitative real-time PCR and / or western blot. The hepatic ATP level, hepatic and serum lipids contents, and mitochondria oxidative phosphorylation complex activities were measured using specific assay kits. The uptake and oxidation of fatty acid by hepatocytes were assessed using 14C-palmitate. LRPPRC regulated the expression of genes encoded by mitochondrial genome but not those by nuclear genome involved in mitochondria biogenesis, oxidative phosphorylation, and lipid metabolism. Increased oxidative phosphorylation in liver mediated by LRPPRC resulted in the increase of hepatic ATP level. Lrpprc promoted palmitate uptake and oxidation by hypatocytes. The hepatic and serum triglyceride and total cholesterol levels were inversely associated with the hepatic LRPPRC level. These data demonstrated that LRPPRC-driven hepatic oxidative phosphorylation could promote fatty acids uptake and oxidation by hepatocytes and reduce both hepatic and circulating triglyceride and cholesterol levels.

  12. Time resolved study of hydroxyl radical oxidation of oleic acid at the air-water interface

    Science.gov (United States)

    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.

  13. The rationale for preventing cancer cachexia: targeting excessive fatty acid oxidation.

    Science.gov (United States)

    Qian, Chao-Nan

    2016-07-21

    Cachexia commonly occurs at the terminal stage of cancer and has largely unclear molecular mechanisms. A recent study published in Nature Medicine, entitled "Excessive fatty acid oxidation induces muscle atrophy in cancer cachexia," reveals that cachectic cancer cells can secrete multiple cytokines that induce excessive fatty acid oxidation, which is responsible for muscle loss in cancer cachexia. Inhibition of fatty acid oxidation using etomoxir can increase muscle mass and body weight in cancer cachexia animal models. The usage of stable cachexia animal models is also discussed in this research highlight.

  14. The rationale forpreventing cancer cachexia:targeting excessive fatty acid oxidation

    Institute of Scientific and Technical Information of China (English)

    Chao-Nan Qian

    2016-01-01

    Cachexia commonly occurs at the terminal stage of cancer and has largely unclear molecular mechanisms. A recent study published inNature Medicine, entitled “Excessive fatty acid oxidation induces muscle atrophy in cancer cachexia,”reveals that cachectic cancer cells can secrete multiple cytokines that induce excessive fatty acid oxidation, which is responsible for muscle loss in cancer cachexia. Inhibition of fatty acid oxidation using etomoxir can increase muscle mass and body weight in cancer cachexia animal models. The usage of stable cachexia animal models is also dis‑cussed in this research highlight.

  15. Catalytic air oxidation of biomass-derived carbohydrates to formic acid.

    Science.gov (United States)

    Li, Jiang; Ding, Dao-Jun; Deng, Li; Guo, Qing-Xiang; Fu, Yao

    2012-07-01

    An efficient catalytic system for biomass oxidation to form formic acid was developed. The conversion of glucose to formic acid can reach up to 52% yield within 3 h when catalyzed by 5 mol% of H(5)PV(2)Mo(10)O(40) at only 373 K using air as the oxidant. Furthermore, the heteropolyacid can be used as a bifunctional catalyst in the conversion of cellulose to formic acid (yield=35%) with air as the oxidant. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A facile synthesis of MPd (M = Co, Cu) nanoparticles and their catalysis for formic acid oxidation.

    Science.gov (United States)

    Mazumder, Vismadeb; Chi, Miaofang; Mankin, Max N; Liu, Yi; Metin, Önder; Sun, Daohua; More, Karren L; Sun, Shouheng

    2012-02-08

    Monodisperse CoPd nanoparticles (NPs) were synthesized and studied for catalytic formic acid (HCOOH) oxidation (FAO). The NPs were prepared by coreduction of Co(acac)(2) (acac = acetylacetonate) and PdBr(2) at 260 °C in oleylamine and trioctylphosphine, and their sizes (5-12 nm) and compositions (Co(10)Pd(90) to Co(60)Pd(40)) were controlled by heating ramp rate, metal salt concentration, or metal molar ratios. The 8 nm CoPd NPs were activated for HCOOH oxidation by a simple ethanol wash. In 0.1 M HClO(4) and 2 M HCOOH solution, their catalytic activities followed the trend of Co(50)Pd(50) > Co(60)Pd(40) > Co(10)Pd(90) > Pd. The Co(50)Pd(50) NPs had an oxidation peak at 0.4 V with a peak current density of 774 A/g(Pd). As a comparison, commercial Pd catalysts showed an oxidation peak at 0.75 V with peak current density of only 254 A/g(Pd). The synthesis procedure could also be extended to prepare CuPd NPs when Co(acac)(2) was replaced by Cu(ac)(2) (ac = acetate) in an otherwise identical condition. The CuPd NPs were less active catalysts than CoPd or even Pd for FAO in HClO(4) solution. The synthesis provides a general approach to Pd-based bimetallic NPs and will enable further investigation of Pd-based alloy NPs for electro-oxidation and other catalytic reactions. © 2012 American Chemical Society

  17. Fatty acid turnover, substrate oxidation, and heat production in lean and obese cats during the euglycemic hyperinsulinemic clamp.

    Science.gov (United States)

    Hoenig, M; Thomaseth, K; Waldron, M; Ferguson, D C

    2007-05-01

    Simultaneous application of the euglycemic hyperinsulinemic clamp (EHC) and indirect calorimetry was used to examine heat production, fat, and glucose metabolism in lean and obese adult neutered male and female cats. The results show that in lean insulin-sensitive cats glucose oxidation predominated during fasting, whereas lipid oxidation became more prominent in obese cats. Insulin infusion during the EHC in lean cats and obese male cats led to a large increase in glucose oxidation, glycogenesis, and lipogenesis. It also led to an increase in glucose oxidation and glycogenesis in obese female cats but it was significantly less compared to lean cats and obese males. This indicates that obese females show greater metabolic inflexibility. In obese cats of either gender, insulin caused greater suppression of non-esterified fatty acids compared to lean cats suggesting that obese cats show greater fatty acid clearance than lean cats. The heat production per metabolic size was lower in obese cats than lean cats. This would perpetuate obesity unless food intake is decreased. The higher glucose oxidation rate in obese neutered male cats suggests that they are able to replete their glycogen and lipid stores at a faster rate than females in response to insulin and it implies that they gain weight more rapidly. Further studies are needed to investigate if the different response to insulin of male cats is involved in their higher risk to develop diabetes.

  18. Lipid oxidation in fish oil enriched mayonnaise: calcium disodium ethylenediaminetetraacetate, but not gallic acid, strongly inhibited oxidative deterioration.

    Science.gov (United States)

    Jacobsen, C; Hartvigsen, K; Thomsen, M K; Hansen, L F; Lund, P; Skibsted, L H; Hølmer, G; Adler-Nissen, J; Meyer, A S

    2001-02-01

    The antioxidative effects of gallic acid, EDTA, and extra emulsifier Panodan DATEM TR in mayonnaise enriched with 16% fish oil were investigated. EDTA reduced the formation of free radicals, lipid hydroperoxides, volatiles, and fishy and rancid off-flavors. The antioxidative effect of EDTA was attributed to its ability to chelate free metal ions and iron from egg yolk located at the oil-water interface. Gallic acid reduced the levels of both free radicals and lipid hydroperoxides but promoted slightly the oxidative flavor deterioration in mayonnaise and influenced the profile of volatiles. Gallic acid may therefore promote the decomposition of lipid hydroperoxides to volatile oxidation products. Addition of extra emulsifier reduced the lipid hydroperoxide levels but did not influence the level of free radicals or the oxidative flavor deterioration in mayonnaisse; however, it appeared to alter the profile of volatiles. The effect of the emulsifier on the physical structure and rheological properties depended on the presence of antioxidants.

  19. Pyrite oxidation under simulated acid rain weathering conditions.

    Science.gov (United States)

    Zheng, Kai; Li, Heping; Wang, Luying; Wen, Xiaoying; Liu, Qingyou

    2017-07-31

    We investigated the electrochemical corrosion behavior of pyrite in simulated acid rain with different acidities and at different temperatures. The cyclic voltammetry, polarization curve, and electrochemical impedance spectroscopy results showed that pyrite has the same electrochemical interaction mechanism under different simulated acid rain conditions, regardless of acidity or environmental temperature. Either stronger acid rain acidity or higher environmental temperature can accelerate pyrite corrosion. Compared with acid rain having a pH of 5.6 at 25 °C, the prompt efficiency of pyrite weathering reached 104.29% as the acid rain pH decreased to 3.6, and it reached 125.31% as environmental temperature increased to 45 °C. Increasing acidity dramatically decreases the charge transfer resistance, and increasing temperature dramatically decreases the passivation film resistance, when other conditions are held constant. Acid rain always causes lower acidity mine drainage, and stronger acidity or high environmental temperatures cause serious acid drainage. The natural parameters of latitude, elevation, and season have considerable influence on pyrite weathering, because temperature is an important influencing factor. These experimental results are of direct significance for the assessment and management of sulfide mineral acid drainage in regions receiving acid rain.

  20. Evaluation of the Protein Requirement in Chinese Young Adults Using the Indicator Amino Acid Oxidation Technique

    Institute of Scientific and Technical Information of China (English)

    LI Min; ZHANG Yu Hui; WANG Zhi Ling; GOU Ling Yan; LI Wei Dong; TIAN Yuan; HU Yi Chun; WANG Rui; PIAO Jian Hua; YANG Xiao Guang

    2013-01-01

    Objective To accurately calculate the protein requirements in Chinese young adults using the indicator amino acid oxidation technique. Methods Nine women and ten men received a restricted daily level of protein intake (0.75, 0.82, 0.89, 0.97, and 1.05 g/kg), along with L-[1-13C]-leucine. Subjects’ protein requirement was determined by a biphasic linear regression crossover analysis of F13CO2 data. In doing so, a breakpoint at the minimal rate of appearance of 13CO2 expiration specific to each level of dietary protein was identified. This trial was registered with the Chinese clinical trial registry as ChiCTR-ONC-11001407. Results The Estimated Average Requirement (EAR) and the Recommended Nutrient Intake (RNI) of protein for healthy Chinese young adults were determined to be 0.87 and 0.98 g/(kg·d), respectively, based on the indicator amino acid oxidation technique. Conclusion The EAR and RNI of mixed protein are 5% and 16% that are lower than the current proposed EAR and RNI (0.92 and 1.16 g/(kg·d), respectively), as determined by the nitrogen balance method. The respective EAR and RNI recommendations of 0.87 and 0.98 g/(kg·d) of mixed protein are estimated to be reasonable and suitable for Chinese young adults.

  1. [Photocatalytic Oxidation of p-arsanilic Acid by TiO2].

    Science.gov (United States)

    Xu, Wen-ze; Yang, Chun-feng; Li, Jing; Li, Jian-fei; Liu, Hui-fang; Hu, Cheng-zhi

    2016-01-15

    The p-arsanilic acid (ASA) is an important organoarsenical compound and its removal is more difficult compared to inorganic arsenic, however, little attention has been paid to the removal of ASA in aqueous environment. The influence of P25 on the adsorption of ASA, effect of P25 dosage, pH and illumination intensity on the photo-catalysis, the production analysis and main mechanism of photo-degradation were investigated in this study. The results showed that in the P25 catalysis process, simulated natural light could degrade ASA into As (V) by oxidation. The total As was reduced to about 0.34 mg x L(-1) within 0.5 h under the following condition: the initial concentration of ASA was 2 mg x L(-1) and the dosage of TiO2 was 1 g x L(-1). The result showed that the removal rate of ASA in acidic conditions was much higher than that in alkaline conditions. The optimal strength of light was 68.5 mW x Cm(-2). Hydroxide radical played a major role in photocatalytic oxidation of ASA by P25.

  2. Poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide)-templated synthesis of mesoporous alumina: effect of triblock copolymer and acid concentration.

    Science.gov (United States)

    Materna, Kelly L; Grant, Stacy M; Jaroniec, Mietek

    2012-07-25

    Mesoporous alumina was synthesized via a one-pot self-assembly of aluminum isopropoxide and poly(ethylene oxide)-poly(butylene oxide)-poly(ethylene oxide) triblock copolymer in an acidic ethanol solution. The effects of the polymer concentration and nitric acid concentration, independently, on the adsorption properties (such as surface area, pore volume, microporosity, mesoporosity, and pore width) were studied. An increase in the specific surface area and the pore volume was seen for the samples containing a polymer/aluminum isopropoxide wt. ratio up to 0.71 and a polymer/acid wt ratio of 0.88. Titania isopropoxide was also added to the synthesis to illustrate the extension of this approach to alumina-based mixed metal oxides.

  3. Perfluorooctanoic acid exposure triggers oxidative stress in the mouse pancreas

    Directory of Open Access Journals (Sweden)

    Lisa M. Kamendulis

    2014-01-01

    Full Text Available Perfluorooctanoic acid (PFOA is used in the manufacture of many industrial and commercial products. PFOA does not readily decompose in the environment, and is biologically persistent. Human epidemiologic and animal studies suggest that PFOA exposure elicits adverse effects on the pancreas. While multiple animal studies have examined PFOA-mediated toxicity in the liver, little is known about the potential adverse effects of PFOA on the pancreas. To address this, we treated C57Bl/6 mice with vehicle, or PFOA at doses of 0.5, 2.5 or 5.0 mg/kg BW/day for 7 days. Significant accumulation of PFOA was found in the serum, liver and pancreas of PFOA-treated animals. Histopathologic examination of the pancreas revealed focal ductal hyperplasia in mice treated with 2.5 and 5.0 mg/kg BW/day PFOA, while inflammation was observed only in the high dose group. Elevated serum levels of amylase and lipase were observed in the 2.5 mg/kg BW/day PFOA treatment group. In addition, PFOA exposure resulted in a dose-dependent increase in the level of the lipid peroxidation product 8-iso-PGF2α and induction of the antioxidant response genes Sod1, Sod2, Gpx2 and Nqo1. Our findings provide additional evidence that the pancreas is a target organ for PFOA-mediated toxicity and suggest that oxidative stress may be a mechanism through which PFOA induces histopathological changes in the pancreas.

  4. Formic-acid-induced depolymerization of oxidized lignin to aromatics.

    Science.gov (United States)

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J; Stahl, Shannon S

    2014-11-13

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  5. Formic-acid-induced depolymerization of oxidized lignin to aromatics

    Science.gov (United States)

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.; Stahl, Shannon S.

    2014-11-01

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  6. Hydrogen Peroxide Cycling in Acidic Geothermal Environments and Potential Implications for Oxidative Stress

    Science.gov (United States)

    Mesle, M.; Beam, J.; Jay, Z.; Bodle, B.; Bogenschutz, E.; Inskeep, W.

    2014-12-01

    Hydrogen peroxide (H2O2) may be produced in natural waters via photochemical reactions between dissolved oxygen, organic carbon and light. Other reactive oxygen species (ROS) such as superoxide and hydroxyl radicals are potentially formed in environments with high concentrations of ferrous iron (Fe(II), ~10-100 μM) by reaction between H2O2 and Fe(II) (i.e., Fenton chemistry). Thermophilic archaea and bacteria inhabiting acidic iron-oxide mats have defense mechanisms against both extracellular and intracellular peroxide, such as peroxiredoxins (which can degrade H2O2) and against other ROS, such as superoxide dismutases. Biological cycling of H2O2 is not well understood in geothermal ecosystems, and geochemical measurements combined with molecular investigations will contribute to our understanding of microbial response to oxidative stress. We measured H2O2 and other dissolved compounds (Fe(II), Fe(III), H2S, O2), as well as photon flux, pH and temperature, over time in surface geothermal waters of several acidic springs in Norris Geyser Basin, Yellowstone National Park, WY (Beowulf Spring and One Hundred Spring Plain). Iron-oxide mats were sampled in Beowulf Spring for on-going analysis of metatranscriptomes and RT-qPCR assays of specific stress-response gene transcription (e.g., superoxide dismutases, peroxiredoxins, thioredoxins, and peroxidases). In situ analyses show that H2O2 concentrations are lowest in the source waters of sulfidic systems (ca. 1 μM), and increase by two-fold in oxygenated waters corresponding to Fe(III)-oxide mat formation (ca. 2 - 3 μM). Channel transects confirm increases in H2O2 as a function of oxygenation (distance). The temporal dynamics of H2O2, O2, Fe(II), and H2S in Beowulf geothermal waters were also measured during a diel cycle, and increases in H2O2 were observed during peak photon flux. These results suggest that photochemical reactions may contribute to changes in H2O2. We hypothesize that increases in H2O2 and O2

  7. Photo-oxidation of Acetone to Formic Acid in Synthetic Air and Its Atmospheric Implication.

    Science.gov (United States)

    Chattopadhyay, Aparajeo; Chatterjee, Piyali; Chakraborty, Tapas

    2015-07-23

    Acetone photo-oxidation in synthetic air under exposure of 311 nm ultraviolet light has been studied, and the photo-oxidation products are identified by means of infrared spectroscopy. Analysis reveals that formic acid is one of the major products, although there have been debates in the past concerning the authenticity of formation of this acid in synthetic air via the photo-oxidation pathway. The quantum yield of formation of this acid is similar to that of other major photoproducts like methanol, formaldehyde, and carbon monoxide. The reaction yield, however, decreases with an increase in total air pressure in the reaction cell, but it is still significant at pressures relevant to tropospheric conditions. A kinetic model has been used to simulate the measured reaction kinetics, and the quantum yields predicted by the model are found to be consistent with the measured yields for different durations of light exposure. The same model has also been used to investigate the effect of atmospheric nitric oxide on the fate of formation of this acid in the troposphere. Although nitric oxide is known to be a quencher of peroxy radicals, the precursors of formaldehyde and formic acid in acetone photo-oxidation, but our model predicts that this oxide plays a positive role in the overall reaction kinetics for production of this acid in the troposphere.

  8. Glassy carbon electrodes modified with gelatin functionalized reduced graphene oxide nanosheet for determination of gallic acid

    Indian Academy of Sciences (India)

    Fereshteh Chekin; Samira Bagheri; Sharifah Bee Abd Hamid

    2015-12-01

    A simple approach for the preparation of gelatin functionalized reduced graphene oxide nanosheet (Gel-RGONS) by chemical reduction of graphene oxide (GO) using gelatin as both reducing agent and stabilizing agent in an aqueous solution was developed. The morphology and structure of the Gel-RGONS were examined by X-ray diffraction, transmission electron microscopy, ultraviolet–visible spectroscopy and Raman spectroscopy. Gelatin acted as a functionalizing reagent to guarantee good dispersibility and stability of the r in distilled water. Moreover, a new electrochemical sensor was developed based on Gel-RGONS modified glassy carbon electrode (Gel-RGONS/GCE). Gel-r exhibits excellent electrocatalytic activity to gallic acid (GA) oxidation. The experimental conditions such as pH, adsorption time and scan rate were optimized for the determination of GA. Under optimum conditions, the sensor responded linearly to GA in the concentration of 1.0 × 10−6 to 1.1 × 10−4 M with detection limit of 4.7 × 10−7 M at 3 using linear sweep voltammetry (LSV). The method has been successfully applied to the determination of GA in sample of black tea.

  9. Overexpression of PGC-1α Increases Fatty Acid Oxidative Capacity of Human Skeletal Muscle Cells

    Directory of Open Access Journals (Sweden)

    Nataša Nikolić

    2012-01-01

    Full Text Available We investigated the effects of PGC-1α (peroxisome proliferator-activated receptor γ coactivator-1α overexpression on the oxidative capacity of human skeletal muscle cells ex vivo. PGC-1α overexpression increased the oxidation rate of palmitic acid and mRNA expression of genes regulating lipid metabolism, mitochondrial biogenesis, and function in human myotubes. Basal and insulin-stimulated deoxyglucose uptake were decreased, possibly due to upregulation of PDK4 mRNA. Expression of fast fiber-type gene marker (MHCIIa was decreased. Compared to skeletal muscle in vivo, PGC-1α overexpression increased expression of several genes, which were downregulated during the process of cell isolation and culturing. In conclusion, PGC-1α overexpression increased oxidative capacity of cultured myotubes by improving lipid metabolism, increasing expression of genes involved in regulation of mitochondrial function and biogenesis, and decreasing expression of MHCIIa. These results suggest that therapies aimed at increasing PGC-1α expression may have utility in treatment of obesity and obesity-related diseases.

  10. Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

    Science.gov (United States)

    Fawzy, Ahmed

    2016-03-15

    The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated.

  11. Integrating nitric oxide into salicylic acid and jasmonic acid/ ethylene plant defense pathways.

    Science.gov (United States)

    Mur, Luis A J; Prats, Elena; Pierre, Sandra; Hall, Michael A; Hebelstrup, Kim H

    2013-01-01

    Plant defense against pests and pathogens is known to be conferred by either salicylic acid (SA) or jasmonic acid (JA)/ethylene (ET) pathways, depending on infection or herbivore-grazing strategy. It is well attested that SA and JA/ET pathways are mutually antagonistic allowing defense responses to be tailored to particular biotic stresses. Nitric oxide (NO) has emerged as a major signal influencing resistance mediated by both signaling pathways but no attempt has been made to integrate NO into established SA/JA/ET interactions. NO has been shown to act as an inducer or suppressor of signaling along each pathway. NO will initiate SA biosynthesis and nitrosylate key cysteines on TGA-class transcription factors to aid in the initiation of SA-dependent gene expression. Against this, S-nitrosylation of NONEXPRESSOR OF PATHOGENESIS-RELATED PROTEINS1 (NPR1) will promote the NPR1 oligomerization within the cytoplasm to reduce TGA activation. In JA biosynthesis, NO will initiate the expression of JA biosynthetic enzymes, presumably to over-come any antagonistic effects of SA on JA-mediated transcription. NO will also initiate the expression of ET biosynthetic genes but a suppressive role is also observed in the S-nitrosylation and inhibition of S-adenosylmethionine transferases which provides methyl groups for ET production. Based on these data a model for NO action is proposed but we have also highlighted the need to understand when and how inductive and suppressive steps are used.

  12. Integrating nitric oxide into salicylic acid and jasmonic acid/ ethylene plant defence pathways.

    Directory of Open Access Journals (Sweden)

    Luis A.J. Mur

    2013-06-01

    Full Text Available Plant defence against pests and pathogens is known to be conferred by either salicylic acid (SA or jasmonic acid (JA/ethylene (ET pathways, depending on infection or herbivore-grazing strategy. It is well attested that SA and JA/ET pathways are mutually antagonistic allowing defence responses to be tailored to particular biotic stresses. Nitric oxide (NO has emerged as a major signal influencing resistance mediated by both signalling pathways but no attempt has been made to integrate NO into established SA/JA/ET interactions. NO has been shown to act as an inducer or suppressor of signalling along each pathway. NO will initiate SA biosynthesis and nitrosylate key cysteines on TGA-class transcription factors to aid in the initiation of SA—dependent gene expression. Against this, S-nitrosylation of NONEXPRESSOR OF PATHOGENESIS-RELATED PROTEINS1 (NPR1 will promote the NPR1 oligomerisation within the cytoplasm to reduce TGA activation. In JA biosynthesis, NO will initiate the expression of JA biosynthetic enzymes, presumably to over-come any antagonistic effects of SA on JA-mediated transcription. NO will also initiate the expression of ET biosynthetic genes but a suppressive role is also observed in the S –nitrosylation and inhibition of s-adenosylmethionine transferases which provides methyl groups for ethylene production. Based on these data a model for NO action is proposed but we have also highlighted the need to understand when and how inductive and suppressive steps are used.

  13. Lipid oxidation stability of omega-3- and conjugated linoleic acid-enriched sous vide chicken meat.

    Science.gov (United States)

    Narciso-Gaytán, C; Shin, D; Sams, A R; Keeton, J T; Miller, R K; Smith, S B; Sánchez-Plata, M X

    2011-02-01

    Lipid oxidation is known to occur rather rapidly in cooked chicken meat containing relatively high amounts of polyunsaturated fatty acids. To assess the lipid oxidation stability of sous vide chicken meat enriched with n-3 and conjugated linoleic acid (CLA) fatty acids, 624 Cobb × Ross broilers were raised during a 6-wk feeding period. The birds were fed diets containing CLA (50% cis-9, trans-11 and 50% trans-10, cis-12 isomers), flaxseed oil (FSO), or menhaden fish oil (MFO), each supplemented with 42 or 200 mg/kg of vitamin E (dl-α-tocopheryl acetate). Breast or thigh meat was vacuum-packed, cooked (74°C), cooled in ice water, and stored at 4.4°C for 0, 5, 10, 15, and 30 d. The lipid oxidation development of the meat was estimated by quantification of malonaldehyde (MDA) values, using the 2-thiobarbituric acid reactive substances analysis. Fatty acid, nonheme iron, moisture, and fat analyses were performed as well. Results showed that dietary CLA induced deposition of cis-9, trans-11 and trans-10, cis-12 CLA isomers, increased the proportion of saturated fatty acids, and decreased the proportions of monounsaturated and polyunsaturated fatty acids. Flaxseed oil induced higher deposition of C18:1, C18:2, C18:3, and C20:4 fatty acids, whereas MFO induced higher deposition of n-3 fatty acids, eicosapentaenoic acid (C20:5), and docosahexaenoic acid (C22:6; P 0.05) lipid oxidation development. In conclusion, dietary CLA, FSO, and MFO influenced the fatty acid composition of chicken muscle and the lipid oxidation stability of meat over the storage time. Supranutritional supplementation of vitamin E enhanced the lipid oxidation stability of sous vide chicken meat.

  14. Parabola-like shaped pH-rate profile for phenols oxidation by aqueous permanganate.

    Science.gov (United States)

    Du, Juanshan; Sun, Bo; Zhang, Jing; Guan, Xiaohong

    2012-08-21

    Oxidation of phenols by permanganate in the pH range of 5.0-9.0 generally exhibits a parabola-like shape with the maximum reaction rate obtained at pH close to phenols' pK(a). However, a monotonic increase or decrease is observed if phenols' pK(a) is beyond the pH range of 5.0-9.0. A proton transfer mechanism is proposed in which the undissociated phenol is directly oxidized by permanganate to generate products while a phenolate-permanganate adduct, intermediate, is formed between dissociated phenol and permanganate ion and this is the rate-limiting step for phenolates oxidation by permanganate. The intermediate combines with H(+) and then decomposes to products. Rate equations derived based on the steady-state approximation can well simulate the experimentally derived pH-rate profiles. Linear free energy relationships (LFERs) were established among the parameters obtained from the modeling, Hammett constants, and oxygen natural charges in phenols and phenolates. LFERs reveal that chlorine substituents have opposite influence on the susceptibility of phenols and phenolates to permanganate oxidation and phenolates are not necessarily more easily oxidized than their neutral counterparts. The chlorine substituents regulate the reaction rate of chlorophenolates with permanganate mainly by influencing the natural charges of the oxygen atoms of dissociated phenols while they influence the oxidation of undissociated chlorophenols by permanganate primarily by forming intramolecular hydrogen bonding with the phenolic group.

  15. Activated Persulfate Oxidation of Perfluorooctanoic Acid (PFOA in Groundwater under Acidic Conditions

    Directory of Open Access Journals (Sweden)

    Penghua Yin

    2016-06-01

    Full Text Available Perfluorooctanoic acid (PFOA is an emerging contaminant of concern due to its toxicity for human health and ecosystems. However, successful degradation of PFOA in aqueous solutions with a cost-effective method remains a challenge, especially for groundwater. In this study, the degradation of PFOA using activated persulfate under mild conditions was investigated. The impact of different factors on persulfate activity, including pH, temperature (25 °C–50 °C, persulfate dosage and reaction time, was evaluated under different experimental conditions. Contrary to the traditional alkaline-activated persulfate oxidation, it was found that PFOA can be effectively degraded using activated persulfate under acidic conditions, with the degradation kinetics following the pseudo-first-order decay model. Higher temperature, higher persulfate dosage and increased reaction time generally result in higher PFOA degradation efficiency. Experimental results show that a PFOA degradation efficiency of 89.9% can be achieved by activated persulfate at pH of 2.0, with the reaction temperature of 50 °C, molar ratio of PFOA to persulfate as 1:100, and a reaction time of 100 h. The corresponding defluorination ratio under these conditions was 23.9%, indicating that not all PFOA decomposed via fluorine removal. The electron paramagnetic resonance spectrometer analysis results indicate that both SO4−• and •OH contribute to the decomposition of PFOA. It is proposed that PFOA degradation occurs via a decarboxylation reaction triggered by SO4−•, followed by a HF elimination process aided by •OH, which produces one-CF2-unit-shortened perfluoroalkyl carboxylic acids (PFCAs, Cn−1F2n−1COOH. The decarboxylation and HF elimination processes would repeat and eventually lead to the complete mineralization all PFCAs.

  16. Citric Acid-Modified Fenton's Reaction for the Oxidation of Chlorinated Ethylenes in Soil Solution Systems

    Energy Technology Data Exchange (ETDEWEB)

    Seol, Yongkoo; Javandel, Iraj

    2008-03-15

    Fenton's reagent, a solution of hydrogen peroxide and ferrous iron catalyst, is used for an in-situ chemical oxidation of organic contaminants. Sulfuric acid is commonly used to create an acidic condition needed for catalytic oxidation. Fenton's reaction often involves pressure buildup and precipitation of reaction products, which can cause safety hazards and diminish efficiency. We selected citric acid, a food-grade substance, as an acidifying agent to evaluate its efficiencies for organic contaminant removal in Fenton's reaction, and examined the impacts of using citric acid on the unwanted reaction products. A series of batch and column experiments were performed with varying H{sub 2}O{sub 2} concentrations to decompose selected chlorinated ethylenes. Either dissolved iron from soil or iron sulfate salt was added to provide the iron catalyst in the batch tests. Batch experiments revealed that both citric and sulfuric acid systems achieved over 90% contaminant removal rates, and the presence of iron catalyst was essential for effective decontamination. Batch tests with citric acid showed no signs of pressure accumulation and solid precipitations, however the results suggested that an excessive usage of H{sub 2}O{sub 2} relative to iron catalysts (Fe{sup 2+}/H{sub 2}O{sub 2} < 1/330) would result in lowering the efficiency of contaminant removal by iron chelations in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.

  17. Oxidation of Co(II) by ozone and reactions of Co(III) in solutions of sulfuric acid

    Science.gov (United States)

    Levanov, A. V.; Isaikina, O. Ya.; Lunin, V. V.

    2016-12-01

    Reactions of the oxidation of bivalent cobalt ions by ozone, of the spontaneous decomposition of trivalent cobalt, and of interactions between Co(III) and chloride ions in solutions of sulfuric acid are studied. The order and rate constant of the process of decomposition of Co(III) are determined. Information on the kinetics of the interaction between Co(III) and Cl- is obtained. Kinetic patterns of the accumulation of Co(III) during the ozonation of solutions of CoSO4 in sulfuric acid are explained. Molar absorption coefficients of Co(III) and Co2+ ions in the visible range of wavelengths are determined.

  18. Bio-based nitriles from the heterogeneously catalyzed oxidative decarboxylation of amino acids.

    Science.gov (United States)

    Claes, Laurens; Matthessen, Roman; Rombouts, Ine; Stassen, Ivo; De Baerdemaeker, Trees; Depla, Diederik; Delcour, Jan A; Lagrain, Bert; De Vos, Dirk E

    2015-01-01

    The oxidative decarboxylation of amino acids to nitriles was achieved in aqueous solution by in situ halide oxidation using catalytic amounts of tungstate exchanged on a [Ni,Al] layered double hydroxide (LDH), NH4 Br, and H2 O2 as the terminal oxidant. Both halide oxidation and oxidative decarboxylation were facilitated by proximity effects between the reactants and the LDH catalyst. A wide range of amino acids was converted with high yields, often >90 %. The nitrile selectivity was excellent, and the system is compatible with amide, alcohol, and in particular carboxylic acid, amine, and guanidine functional groups after appropriate neutralization. This heterogeneous catalytic system was applied successfully to convert a protein-rich byproduct from the starch industry into useful bio-based N-containing chemicals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. DNA damage and oxidative stress induced by acetylsalicylic acid in Daphnia magna.

    Science.gov (United States)

    Gómez-Oliván, Leobardo Manuel; Galar-Martínez, Marcela; Islas-Flores, Hariz; García-Medina, Sandra; SanJuan-Reyes, Nely

    2014-08-01

    Acetylsalicylic acid is a nonsteroidal anti-inflammatory widely used due to its low cost and high effectiveness. This compound has been found in water bodies worldwide and is toxic to aquatic organisms; nevertheless its capacity to induce oxidative stress in bioindicators like Daphnia magna remains unknown. This study aimed to evaluate toxicity in D. magna induced by acetylsalicylic acid in water, using oxidative stress and DNA damage biomarkers. An acute toxicity test was conducted in order to determine the median lethal concentration (48-h LC50) and the concentrations to be used in the subsequent subacute toxicity test in which the following biomarkers were evaluated: lipid peroxidation, oxidized protein content, activity of the antioxidant enzymes superoxide dismutase, catalase, and glutathione peroxidase, and level of DNA damage. Lipid peroxidation level and oxidized protein content were significantly increased (pacetylsalicylic acid induces oxidative stress and DNA damage in D. magna.

  20. Flavin-catalyzed aerobic oxidation of sulfides and thiols with formic acid/triethylamine.

    Science.gov (United States)

    Murahashi, Shun-Ichi; Zhang, Dazhi; Iida, Hiroki; Miyawaki, Toshio; Uenaka, Masaaki; Murano, Kenji; Meguro, Kanji

    2014-09-14

    An efficient and practical catalytic method for the aerobic oxidative transformation of sulfides into sulfoxides, and thiols into disulfides with formic acid/TEA in the presence of a new, readily available, and stable flavin catalyst 5d is described.

  1. High-efficiency palladium catalysts supported on ppy-modified C60 for formic acid oxidation.

    Science.gov (United States)

    Bai, Zhengyu; Yang, Lin; Guo, Yuming; Zheng, Zhi; Hu, Chuangang; Xu, Pengle

    2011-02-14

    A facile preparation of polypyrrole-modified fullerene supported Pd nanoparticles catalyst is introduced; electrochemical measurements demonstrate that the obtained Pd/ppy-C(60) catalyst shows a good electrocatalytic activity and stability for the oxidation of formic acid.

  2. Hydrogen peroxide and ferulic acid-mediated oxidative cross-linking ...

    African Journals Online (AJOL)

    STORAGESEVER

    2009-12-15

    Dec 15, 2009 ... Oxidative cross-linked casein mediated by hydrogen peroxide and ferulic acid was prepared at ... functional properties of food proteins treated (Motoki and. Seguro, 1998 ..... Team of Northeast Agricultural University (No.

  3. Insights into support wettability in tuning catalytic performance in the oxidation of aliphatic alcohols to acids.

    Science.gov (United States)

    Wang, Min; Wang, Feng; Ma, Jiping; Chen, Chen; Shi, Song; Xu, Jie

    2013-07-28

    A superhydrophobic catalyst was prepared by immobilizing Pt nanoparticles on superhydrophobic organic-inorganic hybrid silicas, which showed high activity and selectivity in the oxidation of aliphatic alcohols to carboxylic acids.

  4. Ascorbate and dehydroascorbic acid as reliable biomarkers of oxidative stress

    DEFF Research Database (Denmark)

    Lykkesfeldt, Jens

    2007-01-01

    , the analytical reproducibility was tested by repeated analysis of plasma aliquots from one individual over four years. The plasma was subjected to acidic deproteinization with an equal volume of 10% meta-phosphoric acid containing 2 mM EDTA and analyzed for ascorbate and dehydroascorbic acid by high...

  5. Hg (II Catalysed Oxidation of D-Arabinose and D-Mannose by Acidic Solution of Potassium Permanganate: Kinetics and Mechanism

    Directory of Open Access Journals (Sweden)

    *1R. Naz

    2014-09-01

    Full Text Available The kinetics of Hg (II catalyzed oxidation of D-Arabinose (Ara and D-Mannose (Man by potassium permanganate in acidic medium have been studied spectrophotometrically in the temperature range 30-50oC. The reactions exhibit first order kinetics with respect to [Man] and [MnO4-] while second order with [Ara]. The reaction rates were found to be unaffected by the change in [H+]. It has been observed that Hg (II catalyzed the reaction but as the [Hg(II] increases, reaction rate becomes independent. Negligible effect of ionic strength (μ on the rate of oxidation has also been noted which supports the presence of at least one neutral specie in the rate determining step. The rate of oxidation was influenced by the change in temperature. Various activation parameters have been calculated. Formic acid and erythronic acid were identified as main oxidation product in case of arabinose while for mannose formic acid and arabinonic acid were identified. A mechanism consistent with the above findings has also been proposed.

  6. Acid-base and catalytic properties of the products of oxidative thermolysis of double complex compounds

    Science.gov (United States)

    Pechenyuk, S. I.; Semushina, Yu. P.; Kuz'mich, L. F.; Ivanov, Yu. V.

    2016-01-01

    Acid-base properties of the products of thermal decomposition of [M(A)6] x; [M1(L)6] y (where M is Co, Cr, Cu, Ni; M1 is Fe, Cr, Co; A is NH3, 1/2 en, 1/2 pn, CO(NH2)2; and L is CN, 1/2C2O4) binary complexes in air and their catalytic properties in the oxidation reaction of ethanol with atmospheric oxygen are studied. It is found that these thermolysis products are mixed oxides of the central atoms of complexes characterized by pH values of the zero charge point in the region of 4-9, OH-group sorption limits from 1 × 10-4 to 4.5 × 10-4 g-eq/g, OH-group surface concentrations of 10-50 nm-2 in 0.1 M NaCl solutions, and S sp from 3 to 95 m2/g. Their catalytic activity is estimated from the apparent rate constant of the conversion of ethanol in CO2. The values of constants are (1-6.5) × 10-5 s-1, depending on the gas flow rate and the S sp value.

  7. Removal of colour and COD from wastewater containing acid blue 22 by electrochemical oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Panizza, Marco [Dipartimento di Ingegneria Chimica e di Processo ' G.B. Bonino' , Universita degli Studi di Genova, p.le J.F. Kennedy 1, 16129 Genova (Italy)], E-mail: marco.panizza@unige.it; Cerisola, Giacomo [Dipartimento di Ingegneria Chimica e di Processo ' G.B. Bonino' , Universita degli Studi di Genova, p.le J.F. Kennedy 1, 16129 Genova (Italy)

    2008-05-01

    Electrochemical oxidation of synthetic wastewater containing acid blue 22 on a boron-doped diamond electrode (BDD) was studied, using cyclic voltammetry and bulk electrolysis. The influence of current density, dye concentration, flow rate, and temperature was investigated, in order to find the best conditions for COD and colour removal. It was found that, during oxidation, a polymeric film, causing BDD deactivation, was formed in the potential region of water stability, and that it was removed by anodic polarisation at high potentials in the region of O{sub 2} evolution. Bulk electrolysis results showed that the electrochemical process was suitable for completely removing COD and effectively decolourising wastewaters, due to the production of hydroxyl radicals on the diamond surface. In particular, under optimal experimental conditions of flow rates (i.e. 300 dm{sup 3} h{sup -1}) and current density (i.e. 20 mA cm{sup -2}), 97% of COD was removed in 12 h electrolysis, with 70 kWh m{sup -3}energy consumption.

  8. Uranium Oxide Rate Summary for the Spent Nuclear Fuel (SNF) Project (OCRWM)

    Energy Technology Data Exchange (ETDEWEB)

    PAJUNEN, A.L.

    2000-09-20

    The purpose of this document is to summarize the uranium oxidation reaction rate information developed by the Hanford Spent Nuclear Fuel (SNF) Project and describe the basis for selecting reaction rate correlations used in system design. The selection basis considers the conditions of practical interest to the fuel removal processes and the reaction rate application during design studies. Since the reaction rate correlations are potentially used over a range of conditions, depending of the type of evaluation being performed, a method for transitioning between oxidation reactions is also documented. The document scope is limited to uranium oxidation reactions of primary interest to the SNF Project processes. The reactions influencing fuel removal processes, and supporting accident analyses, are: uranium-water vapor, uranium-liquid water, uranium-moist air, and uranium-dry air. The correlation selection basis will consider input from all available sources that indicate the oxidation rate of uranium fuel, including the literature data, confirmatory experimental studies, and fuel element observations. Trimble (2000) summarizes literature data and the results of laboratory scale experimental studies. This document combines the information in Trimble (2000) with larger scale reaction observations to describe uranium oxidation rate correlations applicable to conditions of interest to the SNF Project.

  9. A novel application of horseradish peroxidase: Oxidation of alcohol ethoxylate to alkylether carboxylic acid

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A novel application of horseradish peroxidase (HRP) in the oxidation of alcohol ethoxylate to alkylether carboxylie acid in the present of H2O2 was reported in this paper. We propose the mechanism for the catalytic oxidation reaction is that the hydrogen transfers from the substrate to the ferryl oxygen to form the a-hydroxy carbon radical intermediate. The reaction offers a new approach for further research structure and catalytic mechanism of HRP and production of alkylether carboxylic acid.

  10. Characterization of sulfur oxidizing bacteria related to biogenic sulfuric acid corrosion in sludge digesters

    OpenAIRE

    Huber, Bettina;Herzog, Bastian;Drewes, Jörg E.;Koch, Konrad;Müller, Elisabeth

    2017-01-01

    Background Biogenic sulfuric acid (BSA) corrosion damages sewerage and wastewater treatment facilities but is not well investigated in sludge digesters. Sulfur/sulfide oxidizing bacteria (SOB) oxidize sulfur compounds to sulfuric acid, inducing BSA corrosion. To obtain more information on BSA corrosion in sludge digesters, microbial communities from six different, BSA-damaged, digesters were analyzed using culture dependent methods and subsequent polymerase chain reaction denaturing gradient ...

  11. Modeling low-dose-rate effects in irradiated bipolar-base oxides

    Energy Technology Data Exchange (ETDEWEB)

    Graves, R.J.; Cirba, C.R.; Schrimpf, R.D.; Milanowski, R.J.; Saigne, F. [Vanderbilt Univ., Nashville, TN (United States); Michez, A. [Univ. Montpellier 2 (France); Fleetwood, D.M. [Sandia National Labs., Albuquerque, NM (United States); Witczak, S.C. [Aerospace Corp., Los Angeles, CA (United States)

    1997-02-01

    A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in BJTs. Simulations show that space charge limited transport is partially responsible for the low-dose-rate enhancement.

  12. Phytoagents for Cancer Management: Regulation of Nucleic Acid Oxidation, ROS, and Related Mechanisms

    Directory of Open Access Journals (Sweden)

    Wai-Leng Lee

    2013-01-01

    Full Text Available Accumulation of oxidized nucleic acids causes genomic instability leading to senescence, apoptosis, and tumorigenesis. Phytoagents are known to reduce the risk of cancer development; whether such effects are through regulating the extent of nucleic acid oxidation remains unclear. Here, we outlined the role of reactive oxygen species in nucleic acid oxidation as a driving force in cancer progression. The consequential relationship between genome instability and cancer progression highlights the importance of modulation of cellular redox level in cancer management. Current epidemiological and experimental evidence demonstrate the effects and modes of action of phytoagents in nucleic acid oxidation and provide rationales for the use of phytoagents as chemopreventive or therapeutic agents. Vitamins and various phytoagents antagonize carcinogen-triggered oxidative stress by scavenging free radicals and/or activating endogenous defence systems such as Nrf2-regulated antioxidant genes or pathways. Moreover, metal ion chelation by phytoagents helps to attenuate oxidative DNA damage caused by transition metal ions. Besides, the prooxidant effects of some phytoagents pose selective cytotoxicity on cancer cells and shed light on a new strategy of cancer therapy. The “double-edged sword” role of phytoagents as redox regulators in nucleic acid oxidation and their possible roles in cancer prevention or therapy are discussed in this review.

  13. Thermal properties of poly(ethylene oxide)/lauric acid blends. A SSA-DSC study

    Energy Technology Data Exchange (ETDEWEB)

    Pielichowski, Krzysztof; Flejtuch, Kinga [Department of Chemistry and Technology of Polymers, Cracow University of Technology, ul. Warszawska 24, 31-155 Krakow (Poland)

    2006-03-15

    A series of poly(ethylene oxide) (PEO)/lauric acid blends with different compositions has been prepared and characterised by differential scanning calorimetry (DSC) in dynamic mode. It has been found that the enthalpy of melting and crystallisation reaches its highest value for PEO/lauric acid blend (1:1, w/w) which makes this system a promising candidate for thermal energy storage applications. Further studies by step-scan alternating (SSA)-DSC revealed that an increase of the temperature step causes that the average total heating rate is also increasing and the heat flow is characterised by higher values. Reversing component of the heat flow during melting reaches lowest values at highest step (step=1{sup o}) when the re-crystallisation of PEO is hindered. An increase of step generally leads to an increase of the number of non-equilibrium effects and facilitates the activation of kinetic non-reversing processes, hindering the overall crystallisation of PEO. For lauric acid, due to facile crystallisation and self-association, formation of ordered regular structures takes place faster and is influenced by non-reversing processes in higher proportion. (author)

  14. Efficient decomposition of environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant.

    Science.gov (United States)

    Hori, Hisao; Yamamoto, Ari; Hayakawa, Etsuko; Taniyasu, Sachi; Yamashita, Nobuyoshi; Kutsuna, Shuzo; Kiatagawa, Hiroshi; Arakawa, Ryuichi

    2005-04-01

    Photochemical decomposition of persistent perfluorocarboxylic acids (PFCAs) in water by use of persulfate ion (S2O8(2-)) was examined to develop a technique to neutralize stationary sources of PFCAs. Photolysis of S2O8(2-) produced highly oxidative sulfate radical anions (SO4-), which efficiently decomposed perfluorooctanoic acid (PFOA) and other PFCAs bearing C4-C8 perfluoroalkyl groups. The major products were F- and CO2; also, small amounts of PFCAs with shorter than initial chain lengths were detected in the reaction solution. PFOA at a concentration of 1.35 mM (typical of that in untreated wastewater after an emulsifying process in fluoropolymer manufacture) was completely decomposed by a photochemical system with 50 mM S2O8(2-) and 4 h of irradiation from a 200-W xenon-mercury lamp. The initial PFOA decomposition rate was 11 times higherthan with photolysis alone. All sulfur-containing species in the reaction solution were eventually transformed to sulfate ions by this method. This method was successfully applied to the decomposition of perfluorononanoic acid contained in a floor wax solution.

  15. A novel glutathione-hydroxycinnamic acid product generated in oxidative wine conditions.

    Science.gov (United States)

    Bouzanquet, Quentin; Barril, Celia; Clark, Andrew C; Dias, Daniel A; Scollary, Geoffrey R

    2012-12-12

    This study characterizes a novel glutathione-substituted dihydroxyphenyl compound formed during the oxidation of white wine and model wine solutions, which may contribute to the synergistic role of glutathione and hydroxycinnamic acids in delaying oxidative coloration. The critical components for the formation of the compound were found to be hydroxycinnamic acids and glutathione, while ascorbic acid enabled the product to accumulate to higher concentrations. The presence of the wine components important in other wine oxidation mechanisms, (+)-catechin, ethanol and/or tartaric acid, was not essential for the formation of this new compound. Via LC-MS/MS, HR-MS and (1)H NMR (1D and 2D NMR) analyses, the major isomer of the compound formed from glutathione and caffeic acid was found to be 4-[(E)-2'-(S)-glutathionyl ethenyl]-catechol (GEC). Equivalent products were also confirmed via LC-MS/MS for other hydroxycinnamic acids (i.e., ferulic and coumaric acids). Only trace amounts of GEC were formed with the quinic ester of caffeic acid (i.e., chlorogenic acid), and no equivalent product was found for cinnamic acid. GEC was detected in a variety of white wines supplemented with glutathione and caffeic acid. A radical mechanism for the formation of the styrene-glutathione derivatives is proposed.

  16. β-Cyclodextrin promoted oxidation of aldehydes to carboxylic acids in water

    Institute of Scientific and Technical Information of China (English)

    Dong Po Shi; Hong Bing Ji

    2009-01-01

    A facile,efficient and substrate-selective oxidation of aldehydes to carboxylic acids with NaC10 catalyzed by β-cyclodextdn in water has been developed.A series of aldehydes which could form inclusion complex with β-cyclodextrin(β-CD)were oxidized selectively with excellent yields.

  17. Catalytic Degradation of Methylphosphonic Acid Using Iron Powder/Iron Oxides

    Science.gov (United States)

    2005-11-01

    aluminium/ aluminium oxide on the degradation of methylphosphonic acid (MPA), the final hydrolysis product of most nerve agents. EGA-FTIR provides... ALUMINIUM OXIDE ) UNDER AIR (BOTTOM). .................. 37 DSTO-TR-1849 1 1. Introduction The Convention on the Prohibition of the...as well as aluminium/ aluminium oxide , using temperature programmed EGA-FTIR. Since MPA is a Schedule II chemical the above requirement can only be

  18. Multi-objective Optimization of Industrial Purified Terephthalic Acid Oxidation Process

    Institute of Scientific and Technical Information of China (English)

    牟盛静; 苏宏业; 古勇; 褚健

    2003-01-01

    Multi-objective optimization of a purified terephthalic acid (PTA) oxidation unit is carried out in this paper by using a process model that has been proved to describe industrial process quite well. The model is a semiempirical structured into two series ideal continuously stirred tank reactor (CSTR) models. The optimal objectives include maximizing the yield or inlet rate and minimizing the concentration of 4-carboxy-benzaldhyde, which is the main undesirable intermediate product in the reaction process. The multi-objective optimization algorithm applied in this study is non-dominated sorting genetic algorithm Ⅱ(NSGA-Ⅱ). The performance of NSGA-II is further illustrated by application to the title process.

  19. Energetics of methanol and formic acid oxidation on Pt(111): Mechanistic insights from adsorption calorimetry

    Science.gov (United States)

    Silbaugh, Trent L.; Karp, Eric M.; Campbell, Charles T.

    2016-08-01

    The catalytic and electrocatalytic oxidation and reforming of methanol and formic acid have received intense interest due to potential use in direct fuel cells and as prototype models for understanding electrocatalysis. Consequently, the reaction energy diagram (energies of all the adsorbed intermediates and activation energies of all the elementary steps) have been estimated for these reactions on Pt(111) by density functional theory (DFT) in several studies. However, no experimental measurement of these energy diagrams have been reported, nor is there a consensus on the mechanisms. Here, we use energies of key intermediates on Pt(111) from single crystal adsorption calorimetry (SCAC) and temperature programmed desorption (TPD) to build a combined energy diagram for these reactions. It suggests a new pathway involving monodentate formate as a key intermediate, with bidentate formate only being a spectator species that slows the rate. This helps reconcile conflicting proposed mechanisms.

  20. Influence of solution volume on the dissolution rate of silicon dioxide in hydrofluoric acid.

    Science.gov (United States)

    Shvartsev, Boris; Gelman, Danny; Komissarov, Ilia; Epshtein, Alon; Starosvetsky, David; Ein-Eli, Yair

    2015-02-01

    Experimental data and modeling of the dissolution of various Si/SiO2 thermal coatings in different volumes of hydrofluoric acid (HF) are reported. The rates of SiO2 -film dissolution, measured by means of various electrochemical techniques, and alteration in HF activity depend on the thickness of the film coating. Despite the small volumes (0.6-1.2 mL) of the HF solution, an effect of SiO2 -coating thickness on the dissolution rate was detected. To explain alterations detected in HF activity after SiO2 dissolution, spectroscopic analyses (NMR and FTIR) of the chemical composition of the solutions were conducted. This is associated with a modification in the chemical composition of the HF solution, which results in either the formation of an oxidized species in solution or the precipitation of dissolution products. HF2 (-) accumulation in the HF solution, owing to SiO2 dissolution was identified as the source of the chemical alteration.

  1. Nitrogen dioxide-dependent oxidation of uric acid in the human oral cavity under acidic conditions: implications for its occurrence in acidic dental plaque.

    Science.gov (United States)

    Takahama, Umeo; Hirota, Sachiko

    2010-06-21

    The pH in dental plaque falls to below 5 after the ingestion of foods, and it may remain low if acid-tolerant bacteria grow in the plaque. Certain nitrate-reducing bacteria in the oral cavity can proliferate in dental plaque at low pH, and nitrite is detected in such plaque. In acidic dental plaque, NO(2) can be produced by self-decomposition of nitrous acid and also by peroxidase-catalyzed oxidation of nitrite, and it may oxidize uric acid, a major antioxidant in the oral cavity. Under experimental conditions that simulate oral cavity, the oxidation of uric acid by nitrite and by nitrite/peroxidase systems was much more rapid at pH 5 than at pH 7, suggesting the more rapid production of NO(2) in dental plaque at lower pH. We propose that if the pH of plaque developed in a dental crevice decreased, NO(2) and other nitrogen oxides produced in the plaque would diffuse into the adjoining gingival tissues. The results of this study seem to contribute to the understanding of the induction of periodontal diseases in the context of nitrite-dependent production of nitrogen oxides in acidic dental plaque.

  2. Electrochemical determination of hydrochlorothiazide and folic acid in real samples using a modified graphene oxide sheet paste electrode

    Energy Technology Data Exchange (ETDEWEB)

    Beitollahi, Hadi, E-mail: h.beitollahi@yahoo.com [Environment Department, Institute of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology, Kerman (Iran, Islamic Republic of); Hamzavi, Mozhdeh [Department of Chemistry, Graduate University of Advanced Technology, Kerman (Iran, Islamic Republic of); Torkzadeh-Mahani, Masoud [Biotechnology Department, Institute of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology, Kerman (Iran, Islamic Republic of)

    2015-07-01

    A new ferrocene-derivative compound, 2-chlorobenzoyl ferrocene, was synthesized and used to construct a modified graphene oxide sheet paste electrode. The electrooxidation of hydrochlorothiazide at the surface of the modified electrode was studied. Under optimized conditions, the square wave voltammetric (SWV) peak current of hydrochlorothiazide increased linearly with hydrochlorothiazide concentration in the range of 5.0 × 10{sup −8} to 2.0 × 10{sup −4} M and a detection limit of 20.0 nM was obtained for hydrochlorothiazide. The diffusion coefficient and kinetic parameters (such as electron transfer coefficient and the heterogeneous rate constant) for hydrochlorothiazide oxidation were also determined. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of hydrochlorothiazide and folic acid which makes it suitable for the detection of hydrochlorothiazide in the presence of folic acid in real samples. - Highlights: • A novel modified-graphene oxide nanosheet paste electrode has been fabricated. • This electrode reduced the oxidation potential of hydrochlorothiazide by about 315 mV. • Hydrochlorothiazide was measured in the range of 5.0 × 10{sup −8} to 2.0 × 10{sup −4} M. • The detection limit for hydrochlorothiazide was obtained at 20.0 nM. • It resolved the voltammetric waves of hydrochlorothiazide and folic acid.

  3. Preparation of nitric humic acid by catalytic oxidation from Guizhou coal with catalysts

    Institute of Scientific and Technical Information of China (English)

    Yang Zhiyuan; Gong Liang; Ran Pan

    2012-01-01

    Nitric humic acid was prepared by catalytic oxidation between nitric acid and Guizhou coal,with added catalysts.We investigated catalytic oxidation processes and the factors that affect the reactions.The effects of different catalysts,including NiSO4 support on active carbon (AC-NiSO4),NiSO4 support on silicon dioxide (SiO2-NiSO4),composites of SO42-/Fe2O3,Zr-iron and vanadium-iron composite were studied.As well.we investigated nitric humic acid yields and the chemical structure of products by element analysis,FT-IR and E4/E6 (an absorbance ratio at wavelengths of 465 and 665 nm of humic acid alkaline extraction solutions).The results show that the catalytic oxidation reaction with added catalysts can increase humic acid yields by 18.7%,16.36%,12.94%,5.61% and 8.59%,respectively.The highest yield of humic acid,i.e.,36.0%,was obtained with AC-NiSO4 as the catalyst.The amounts of C and H decreased with the amount of nitrogen.The increase in the E4/E6 ratio in catalytic oxidation of (Guizhou) coal shows that small molecular weights and high yields of nitric humic acid can be obtained by catalytic oxidation reactions.

  4. Comparison between conjugated linoleic acid and essential fatty acids in preventing oxidative stress in bovine mammary epithelial cells.

    Science.gov (United States)

    Basiricò, L; Morera, P; Dipasquale, D; Tröscher, A; Bernabucci, U

    2017-03-01

    Some in vitro and in vivo studies have demonstrated protective effects of conjugated linoleic acid (CLA) isomers against oxidative stress and lipid peroxidation. However, only a few and conflicting studies have been conducted showing the antioxidant potential of essential fatty acids. The objectives of the study were to compare the effects of CLA to other essential fatty acids on the thiol redox status of bovine mammary epithelia cells (BME-UV1) and their protective role against oxidative damage on the mammary gland by an in vitro study. The BME-UV1 cells were treated with complete medium containing 50 μM of cis-9,trans-11 CLA, trans-10,cis-12 CLA, α-linolenic acid, γ-linolenic acid, and linoleic acid. To assess the cellular antioxidant response, glutathione, NADPH, and γ-glutamyl-cysteine ligase activity were measured 48 h after addition of fatty acids (FA). Intracellular reactive oxygen species and malondialdehyde production were also assessed in cells supplemented with FA. Reactive oxygen species production after 3 h of H2O2 exposure was assessed to evaluate and to compare the potential protection of different FA against H2O2-induced oxidative stress. All FA treatments induced an intracellular GSH increase, matched by high concentrations of NADPH and an increase of γ-glutamyl-cysteine ligase activity. Cells supplemented with FA showed a reduction in intracellular malondialdehyde levels. In particular, CLA isomers and linoleic acid supplementation showed a better antioxidant cellular response against oxidative damage induced by H2O2 compared with other FA. The Authors. Published by the Federation of Animal Science Societies and Elsevier Inc. on behalf of the American Dairy Science Association®. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

  5. Biologically relevant oxidants and terminology, classification and nomenclature of oxidatively generated damage to nucleobases and 2-deoxyribose in nucleic acids

    DEFF Research Database (Denmark)

    Cadet, Jean; Loft, Steffen; Olinski, Ryszard

    2012-01-01

    A broad scientific community is involved in investigations aimed at delineating the mechanisms of formation and cellular processing of oxidatively generated damage to nucleic acids. Perhaps as a consequence of this breadth of research expertise, there are nomenclature problems for several of the ...

  6. The effect of linoleic acid on the whole body synthesis rates of polyunsaturated fatty acids from α-linolenic acid and linoleic acid in free-living rats.

    Science.gov (United States)

    Domenichiello, Anthony F; Kitson, Alex P; Chen, Chuck T; Trépanier, Marc-Olivier; Stavro, P Mark; Bazinet, Richard P

    2016-04-01

    Docosahexaenoic acid (DHA) is thought to be important for brain function. The main dietary source of DHA is fish, however, DHA can also be synthesized from precursor omega-3 polyunsaturated fatty acids (n-3 PUFA), the most abundantly consumed being α-linolenic acid (ALA). The enzymes required to synthesize DHA from ALA are also used to synthesize longer chain omega-6 (n-6) PUFA from linoleic acid (LNA). The large increase in LNA consumption that has occurred over the last century has led to concern that LNA and other n-6 PUFA outcompete n-3 PUFA for enzymes involved in DHA synthesis, and therefore, decrease overall DHA synthesis. To assess this, rats were fed diets containing LNA at 53 (high LNA diet), 11 (medium LNA diet) or 1.5% (low LNA diet) of the fatty acids with ALA being constant across all diets (approximately 4% of the fatty acids). Rats were maintained on these diets from weaning for 8 weeks, at which point they were subjected to a steady-state infusion of labeled ALA and LNA to measure DHA and arachidonic acid (ARA) synthesis rates. DHA and ARA synthesis rates were generally highest in rats fed the medium and high LNA diets, while the plasma half-life of DHA was longer in rats fed the low LNA diet. Therefore, increasing dietary LNA, in rats, did not impair DHA synthesis; however, low dietary LNA led to a decrease in DHA synthesis with tissue concentrations of DHA possibly being maintained by a longer DHA half-life.

  7. Effect of UVA Fluence Rate on Indicators of Oxidative Stress in Human Dermal Fibroblasts

    Directory of Open Access Journals (Sweden)

    James D. Hoerter, Christopher S. Ward, Kyle D. Bale, Admasu N. Gizachew, Rachelle Graham, Jaclyn Reynolds, Melanie E. Ward, Chesca Choi, Jean-Leonard Kagabo, Michael Sauer, Tara Kuipers, Timothy Hotchkiss, Nate Banner, Renee A. Chellson, Theresa Ohaeri, L

    2008-01-01

    Full Text Available During the course of a day human skin is exposed to solar UV radiation that fluctuates in fluence rate within the UVA (290-315 nm and UVB (315-400 nm spectrum. Variables affecting the fluence rate reaching skin cells include differences in UVA and UVB penetrating ability, presence or absence of sunscreens, atmospheric conditions, and season and geographical location where the exposure occurs. Our study determined the effect of UVA fluence rate in solar-simulated (SSR and tanning-bed radiation (TBR on four indicators of oxidative stress---protein oxidation, glutathione, heme oxygenase-1, and reactive oxygen species--in human dermal fibroblasts after receiving equivalent UVA and UVB doses. Our results show that the higher UVA fluence rate in TBR increases the level of all four indicators of oxidative stress. In sequential exposures when cells are exposed first to SSR, the lower UVA fluence rate in SSR induces a protective response that protects against oxidative stress following a second exposure to a higher UVA fluence rate. Our studies underscore the important role of UVA fluence rate in determining how human skin cells respond to a given dose of radiation containing both UVA and UVB radiation.

  8. Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum; Etude de l`oxydation electrochimique directe et indirecte de l`hydrazine en milieu acide nitrique sur platine

    Energy Technology Data Exchange (ETDEWEB)

    Cames, B

    1997-12-31

    In nuclear fuel processing by the PUREX process, the purification of plutonium in nitric acid medium requires the oxidation of Pu(III) to Pu(IV), and of hydrazinium nitrate to nitrogen. The study helped to characterize the electrochemical behavior of the oxidation of hydrazinium nitrate and the reduction of nitric acid to nitrous acid, a compound which can chemically oxidize hydrazinium nitrate and Pu(III). Electro-analytical studies on polycrystalline platinum showed that hydrazine is oxidized in two potential zones, which depend on the surface texture of the platinum anode. Electrolysis in separate compartments, carried out in medium-acid media (2 and 4 mo/l) in the potential zone where these processes take place, showed that, at 0.9 V/ECS, the hydrazine oxidation reactions involved are: a four-electron process (75 %) with nitrogen formation and a one-electron process (25 %) with formation of nitrogen and ammonium ion. By contrast, electrolysis carried out at 0.65 V/ECS (with reactivation of the electrode at - 0.2 V/ECS to remove the poison from the platinum) allowed the selective oxidation of hydrazine to nitrogen by the four-electron reaction. Nitric acid can only be reduced to nitrous acid in the absence of hydrazine. For medium-acid media ({<=} 6 mol/l), this reaction takes place at potentials below - 0.2 V/ECS. However, the production rate of nitrous acid (partial order 0 with respect to nitric acid) is very low compared with the values obtained for strongly-acid media (6 to 10 mol/l) at the potential of - 0.1 V/ECS. Note that, in concentrated nitric medium, the selectivity of the reduction reaction is 47 to 85 % for nitrous acid, depending on the nitric acid concentration (6 to 10 mol/l) and the potential imposed (- 0.1 {<=} E {<=} 0.6 V/ECS). A kinetic study helped to determine the hydrazine oxidation rates as a function of the operating conditions. In all cases, the reaction rate is of partial order 0 with respect to hydrazine. These studies accordingly

  9. Non-linear direct effects of acid rain on leaf photosynthetic rate of terrestrial plants.

    Science.gov (United States)

    Dong, Dan; Du, Enzai; Sun, Zhengzhong; Zeng, Xuetong; de Vries, Wim

    2017-09-12

    Anthropogenic emissions of acid precursors have enhanced global occurrence of acid rain, especially in East Asia. Acid rain directly suppresses leaf function by eroding surface waxes and cuticle and leaching base cations from mesophyll cells, while the simultaneous foliar uptake of nitrates in rainwater may directly benefit leaf photosynthesis and plant growth, suggesting a non-linear direct effect of acid rain. By synthesizing data from literature on acid rain exposure experiments, we assessed the direct effects of acid rain on leaf photosynthesis across 49 terrestrial plants in China. Our results show a non-linear direct effect of acid rain on leaf photosynthetic rate, including a neutral to positive effect above pH 5.0 and a negative effect below that pH level. The acid rain sensitivity of leaf photosynthesis showed no significant difference between herbs and woody species below pH 5.0, but the impacts above that pH level were strongly different, resulting in a significant increase in leaf photosynthetic rate of woody species and an insignificant effect on herbs. Our analysis also indicates a positive effect of the molar ratio of nitric versus sulfuric acid in the acid solution on leaf photosynthetic rate. These findings imply that rainwater acidity and the composition of acids both affect the response of leaf photosynthesis and therefore result in a non-linear direct effect. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Nitrous acid in a street canyon environment: Sources and contributions to local oxidation capacity

    Science.gov (United States)

    Yun, Hui; Wang, Zhe; Zha, Qiaozhi; Wang, Weihao; Xue, Likun; Zhang, Li; Li, Qinyi; Cui, Long; Lee, Shuncheng; Poon, Steven C. N.; Wang, Tao

    2017-10-01

    Nitrous acid (HONO) plays an important role in radical formation and photochemical oxidation processes in the boundary layer. However, its impact on the chemistry in a street canyon microenvironment has not been thoroughly investigated. In this study, we measured HONO in a street canyon in urban Hong Kong and used an observation-based box model (OBM) with the Master Chemical Mechanism (MCM v3.3.1) to investigate the contribution of HONO to local oxidation chemistry. The observed HONO mixing ratios were in the range of 0.4-13.9 ppbv, with an average of 3.91 ppbv in the daytime and 2.86 ppbv at night. A mean HONO/NOx emission ratio of 1.0% (±0.5%) from vehicle traffic was derived. OBM simulations constrained by the observed HONO showed that the maximum concentrations of OH, HO2, and RO2 reached 4.65 × 106, 4.40 × 106, and 1.83 × 106 molecules cm-3, which were 7.9, 5.0, and 7.5 times, respectively, the results in the case without HONO constrained. Photolysis of HONO contributed to 86.5% of the total primary radical production rates and led to efficient NO2 and O3 production under the condition of weak regional transport of O3. The formation of HNO3 contributed to 98.4% of the total radical termination rates. Our results suggest that HONO could significantly increase the atmospheric oxidation capacity in a street canyon and enhance the secondary formation of HNO3 and HCHO, which can damage outdoor building materials and pose health risks to pedestrians.

  11. A novel mechanism for the oxidation reaction of VO2+ on a graphite electrode in acidic solutions

    Science.gov (United States)

    Wang, Wenjun; Fan, Xinzhuang; Liu, Jianguo; Yan, Chuanwei; Zeng, Chaoliu

    2014-09-01

    With the consideration of optimizing the performance of the all-vanadium redox flow battery (VRB), the oxidation reaction mechanism of VO2+ on a rotating graphite disk electrode has been investigated by potentiodynamic polarization in sulfuric acid solutions with various pH and vanadium concentrations. Furthermore, the reaction orders of VO2+ and H+ for the oxidation reaction of VO2+ have been calculated from the polarization results and compared with the theoretical results according to the possible reaction mechanisms available in the literature. However, a new oxidation reaction mechanism has been proposed to describe the oxidation of VO2+ at last, and the theoretic reaction orders of VO2+ and H+ based on the new mechanism are consistent with the experimental results when the electrochemical reaction is the rate-limited process. Moreover, a corresponding kinetic equation has been established for the oxidation reaction of VO2+ on a spectroscopically pure graphite electrode, and can be well used to predict the polarization behavior in V (IV) acidic solutions.

  12. Wet air oxidation of formic acid using nanoparticle-modified polysulfone hollow fibers as gas-liquid contactors.

    Science.gov (United States)

    Hogg, Seth R; Muthu, Satish; O'Callaghan, Michael; Lahitte, Jean-Francois; Bruening, Merlin L

    2012-03-01

    Catalytic wet air oxidation (CWAO) using membrane contactors is attractive for remediation of aqueous pollutants, but previous studies of even simple reactions such as formic acid oxidation required multiple passes through tubular ceramic membrane contactors to achieve high conversion. This work aims to increase single-pass CWAO conversions by using polysulfone (PS) hollow fibers as contactors to reduce diffusion distances in the fiber lumen. Alternating adsorption of polycations and citrate-stabilized platinum colloids in fiber walls provides catalytically active PS hollow fibers. Using a single PS fiber, 50% oxidation of a 50 mM formic acid feed solution results from a single pass through the fiber lumen (15 cm length) with a solution residence time of 40 s. Increasing the number of PS fibers to five while maintaining the same volumetric flow rate leads to over 90% oxidation, suggesting that further scale up in the number of fibers will facilitate high single pass conversions at increased flow rates. The high conversion compared to prior studies with ceramic fibers stems from shorter diffusion distances in the fiber lumen. However, the activity of the Pt catalyst is 20-fold lower than in previous ceramic fibers. Focusing the Pt deposition near the fiber lumen and limiting pore wetting to this region might increase the activity of the catalyst.

  13. Acidic ribosomal proteins and histone H3 from Leishmania present a high rate of divergence

    Directory of Open Access Journals (Sweden)

    Ysabel Montoya

    2000-08-01

    Full Text Available Another additional peculiarity in Leishmania will be discussed about of the amino acid divergence rate of three structural proteins: acidic ribosomal P1 and P2b proteins, and histone H3 by using multiple sequence alignment and dendrograms. These structural proteins present a high rate of divergence regarding to their homologous protein in Trypanosoma cruzi. At this regard, L. (V. peruviana P1 and T. cruzi P1 showed 57.4% of divergence rate. Likewise, L. (V. braziliensis histone H3 and acidic ribosomal P2 protein exhibited 31.8% and 41.7% respectively of rate of divergence in comparison with their homologous in T. cruzi.

  14. Label-free amino acid detection based on nanocomposites of graphene oxide hybridized with gold nanoparticles.

    Science.gov (United States)

    Zhang, Qian; Zhang, Diming; Lu, Yanli; Xu, Gang; Yao, Yao; Li, Shuang; Liu, Qingjun

    2016-03-15

    Nanocomposites of graphene oxide and gold nanoparticles (GO/GNPs) were synthesized for label-free detections of amino acids. Interactions between the composites and amino acids were investigated by both naked-eye observation and optical absorption spectroscopy. The GO/GNPs composites displayed apparent color changes and absorption spectra changes in presences of amino acids including glutamate, aspartate, and cysteine. The interaction mechanisms of the composites and amino acids were discussed and explored with sulfhydryl groups and non-α-carboxylic groups on the amino acids. Sensing properties of the composites were tested, while pure gold particles were used as the control. The results suggested that the GO/GNPs composites had better linearity and stability in dose-dependent responses to the amino acids than those of the particles, especially in detections for acidic amino acids. Therefore, the nanocomposites platform can provide a convenient and efficient approach for label-free optical detections of important molecules such as amino acids.

  15. Physiologic and acid-base measures of gopher snakes during ketamine or halothane-nitrous oxide anesthesia.

    Science.gov (United States)

    Custer, R S; Bush, M

    1980-11-01

    Arterial acid-base and selected physiologic measures of gopher snakes (Pituophis melanoleucus catenifer) during ketamine or halothane-nitrous oxide anesthesia were compared with base-line values. During ketamine anesthesia, significant decreases in pH and HCO-3 concentrations indicated acid-base states of uncompensated metabolic acidosis. In contrast, halothane-nitrous oxide anesthesia induced acidosis of respiratory origin, through a significant depression in respiratory rate. In addition to the conventional measures, the OH-/H+ ratios and the alpha-imidazole (alpha IM) values were calculated to assess acid-base status during anesthesia. Values for both factors decreased significantly during both ketamine and halothane-nitrous oxide anesthesia. Where H+ concentrations nearly doubled, the decline in the OH-/H+ ratio exceeded 70% and the alpha IM decreased less than 20%. It was concluded that these 2 factors may be helpful in evaluation of the acid-base status of ectothermic animals when normal values for the conventional measures of pH and pCO2 are not available for comparison.

  16. Engineering strategies aimed at control of acidification rate of lactic acid bacteria

    DEFF Research Database (Denmark)

    Martinussen, Jan; Solem, Christian; Holm, Anders Koefoed

    2013-01-01

    The ability of lactic acid bacteria to produce lactic acid from various sugars plays an important role in food fermentations. Lactic acid is derived from pyruvate, the end product of glycolysis and thus a fast lactic acid production rate requires a high glycolytic flux. In addition to lactic acid......, alternative end products - ethanol, acetic acid and formic acid - are formed by many species. The central role of glycolysis in lactic acid bacteria has provoked numerous studies aiming at identifying potential bottleneck(s) since knowledge about flux control could be important not only for optimizing food...... fermentation processes, but also for novel applications of lactic acid bacteria, such as cell factories for the production of green fuels and chemicals. With respect to the control and regulation of the fermentation mode, some progress has been made, but the question of which component(s) control the main...

  17. Effect of Sargassum thunbergii on ROS mediated oxidative damage and identification of polyunsaturated fatty acid components.

    Science.gov (United States)

    Kim, Jung-Ae; Kong, Chang-Suk; Kim, Se-Kwon

    2010-05-01

    In this study, we examined protective effect of Sargassum thunbergii on reactive oxygen species (ROS) mediated oxidative stress in cellular systems. In addition, polyunsaturated fatty acids from S. thunbergii were identified and quantified by gas chromatography mass spectroscopy. Intracellular ROS levels were measured using a oxidation sensitive dye, 2',7'-dichlorofluorescein diacetate (DCFH-DA). Treatment with S. thunbergii significantly reduced intracellular ROS mediated cell damage and inhibited myeloperoxidase (MPO) activity assessed in tumor necrosis factor-alpha (TNF-alpha) stimulated human monocytic leukemia in a concentration-dependent manner. Moreover, antioxidative mechanisms by S. thunbergii were evaluated by measuring the expression levels of antioxidative enzymes such as superoxide dismutase (SOD-1), catalase, glutathione peroxidase and glutathione reductase. SOD-1 and glutathione reductase were up-regulated by S. thunbergii. Furthermore, S. thunbergii contains polyunsaturated fatty acids such as arachidonic acid, arachidic acid, palmitic acid, elaidic acid, linoleic acid, stearic acid and cis-5,8,11,14,17-eicosanoic acid. Therefore, these results suggested that S. thunbergii has nutraceutical effectiveness in prevention of ROS-induced tissue damage and potential natural antioxidant related to oxidative stress, which can be traceable to polyunsaturated fatty acids contained in S. thunbergii.

  18. Fe(II) Oxidation and Sources of Acidity on Mars

    Science.gov (United States)

    Niles, P. B.; Peretyazkho, T. S.; Sutter, B.

    2017-01-01

    There is an apparent paradox be-tween the evidence that aqueous environments on Mars were predominantly acidic, and the fact that Mars is predominantly a basaltic (and olivine-rich) planet. The problem being that basalt and olivine will act to neutralize acidic solutions they come into contact with, and that there is a lot more basaltic crust on Mars than water or acid. This is especially true if there is an appreciable amount of water available to bring the acid in contact with the basaltic crust. Several hypotheses for ancient mar-tian environments call on long lived groundwater and aqueous systems.

  19. Oxidative stability of milk drinks containing structured lipids produced from sunflower oil and caprylic acid

    DEFF Research Database (Denmark)

    Timm Heinrich, Maike; Xu, Xuebing; Nielsen, Nina Skall;

    2003-01-01

    of adding potential antioxidants EDTA or gallic acid to the milk drink based on SL was investigated. The lipid type significantly affected the oxidative stability of the milk drinks: Milk drink based on SL oxidized faster than milk drink based on RL or SO. The reduced oxidative stability in the SL milk...... drink could not be ascribed was most likely influenced by the structure of the lipid and to a single factor, differences in the process applied to produce and purify the lipids. EDTA was a strong antioxidant, while gallic acid did not exert a distinct antioxidative effect in the milk drink based on SL....

  20. Synthesis and characterization of poly acrylic acid/graphite oxide nanocomposite

    Institute of Scientific and Technical Information of China (English)

    胡源; 丁溶芳; 徐加艳; 王清安; 陈祖耀; 范维澄

    2003-01-01

    Acrylic acid-intercalated graphite oxide and poly acrylic acid (PAA)-intercalated graphite oxide were prepared and characterized by X-Ray diffraction (XRD), Fourier transform infrared spectra (FTIR) and high resolution electronic microscope (HREM). Results show that the intercalation process is not only a physical diffusion process but also mainly a chemical reaction process. The high resolution electronic microscope results also reveal that the Ic value of PAA-intercalated graphite oxide (GO) could change widely from 1.6nm to 4.0nm.

  1. Comparative reactivity of the myeloperoxidase-derived oxidants hypochlorous acid and hypothiocyanous acid with human coronary artery endothelial cells.

    Science.gov (United States)

    Lloyd, Mitchell M; Grima, Michael A; Rayner, Benjamin S; Hadfield, Katrina A; Davies, Michael J; Hawkins, Clare L

    2013-12-01

    In the immune response, hypohalous acids are generated by activated leukocytes via the release of myeloperoxidase and the formation of H2O2. Although these oxidants have important bactericidal properties, they have also been implicated in causing tissue damage in inflammatory diseases, including atherosclerosis. Hypochlorous acid (HOCl) and hypothiocyanous acid (HOSCN) are the major oxidants formed by myeloperoxidase under physiological conditions, with the ratio of these oxidants dependent on diet and smoking status. HOCl is highly reactive and causes marked cellular damage, but few data are available on the effects of HOSCN on mammalian cells. In this study, we have compared the actions of HOCl and HOSCN on human coronary artery endothelial cells (HCAEC). HOCl reacts rapidly with the cells, resulting in extensive cell death by both apoptosis and necrosis, with necrosis dominating at higher oxidant doses. In contrast, HOSCN is consumed more slowly, with cell death occurring only by apoptosis. Exposure of HCAEC to HOCl and HOSCN induces changes in mitochondrial membrane permeability, which, in the case of HOSCN, is associated with mitochondrial release of proapoptotic factors, including cytochrome c, apoptosis-inducing factor, and endonuclease G. With each oxidant, apoptosis appears to be caspase-independent, with the inactivation of caspases 3/7 observed, and pretreatment of the cells with the caspase inhibitor Z-VAD-fmk having no effect on the extent of cell death. Loss of cellular thiols, depletion of glutathione, and the inactivation of thiol-dependent enzymes, including glyceraldehyde-3-phosphate dehydrogenase, were seen with both oxidants, though to a much greater extent with HOCl. The ability of myeloperoxidase-derived oxidants to induce endothelial cell apoptosis may contribute to the formation of unstable lesions in atherosclerosis. The results with HOSCN may be particularly significant for smokers, who have elevated plasma levels of SCN(-), the precursor

  2. Anodically generated manganese(III) sulphate for the oxidation of dipeptides in aqueous sulphuric acid medium: A kinetic study

    Indian Academy of Sciences (India)

    M N Kumara; D Channe Gowda; A Thimme Gowda; K S Rangappa

    2004-01-01

    The kinetic of oxidation of dipeptides (DP) namely valyl-glycine (Val-Gly), alanyl-glycine (Ala-Gly) and glycyl-glycine (Gly-Gly), by Mn(III) have been studied in the presence of sulphate ions in acid medium at 26°C. The reaction was followed spectrophotometrically at max = 500 nm. A firstorder dependence of the rate on both [Mn(III)]$_o$ and [DP]o was observed. The rate is independent of the concentration of reduction product, Mn(II) and hydrogen ions. The effects of varying the dielectric constant of the medium and addition of anions such as sulphate, chloride and perchlorate were studied. The activation parameters have been evaluated using Arrhenius and Eyring plots. The oxidation products were isolated and characterized. A mechanism involving the reaction of DP with Mn(III) in the ratelimiting step is suggested. An apparent correlation was noted between the rate of oxidation and the hydrophobicity of these dimers, where increased hyphobicity results in increased rate of oxidation.

  3. Detailed electrochemical studies of the tetraruthenium polyoxometalate water oxidation catalyst in acidic media: identification of an extended oxidation series using Fourier transformed alternating current voltammetry.

    Science.gov (United States)

    Lee, Chong-Yong; Guo, Si-Xuan; Murphy, Aidan F; McCormac, Timothy; Zhang, Jie; Bond, Alan M; Zhu, Guibo; Hill, Craig L; Geletii, Yurii V

    2012-11-05

    The electrochemistry of the water oxidation catalyst, Rb(8)K(2)[{Ru(4)O(4)(OH)(2)(H(2)O)(4)}(γ-SiW(10)O(36))(2)] (Rb(8)K(2)-1(0)) has been studied in the presence and absence of potassium cations in both hydrochloric and sulfuric acid solutions by transient direct current (dc) cyclic voltammetry, a steady state dc method in the rotating disk configuration and the kinetically sensitive technique of Fourier transformed large-amplitude alternating current (ac) voltammetry. In acidic media, the presence of potassium ions affects the kinetics (apparent rate of electron transfer) and thermodynamics (reversible potentials) of the eight processes (A'/A to H/H') that are readily detected under dc voltammetric conditions. The six most positive processes (A'/A to F/F'), each involve a one electron ruthenium based charge transfer step (A'/A, B'/B are Ru(IV/V) oxidation and C/C' to F/F' are Ru(IV/III) reduction). The apparent rate of electron transfer of the ruthenium centers in sulfuric acid is higher than in hydrochloric acid. The addition of potassium cations increases the apparent rates and gives rise to a small shift of reversible potential. Simulations of the Fourier transformed ac voltammetry method show that the B'/B, E/E', and F/F' processes are quasi-reversible, while the others are close to reversible. A third Ru(IV/V) oxidation process is observed just prior to the positive potential limit via dc methods. Importantly, the ability of the higher harmonic components of the ac method to discriminate against the irreversible background solvent process allows this (process I) as well as an additional fourth reversible ruthenium based process (J) to be readily identified. The steady-state rotating disk electrode (RDE) method confirmed that all four Ru-centers in Rb(8)K(2)-1(0) are in oxidation state IV. The dc and ac data indicate that reversible potentials of the four ruthenium centers are evenly spaced, which may be relevant to understanding of the water oxidation

  4. Biological iron(II) oxidation as pre-treatment to limestone neutralisation of acid water

    CSIR Research Space (South Africa)

    Maree, JP

    1998-01-01

    Full Text Available Iron (II) should be oxidised to iron (III) before the neutralisation of acid water with limestone, otherwise the oxidation will occur downstream of the neutralisation plant with the formation of acid (reactions 1 and 2). This study aimed...

  5. Selective Oxidative Decarboxylation of Amino Acids to Produce Industrially Relevant Nitriles by Vanadium Chloroperoxidase

    NARCIS (Netherlands)

    But, A.; Notre, le J.E.L.; Scott, E.L.; Wever, R.; Sanders, J.P.M.

    2012-01-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative

  6. Natural and pyrogenic humic acids at goethite and natural oxide surfaces interacting with phosphate

    NARCIS (Netherlands)

    Hiemstra, T.; Mia, S.; Duhaut, P.B.; Molleman, B.

    2013-01-01

    Fulvic and humic acids have a large variability in binding to metal (hydr) oxide surfaces and interact differently with oxyanions, as examined here experimentally. Pyrogenic humic acid has been included in our study since it will be released to the environment in the case of large-scale application

  7. Serum uric acid levels and leukocyte nitric oxide production in multiple sclerosis patients outside relapses

    NARCIS (Netherlands)

    Mostert, JP; Ramsaransing, GSM; Heerserna, DJ; Heerings, M; Wilczak, N; De Keyser, J

    2005-01-01

    Background: A number of studies found that patients with multiple sclerosis (MS) have low serum levels of uric acid. It is unclear whether this represents a primary deficit or secondary effect. Uric acid is a scavenger of peroxynitrite, which is the product of nitric oxide (NO) and superoxide. Becau

  8. Selective Oxidative Decarboxylation of Amino Acids to Produce Industrially Relevant Nitriles by Vanadium Chloroperoxidase

    NARCIS (Netherlands)

    But, A.; Notre, le J.E.L.; Scott, E.L.; Wever, R.; Sanders, J.P.M.

    2012-01-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative dec

  9. Primary oxidation and reduction products in x-irradiated aspartic acid

    Energy Technology Data Exchange (ETDEWEB)

    Adams, S.M.; Budzinski, E.E.; Box, H.C.

    1976-08-01

    The primary reduction products identified by ESR--ENDOR spectroscopy in single crystals of DL-aspartic acid hydrochloride irradiated at 4.2degreeK are anions formed by addition of an electron to the carbonyl oxygen atoms of the carboxylic acid groups. The main consequence of the oxidation process is to produce a hole centered mainly on atomic chlorine. (AIP)

  10. Selective Oxidative Decarboxylation of Amino Acids to Produce Industrially Relevant Nitriles by Vanadium Chloroperoxidase

    NARCIS (Netherlands)

    But, A.; Notre, le J.E.L.; Scott, E.L.; Wever, R.; Sanders, J.P.M.

    2012-01-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative dec

  11. An innovative zinc oxide-coated zeolite adsorbent for removal of humic acid

    Science.gov (United States)

    Zinc oxide (ZnO)-coated zeolite adsorbents were developed by both nitric acid modification and Zn(NO3)2•6H2O functionalization of zeolite. The developed adsorbents were used for the removal of humic acid (HA) from aqueous solutions. The adsorption capacity of the adsorbents at 21...

  12. Furan fatty acids efficiently rescue brain cells from cell death induced by oxidative stress

    NARCIS (Netherlands)

    Teixeira, A.; Cox, R.C.; Egmond, M.R.

    2013-01-01

    Treatment of rat brain C6 astroglioma cells with furan fatty acid F6 prior to exposure to hydrogen peroxide shows a strong protective effect of F6 against cell death resulting from oxidative stress. This protective effect is obtained only for F6 administered as a free fatty acid and with an intact f

  13. Copper-catalyzed tandem phosphination-decarboxylation-oxidation of alkynyl acids with H-phosphine oxides: a facile synthesis of β-ketophosphine oxides.

    Science.gov (United States)

    Zhang, Pengbo; Zhang, Liangliang; Gao, Yuzhen; Xu, Jian; Fang, Hua; Tang, Guo; Zhao, Yufen

    2015-05-07

    The general method for the tandem phosphination-decarboxylation-oxidation of alkynyl acids under aerobic conditions has been developed. In the presence of CuSO4·5H2O and TBHP, the reactions provide a novel access to β-ketophosphine oxides in good to excellent yields. This transformation allows the direct formation of a P-C bond and the construction of a keto group in one reaction.

  14. Catalytic Effect of Cetyltrimethylammonium Bromide on the Oxidation of Triethylene glycol by Chloramine-T in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Vandana Sharma

    2008-01-01

    Full Text Available The kinetics and mechanism of cetyltrimethylammonium bromide catalyzed oxidation of triethylene glycol [2,2'-ethylene diqxybis(ethanol] by chloramine-T in acidic acid medium have been investigated. The reaction is first order dependence on chloramine-T and fractional order for triethylene glycol with excess concentration of other reactants. The catalytic effect due to cetyletrimethylammonium bromide has been studied. The small salt effect and increase in the reaction rate with increasing dielectric constant suggest the involvement of neutral molecule in the rate-determining step. The addition of p-toluene sulfonamide retards the reaction rate. The effect of chloride ion on the reaction also studied. The effect of temperature on the reaction has been investigated in the temperature range 313-333K and thermodynamic parameters were calculated from the Arrhenious plot. A tentative mechanism consistent with the experimental results has been proposed.

  15. Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid.

    Science.gov (United States)

    Tavafoghi, M; Brodusch, N; Gauvin, R; Cerruti, M

    2016-01-01

    Hydroxyapatite (HA, Ca5(PO4)3OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca(2+) and PO4(3-) ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca(2+) and PO4(3-) ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca(2+) and PO4(3-) ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only.

  16. Effect of Heating Rates on the Formable Oxide Scale on a C-Steel Surface

    Institute of Scientific and Technical Information of China (English)

    A.A.El-Meligi

    2004-01-01

    Oxide scale formation on a C-steel surface has been investigated using linear heating rates ranging from 0.1℃/min to 10℃/min at high temperatures. The studies on the oxide scale formation at high temperature (650℃) at slower heating rate (0.1℃/min) shows that the kinetic regime is linear. X-ray diffraction measurements revealed that the scale constituents are significantly influenced by the heating rate. The adherence of the scale was improved by using slower heating rate (0.1℃/min-≤650℃),while above such degree the scale was susceptible to cracking and flaking out of the alloy surface. In fact, the development of oxide growth stresses can cause considerable scale cracking. As well, variation of the crystallite sizes under the aforementioned conditions might affect the scale stacking to the alloy surface. The secondary electron detector images of the oxide scale shows that the scale was imperfectly smooth and there were a number of voids and defects in the scale skin, especially at fast heating rate. This observation could be attributed to defects of the as-received alloy. In general, slower heating rate reduced the defects of the scale and improved its adherence.

  17. Potential for in situ chemical oxidation of acid extractable organics in oil sands process affected groundwater.

    Science.gov (United States)

    Sohrabi, V; Ross, M S; Martin, J W; Barker, J F

    2013-11-01

    The process of bitumen extraction from oil sands in Alberta, Canada leads to an accumulation of toxic acid-extractable organics (AEOs) in oil sands process water (OSPW). Infiltration of OSPW from tailings ponds and from their retaining sand dykes and subsequent transport towards surface water has occurred. Given the apparent lack of significant natural attenuation of AEOs in groundwater, remediation may be required. This laboratory study evaluates the potential use of unactivated persulfate and permanganate as in situ oxidation agents for remediation of AEOs in groundwater. Naphthenic acids (NAs; CnH2n+zO2), which are a component of the acutely toxic AEOs, were degraded by both oxidants in OSPW samples. Permanganate oxidation yielded some residual dissolved organic carbon (DOC) whereas persulfate mineralized the AEO compounds with less residual DOC. Acid-extractable organics from oxidized OSPW had essentially no Microtox toxicity.

  18. Lipid oxidation and fatty acid composition in salt-dried yellow croaker ( Pseudosciaena polyactis) during processing

    Science.gov (United States)

    Cai, Qiuxing; Wu, Yanyan; Li, Laihao; Wang, Yueqi; Yang, Xianqing; Zhao, Yongqiang

    2017-10-01

    Lipid oxidation in salt-dried yellow croaker ( Pseudosciaena polyactis) was evaluated during processing with commonly used analytical indices, such as the peroxide value (POV), the thiobarbituric acid reactive substances (TBARS) value, and oxidative-relative lipoxygenase (LOX) activity. Additionally, fatty acids were analyzed using gas chromatography-mass spectrometry. Both POV and TBARS increased significantly ( P lipid oxidation. C18:0, C16:1n7, C19:0, and C22:6n3 showed clear changes in principle component one of a principle components analysis. These fatty acids are potential markers for evaluating lipid oxidation in fish muscle because there was a significant correlation between these markers and TBARS and LOX activity ( P 0.931.

  19. Silver-catalyzed arylation of (hetero)arenes by oxidative decarboxylation of aromatic carboxylic acids.

    Science.gov (United States)

    Kan, Jian; Huang, Shijun; Lin, Jin; Zhang, Min; Su, Weiping

    2015-02-09

    A long-standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver-catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron-deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho-substituted aromatic carboxylic acids, which were a limitation of previously reported methods.

  20. Acetylation control of cardiac fatty acid β-oxidation and energy metabolism in obesity, diabetes, and heart failure.

    Science.gov (United States)

    Fukushima, Arata; Lopaschuk, Gary D

    2016-12-01

    Alterations in cardiac energy metabolism are an important contributor to the cardiac pathology associated with obesity, diabetes, and heart failure. High rates of fatty acid β-oxidation with cardiac insulin resistance represent a cardiac metabolic hallmark of diabetes and obesity, while a marginal decrease in fatty acid oxidation and a prominent decrease in insulin-stimulated glucose oxidation are commonly seen in the early stages of heart failure. Alterations in post-translational control of energy metabolic processes have recently been identified as an important contributor to these metabolic changes. In particular, lysine acetylation of non-histone proteins, which controls a diverse family of mitochondrial metabolic pathways, contributes to the cardiac energy derangements seen in obesity, diabetes, and heart failure. Lysine acetylation is controlled both via acetyltransferases and deacetylases (sirtuins), as well as by non-enzymatic lysine acetylation due to increased acetyl CoA pool size or dysregulated nicotinamide adenine dinucleotide (NAD(+)) metabolism (which stimulates sirtuin activity). One of the important mitochondrial acetylation targets are the fatty acid β-oxidation enzymes, which contributes to alterations in cardiac substrate preference during the course of obesity, diabetes, and heart failure, and can ultimately lead to cardiac dysfunction in these disease states. This review will summarize the role of lysine acetylation and its regulatory control in the context of mitochondrial fatty acid β-oxidation. The functional contribution of cardiac protein lysine acetylation to the shift in cardiac energy substrate preference that occurs in obesity, diabetes, and especially in the early stages of heart failure will also be reviewed. This article is part of a Special Issue entitled: The role of post-translational protein modifications on heart and vascular metabolism edited by Jason R.B. Dyck & Jan F.C. Glatz.

  1. Fatty acids and oxidative stability of meat from lambs fed carob-containing diets.

    Science.gov (United States)

    Gravador, Rufielyn S; Luciano, Giuseppe; Jongberg, Sisse; Bognanno, Matteo; Scerra, Manuel; Andersen, Mogens L; Lund, Marianne N; Priolo, Alessandro

    2015-09-01

    Male Comisana lambs were individually stalled and, for 56 days, were fed concentrates with 60% barley (n = 8 lambs), or concentrates in which barley was partially replaced by 24% or 35% carob pulp (n = 9 lambs in each group). The intramuscular fatty acids were analyzed and the color stability, lipid and protein oxidation were measured in fresh meat overwrapped with polyvinyl chloride film at 0, 3 or 6 days of storage at 4 °C in the dark. Carob pulp increased the concentration of polyunsaturated fatty acids (PUFA) in muscle, including the rumenic acid (P carob in lamb diet could increase PUFA in muscle without compromising meat oxidative stability.

  2. Oxidation of aromatic alcohols on zeolite-encapsulated copper amino acid complexes

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, S.; Teixeira Florencio, J.M. [Kaiserslautern Univ. (Germany). Dept. of Chemistry, Chemical Technology

    1998-12-31

    Copper complexes of the amino acids histidine, arginine and lysine have been introduced into the supercages of zeolite Y and, for the first time, into the large intracrystalline cavities of zeolites EMT and MCM-22. The resulting host/guest compounds are characterized by X-ray powder diffraction, UV/VIS-spectroscopy in the diffuse reflectance mode and by catalytic tests in the liquid-phase oxidation of aromatic alcohols (viz. benzyl alcohol, 2- and 3-methylbenzyl alcohol and 2,5-dimethylbenzyl alcohol) with tertiary-butylhydroperoxide as oxidant. It was observed that intracrystalline copper-amino acid complexes possess remarkable catalytic activity, yielding the corresponding aromatic aldehydes and acids. (orig.)

  3. Novel Approach: Tungsten Oxide Nanoparticle as a Catalyst for Malonic Acid Ester Synthesis via Ozonolysis

    Directory of Open Access Journals (Sweden)

    Bilal A. Wasmi

    2014-01-01

    Full Text Available Malonic acid ester was synthesized via the one-step ozonolysis of palm olein. Malonic acid ester was spectroscopically characterized using gas chromatography mass spectroscopy (GC-MS. Tungsten oxide nanoparticles were used as the catalyst, which was characterized via X-ray powder diffraction (XRD and field emission scanning electron microscopy (FE-SEM. Tungsten oxide provided several advantages as a catalyst for the esterification malonic acid such as simple operation for a precise ozonation method, an excellent yield of approximately 10%, short reaction times of 2 h, and reusability due to its recyclability.

  4. Environmental Enteric Dysfunction is Associated with Carnitine Deficiency and Altered Fatty Acid Oxidation

    Directory of Open Access Journals (Sweden)

    Richard D. Semba

    2017-03-01

    Interpretation: EED is a syndrome characterized by secondary carnitine deficiency, abnormal fatty acid oxidation, alterations in polyphenol and amino acid metabolites, and metabolic dysregulation of sulfur amino acids, tryptophan, and the urea cycle. Future studies are needed to corroborate the presence of secondary carnitine deficiency among children with EED and to understand how these metabolic derangements may negatively affect the growth and development of young children.

  5. Selective oxidative decarboxylation of amino acids to produce industrially relevant nitriles by vanadium chloroperoxidase.

    Science.gov (United States)

    But, Andrada; Le Nôtre, Jérôme; Scott, Elinor L; Wever, Ron; Sanders, Johan P M

    2012-07-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative decarboxylation can be applied to mixtures of amino acids obtained from plant waste streams, leading to easily separable nitriles. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. High glucose levels reduce fatty acid oxidation and increase triglyceride accumulation in human placenta

    OpenAIRE

    Visiedo, Francisco; Bugatto, Fernando; Sánchez, Viviana; Cózar-Castellano, Irene; Bartha, Jose L.; Perdomo, Germán

    2013-01-01

    Placentas of women with gestational diabetes mellitus (GDM) exhibit an altered lipid metabolism. The mechanism by which GDM is linked to alterations in placental lipid metabolism remains obscure. We hypothesized that high glucose levels reduce mitochondrial fatty acid oxidation (FAO) and increase triglyceride accumulation in human placenta. To test this hypothesis, we measured FAO, fatty acid esterification, de novo fatty acid synthesis, triglyceride levels, and carnitine palmitoyltransferase...

  7. A spectroelectrochemical and chemical study on oxidation of hydroxycinnamic acids in aprotic medium

    Energy Technology Data Exchange (ETDEWEB)

    Petrucci, Rita [Dipartimento di Ingegneria Chimica M.M.P.M., Universita di Roma ' La Sapienza' , via del Castro Laurenziano 7, I-00161 Rome (Italy)]. E-mail: rita.petrucci@uniroma1.it; Astolfi, Paola [Dipartimento di Scienze dei Materiali e della Terra, Universita Politecnica delle Marche, via Brecce Bianche, I-60131 Ancona (Italy); Greci, Lucedio [Dipartimento di Scienze dei Materiali e della Terra, Universita Politecnica delle Marche, via Brecce Bianche, I-60131 Ancona (Italy); Firuzi, Omidreza [Dipartimento di Farmacologia delle Sostanze Naturali e Fisiologia Generale, Universita di Roma ' La Sapienza' , p.le Aldo Moro 5, I-00185 Rome (Italy); Saso, Luciano [Dipartimento di Farmacologia delle Sostanze Naturali e Fisiologia Generale, Universita di Roma ' La Sapienza' , p.le Aldo Moro 5, I-00185 Rome (Italy); Marrosu, Giancarlo [Dipartimento di Ingegneria Chimica M.M.P.M., Universita di Roma ' La Sapienza' , via del Castro Laurenziano 7, I-00161 Rome (Italy)

    2007-02-01

    Electrochemical and chemical oxidation of hydroxycinnamic acids (HCAs) was studied to investigate the mechanisms occurring in their antioxidant activities in a protons poor medium. Electrolyses and chemical reactions were followed on-line by monitoring the UV-spectral changes with time; final solutions were analysed by HPLC-MS. Anodic oxidation of mono- and di-HCAs, studied by cyclic voltammetry and controlled potential electrolyses, occurs via a reversible one-step two-electrons process, yielding the corresponding stable phenoxonium cation. A cyclization product was also proposed, as supported by ESR studies. Chemical oxidation with lead dioxide leads to different oxidation products according to the starting substrate. Di-HCAs like chlorogenic and rosmarinic acids and the ethyl ester of caffeic acid gave the corresponding neutral o-quinones, while mono-HCAs like cumaric, ferulic and sinapinic acids yielded the corresponding unstable neutral phenoxyl radical, as supported by the formation of dimerization products evidenced by HPLC-MS. In the case of caffeic acid, traces of the dimerization product suggest that the neutral phenoxyl radical may competitively undergo dimerization or decomposition of the neutral quinone. Chemical oxidation of HCAs was also followed by ESR spectroscopy: the di-HCAs radical anions were generated and detected, whereas among the mono-HCAs only the phenoxyl radical of the sinapinic acid was recorded.

  8. Cyclobutyl methyl ketone as a model compound for pinonic acid to elucidate oxidation mechanisms

    Directory of Open Access Journals (Sweden)

    A. P. Praplan

    2012-04-01

    Full Text Available 3-Methyl-1,2,3-tricarboxylic acid (MBTCA, terpenylic acid and diaterpenylic acid acetate were identified in secondary organic aerosol (SOA from α-pinene photooxidation or ozonolysis. These compounds display interesting structural features: MBTCA has a high oxygen to carbon ratio, terpenylic acid contains a lactone ring in its structure and diaterpenylic acid acetate possesses an ester functional group. The reaction mechanisms leading to these products are still unknown, but it was demonstrated experimentally in earlier studies that MBTCA is formed from pinonic acid, a primary ozonolysis product of α-pinene. Because the direct observation of pinonic acid oxidation in a smog chamber would be difficult due to its relatively low volatility, a model compound possessing the substructure of interest was used instead: cyclobutyl methyl ketone (CMK. From its oxidation, several organic acids could be measured with ion chromatography (IC coupled to a mass spectrometer (MS. Succinic acid, the analogous product of MBTCA is formed at molar yields of 2 to 5%. Butyrolactone is detected as butanoic acid, due to hydrolysis in the sampling device. A monocarboxylic acid with nominal mass 146 was detected in the absence of nitrogen oxides (NOx and could be the analogous product of diaterpenylic acid acetate. However, due to a lack of available standards, the exact structure of this compound remains unelucidated. Finally, 4-oxobutanoic acid could also be measured and two structures of its expected analogous compound from pinonic acid oxidation are proposed. Because these compounds are primary products of the CMK oxidation, reaction mechanisms capable of adding one or two carboxylic functional groups without formation of stable intermediate products needs to be formulated. Such a formation mechanism of MBTCA from pinonic acid was found in the literature; however, it includes a hydrogen atom migration to an acyloxy radical, which is expected to loose

  9. The effect of valinomycin in fibroblasts from patients with fatty acid oxidation disorders

    Energy Technology Data Exchange (ETDEWEB)

    Ndukwe Erlingsson, Uzochi Chimdinma [Division of Medical Genetics, Department of Pediatrics, University of Utah, 2C412 SOM, 50 North Mario Capecchi Drive, Salt Lake City, UT 84132 (United States); Iacobazzi, Francesco [Division of Medical Genetics, Department of Pediatrics, University of Utah, 2C412 SOM, 50 North Mario Capecchi Drive, Salt Lake City, UT 84132 (United States); Department of Basic Medical Sciences, University of Bari, Piazza Giulio Cesare 11, Policlinico, I-70124 Bari (Italy); Liu, Aiping [ARUP Institute for Clinical and Experimental Pathology, ARUP Laboratories, 500 Chipeta Way, Salt Lake City, UT 84108 (United States); Ardon, Orly; Pasquali, Marzia [Division of Medical Genetics, Department of Pediatrics, University of Utah, 2C412 SOM, 50 North Mario Capecchi Drive, Salt Lake City, UT 84132 (United States); ARUP Institute for Clinical and Experimental Pathology, ARUP Laboratories, 500 Chipeta Way, Salt Lake City, UT 84108 (United States); Department of Pathology, University of Utah, Salt Lake City, UT 84132 (United States); Longo, Nicola, E-mail: Nicola.Longo@hsc.utah.edu [Division of Medical Genetics, Department of Pediatrics, University of Utah, 2C412 SOM, 50 North Mario Capecchi Drive, Salt Lake City, UT 84132 (United States); ARUP Institute for Clinical and Experimental Pathology, ARUP Laboratories, 500 Chipeta Way, Salt Lake City, UT 84108 (United States); Department of Pathology, University of Utah, Salt Lake City, UT 84132 (United States)

    2013-08-09

    Highlights: •Valinomycin can cause mitochondrial stress and stimulate fatty acid oxidation. •Cells with VLCAD deficiency fail to increase fatty acid oxidation in response to valinomycin. •Response to valinomycin can help in the diagnosis of VLCAD deficiency. -- Abstract: Disorders of the carnitine cycle and of the beta oxidation spiral impair the ability to obtain energy from fats at time of fasting and stress. This can result in hypoketotic hypoglycemia, cardiomyopathy, cardiac arrhythmia and other chronic medical problems. The in vitro study of fibroblasts from patients with these conditions is impaired by their limited oxidative capacity. Here we evaluate the capacity of valinomycin, a potassium ionophore that increases mitochondrial respiration, to increase the oxidation of fatty acids in cells from patients with inherited fatty acid oxidation defects. The addition of valinomycin to fibroblasts decreased the accumulation of the lipophilic cation tetraphenylphosphonium (TPP{sup +}) at low concentrations due to the dissipation of the mitochondrial membrane potential. At higher doses, valinomycin increased TPP{sup +} accumulation due to the increased potassium permeability of the plasma membrane and subsequent cellular hyperpolarization. The incubation of normal fibroblasts with valinomycin increased [{sup 14}C]-palmitate oxidation (measured as [{sup 14}C]O{sub 2} release) in a dose-dependent manner. By contrast, valinomycin failed to increase palmitate oxidation in fibroblasts from patients with very long chain acyl CoA dehydrogenase (VLCAD) deficiency. This was not observed in fibroblasts from patients heterozygous for this condition. These results indicate that valinomycin can increase fatty acid oxidation in normal fibroblasts and could be useful to differentiate heterozygotes from patients affected with VLCAD deficiency.

  10. Impact of Association Colloids on Lipid Oxidation in Triacylglycerols and Fatty Acid Ethyl Esters.

    Science.gov (United States)

    Homma, Rika; Suzuki, Karin; Cui, Leqi; McClements, David Julian; Decker, Eric A

    2015-11-25

    The impact of association colloids on lipid oxidation in triacylglycerols and fatty acid ethyl esters was investigated. Association colloids did not affect lipid oxidation of high oleic safflower and high linoleic safflower triacylglycerols, but were prooxidative in fish triacylglycerols. Association colloids retarded aldehyde formation in stripped ethyl oleate, linoleate, and fish oil ethyl esters. Interfacial tension revealed that lipid hydroperoxides were surface active in the presence of the surfactants found in association colloids. The lipid hydroperoxides from ethyl esters were less surface active than triacylglycerol hydroperoxides. Stripping decreased iron and copper concentrations in all oils, but more so in fatty acid ethyl esters. The combination of lower hydroperoxide surface activity and low metal concentrations could explain why association colloids inhibited lipid oxidation in fatty acid ethyl esters. This research suggests that association colloids could be used as an antioxidant technology in fatty acid ethyl esters.

  11. Fatty Acid Oxidation and Cardiovascular Risk during Menopause: A Mitochondrial Connection?

    Directory of Open Access Journals (Sweden)

    Paulo J. Oliveira

    2012-01-01

    Full Text Available Menopause is a consequence of the normal aging process in women. This fact implies that the physiological and biochemical alterations resulting from menopause often blur with those from the aging process. It is thought that menopause in women presents a higher risk for cardiovascular disease although the precise mechanism is still under discussion. The postmenopause lipid profile is clearly altered, which can present a risk factor for cardiovascular disease. Due to the role of mitochondria in fatty acid oxidation, alterations of the lipid profile in the menopausal women will also influence mitochondrial fatty acid oxidation fluxes in several organs. In this paper, we propose that alterations of mitochondrial bioenergetics in the heart, consequence from normal aging and/or from the menopausal process, result in decreased fatty acid oxidation and accumulation of fatty acid intermediates in the cardiomyocyte cytosol, resulting in lipotoxicity and increasing the cardiovascular risk in the menopausal women.

  12. Photoelectrocatalytic Oxidation of Formic Acid at Titania@Polyoxometalate/Gold Nanocomposite Material Modified Electrode.

    Science.gov (United States)

    Pandiyarajan, Chinnappan; Pandikumar, Alagarsamy; Ramaraj, Ramasamy

    2015-09-01

    Amine functionalized silicate sol-gel stabilized titania (P25)-polyoxometalate (PTA)-gold (Au) nanocomposite materials (APS/(P25-PTA-Au)(NCM)) were prepared by a simple chemical reduction method and were used to fabricate modified photoelectrode for the photoelectrocatalytic oxidation of formic acid. The APS/(P25-PTA-Au)(NCM) photoelectrode showed synergistic photoelectrocatalytic behavior towards the oxidation of formic acid. The photoresponse of the APS/(P25-PTA-Au)(NCM) modified photoelectrode was found to be higher when compared to the controlled photoelectrodes. The present study shows that the loading of Au(nps) on APS/P25-PTA is more beneficial to enhance the photoinduced interfacial charge transfer process, which leads to increased photocurrent generation. The present study concludes that the photoelectrocatalytic oxidation of formic acid at the APS/(P25-PTA-Au)(NCM) photoelectrode will boost the formic acid fuel cell performance.

  13. Oxidation and hydrolysis of lactic acid in near-critical water

    Energy Technology Data Exchange (ETDEWEB)

    Li, L.; Vallejo, D.; Gloyna, E.F. [Univ. of Texas, Austin, TX (United States). Civil Engineering Dept.; Portela, J.R. [Univ. de Cadiz (Spain). Dept. de Ingenieria Quimica

    1999-07-01

    Hydrothermal reactions (oxidation and hydrolysis) involving lactic acid (LA) were studied at temperatures ranging from 300 to 400 C and a nominal pressure of 27.6 MPa. Kinetic models were developed with respect to concentrations of LA and total organic carbon (TOC), respectively. On the basis of identified liquid and gaseous products, pathways for hydrothermal reactions involving lactic acid were proposed. Acetic acid and acetaldehyde were confirmed as the major liquid intermediates for oxidation and hydrolysis reactions, respectively. Carbon monoxide and methane were identified as the major gaseous byproducts from these reactions. These results demonstrate the potential of completely oxidizing, as well as converting, lactic acid into other organic products, in high-temperature water.

  14. Carotenoids, birdsong and oxidative status: administration of dietary lutein is associated with an increase in song rate and circulating antioxidants (albumin and cholesterol and a decrease in oxidative damage.

    Directory of Open Access Journals (Sweden)

    Stefania Casagrande

    Full Text Available Despite the appealing hypothesis that carotenoid-based colouration signals oxidative status, evidence supporting the antioxidant function of these pigments is scarce. Recent studies have shown that lutein, the most common carotenoid used by birds, can enhance the expression of non-visual traits, such as birdsong. Nevertheless, the underlying physiological mechanisms remain unclear. In this study we hypothesized that male European starlings (Sturnus vulgaris fed extra lutein increase their song rate as a consequence of an improved oxidative status. Although birdsong may be especially sensitive to the redox status, this has, to the best of our knowledge, never been tested. Together with the determination of circulating oxidative damage (ROMs, reactive oxygen metabolites, we quantified uric acid, albumin, total proteins, cholesterol, and testosterone, which are physiological parameters potentially sensitive to oxidation and/or related to both carotenoid functions and birdsong expression. We found that the birds fed extra lutein sang more frequently than control birds and showed an increase of albumin and cholesterol together with a decrease of oxidative damage. Moreover, we could show that song rate was associated with high levels of albumin and cholesterol and low levels of oxidative damage, independently from testosterone levels. Our study shows for the first time that song rate honestly signals the oxidative status of males and that dietary lutein is associated with the circulation of albumin and cholesterol in birds, providing a novel insight to the theoretical framework related to the honest signalling of carotenoid-based traits.

  15. Carotenoids, birdsong and oxidative status: administration of dietary lutein is associated with an increase in song rate and circulating antioxidants (albumin and cholesterol) and a decrease in oxidative damage.

    Science.gov (United States)

    Casagrande, Stefania; Pinxten, Rianne; Zaid, Erika; Eens, Marcel

    2014-01-01

    Despite the appealing hypothesis that carotenoid-based colouration signals oxidative status, evidence supporting the antioxidant function of these pigments is scarce. Recent studies have shown that lutein, the most common carotenoid used by birds, can enhance the expression of non-visual traits, such as birdsong. Nevertheless, the underlying physiological mechanisms remain unclear. In this study we hypothesized that male European starlings (Sturnus vulgaris) fed extra lutein increase their song rate as a consequence of an improved oxidative status. Although birdsong may be especially sensitive to the redox status, this has, to the best of our knowledge, never been tested. Together with the determination of circulating oxidative damage (ROMs, reactive oxygen metabolites), we quantified uric acid, albumin, total proteins, cholesterol, and testosterone, which are physiological parameters potentially sensitive to oxidation and/or related to both carotenoid functions and birdsong expression. We found that the birds fed extra lutein sang more frequently than control birds and showed an increase of albumin and cholesterol together with a decrease of oxidative damage. Moreover, we could show that song rate was associated with high levels of albumin and cholesterol and low levels of oxidative damage, independently from testosterone levels. Our study shows for the first time that song rate honestly signals the oxidative status of males and that dietary lutein is associated with the circulation of albumin and cholesterol in birds, providing a novel insight to the theoretical framework related to the honest signalling of carotenoid-based traits.

  16. Phytochemicals in regulating fatty acid β-oxidation: Potential underlying mechanisms and their involvement in obesity and weight loss.

    Science.gov (United States)

    Rupasinghe, H P Vasantha; Sekhon-Loodu, Satvir; Mantso, Theodora; Panayiotidis, Mihalis I

    2016-09-01

    Excessive accumulation of fat as the result of more energy intake and less energy expenditure is known as obesity. Lipids are essential components in the human body and are vital for maintaining homeostasis and physiological as well as cellular metabolism. Fatty acid synthesis and catabolism (by fatty acid oxidation) are normal part of basic fuel metabolism in animals. Fatty acids are degraded in the mitochondria by a biochemical process called β-oxidation in which two-carbon fragments are produced in each cycle. The increase in fatty acid β-oxidation is negatively correlated with body mass index. Although healthy life style, avoiding Western diet, dieting and strenuous exercise are the commonly used methods to lose weight, they are not considered a permanent solution in addition to risk attenuation of basal metabolic rate (BMR). Pharmacotherapy offers benefits of weight loss by altering the satiety and lowering absorption of fat from the food; however, its side effects may outweigh the benefits of weight loss. Alternatively, dietary phytochemicals and natural health products offer great potential as an efficient weight loss strategy by modulating lipid metabolism and/or increasing BMR and thermogenesis. Specifically, polyphenols such as citrus flavonoids, green tea epigallocatechin gallate, resveratrol, capsaicin and curcumin, have been reported to increase lipolysis and induce fatty acid β-oxidation through modulation of hormone sensitive lipase, acetyl-coA carboxylase, carnitine acyl transferase and peroxisome proliferator-activated receptor gamma coactivator-1. In this review article, we discuss selected phytochemicals in relation to their integrated functionalities and specific mechanisms for weight loss. Copyright © 2016 Elsevier Inc. All rights reserved.

  17. Oxidative diversification of amino acids and peptides by small-molecule iron catalysis

    Science.gov (United States)

    Osberger, Thomas J.; Rogness, Donald C.; Kohrt, Jeffrey T.; Stepan, Antonia F.; White, M. Christina

    2016-09-01

    Secondary metabolites synthesized by non-ribosomal peptide synthetases display diverse and complex topologies and possess a range of biological activities. Much of this diversity derives from a synthetic strategy that entails pre- and post-assembly oxidation of both the chiral amino acid building blocks and the assembled peptide scaffolds. The vancomycin biosynthetic pathway is an excellent example of the range of oxidative transformations that can be performed by the iron-containing enzymes involved in its biosynthesis. However, because of the challenges associated with using such oxidative enzymes to carry out chemical transformations in vitro, chemical syntheses guided by these principles have not been fully realized in the laboratory. Here we report that two small-molecule iron catalysts are capable of facilitating the targeted C-H oxidative modification of amino acids and peptides with preservation of α-centre chirality. Oxidation of proline to 5-hydroxyproline furnishes a versatile intermediate that can be transformed to rigid arylated derivatives or flexible linear carboxylic acids, alcohols, olefins and amines in both monomer and peptide settings. The value of this C-H oxidation strategy is demonstrated in its capacity for generating diversity: four ‘chiral pool’ amino acids are transformed to twenty-one chiral unnatural amino acids representing seven distinct functional group arrays; late-stage C-H functionalizations of a single proline-containing tripeptide furnish eight tripeptides, each having different unnatural amino acids. Additionally, a macrocyclic peptide containing a proline turn element is transformed via late-stage C-H oxidation to one containing a linear unnatural amino acid.

  18. Role Of Ascorbic Acid In Imparting Tolerance To Plants Against Oxidizing Pollutants

    Directory of Open Access Journals (Sweden)

    Priyanka Sharma

    2015-08-01

    Full Text Available Ascorbic acid is an antioxidant in plants which play important role in activation of many physiological and defense mechanisms. The level of ascorbic acid in plants is determinant of its tolerance against the adverse effect of oxidizing pollutants. The present study tries to relate the variation in ascorbic acid content with the tolerance and sensitivity of two selected plant species viz. Azadirachtaindica and Pongamiapinnata by calculating their Air Pollution Tolerance Index APTI during winter season from November to March in the urban city Delhi of North India. Moreover ascorbic acid is also an important part of chloroplast it protects different components of photosynthetic system from oxidative stress. Thus to understand the role of ascorbic acid in imparting tolerance to plants against oxidizing pollutants the changes in chlorophyll content of the selected plant species with variation in ambient ozone concentration was analysed. It was found that as per APTI values Azadirachta sp. came under tolerant range with highest ascorbic acid content whereas Pongamia sp. was under intermediate range with less ascorbic acid content. It was statistically established that ozone has no significant relation with chlorophyll content of Azadirachta sp. which has the highest ascorbic acid content. Whereas ambient ozone concentrations showed significant negative relation with the chlorophyll content of Pongamia sp. p 0.05. Thus it was observed that the plants with high ascorbic acid content are tolerant and have greater ability to remediate pollutants.

  19. Oxidative acid treatment and characterization of new biocarbon from sustainable Miscanthus biomass

    Energy Technology Data Exchange (ETDEWEB)

    Anstey, Andrew [Bioproducts Discovery and Development Centre (BDDC), Department of Plant Agriculture, Crop Science Building, University of Guelph, Guelph, ON N1G 2W1 (Canada); School of Engineering, Thornbrough Building, University of Guelph, Guelph, ON N1G 2W1 (Canada); Vivekanandhan, Singaravelu [Bioproducts Discovery and Development Centre (BDDC), Department of Plant Agriculture, Crop Science Building, University of Guelph, Guelph, ON N1G 2W1 (Canada); Sustainable Materials and Nanotechnology Lab, Department of Physics, VHNSN College, Virudhunagar 626 001, Tamilnadu (India); Rodriguez-Uribe, Arturo [Bioproducts Discovery and Development Centre (BDDC), Department of Plant Agriculture, Crop Science Building, University of Guelph, Guelph, ON N1G 2W1 (Canada); Misra, Manjusri [Bioproducts Discovery and Development Centre (BDDC), Department of Plant Agriculture, Crop Science Building, University of Guelph, Guelph, ON N1G 2W1 (Canada); School of Engineering, Thornbrough Building, University of Guelph, Guelph, ON N1G 2W1 (Canada); Mohanty, Amar Kumar, E-mail: mohanty@uoguelph.ca [Bioproducts Discovery and Development Centre (BDDC), Department of Plant Agriculture, Crop Science Building, University of Guelph, Guelph, ON N1G 2W1 (Canada); School of Engineering, Thornbrough Building, University of Guelph, Guelph, ON N1G 2W1 (Canada)

    2016-04-15

    Oxidative acid treatments of biochar produced from Miscanthus were performed in this study using nitric acid, sulfuric acid, and a mixture of both. The structural and morphological changes of the acid-treated biochar were investigated using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Raman spectroscopy, organic elemental analysis and energy-dispersive X-ray spectroscopy (EDS). Improved surface functionality of the treated biochars was observed in their respective FT-IR spectra through the presence of nitro and carboxylic acid functional groups. SEM–EDS and elemental analysis revealed a large increase in the oxygen to carbon ratio in the biochar, which was evidence of chemical oxidation from the acid treatment. Further, TGA study showed the reduced thermal stability of acid-treated biochar over 200 °C due to the increased oxygen content. Acid treatments also influenced the graphitic structure of the biochar, as observed in the Raman spectra. The results suggest that biochar can be successfully functionalized for composite applications and provide a sustainable alternative to petroleum-based carbon additives. - Highlights: • Biochar was investigated as a candidate for renewable functionalized carbon. • Oxidative acid treatment was used to modify the carbon structure. • The chemical and morphological properties of the treated biochar were examined. • Successful chemical modification of biochar was verified through characterization. • Biochar shows potential as a sustainable carbon additive for polymer composites.

  20. Growth behavior of anodic oxide formed by aluminum anodizing in glutaric and its derivative acid electrolytes

    Science.gov (United States)

    Nakajima, Daiki; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

    2014-12-01

    The growth behavior of anodic oxide films formed via anodizing in glutaric and its derivative acid solutions was investigated based on the acid dissociation constants of electrolytes. High-purity aluminum foils were anodized in glutaric, ketoglutaric, and acetonedicarboxylic acid solutions under various electrochemical conditions. A thin barrier anodic oxide film grew uniformly on the aluminum substrate by glutaric acid anodizing, and further anodizing caused the film to breakdown due to a high electric field. In contrast, an anodic porous alumina film with a submicrometer-scale cell diameter was successfully formed by ketoglutaric acid anodizing at 293 K. However, the increase and decrease in the temperature of the ketoglutaric acid resulted in non-uniform oxide growth and localized pitting corrosion of the aluminum substrate. An anodic porous alumina film could also be fabricated by acetonedicarboxylic acid anodizing due to the relatively low dissociation constants associated with the acid. Acid dissociation constants are an important factor for the fabrication of anodic porous alumina films.

  1. Correlation between the different chain lengths of free fatty acid oxidation and ability of trophoblastic invasion

    Institute of Scientific and Technical Information of China (English)

    Yu Huan; Yang Zi; Ding Xiaoyan; Wang Yanling; Han Yiwei

    2014-01-01

    Background Preeclampsia (PE) is associated with abnormal fatty acid beta-oxidation (FAO),especially metabolic disorders of long-chain fatty acid oxidation.The role of FAO dysfunction in inadequate invasion is unclear.The aim of this study was to explore the influence of various lengths fatty acids oxidation on invasiveness of trophoblasts.Methods Primary human trophoblast cells and HTR8/SVneo cells were treated with fatty acids of various lengths.Morphological changes,lipid deposition and ultrastructure changes of trophoblast cells were detected.Cells invasiveness was determined by transwell insert.CPT1,CPT2 and long-chain 3-hydroxyacyl-CoA dehydrogenase (LCHAD) protein expression were analyzed.The correlation between intracellular lipid droplets deposition and cells invasiveness was evaluated.Results Cells treated with long-chain fatty acids showed significant increased lipid droplets deposition,severe mitochondrial damage,decreased CPT2 and LCHAD protein expression (P <0.05) but no significant difference in CPT1 protein expression (P >0.05).Invasiveness of the trophoblast cells of the LC-FFA group significantly decreased (P <0.05).Intracellular lipid droplets deposition was negatively correlated with invasivenss (R=-0.745,P <0.05).Conclusion Trophoblast cells after stimulation with long chain fatty acids exist fatty acid oxidation disorders,and reduce the ability of trophoblastic invasion.

  2. Mechanism and Kinetics Study for Photocatalytic Oxidation Degradation: A Case Study for Phenoxyacetic Acid Organic Pollutant

    Directory of Open Access Journals (Sweden)

    Kian Mun Lee

    2015-01-01

    Full Text Available Photocatalysis is a rapidly expanding technology for wastewater treatment, including a wide range of organic pollutants. Thus, understanding the kinetics and mechanism of the photocatalytic oxidation (PCO for degradation of phenoxyacetic acid (PAA is an indispensable component of risk assessment. In this study, we demonstrated that the central composite design (CCD coupled with response surface methodology (RSM was successfully employed to probe the kinetics and mechanism of PCO degradation for PAA using an efficient zinc oxide (ZnO photocatalyst. In our current case study, four independent factors such as ZnO dosage, initial concentration of PAA, solution pH, and reaction time on the PCO degradation for PAA were examined in detail. Based on our results obtained from RSM analyses, an efficient pathway leading to the high degradation rate (>90% was applying 0.4 g/L of ZnO dosage with 16 mg/L of concentration of PAA at pH 6.73 for 40 minutes. The experimental results were fitted well with the derived response model with R2 = 0.9922. This study offers a cost-effective way for probing our global environmental water pollution issue.

  3. Destruction of methylphosphonic acid in a supercritical water oxidation bench-scale double wall reactor

    Institute of Scientific and Technical Information of China (English)

    Bambang Veriansyah; Eun-Seok Song; Jae-Duck Kim

    2011-01-01

    The destruction of methylphosphonic acid (MPA), a final product by hydrolysis/neutralization of organophosphorus agents such as satin and VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothionate), was investigated in a a bench-scale, continuous concentric vertical double wall reactor under supercritical water oxidation condition. The experiments were conducted at a temperature range of 450-600~C and a fixed pressure of 25 MPa. Hydrogen peroxide was used as an oxidant. The destruction efficiency (DE) was monitored by analyzing total organic carbon (TOC) and MPA concentrations using ion chromatography on the liquid effluent samples. The results showed that the DE of MPA up to 99.999% was achieved at a reaction temperature of 600~C, oxygen concentration of 113% storichiometric requirement, and reactor residence time of 8 sec. On the basis of the data derived from experiments, a global kinetic rate equation for the DE of MPA and DE of TOC were developed by nonlinear regression analysis. The model predictions agreed well with the experimental data.

  4. Electrocatalytic Oxidation of Formate with Nickel Diphosphane Dipeptide Complexes. Effect of Ligands Modified with Amino Acids

    Energy Technology Data Exchange (ETDEWEB)

    Galan, Brandon R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Reback, Matthew L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Jain, Avijita [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Appel, Aaron M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Shaw, Wendy J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2013-09-03

    A series of nickel bis-diphosphine complexes with dipeptides appended to the ligands were investigated for the catalytic oxidation of formate. Typical rates of ~7 s-1 were found, similar to the parent complex (~8 s-1), with amino acid size and positioning contributing very little to rate or operating potential. Hydroxyl functionalities did result in lower rates, which were recovered by protecting the hydroxyl group. The results suggest that the overall dielectric introduced by the dipeptides does not play an important role in catalysis, but free hydroxyl groups do influence activity suggesting contributions from intra- or intermolecular interactions. These observations are important in developing a fundamental understanding of the affect that an enzyme-like outer coordination sphere can have upon molecular catalysts. This work was funded by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (BRG, AJ, AMA, WJS), the US DOE Basic Energy Sciences, Physical Bioscience program (MLR). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  5. Voltammetric oxidation of dipyridamole in aqueous acid solutions

    Directory of Open Access Journals (Sweden)

    Castilho Marilza

    2000-01-01

    Full Text Available The electrochemical oxidation of dipyridamole (DIP has been studied in acidified aqueous solutions at platinum electrodes employing cyclic voltammetry and controlled-potential electrolysis. The progress of the anodic oxidation as a function of time was monitored by cyclic voltammetry with platinum ultramicroelectrodes, absorption and fluorescence optical spectroscopies, the resulting integrated charge being indicative of a two electron process. The cyclic voltammograms registered for low scan speeds are characterized by a single irreversible diffusion controlled anodic wave, the related cathodic wave being also observable for scan speeds higher than 1 V s-1. Oxidation reaction stoichiommetric parameters were obtained through Tafel slopes resulting in unitary reaction orders for DIP and H+.

  6. Enzymatic Browning in Sugar Beet Leaves (Beta vulgaris L.): Influence of Caffeic Acid Derivatives, Oxidative Coupling, and Coupled Oxidation.

    Science.gov (United States)

    Vissers, Anne; Kiskini, Alexandra; Hilgers, Roelant; Marinea, Marina; Wierenga, Peter Alexander; Gruppen, Harry; Vincken, Jean-Paul

    2017-06-21

    Sugar beet (Beta vulgaris L.) leaves of 8 month (8m) plants showed more enzymatic browning than those of 3 month (3m). Total phenolic content increased from 4.6 to 9.4 mg/g FW in 3m and 8m, respectively, quantitated by reverse-phase-ultrahigh-performance liquid chromatography-ultraviolet-mass spectrometry (RP-UHPLC-UV-MS). The PPO activity was 6.7 times higher in extracts from 8m than from 3m leaves. Substrate content increased from 0.53 to 2.45 mg/g FW in 3m and 8m, respectively, of which caffeic acid glycosyl esters were most important, increasing 10-fold with age. Caffeic acid glycosides and vitexin derivatives were no substrates. In 3m and 8m, nonsubstrate-to-substrate ratios were 8:1 and 3:1, respectively. A model system showed browning at 3:1 ratio due to formation of products with extensive conjugated systems through oxidative coupling and coupled oxidation. The 8:1 ratio did not turn brown as oxidative coupling occurred without much coupled oxidation. We postulate that differences in nonsubstrate-to-substrate ratio and therewith extent of coupled oxidation explain browning.

  7. Characteristics of Oxidative Storage Stability of Canola Fatty Acid Methyl Ester Stabilised with Antioxidants

    Directory of Open Access Journals (Sweden)

    Tirto Prakoso

    2012-11-01

    Full Text Available The storage effects on the oxidation characteristics of fatty acid methyl ester of canola oil (CME were investigated in this study. CME stabilised with two antioxidants, i.e. 2,6-di-tert-bytyl-p-cresol (BHT and 6,6-di-tert-butyl-2, 2’-methylendi-p-cresol (BPH, was stored at 20, 40 and 60°C. The oxidation stability data were measured by the Rancimat test method and it was found that both BHT and BPH addition increased the oxidation resistance of the CME. The results showed that when BPH or BHT was added at a concentration of 100 ppm, the oxidation induction period of the neat CME samples increased from 5.53 h to 6.93 h and 6.14 h, respectively. Comparing both antioxidants, BPH proved to be more effective in increasing the oxidation resistance when both antioxidants were added at the same concentration. Furthermore, the oxidation induction time decreased linearly with the storage time. It was shown that the oxidation occurred rapidly in the first 8 weeks of storage. Later, a kinetic study was undertaken and first-order kinetics were applied to explain the oxidation characteristics of the CME added with antioxidants. This kinetic study focused on exploiting the activation energy values obtained from the Arrhenius equations. Also, the oxidation effects on other quality parameters, including acid value, peroxide value, kinematic viscosity, and water content, were examined.

  8. A metal-free, one-pot method for the oxidative cleavage of internal aliphatic alkenes into carboxylic acids

    NARCIS (Netherlands)

    Spannring, P.; Bruijnincx, P.C.A.; Weckhuysen, B.M.; Klein Gebbink, R.J.M.

    2013-01-01

    The oxidative cleavage of terpenes and unsaturated fatty acids into carbonyl compounds is an industrially interesting reaction. We have developed a metal-free protocol that can oxidatively cleave unsaturated fatty acids, terpenes and a variety of other alkenes into carboxylic acids in a

  9. Comparison of gas-phase acidities of some carbon acids with their rates of hydron exchange in methanolic methoxide

    NARCIS (Netherlands)

    DeTuri, V.F.; Koch, H.F.; Koch, J.G.; Lodder, G.; Mishima, M.; Zuilhof, H.; Abrams, N.M.; Anders, C.E.; Biffinger, J.C.; Han, P.; Kurland, A.R.; Nichols, J.M.; Ruminski, A.M.; Smith, P.R.; Vasey, K.D.J.

    2006-01-01

    Hydron exchange reaction rates, k(exch)M(-1) s(-1), using methanolic sodium methoxide are compared with gas-phase acidities, Delta G(Acid)(0) kcal/mol, for four 9-YPhenylfluorenes-9-H-i, seven (YC6H4CH)-H-i(CF3)(2), seven YC6H4-(CHClCF3)-H-i, and (C6F5H)-H-i. Fourteen of the fluorinated benzylic com

  10. Enhanced photoluminescence in transparent thin films of polyaniline–zinc oxide nanocomposite prepared from oleic acid modified zinc oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Sajimol Augustine, M., E-mail: sajimollazar@gmail.com [Department of Physics, St. Teresa' s College, Kochi-11, Kerala (India); Jeeju, P.P.; Varma, S.J.; Francis Xavier, P.A. [Division for Research in Advanced Materials, Department of Physics, Cochin University of Science and Technology, Kochi-22, Kerala (India); Jayalekshmi, S., E-mail: lakshminathcusat@gmail.com [Division for Research in Advanced Materials, Department of Physics, Cochin University of Science and Technology, Kochi-22, Kerala (India)

    2014-07-01

    Oleic acid capped zinc oxide (ZnO) nanoparticles have been synthesized by a wet chemical route. The chemical oxidative method is employed to synthesize polyaniline (PANI) and PANI/ZnO nanocomposites doped with four different dopants such as orthophosphoric acid (H{sub 3}PO{sub 4}), hydrochloric acid (HCl), naphthalene-2-sulphonic acid and camphor sulphonic acid (CSA). The samples have been structurally characterized by X-ray diffraction (XRD), field emission scanning electron microscopy and Fourier transform infrared (FT-IR) spectroscopic techniques. A comparison of the photoluminescence (PL) emission intensity of PANI and PANI/ZnO nanocomposites is attempted. The enhanced PL intensity in PANI/ZnO nanocomposites is caused by the presence of nanostructured and highly fluorescent ZnO in the composites. It has been observed that, among the composites, the H{sub 3}PO{sub 4} doped PANI/ZnO nanocomposite is found to exhibit the highest PL intensity because of the higher extent of (pi) conjugation and the more orderly arrangement of the benzenoid and quinonoid units. In the present work, transparent thin films of PANI and PANI/ZnO nanocomposite for which PL intensity is found to be maximum, have been prepared after re-doping with CSA by the spin-coating technique. The XRD pattern of the PANI/ZnO film shows exceptionally good crystallanity compared to that of pure PANI, which suggests that the addition of ZnO nanocrystals helps in enhancing the crystallanity of the PANI/ZnO nanocomposite. There is a significant increase in the PL emission intensity of the PANI/ZnO nanocomposite film making it suitable for the fabrication of optoelectronic devices. - Highlights: • Oleic acid capped zinc oxide nanoparticles are synthesized by wet chemical method. • Polyaniline/zinc oxide nanocomposites are prepared by in-situ polymerization. • Polyaniline and polyaniline/zinc oxide thin films are deposited using spin-coating. • Enhanced photoluminescence is observed in polyaniline

  11. Phenol acidity and ease of oxidation in isoflavonoid/β-carotene antioxidant synergism.

    Science.gov (United States)

    Han, Rui-Min; Li, Dan-Dan; Chen, Chang-Hui; Liang, Ran; Tian, Yu-Xi; Zhang, Jian-Ping; Skibsted, Leif H

    2011-09-28

    Regeneration of β-carotene from the β-carotene radical cation by the 4'-propylpuerarin anion (second-order rate constant=1.5×10(9) L mol(-1) s(-1) in methanol/chloroform=1:9 (v/v) solution at 25 °C as determined by laser flash photolysis) was found to be marginally slower than regeneration by the 7-propylpuerarin anion (2.3×10(9) L mol(-1) s(-1)), in agreement with the 7-propylpuerarin anion being more reducing (E'=0.56 V vs NHE) than the 4'-propylpuerarin anion (E'=1.01 V vs NHE). The potentials were calculated from E°=1.12 and 1.44 V (vs NHE) as determined by cyclic voltametry in aqueous solution and pKa=9.51 and 7.23 obtained previously for 7-propylpuerarin and 4'-propylpuerarin, respectively. The less reducing but more acidic 4'-propylpuerarin showed less antioxidant activity in liposome of pH 7.4, but more significant antioxidant synergism with β-carotene than the more reducing but less acidic 7-propylpuerarin for oxidation initiated in the liposome lipid phase. Electrostatic effects are concluded to be important in the regeneration of β-carotene from the radical cation in the water/lipid interface because approximately 50% of 4'-propylpuerarin is present as the anion, whereas only 0.5% of 7-propylpuerarin is present as the anion. In contrast, penetration of the undissociated phenolic group into the lipid phase, more significant for 7-propylpuerarin than for 4'-propylpuerarin according to the calculated water/lipid partition coefficients, becomes important for the chain-breaking action in lipid oxidation of the puerarin derivatives as models for (iso)flavonoids and their glycosides.

  12. Kinetics and Mechanism of the Oxidation of Naphthol Green B by Peroxydisulphate Ion in Aqueous Acidic Medium

    Directory of Open Access Journals (Sweden)

    B. Myek

    2014-01-01

    Full Text Available The kinetics of the oxidation of naphthol green B (NGB3− by peroxydisulphate ion has been carried out in aqueous acidic medium at λmax of 700 nm, T=23±1°C, and I=0.50 mol dm−3 (NaCl. The reaction shows a first-order dependence on oxidant and reductant concentration, respectively. The stoichiometry of the NGB—S2O82- reaction is 1 : 2. Change in hydrogen ions concentration of the reaction medium has no effect on the rate of the reaction. Added cations and anions decreased the rate of the reaction. The results of spectroscopic and kinetic investigation indicate that no intermediate complex is probably formed in the course of this reaction.

  13. Assessment of the role of α-lipoic acid against the oxidative stress of induced iron overload

    Directory of Open Access Journals (Sweden)

    Yasser F. Ali

    2015-01-01

    Full Text Available This work was aimed to study the protective role of α-lipoic acid against the oxidative damage of induced iron overload. Iron (Fe overload is a complication of the treatment, by chronic transfusion, of a number of genetic diseases associated with inadequate red cell production (anemias and of other genetic diseases that lead to excessive iron absorption from the diet. Male rats were injected ip with 5 mg/kg body weight ferrous sulfate for 50 days. The animals were injected ip with α-lipoic acid 20 mg per kg body weight for 21 days. Serum iron, Total Iron Binding Capacity (TIBC, Malonyldialdehyde (MDA, Electron paramagnetic resonance (EPR spectroscopy, UV-visible absorption spectrum of hemoglobin and osmotic fragility were studied. Results showed significant increase in serum iron, total iron binding capacity, and malonyldialdehyde levels in iron-loaded rats. Treatment with lipoic acid (LA resulted in decreasing serum iron and TIBC levels by 47%and 29% respectively. At the same time the lipoic acid decreased the level of the MDA in liver, brain and plasma by 54%, 42% and 74% respectively. Also LA diminished the effect of iron-induced free radicals on erythrocyte membrane integrity; it decreased the elevated average osmotic fragility and decreased the elevated rate of hemolysis. Results from UV-visible spectrophotometric measurement of hemoglobin revealed that no oxidative changes of hemoglobin occurred in iron-loaded rats. EPR spectra showed increased in non-heme ferric ions Fe+3 and free radicals in iron-loaded rats. Whereas the injection of the lipoic acid leads to decreased in such toxic result. In conclusion, these observations suggested that lipoic acid might be a beneficial antioxidant that can be effective for limiting damage from oxidative stress of iron overload.

  14. Rate law of Fe(II) oxidation under low O2 conditions

    Science.gov (United States)

    Kanzaki, Yoshiki; Murakami, Takashi

    2013-12-01

    Despite intensive studies on Fe(II) oxidation kinetics, the oxidation rate law has not been established under low O2 conditions. The importance of Fe(II) oxidation under low O2 conditions has been recently recognized; for instance, the Fe(II)/Fe(III) compositions of paleosols, ancient soils formed by weathering, can produce a quantitative pattern of the atmospheric oxygen increase during the Paleoproterozoic. The effects of partial pressure of atmospheric oxygen (PO2) on the Fe(II) oxidation rate were investigated to establish the Fe(II) oxidation rate - PO2 relationships under low O2 conditions. All oxidation experiments were carried out in a glove box by introducing Ar gas at ∼10-5-∼10-4 atm of PO2, pH 7.57-8.09 and 22 °C. Luminol chemiluminescence was adopted to measure low Fe(II) concentrations (down to ∼2 nM). Combining previous data under higher PO2 conditions (10-3-0.2 atm) with the present data, the rate law for Fe(II) oxidation over a wide range of PO2 (10-5-0.2 atm) was found to be written as: d[Fe(II)]/dt=-k[Fe(II)][[]2 where the exponent of [O2], x, and the rate constant, k, change from x = 0.98 (±0.04) and log k = 15.46 (±0.06) at ∼6 × 10-3-0.2 atm of PO2 to x = 0.58 (±0.02) and log k = 13.41 (±0.03) at 10-5-∼6 × 10-3 atm of PO2. The most plausible mechanism that explains the change in x under low O2 conditions is that, instead of O2, oxygen-derived oxidants, H2O2 and to some extent, O2rad -, dominate the oxidation reactions at oxygen in the Precambrian.

  15. Reliability of Urinary Excretion Rate Adjustment in Measurements of Hippuric Acid in Urine

    Directory of Open Access Journals (Sweden)

    Annamaria Nicolli

    2014-07-01

    Full Text Available The urinary excretion rate is calculated based on short-term, defined time sample collections with a known sample mass, and this measurement can be used to remove the variability in urine concentrations due to urine dilution. Adjustment to the urinary excretion rate of hippuric acid was evaluated in 31 healthy volunteers (14 males and 17 females. Urine was collected as short-term or spot samples and tested for specific gravity, creatinine and hippuric acid. Hippuric acid values were unadjusted or adjusted to measurements of specific gravity, creatinine or urinary excretion rate. Hippuric acid levels were partially independent of urinary volume and urinary flow rate, in contrast to specific gravity and creatinine, which were both highly dependent on the hippuric acid level. Accordingly, hippuric acid was independent on urinary specific gravity and creatinine excretion. Unadjusted and adjusted values for specific gravity or creatinine were generally closely correlated, especially in spot samples. Values adjusted to the urinary excretion rate appeared well correlated to those unadjusted and adjusted to specific gravity or creatinine values. Thus, adjustment of crude hippuric acid values to the urinary excretion rate is a valid procedure but is difficult to apply in the field of occupational medicine and does not improve the information derived from values determined in spot urine samples, either unadjusted or adjusted to specific gravity and creatinine.

  16. Passivation Mechanism of 316L Stainless Steel in Oxidizing Acid Solution

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The compositions and the chemical valence states of elements of 316L stainless steel passive film formed in the oxidizing acid solution were studied by X-ray Photoelectron Spectroscopic (XPS) analysis. The electrochemical polarization curve was measured. The passivation process in the oxidizing acid solution was studied by AC impedance technology. The results indicated that the stable compounds layer was formed on the surface of the sample and the adsorption was the main step in the nitrite solution during passivation process. The catalysis passivation mechanism was put forward according to the experimental results. During passivation process, the water molecule was adsorbed on the surface of the sample at first in the oxidizing acid solution. The oxidizer in the solution played a role as catalyst. The oxide and hydroxide, which could be changed each other and finally formed stable passive film, were generated from adsorbing intermediate under the catalytic action. The mathematical models for predicting the steady polarization curve and the AC impedance spectra at certain conditions have been obtained. The passivation mechanism of 316L stainless steel in the oxidizing acid solution can be interpreted by the catalysis passivation mechanism.

  17. Hypochlorite-induced oxidation of amino acids, peptides and proteins

    DEFF Research Database (Denmark)

    Hawkins, C L; Pattison, D I; Davies, Michael Jonathan

    2003-01-01

    Activated phagocytes generate the potent oxidant hypochlorite (HOCl) via the release of the enzyme myeloperoxidase and hydrogen peroxide. HOCl is known to react with a number of biological targets including proteins, DNA, lipids and cholesterol. Proteins are likely to be major targets for reaction...

  18. Formic acid oxidation at spontaneously deposited palladium on polyaniline modified carbon fibre paper

    Energy Technology Data Exchange (ETDEWEB)

    Moghaddam, Reza B. [Department of Chemistry, Memorial University of Newfoundland, St. John' s, Newfoundland A1B 3X7 (Canada); Pickup, Peter G., E-mail: ppickup@mun.ca [Department of Chemistry, Memorial University of Newfoundland, St. John' s, Newfoundland A1B 3X7 (Canada)

    2011-09-01

    Highlights: {center_dot} Extended reaction zone anodes for formic acid oxidation have been prepared by the spontaneous deposition of Pd on polyaniline coated carbon fibre paper. {center_dot} The electrochemical mode used for formation of the polyaniline can strongly influence the morphology, particle size, and activity of the Pd. {center_dot} PANI deposited galvanostatically produced electrodes that were much more active for formic acid oxidation than PANI deposited potentiodynamically. - Abstract: Extended reaction zone anodes for formic acid oxidation have been prepared by the spontaneous deposition of Pd on polyaniline coated carbon fibre paper. The PANI supports, deposited on carbon fibre paper either galvanostatically, potentiostatically, or potentiodynamically, were characterized by electron microscopy, cyclic voltammetry and impedance spectroscopy. Pd was deposited on them by spontaneous reduction of Pd(II) by the reduced form of the PANI in order to preserve the characteristics of each type of PANI layer. It was found that galvanostatically deposited PANI produced electrodes that were much more active for formic acid oxidation than PANI produced under potential control. The morphology and mean particle size of Pd was found to depend strongly on the way in which the PANI was prepared and also correlated with the resistance and capacitance of the PANI at low potentials. It is proposed that the electrochemical characteristics of the PANI play a significant role in determining the morphology, particle size, and electrocatalytic activity for formic acid oxidation of the spontaneously deposited Pd.

  19. Engineering cytochrome P450 BM3 of Bacillus megaterium for terminal oxidation of palmitic acid.

    Science.gov (United States)

    Brühlmann, Fredi; Fourage, Laurent; Ullmann, Christophe; Haefliger, Olivier P; Jeckelmann, Nicolas; Dubois, Cédric; Wahler, Denis

    2014-08-20

    Directed evolution via iterative cycles of random and targeted mutagenesis was applied to the P450 domain of the subterminal fatty acid hydroxylase CYP102A1 of Bacillus megaterium to shift its regioselectivity towards the terminal position of palmitic acid. A powerful and versatile high throughput assay based on LC-MS allowed the simultaneous detection of primary and secondary oxidation products, which was instrumental for identifying variants with a strong preference for the terminal oxidation of palmitic acid. The best variants identified acquired up to 11 amino acid alterations. Substitutions at F87, I263, and A328, relatively close to the bound substrate based on available crystallographic information contributed significantly to the altered regioselectivity. However, non-obvious residues much more distant from the bound substrate showed surprising strong contributions to the increased selectivity for the terminal position of palmitic acid.

  20. The graphene nanopowder for electro-catalytic oxidation of dopamine and uric acid in the presence of ascorbic acid

    Institute of Scientific and Technical Information of China (English)

    Yuan; Bu; Wenle; Dai; Nan; Li; Xinran; Zhao; Xia; Zuo

    2013-01-01

    The graphene nanopowder for electro-catalytic oxidation of dopamine and uric acid in the presence of ascorbic acid has been investigated by cyclic voltammetry,linear polarization and chronoamperometry.The graphene nanopowder modified electrode was prepared using the drop coating method,which displayed excellent electrocatalytic activity towards the oxidation of dopamine and uric acid compared with the bare glassy carbon electrode in phosphate buffer solution at pH=7.0.Linear responses for dopamine and uric acid were obtained in the ranges of3.3μmol/L to 249.1μmol/L and 6.7μmol/L to 386.3μmol/L with detection limits of 1.5μmol/L and 2.7μmol/L(S/N=3),respectively.The response time was less than 2 s in case of dopamine and 3 s in case of uric acid,respectively.The results demonstrated that the graphene nanopowder had potential for detecting dopamine and uric acid.

  1. Correlating dynamic amino acid properties with success rate of crystallization of proteins from Bacteroides vulgatus

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Shaomin [State Key Laboratory of Non-food Biomass Enzyme Technology, National Engineering Research Center for Non-food Biorefinery, Guangxi Key Laboratory of Biorefinery, Guangxi Academy of Sciences, 98 Daling Road, Nanning, Guangxi, 530007 (China); Wu, Guang [State Key Laboratory of Non-food Biomass Enzyme Technology, National Engineering Research Center for Non-food Biorefinery, Guangxi Key Laboratory of Biorefinery, Guangxi Academy of Sciences, 98 Daling Road, Nanning, Guangxi, 530007 (China); DreamSciTech Consulting, 301, Building 12, Nanyou A-zone, Jiannan Road, Shenzhen, Guangdong, 518054 (China)

    2012-05-15

    To enhance the success rate of protein crystallization, many studies were conducted to determine the relationship between amino acid properties and the success rate of protein crystallization. Although those were successful, new efforts should be made to search for the new factors, which affect protein crystallization. In this study, two dynamic amino acid properties were used to correlate with the success rate of crystallization of proteins from Bacteroides vulgatus, because the amino acid properties used in previous studies were steady. As previously done, logistic regression and neural network were used to model that relationship, and the results were compared against those obtained from each of 532 amino acid properties, which severed as benchmark. The results demonstrated that dynamic amino acid properties should be taken into consideration of protein crystallization. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  2. Tumor necrosis factor alpha is associated with insulin-mediated suppression of free fatty acids and net lipid oxidation in HIV-infected patients with lipodystrophy

    DEFF Research Database (Denmark)

    Haugaard, Steen B; Andersen, Ove; Pedersen, SB;

    2006-01-01

    Tumor necrosis factor alpha (TNF-alpha) stimulates lipolysis in man. We examined whether plasma TNF-alpha is associated with the degree by which insulin suppresses markers of lipolysis, for example, plasma free fatty acid (FFA) and net lipid oxidation (LIPOX) rate in HIV-infected patients...

  3. Effects of Bronsted acidity in the mechanism of selective oxidation of propane to acetone on CaY zeolite at room temperature.

    NARCIS (Netherlands)

    Xu, Jiang; Mojet, Barbara L.; Ommen, van Jan G.; Lefferts, Leon

    2005-01-01

    The importance of Brønsted acid sites for partial oxidation of propane to acetone in CaY was investigated by in situ FTIR spectroscopy. With an increasing number of protons in Ca-Y, Volcano plots were observed for (1) amount of adsorbed propane; (2) initial acetone formation rate; (3) total amount o

  4. The Oxidation of Fe(II) in Acidic Sulfate Solutions with Air at Elevated Pressures. Part 1. Kinetics above 1 M H2SO4

    NARCIS (Netherlands)

    Wermink, Wouter N.; Versteeg, Geert F.

    2017-01-01

    The oxidation of ferrous ions in acidic sulfate solutions at elevated air pressures was investigated. The effect of the Fe2+ concentration, initial H2SO4 concentration and partial oxygen pressure on the reaction rate were determined at three different temperatures, that is, T = 90, 70, and 50

  5. Inhibition of acetaminophen oxidation by cimetidine and the effects on glutathione and activated sulphate synthesis rates

    DEFF Research Database (Denmark)

    Dalhoff, K; Poulsen, H E

    1993-01-01

    inhibition of cytochrome P-450 drug oxidation by cimetidine in isolated rat hepatocytes. The synthesis rates of glutathione and PAPS were determined simultaneously by an established method based on trapping of radioactivity (35S) in the prelabelled glutathione and PAPS pools. Preincubation of the hepatocytes...

  6. High-rate lithium-sulfur batteries promoted by reduced graphene oxide coating.

    Science.gov (United States)

    Li, Nianwu; Zheng, Mingbo; Lu, Hongling; Hu, Zibo; Shen, Chenfei; Chang, Xiaofeng; Ji, Guangbin; Cao, Jieming; Shi, Yi

    2012-04-28

    Lithium-sulfur batteries have a poor rate performance and low cycle stability due to the shuttling loss of intermediate lithium polysulfides. To address this issue, a carbon-sulfur nanocomposite coated with reduced graphene oxide was designed to confine the polysulfides.

  7. Attenuation of cyclosporine A-induced testicular and spermatozoal damages associated with oxidative stress by ellagic acid.

    Science.gov (United States)

    Türk, Gaffari; Sönmez, Mustafa; Ceribaşi, Ali Osman; Yüce, Abdurrauf; Ateşşahin, Ahmet

    2010-02-01

    This study was conducted to investigate the possible protective effect of ellagic acid (EA) on cyclosporine A (CsA)-induced testicular and spermatozoal damages associated with oxidative stress in male rats. Forty adult male Sprague-Dawley rats were divided into 4 groups of 10 animals each. Control group was used as placebo. Cyclosporine group received CsA at the dose of 15 mg/kg/day. Ellagic acid group was treated with EA (10 mg/kg/day). Cyclosporine plus ellagic acid group received CsA+EA. Reproductive organs were weighed and epididymal sperm characteristics and histopathological structure of testes were examined along with malondialdehyde (MDA) and glutathione (GSH) levels, glutathione-peroxidase (GSH-Px) and catalase (CAT) activities in testicular tissue. CsA significantly decreased the weights of testes and ventral prostate, epididymal sperm concentration, motility, testicular tissue glutathione (GSH), glutathione-peroxidase (GSH-Px) and catalase (CAT), diameters of seminiferous tubules and germinal cell layer thickness, and it significantly increased malondialdehyde (MDA) level and abnormal sperm rates along with degeneration, necrosis, immature germ cells, congestion and atrophy in testicular tissue. However, the CsA plus EA treatment attenuated all the CsA-induced negative changes observed in the testicular tissue, sperm and oxidant/antioxidant parameters. In conclusion, CsA-induced oxidative stress leads to the structural and functional damages in the testicular tissue and sperm quality of rats, and also EA has a protective effect on these damages.

  8. Protective effects of gallic acid against spinal cord injury-induced oxidative stress.

    Science.gov (United States)

    Yang, Yong Hong; Wang, Zao; Zheng, Jie; Wang, Ran

    2015-08-01

    The present study aimed to investigate the role of gallic acid in oxidative stress induced during spinal cord injury (SCI). In order to measure oxidative stress, the levels of lipid peroxide, protein carbonyl, reactive oxygen species and nitrates/nitrites were determined. In addition, the antioxidant status during SCI injury and the protective role of gallic acid were investigated by determining glutathione levels as well as the activities of catalase, superoxide dismutase, glutathione peroxidase and glutathione-S-transferase. Adenosine triphophatase (ATPase) enzyme activities were determined to evaluate the role of gallic acid in SCI-induced deregulation of the activity of enzymes involved in ion homeostasis. The levels of inflammatory markers such as nuclear factor (NF)-κB and cycloxygenase (COX)-2 were determined by western blot analysis. Treatment with gallic acid was observed to significantly mitigate SCI-induced oxidative stress and the inflammatory response by reducing the oxidative stress, decreasing the expression of NF-κB and COX-2 as well as increasing the antioxidant status of cells. In addition, gallic acid modulated the activity of ATPase enzymes. Thus the present study indicated that gallic acid may have a role as a potent antioxidant and anti-inflammatory agent against SCI.

  9. Peracetic acid oxidation of saline waters in the absence and presence of H ₂O ₂: secondary oxidant and disinfection byproduct formation.

    Science.gov (United States)

    Shah, Amisha D; Liu, Zheng-Qian; Salhi, Elisabeth; Höfer, Thomas; von Gunten, Urs

    2015-02-03

    Peracetic acid (PAA) is a disinfectant considered for use in ballast water treatment, but its chemical behavior in such systems (i.e., saline waters) is largely unknown. In this study, the reactivity of PAA with halide ions (chloride and bromide) to form secondary oxidants (HOCl, HOBr) was investigated. For the PAA-chloride and PAA-bromide reactions, second-order rate constants of (1.47 ± 0.58) × 10(-5) and 0.24 ± 0.02 M(-1) s(-1) were determined for the formation of HOCl or HOBr, respectively. Hydrogen peroxide (H2O2), which is always present in PAA solutions, reduced HOCl or HOBr to chloride or bromide, respectively. As a consequence, in PAA-treated solutions with [H2O2] > [PAA], the HOBr (HOCl) steady-state concentrations were low with a limited formation of brominated (chlorinated) disinfection byproducts (DBPs). HOI (formed from the PAA-iodide reaction) affected this process because it can react with H2O2 back to iodide. H2O2 is thus consumed in a catalytic cycle and leads to less efficient HOBr scavenging at even low iodide concentrations (acid (MBAA), dibromoacetic acid (DBAA), and tribromoacetic acid (TBAA) formed at up to 260, 106, 230, and 89 μg/L, respectively for doses of 2 mM (ca. 150 mg/L) PAA and [H2O2] acid concentrations.

  10. Protodeboronation of Heteroaromatic, Vinyl, and Cyclopropyl Boronic Acids: pH-Rate Profiles, Autocatalysis, and Disproportionation.

    Science.gov (United States)

    Cox, Paul A; Leach, Andrew G; Campbell, Andrew D; Lloyd-Jones, Guy C

    2016-07-27

    pH-rate profiles for aqueous-organic protodeboronation of 18 boronic acids, many widely viewed as unstable, have been studied by NMR and DFT. Rates were pH-dependent, and varied substantially between the boronic acids, with rate maxima that varied over 6 orders of magnitude. A mechanistic model containing five general pathways (k1-k5) has been developed, and together with input of [B]tot, KW, Ka, and KaH, the protodeboronation kinetics can be correlated as a function of pH (1-13) for all 18 species. Cyclopropyl and vinyl boronic acids undergo very slow protodeboronation, as do 3- and 4-pyridyl boronic acids (t0.5 > 1 week, pH 12, 70 °C). In contrast, 2-pyridyl and 5-thiazolyl boronic acids undergo rapid protodeboronation (t0.5 ≈ 25-50 s, pH 7, 70 °C), via fragmentation of zwitterionic intermediates. Lewis acid additives (e.g., Cu, Zn salts) can attenuate (2-pyridyl) or accelerate (5-thiazolyl and 5-pyrazolyl) fragmentation. Two additional processes compete when the boronic acid and the boronate are present in sufficient proportions (pH = pKa ± 1.6): (i) self-/autocatalysis and (ii) sequential disproportionations of boronic acid to borinic acid and borane.

  11. PPAR{delta} is a fatty acid sensor, which enhances mitochondrial oxidation in insulin

    DEFF Research Database (Denmark)

    Ravnskjaer, Kim; Frigerio, Francesca; Boergesen, Michael;

    2010-01-01

    against adverse effects on GSIS associated with prolonged fatty acid exposure. The presented results indicate that the nuclear receptor PPARdelta is a fatty acid sensor that adapts beta-cell mitochondrial function to long-term changes in unsaturated fatty acid levels. As maintenance of mitochondrial...... is the PPAR subtype expressed at the highest level in insulinoma cells and rat pancreatic islets. Furthermore, PPARdelta displays high transcriptional activity and acts in pronounced synergy with RXR. Interestingly, unsaturated fatty acids mimic the effects of synthetic PPARdelta agonists. Using sh......RNA-mediated knockdown we demonstrate that the ability of unsaturated fatty acids to stimulate fatty acid metabolism is dependent on PPARdelta. Activation of PPARdelta increases the fatty acid oxidation potential in INS-1E beta-cells, enhances glucose-stimulated insulin secretion (GSIS) from islets, and protects GSIS...

  12. The role of peroxisomal fatty acyl-CoA beta-oxidation in bile acid biosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, H.; Miwa, A. (Josai Univ., Saitama (Japan))

    1989-11-01

    The physiological role of the peroxisomal fatty acyl-CoA beta-oxidizing system (FAOS) is not yet established. We speculated that there might be a relationship between peroxisomal degradation of long-chain fatty acids in the liver and the biosynthesis of bile acids. This was investigated using (1-{sup 14}C)butyric acid and (1-{sup 14}C)lignoceric acid as substrates of FAOS in mitochondria and peroxisomes, respectively. The incorporation of ({sup 14}C)lignoceric acid into primary bile acids was approximately four times higher than that of ({sup 14}C)butyric acid (in terms of C-2 units). The pools of these two fatty acids in the liver were exceedingly small. The incorporations of radioactivity into the primary bile acids were strongly inhibited by administration of aminotriazole, which is a specific inhibitor of peroxisomal FAOS in vivo. Aminotriazole inhibited preferentially the formation of cholate, the major primary bile acid, from both ({sup 14}C)lignoceric acid and ({sup 14}C)butyric acid, rather than the formation of chenodeoxycholate. The former inhibition was about 70% and the latter was approximately 40-50%. In view of reports that cholate is biosynthesized from endogenous cholesterol, the above results indicate that peroxisomal FAOS may have an anabolic function, supplying acetyl CoA for bile acid biosynthesis.

  13. Inhibition of nitric oxide synthase lowers fatty acid oxidation in preeclampsia-like mice at early gestational stage

    Institute of Scientific and Technical Information of China (English)

    MA Rui-qiong; SUN Min-na; YANG Zi

    2011-01-01

    Background Preeclampsia is one of hypertensive disorders in pregnancy. It is associated with abnormal lipid metabolism, including fatty acid oxidation metabolism. Long chain 3-hydroxyacyI-CoA dehydrogenase (LCHAD) plays an indispensable role in the oxidation of fatty acids. It has been reported that nitric oxide (NO) is one of the regulatory factors of the fatty acid oxidation pathway. The aim of this research was to investigate whether the nitric oxide synthase (NOS)inhibitor L-NAME may cause down-regulation of LCHAD in the pathogenesis of preeclampsia.Methods Pregnant wild-type (WT) mice were treated with L-NAME or normal saline (NS) during gestation days 7-18 (early group), days 11-18 (mid group) and days 16-18 (late group), and apoE-/- mice served as a control. Systolic blood pressure (SBP), urine protein, feto-placental outcome, plasma lipid levels and NO concentrations were measured, and the expression of mRNA and protein for LCHAD in placental tissue were determined by real-time polymerase chain reaction (RT-PCR) and Western blotting, respectively.Results In WT and apoE-/- mice, SBP and urinary protein increased following L-NAME injection. Fetal and placental weights and NO concentrations were reduced and total cholesterol, triglycerides and free fatty acid levels were increased in early and mid L-NAME groups in WT and apoE-/- mice, compared with the NS group. There was no significant difference between the late L-NAME group and NS group. RT-PCR and Western blotting analysis showed that the mRNA and protein levels of LCHAD expression were significantly down-regulated in the early and mid L-NAME groups but not in the late L-NAME group in the WT and apoE-/- mice compared with the corresponding NS groups.Conclusions Inhibition of NO in early and mid gestation in mice may cause hyperlipidemia and suppression of fatty acid oxidation, whereas preeclampsia-like conditions in late gestation may be a maternal vascular response to inhibition of NO.

  14. The fatty acid beta-oxidation pathway is important for decidualization of endometrial stromal cells in both humans and mice.

    Science.gov (United States)

    Tsai, Jui-He; Chi, Maggie M-Y; Schulte, Maureen B; Moley, Kelle H

    2014-02-01

    Embryo implantation and development requires the endometrial stromal cells (ESCs) to undergo decidualization. This differentiation process requires glucose utilization, and blockade of the pentose phosphate pathway inhibits decidualization of ESCs both in vitro and in vivo. Glucose and fatty acids are energy substrates for many cell types, and fatty acid beta-oxidation is critical for embryo implantation. Here, we investigated whether beta-oxidation is required for decidualization of ESCs. As assessed by marker gene expression, decidualization of human primary ESCs was blocked by reducing activity of carnitine calmitoyltransferase I, the rate-limiting enzyme in beta-oxidation, either by short hairpin RNA-mediated silencing or by treatment with the inhibitor etomoxir. Ranolazine (RAN), a partial beta-oxidation inhibitor, blocked early decidualization of a human ESC line. However, decidualization resumed after several days, most likely due to a compensatory up-regulation of GLUT1 expression and an increase in glucose metabolism. Simultaneous inhibition of the beta-oxidation pathway with RAN and the pentose phosphate pathway with glucosamine (GlcN) impaired in vitro decidualization of human ESCs more strongly than inhibition of either pathway alone. These findings were confirmed in murine ESCs in vitro, and exposure to RAN plus GlcN inhibited decidualization in vivo in a deciduoma model. Finally, intrauterine implantation of time-release RAN and GlcN pellets reduced pup number. Importantly, pup number returned to normal after the end of the pellet-active period. This work indicates that both fatty acids and glucose metabolism pathways are important for ESC decidualization, and suggests novel pathways to target for the design of future nonhormonal contraceptives.

  15. Mechanistic Details and Reactivity Descriptors in Oxidation and Acid Catalysis of Methanol

    Energy Technology Data Exchange (ETDEWEB)

    Deshlahra, Prashant; Carr, Robert T.; Chai, Song-Hai; Iglesia, Enrique

    2015-02-06

    Acid and redox reaction rates of CH₃OH-O₂ mixtures on polyoxometalate (POM) clusters, together with isotopic, spectroscopic, and theoretical assessments of catalyst properties and reaction pathways, were used to define rigorous descriptors of reactivity and to probe the compositional effects for oxidative dehydrogenation (ODH) and dehydration reactions. ³¹P-MAS NMR, transmission electron microscopy and titrations of protons with di-tert-butylpyridine during catalysis showed that POM clusters retained their Keggin structure upon dispersion on SiO₂ and after use in CH₃OH reactions. The effects of CH₃OH and O₂ pressures and of D-substitution on ODH rates show that C-H activation in molecularly adsorbed CH₃OH is the sole kinetically relevant step and leads to reduced centers as intermediates present at low coverages; their concentrations, measured from UV-vis spectra obtained during catalysis, are consistent with the effects of CH₃OH/O₂ ratios predicted from the elementary steps proposed. First-order ODH rate constants depend strongly on the addenda atoms (Mo vs W) but weakly on the central atom (P vs Si) in POM clusters, because C-H activation steps inject electrons into the lowest unoccupied molecular orbitals (LUMO) of the clusters, which are the d-orbitals at Mo⁶⁺ and W⁶⁺ centers. H-atom addition energies (HAE) at O-atoms in POM clusters represent the relevant theoretical probe of the LUMO energies and of ODH reactivity. The calculated energies of ODH transition states at each O-atom depend linearly on their HAE values with slopes near unity, as predicted for late transition states in which electron transfer and C-H cleavage are essentially complete. HAE values averaged over all accessible O-atoms in POM clusters provide the appropriate reactivity descriptor for oxides whose known structures allow accurate HAE calculations. CH₃OH dehydration proceeds via parallel pathways mediated by late carbenium-ion transition states; effects of

  16. Graphene Oxide Reinforced Polylactic Acid/Polyurethane Antibacterial Composites

    OpenAIRE

    Xiaoli An; Haibin Ma; Bin Liu; Jizeng Wang

    2013-01-01

    Nanocomposites from PLA/PU containing small concentrations of graphene oxide (GO) were prepared by simple liquid-phase mixing followed by casting. The as-prepared ternary PLA/PU/GO composite films exhibited good antibacterial activity against the gram-positive Staphylococcus aureus and the gram-negative Escherichia coli, due to the excellent antibacterial property of GO sheets with high specific surface area. The addition of GO inhibited the attachment and proliferation of microbes on the fil...

  17. Copper-catalyzed decarboxylative C-P cross-coupling of alkynyl acids with H-phosphine oxides: a facile and selective synthesis of (E)-1-alkenylphosphine oxides.

    Science.gov (United States)

    Hu, Gaobo; Gao, Yuxing; Zhao, Yufen

    2014-09-05

    A novel and efficient copper-catalyzed decarboxylative cross-coupling of alkynyl acids for the stereoselective synthesis of E-alkenylphosphine oxides has been developed. In the presence of 10 mol % of CuCl without added ligand, base, and additive, various alkynyl acids reacted with H-phosphine oxides to afford E-alkenylphosphine oxides with operational simplicity, broad substrate scope, and the stereoselectivity for E-isomers.

  18. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    CERN Document Server

    Schobesberger, Siegfried; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-01-01

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molec...

  19. Effect of Amine Adlayer on Electrochemical Uric Acid Sensor Conducted on Electrochemically Reduced Graphene Oxide

    Energy Technology Data Exchange (ETDEWEB)

    Park, Sumi; Kim, Kyuwon [Incheon National University, Incheon (Korea, Republic of)

    2016-03-15

    The electrochemical biosensing efficiency of uric acid (UA) detection on an electrochemically reduced graphene oxide (ERGO)-decorated electrode surface was studied by using various amine linkers used to immobilize ERGO. The amine linkers aminoethylphenyldiazonium , 2,2'-(ethylenedioxy)bis(ethylamine), 3-aminopro-pyltriethoxysilane, and polyethyleneimine were coated on indium-tin-oxide electrode surfaces through chemical or electrochemical deposition methods. ERGO-decorated surfaces were prepared by the electrochemical reduction of graphene oxide (GO), which was immobilized on the amine-coated electrode surfaces through the electrostatic interaction between GO and the ammonium ion of the linker on the surface. We monitored the sensing results of electrochemical UA detection with differential pulse voltammetry. The ERGO-modified surface presented electrocatalytic oxidation of UA and ascorbic acid. Among the different amines tested, 3-aminopropyltriethoxysilane provided the best biosensing performance in terms of sensitivity and reproducibility.

  20. Electrochemical oxidation of 243Am(III) in nitric acid by a terpyridyl-derivatized electrode

    Energy Technology Data Exchange (ETDEWEB)

    Dares, C. J.; Lapides, A. M.; Mincher, B. J.; Meyer, T. J.

    2015-11-05

    A high surface area, tin-doped indium oxide electrode surface-derivatized with a terpyridine ligand has been applied to the oxidation of trivalent americium to Am(V) and Am(VI) in nitric acid. Potentials as low as 1.8 V vs. the saturated calomel electrode are used, 0.7 V lower than the 2.6 V potential for one-electron oxidation of Am(III) to Am(IV) in 1 M acid. This simple electrochemical procedure provides, for the first time, a method for accessing the higher oxidation states of Am in non-complexing media for developing the coordination chemistries of Am(V) and Am(VI) and, more importantly, for separation of americium from nuclear waste streams.

  1. Covalent interactions between proteins and oxidation products of caffeoylquinic acid (chlorogenic acid)

    NARCIS (Netherlands)

    Prigent, S.V.E.; Voragen, A.G.J.; Visser, A.J.W.G.; Koningsveld, van G.A.; Gruppen, H.

    2007-01-01

    BACKGROUND: The interactions between phenolic compounds and proteins can modify protein properties important in the food industry. To understand the effects of these interactions, the covalent interactions between caffeoylquinic acid (chlorogenic acid, CQA) oxidised by polyphenol oxidase (PPO) at ac

  2. Kinetics and mechanism of the oxidation of pentathionate ion by chlorine dioxide in a slightly acidic medium.

    Science.gov (United States)

    Xu, Li; Csekő, György; Petz, Andrea; Horváth, Attila K

    2014-02-27

    The chlorine dioxide-pentathionate reaction has been studied at a slightly acidic medium by conventional UV-vis spectroscopy monitoring the absorbance at 430 nm. We have shown that pentathionate was oxidized to sulfate, but chlorate is also a marginal product of the reaction besides the chloride ion. The stoichiometry of the reaction can be established as a linear combination of two limiting stoichiometries under our experimental conditions. Kinetics of the reaction was found to be also complex because initial rate studies revealed that formal kinetic orders of both the hydrogen ion and chlorine dioxide is far from unity. Moreover, log-log plot of the initial rate against pentathionate concentration indicated a nonconstant formal kinetic order. We also observed a significant catalytic effect of chloride ion. Based on our observations and simultaneous evaluation of the kinetic curves, an 11-step kinetic model is obtained with 6 fitted rate coefficients. A relatively simple rate equation has also been derived and discussed.

  3. Catalytic ozonation of sulfosalicylic acid over manganese oxide supported on mesoporous ceria.

    Science.gov (United States)

    Xing, Shengtao; Lu, Xiaoyang; Liu, Jia; Zhu, Lin; Ma, Zichuan; Wu, Yinsu

    2016-02-01

    Manganese oxide supported on mesoporous ceria was prepared and used as catalyst for catalytic ozonation of sulfosalicylic acid (SA). Characterization results indicated that the manganese oxide was mostly incorporated into the pores of ceria. The synthesized catalyst exhibited high activity and stability for the mineralization of SA in aqueous solution by ozone, and more than 95% of total organic carbon was removed in 30 min under various conditions. Mechanism studies indicated that SA was mainly degraded by ozone molecules, and hydroxyl radical reaction played an important role for the degradation of its ozonation products (small molecular organic acids). The manganese oxide in the pores of CeO2 improved the adsorption of small molecular organic acids and the generation of hydroxyl radicals from ozone decomposition, resulting in high TOC removal efficiency.

  4. Furan fatty acids efficiently rescue brain cells from cell death induced by oxidative stress.

    Science.gov (United States)

    Teixeira, Antoinette; Cox, Ruud C; Egmond, Maarten R

    2013-08-01

    Treatment of rat brain C6 astroglioma cells with furan fatty acid F6 prior to exposure to hydrogen peroxide shows a strong protective effect of F6 against cell death resulting from oxidative stress. This protective effect is obtained only for F6 administered as a free fatty acid and with an intact furan ring. It is proposed that brain cells are rescued by F6 scavenging radicals elicited by lipid peroxidation within the cell membrane. Oxidative processes outside the cell membrane, such as protein carbonylation, are not affected by F6. Furan fatty acids such as those present in fish oils and marine organisms are likely beneficial for consumption in reducing the risk of diseases that have been implicated to arise from oxidative stress, such as Alzheimer's disease.

  5. Vanadium oxides supported on hydrotalcite-type precursors: the effect of acid base properties on the oxidation of isopropanol

    Energy Technology Data Exchange (ETDEWEB)

    Meira, D.M.; Cortez, G.G. [Faculdade de Engenharia Quimica de Lorena, Lorena, SP (Brazil). Dept. de Engenharia Quimica. Lab. de Catalise II]. E-mail: cortez@dequi.faenquil.br; Monteiro, W.R.; Rodrigues, J.A.J. [Instituto Nacional de Pesquisas Espaciais (INPE), Sao Jose dos Campos, SP (Brazil). Lab. Associado de Combustao e Propulsao]. E-mail: jajr@lcp.inpe.br

    2006-07-15

    Vanadium oxide supported on hydrotalcite-type precursors was studied in the oxidation of isopropanol. Hydrotalcites with different y = Mg/Al ratios were synthesized by the method of coprecipitation nitrates of Mg and Al cations with K{sub 2}CO{sub 3} as precipitant. The decomposition of these hydrotalcite precursors at 450 deg C yielded homogeneous MgyAlOx mixed oxides that contain the Al{sup +3} cations totally incorporated into the MgO framework. The materials were characterized by chemical analysis, BET superficial area, X-ray diffraction, temperature-programmed reduction (TPR) and the reaction of isopropanol, a probe molecule used to evaluate the acid-base properties. The results of TPR showed that the reducibility of V{sup +5} decreased with the increase in magnesium loading in catalysts. The X-ray diffraction patterns of Al-rich hydrotalcite precursors showed the presence of crystalline phases of brucite and gibbsite. It was shown that chemical composition, texture, acid-base properties of the active sites and also Mg/Al ratio strongly affect the formation of the products in the oxidation of isopropanol. The Al-rich catalysts were much more active than the Mg-rich ones, converting isopropanol mainly to propylene. (author)

  6. Vanadium oxides supported on hydrotalcite-type precursors: the effect of acid-base properties on the oxidation of isopropanol

    Directory of Open Access Journals (Sweden)

    D. M. Meira

    2006-09-01

    Full Text Available Vanadium oxide supported on hydrotalcite-type precursors was studied in the oxidation of isopropanol. Hydrotalcites with different y = Mg/Al ratios were synthesized by the method of coprecipitation nitrates of Mg and Al cations with K2CO3 as precipitant. The decomposition of these hydrotalcite precursors at 450°C yielded homogeneous MgyAlOx mixed oxides that contain the Al+3 cations totally incorporated into the MgO framework. The materials were characterized by chemical analysis, BET superficial area, X-ray diffraction, temperature-programmed reduction (TPR and the reaction of isopropanol, a probe molecule used to evaluate the acid-base properties. The results of TPR showed that the reducibility of V+5 decreased with the increase in magnesium loading in catalysts. The X-ray diffraction patterns of Al-rich hydrotalcite precursors showed the presence of crystalline phases of brucite and gibbsite. It was shown that chemical composition, texture, acid-base properties of the active sites and also Mg/Al ratio strongly affect the formation of the products in the oxidation of isopropanol. The Al-rich catalysts were much more active than the Mg-rich ones, converting isopropanol mainly to propylene.

  7. INVESTIGATION OF THE OPTIMUM DISSOLUTION TEMPERATURES OF PHOSPHORUS IN SULPHURIC, NITRIC AND OXALIC ACID SOLUTIONS DURING LEACHING OF IRON OXIDE ORE

    Directory of Open Access Journals (Sweden)

    C. I. NWOYE

    2009-12-01

    Full Text Available Studies were carried out to determine the optimum dissolution temperatures of phosphorus in oxalic, nitric and sulphuric acid solutions during leaching of iron oxide ore. Phosphorus dissolution rates and dissolution per unit rise in temperature were determined and compared to ascertain the preferred acid in terms of effective dephosphorization of iron oxide ore using leaching process. The results of the investigation show that the optimum dissolution temperatures of phosphorus in these acids were found to be 45, 55 and 70ºC respectively. Phosphorus dissolutions per unit rise in temperature in these acid solutions during the increasing and decreasing stage of dissolution were 9.4 and -3.07 mg/kg/ºC 2.88 and -4.7 mg/kg/ºC and also 2.16 and -7.95 mg/kg/ºC respectively. Phosphorus dissolution rates in these acid solutions during the increasing and decreasing stage of dissolution were also determined as 0.67 and -0.13 mg/kg/s, 0.14 and -0.19 mg/kg/s and also 0.1 and 0.44 mg/kg/s for oxalic, nitric and sulphuric acid solutions respectively. This confers to oxalic acid a better dissolution power on phosphorus over nitric and sulphuric acid, followed by nitric acid.

  8. Investigation of Influential Parameters in Deep Oxidative Desulfurization of Dibenzothiophene with Hydrogen Peroxide and Formic Acid

    Directory of Open Access Journals (Sweden)

    Alireza Haghighat Mamaghani

    2013-01-01

    Full Text Available An effective oxidative system consisting of hydrogen peroxide, formic acid, and sulfuric acid followed by an extractive stage were implemented to remove dibenzothiophene in the simulated fuel oil. The results revealed such a great performance in the case of H2O2 in the presence of formic and sulfuric acids that led to the removal of sulfur compounds. Sulfuric acid was employed to increase the acidity of media as well as catalytic activity together with formic acid. The oxidation reaction was followed by a liquid-liquid extraction stage using acetonitrile as a polar solvent to remove produced sulfones from the model fuel. The impact of operating parameters including the molar ratio of formic acid to sulfur (, hydrogen peroxide to sulfur (, and the time of reaction was investigated using Box-Behnken experimental design for oxidation of the model fuel. A significant quadratic model was introduced for the sulfur removal as a function of effective parameters by the statistic analysis.

  9. Effects of ascorbic acid and antioxidants on color, lipid oxidation and volatiles of irradiated ground beef

    Science.gov (United States)

    Ahn, D. U.; Nam, K. C.

    2004-09-01

    Beef loins with 3 different aging times after slaughter were ground, added with none, 0.1% ascorbic acid, 0.01% sesamol+0.01% α-tocopherol, or 0.1% ascorbic acid+0.01% sesamol+0.01% tocopherol. The meats were packaged in oxygen-permeable bags, irradiated at 2.5 kGy, and color, oxidation-reduction potential (ORP), lipid oxidation and volatile profiles were determined. Irradiation decreased the redness of ground beef, and visible color of beef changed from a bright red to a green/brown depending on the age of meat. Addition of ascorbic acid prevented color changes in irradiated beef, and the effect of ascorbic acid became greater as the age of meat or storage time after irradiation increased. The ground beef added with ascorbic acid had lower ORP than control, and the low ORP of meat helped maintaining the heme pigments in reduced form. During aerobic storage, S-volatiles disappeared while volatile aldehydes significantly increased in irradiated beef. Addition of ascorbic acid at 0.1% or sesamol+α-tocopherol at each 0.01% level to ground beef prior to irradiation were effective in reducing lipid oxidation and S-volatiles. As storage time increased, however, the antioxidant effect of sesamol+tocopherol in irradiated ground beef was superior to that of ascorbic acid.

  10. Effects of ascorbic acid and antioxidants on color, lipid oxidation and volatiles of irradiated ground beef

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, D.U. E-mail: duahn@iastate.edu; Nam, K.C

    2004-10-01

    Beef loins with 3 different aging times after slaughter were ground, added with none, 0.1% ascorbic acid, 0.01% sesamol+0.01% {alpha}-tocopherol, or 0.1% ascorbic acid+0.01% sesamol+0.01% tocopherol. The meats were packaged in oxygen-permeable bags, irradiated at 2.5 kGy, and color, oxidation-reduction potential (ORP), lipid oxidation and volatile profiles were determined. Irradiation decreased the redness of ground beef, and visible color of beef changed from a bright red to a green/brown depending on the age of meat. Addition of ascorbic acid prevented color changes in irradiated beef, and the effect of ascorbic acid became greater as the age of meat or storage time after irradiation increased. The ground beef added with ascorbic acid had lower ORP than control, and the low ORP of meat helped maintaining the heme pigments in reduced form. During aerobic storage, S-volatiles disappeared while volatile aldehydes significantly increased in irradiated beef. Addition of ascorbic acid at 0.1% or sesamol+{alpha}-tocopherol at each 0.01% level to ground beef prior to irradiation were effective in reducing lipid oxidation and S-volatiles. As storage time increased, however, the antioxidant effect of sesamol+tocopherol in irradiated ground beef was superior to that of ascorbic acid.

  11. Chlorogenic and caftaric acids in liver toxicity and oxidative stress induced by methamphetamine.

    Science.gov (United States)

    Koriem, Khaled M M; Soliman, Rowan E

    2014-01-01

    Methamphetamine intoxication can cause acute hepatic failure. Chlorogenic and caftaric acids are the major dietary polyphenols present in various foods. The aim of this study was to evaluate the protective role of chlorogenic and caftaric acids in liver toxicity and oxidative stress induced by methamphetamine in rats. Thirty-two male albino rats were divided into 4 equal groups. Group 1, which was control group, was injected (i.p) with saline (1 mL/kg) twice a day over seven-day period. Groups 2, 3, and 4 were injected (i.p) with methamphetamine (10 mg/kg) twice a day over seven-day period, where groups 3 and 4 were injected (i.p) with 60 mg/kg chlorogenic acid and 40 mg/kg caftaric acid, respectively, one day before methamphetamine injections. Methamphetamine increased serum aspartate aminotransferase, alanine aminotransferase, alkaline phosphatase, bilirubin, cholesterol, low-density lipoprotein, and triglycerides. Also, malondialdehyde in serum, liver, and brain and plasma and liver nitric oxide levels were increased while methamphetamine induced a significant decrease in serum total protein, albumin, globulin, albumin/globulin ratio, brain serotonin, norepinephrine and dopamine, blood and liver superoxide dismutase, and glutathione peroxidase levels. Chlorogenic and caftaric acids prior to methamphetamine injections restored all the above parameters to normal values. In conclusion, chlorogenic and caftaric acids before methamphetamine injections prevented liver toxicity and oxidative stress where chlorogenic acid was more effective.

  12. Oxidation mechanism and overall removal rates of endocrine disrupting chemicals by aquatic plants.

    Science.gov (United States)

    Reis, A R; Tabei, K; Sakakibara, Y

    2014-01-30

    The purpose of this study was to evaluate experimentally and theoretically the oxidation mechanisms and overall removal rates of phenolic endocrine disrupting chemicals (EDCs) by aquatic plants. EDCs used in this study were bisphenol-A (BPA), 2,4-dichlorophenol (2,4-DCP), 4-tert-octylphenol (4-t-OP), and pentachlorophenol (PCP). Referring to reported detection levels in aquatic environments and contaminated sites, the feed concentration of each EDC was set from 1 to 100μg/L. Experimental results showed that, except for PCP, phenolic EDCs were stably and concurrently removed by different types of aquatic plants over 70 days in long-term continuous treatments. Primal enzymes responsible for oxidation of BPA, 2,4-DCP, and 4-t-OP were peroxidases (POs). Moreover, enzymatic removal rates of BPA, 2,4-DCP, and 4-t-OP by POs were more than 2 orders of magnitude larger than those by aquatic plants. Assuming that overall removal rates of EDCs are controlled by mass transfer rates onto liquid films on the surface of aquatic plants, an electrochemical method based on the limiting current theory was developed to measure the mass transfer rates of EDCs. Because of extremely large removal rates of EDCs by POs, observed removal rates by aquatic plants were in reasonably good agreement with calculated results by a mathematical model developed based on an assumption that mass transfer limitation is a rate-limiting step.

  13. Fatty acid oxidation is essential for egg production by the parasitic flatworm Schistosoma mansoni.

    Directory of Open Access Journals (Sweden)

    Stanley Ching-Cheng Huang

    Full Text Available Schistosomes, parasitic flatworms that cause the neglected tropical disease schistosomiasis, have been considered to have an entirely carbohydrate based metabolism, with glycolysis playing a dominant role in the adult parasites. However, we have discovered a close link between mitochondrial oxygen consumption by female schistosomes and their ability to produce eggs. We show that oxygen consumption rates (OCR and egg production are significantly diminished by pharmacologic inhibition of carnitine palmitoyl transferase 1 (CPT1, which catalyzes a rate limiting step in fatty acid β-oxidation (FAO and by genetic loss of function of acyl CoA synthetase, which complexes with CPT1 and activates long chain FA for use in FAO, and of acyl CoA dehydrogenase, which catalyzes the first step in FAO within mitochondria. Declines in OCR and egg production correlate with changes in a network of lipid droplets within cells in a specialized reproductive organ, the vitellarium. Our data point to the importance of regulated lipid stores and FAO for the compartmentalized process of egg production in schistosomes.

  14. Compensation effect in reactions between trans-4,4'-dinitrostilbene oxide and arylsulfonic acids

    Science.gov (United States)

    Shpan'ko, I. V.; Sadovaya, I. V.

    2016-12-01

    The effect structure and temperature have on the rate and free activation energy of reactions between trans-4,4'-dinitrostilbene oxide and Y-substituted arylsulfonic acids YC6H4SO3H in a mixture of dioxane with 1,2-dichloroethane (7: 3 vol/vol) at 265, 281, and 298 K is studied. It is found that as a result of the nonadditivity of the joint effect of substituents Y and temperature on the rate of the process of oxirane ring opening, the cross reaction series exhibits isoparametric properties in the aspect of enthalpy-entropy compensation. This allows the experimental determination of an isoparametric point with respect to the constant of substituent Y (σY IP= 0.52), in which activation entropy Δ S ≠ = 0 and free activation energy Δ G ≠ do not depend on temperature (Δ G ≠ = Δ H ≠), and to conduct the transition through this point with inversion of the order of the effect temperature has on the value of Δ G ≠ as a result of reversing the sign of Δ S ≠: in the series Y (σY) = 4-OCH3 (-0.27), 4-CH3 (-0.17), H (0), 4-Cl (0.23), and 3-NO2 (0.71), the values of Δ S ≠ (J/(mol K)) are-140,-119,-85,-42, and 44, respectively. The possibility of using isoparametric points as quantitative mechanistic criteria is demonstrated.

  15. "Raisin bun"-like nanocomposites of palladium clusters and porphyrin for superior formic acid oxidation.

    Science.gov (United States)

    Wang, Xiuxin; Yang, Jiandong; Yin, Huajie; Song, Rui; Tang, Zhiyong

    2013-05-21

    A novel "raisin bun"-like nanocomposite, where Pd clusters are embedded in porphyrin matrix, is developed as a promising electrocatalyst. Thanks to the synergy between the Pd clusters and the porphyrin matrix, this composite exhibits a low oxidation potential, high mass activity and excellent stability toward electrochemical oxidation of formic acid, which opens new routes for the design of high-performance catalysts in fuel cells. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Arsine oxidation with heteropoly acid in the presence of halide ions

    Energy Technology Data Exchange (ETDEWEB)

    Dorfman, Ya.A.; Aleshkova, M.M.; Doroshkevich, D.M.; Kel' man, I.V. (AN Kazakhskoj SSR, Alma-Ata. Inst. Organicheskogo Kataliza i Ehlektrokhimii)

    1984-12-01

    Kinetics and mechanism of arsine oxidation by phosphomolybdovanadium heteropoly acid are studied in the presense of halide ions as catalysts. It is established that intrasphere arsine oxidation in an intermediate V(5) complex with AsH/sub 3/ and halide-ion is a limiting stage of the proposed mechanism. The quantum-chemical calculation of the electronic structure of intermediate complexes, which supports the above mechanism is carried out. The method of theoretical estimation of the activation energy is proposed.

  17. Susceptibility of podocytes to palmitic acid is regulated by fatty acid oxidation and inversely depends on acetyl-CoA carboxylases 1 and 2.

    Science.gov (United States)

    Kampe, Kapil; Sieber, Jonas; Orellana, Jana Marina; Mundel, Peter; Jehle, Andreas Werner

    2014-02-15

    Type 2 diabetes is characterized by dyslipidemia with elevated free fatty acids (FFAs). Loss of podocytes is a hallmark of diabetic nephropathy, and podocytes are susceptible to saturated FFAs, which induce endoplasmic reticulum (ER) stress and podocyte death. Genome-wide association studies indicate that expression of acetyl-CoA carboxylase (ACC) 2, a key enzyme of fatty acid oxidation (FAO), is associated with proteinuria in type 2 diabetes. Here, we show that stimulation of FAO by aminoimidazole-4-carboxamide-1β-D-ribofuranoside (AICAR) or by adiponectin, activators of the low-energy sensor AMP-activated protein kinase (AMPK), protects from palmitic acid-induced podocyte death. Conversely, inhibition of carnitine palmitoyltransferase (CPT-1), the rate-limiting enzyme of FAO and downstream target of AMPK, augments palmitic acid toxicity and impedes the protective AICAR effect. Etomoxir blocked the AICAR-induced FAO measured with tritium-labeled palmitic acid. The beneficial effect of AICAR was associated with a reduction of ER stress, and it was markedly reduced in ACC-1/-2 double-silenced podocytes. In conclusion, the stimulation of FAO by modulating the AMPK-ACC-CPT-1 pathway may be part of a protective mechanism against saturated FFAs that drive podocyte death. Further studies are needed to investigate the potentially novel therapeutic implications of these findings.

  18. The facile synthesis of single crystalline palladium arrow-headed tripods and their application in formic acid electro-oxidation.

    Science.gov (United States)

    Su, Na; Chen, Xueying; Ren, Yuanhang; Yue, Bin; Wang, Han; Cai, Wenbin; He, Heyong

    2015-04-28

    Single crystalline palladium arrow-headed tripods prepared via a simple one-pot strategy exhibit high electro-activity in formic acid oxidation, which could be a promising anodic catalyst for direct formic acid fuel cells.

  19. Effect of Oxidizer Particle Size on Burning Rate and Thermal Decomposition of Composite Solid Propellants

    Directory of Open Access Journals (Sweden)

    K. Kishore

    1982-07-01

    Full Text Available Studies on Thermal decomposition of ammonium perchlorarte(AP- polystyrene(PS propellant and burning rate of PS/AP propellant have been carried out as a function of oxidizer particle size. Thermal decomposition of AP and AP/PS propellant as function of AP particle size shows a maximum rate around 100 micro particle size which has been explained on the basis of Mample's theory. No such maximum is observed in the case of PS/AP propellant burning rate.

  20. 1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

    Science.gov (United States)

    Ruggiero, P.; Interesse, F. S.; Cassidei, L.; Sciacovelli, O.

    1980-04-01

    1H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -( CH2) n - CH3 ( n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.

  1. Oxidation Effect on Tribological Pproperties of Rapeseed oil and Lard Mixtures Containing Monoglycerides and Fatty Acids

    Directory of Open Access Journals (Sweden)

    Violeta Makareviciene

    2012-10-01

    Full Text Available Vegetable oils and animal fats are increasingly popular base material to produce environmentally friendly lubricants. This is a renewable and easily biodegradable in the natural environment material. The main disadvantage of vegetable oils and animal fats as raw materials and its lubricants is pour oxidation stability. There are already a wide range of environmentally friendly lubricants in the market, while the variety of greases offer is not so high. This research aims to explore the properties of prepared compositions of lubricating greases produced from rapeseed oil and lard, modifying them with monoglycerides, stearic and oleic acids. The plastic properties (penetration and oxidation influence on tribological and corrosive properties of these compositions were studied. It was found that modifying rapeseed oil and lard with monoglycerides, oleic and stearic acids a few lubricating compositions of NLGI grades can be achieved: soft or very soft rapeseed oil based greases and medium or nearly hard consistency lard based compositions. The oxidation studies showed that it decreases the tribological properties of base and monoglycerides modified lubricants. Oxidation has greater negative impact on lard and lard based compositions. Oleic and stearic acids reduces or completely eliminates the negative influence of oxidation. Corrosion studies have shown that both fresh and oxidized lubricant compositions have no significant affect on copper strip corrosion.DOI: http://dx.doi.org/10.5755/j01.erem.61.3.1763

  2. Low ascorbic acid and increased oxidative stress in gulo(-/-) mice during development.

    Science.gov (United States)

    Harrison, Fiona E; Meredith, M Elizabeth; Dawes, Sean M; Saskowski, Jeanette L; May, James M

    2010-08-19

    Vitamin C (ascorbic acid, AA) depletion during prenatal and postnatal development can lead to oxidative stress in the developing brain and other organs. Such damage may lead to irreversible effects on later brain function. We studied the relationship between AA deficiency and oxidative stress during development in gulonolactone oxidase (gulo) knockout mice that are unable to synthesize their own ascorbic acid. Heterozygous gulo(+/-) mice can synthesize AA and typically have similar tissue levels to wild-type mice. Gulo(+/-) dams were mated with gulo(+/-) males to provide offspring of each possible genotype. Overall, embryonic day 20 (E20) and postnatal day 1 (P1) pups were protected against oxidative stress by sufficient AA transfer during pregnancy. On postnatal day 10 (P10) AA levels were dramatically lower in liver and cerebellum in gulo(-/-) mice and malondialdehyde (MDA) levels were significantly increased. In postnatal day 18 pups (P18) AA levels decreased further in gulo(-/-) mice and oxidative stress was observed in the accompanying elevations in MDA in liver, and F(2)-isoprostanes in cortex. Further, total glutathione levels were higher in gulo(-/-) mice in cortex, cerebellum and liver, indicating that a compensatory antioxidant system was activated. These data show a direct relationship between AA level and oxidative stress in the gulo(-/-) mice. They reinforce the critical role of ascorbic acid in preventing oxidative stress in the developing brain in animals that, like humans, cannot synthesize their own AA.

  3. Kinetics and Mechanism of Electron Transfer Reaction: Oxidation of Sulfanilic Acid by N-Chloro-p-Toluene Sulfonamide in Acid Perchlorate Medium

    Energy Technology Data Exchange (ETDEWEB)

    Sailani, Riya; Bhasin, Meneka; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

    2014-01-15

    The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be (61.67 ± 0.47) kJ mol{sup -1} and (-62.71 ± 2.48) JK{sup -1}mol{sup -1} respectively employing Eyring equation.

  4. Electrochemical oxidation of substituted benzylamines in aquo-acetic acid medium: substituent and solvent effects

    Indian Academy of Sciences (India)

    A Thirumoorthi; K P Elango

    2007-07-01

    Electrochemical oxidation of nine para- and meta-substituted benzylamines in varying mole fractions of acetic acid in water has been investigated in the presence of 0.1 M sulphuric acid as supporting electrolyte. The oxidation potentials correlate well with Hammett’s substituent constants affording negative reaction constants. The correlation of potential values with macroscopic solvent parameters is non-linear suggesting that the operation of both specific and non-specific solvent-solvent-solute interaction mechanisms. Multiple correlation analysis of the experimental data with Kamlet-Taft solvatochromic parameters is employed.

  5. Oxidative stability of structured lipids produced from sunflower oil and caprylic acid

    DEFF Research Database (Denmark)

    Timm Heinrich, Maike; Xu, Xuebing; Nielsen, Nina Skall

    2003-01-01

    and differences in production/purification, which caused lower tocopherol content and higher initial levels of primary and secondary oxidation products in SL compared with RL and SO. Grindox 117 and gallic acid did not exert a distinct antioxidative effect in the SL oil samples during storage......Traditional sunflower oil (SO), randomized lipid (RL) and specific structured lipid (SL), both produced from SO and tricaprylin/caprylic acid, respectively, were stored for up to 12 wk to compare their oxidative stabilities by chemical and sensory analyses. Furthermore, the effect of adding...

  6. Acetic Acid Formation by Selective Aerobic Oxidation of Aqueous Ethanol over Heterogeneous Ruthenium Catalysts

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Hanning, Christopher William

    2012-01-01

    Heterogeneous catalyst systems comprising ruthenium hydroxide supported on different carrier materials, titania, alumina, ceria, and spinel (MgAl2O4), were applied in selective aerobic oxidation ethanol to form acetic acid, an important bulk chemical and food ingredient. The catalysts were...... of catalysts, oxidant pressure, reaction temperature, and substrate concentration were investigated. Quantitative yield of acetic acid was obtained with 1.2 wt % Ru(OH)x/CeO2 under optimized conditions (150 °C, 10 bar O2, 12 h of reaction time, 0.23 mol % Ru to substrate)....

  7. All-trans retinoic acid increases oxidative metabolism in mature adipocytes

    DEFF Research Database (Denmark)

    Mercader, Josep; Madsen, Lise; Felipe, Francisco

    2007-01-01

    BACKGROUND/AIMS: In rodents, retinoic acid (RA) treatment favors loss of body fat mass and the acquisition of brown fat features in white fat depots. In this work, we sought to examine to what extent these RA effects are cell autonomous or dependent on systemic factors. METHODS: Parameters of lipid......), and to an increased expression of proteins favoring fat oxidation (peroxisome proliferator-activated receptor gamma coactivator-1alpha, uncoupling protein 2, fasting-induced adipose factor, enzymes of mitochondrial fatty acid oxidation). These changes paralleled inactivation of the retinoblastoma protein and were...

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