Ascorbic acid reduces noise-induced nitric oxide production in the guinea pig ear.

Science.gov (United States)

Heinrich, Ulf-Rüdiger; Fischer, Ilka; Brieger, Jürgen; Rümelin, Andreas; Schmidtmann, Irene; Li, Huige; Mann, Wolf J; Helling, Kai

2008-05-01

Noise-induced hearing loss can be caused, among other causes, by increased nitric oxide (NO) production in the inner ear leading to nitroactive stress and cell destruction. Some studies in the literature suggest that the degree of hearing loss (HL) could be reduced in an animal model through ascorbic acid supplementation. To identify the effect of ascorbic acid on tissue-dependent NO content in the inner ear of the guinea pig, we determined the local NO production in the organ of Corti and the lateral wall separately 6 hours after noise exposure. Prospective animal study in guinea pigs. Over a period of 7 days, male guinea pigs were supplied with minimum (25 mg/kg body weight/day) and maximum (525 mg/kg body weight/day) ascorbic acid doses, and afterwards exposed to noise (90 dB sound pressure level for 1 hour). The acoustic-evoked potentials were recorded before and after noise exposure. The organ of Corti and the lateral wall were incubated differently for 6 hours in culture medium, and the degree of NO production was determined by chemiluminescence. Ascorbic acid treatment reduced the hearing threshold shift after noise exposure depending on concentration. When the maximum ascorbic acid dose was substituted, NO production was significantly reduced in the lateral wall after noise exposure and slightly reduced in the organ of Corti. Oral supplementation of the natural radical scavenger ascorbic acid reduces the NO-production rate in the inner ear in noisy conditions. This finding supports the concept of inner ear protection by ascorbic acid supplementation.

Products obtained after in vitro reaction of 7,12-dimethylbenz[alpha]anthracene 5,6-oxide with nucleic acids.

Science.gov (United States)

Blobstein, S H; Weinstein, I B; Grunberger, D; Weisgras, J; Harvey, R G

1975-07-29

Several lines of evidence suggest that oxide derivatives of carcinogenic polycyclic hydrocarbons are the reactive intermediates for in vivo binding to cellular nucleic acids. In the present study the covalent binding of 7,12-dimethylbenz[alpha]anthracene 5,6-oxide to synthetic homopolymers and nucleic acids in aqueous-acetone solutions has been investigated. Poly(G) was found to be the most reactive nucleic acid and underwent approximately 7-10% modification. Alkaline hydrolysis of the poly(G)-dimethylbenzathracene conjugate yielded chromatographically distinct polycyclic hydrocarbon-modified nucleotides which were further characterized by spectral analyses and enzymatic and chemical degradation. When the oxide was allowed to react with GMP or dGMP, at least two products were obtained in about 1% yield. Acid hydrolysis of the dGMP-dimethylbenzanthracene conjugates liberated the corresponding guanine-dimethylbenzathracene products. Mass spectral analysis of the modified bases provided direct evidence that we had obtained covalent binding of the poly-cyclic hydrocarbon to guanine. The mass spectral cleavage pattern suggest that one of these products is a hydroxydihydro derivative of dimethylbenzanthracene bound to guanine and the other is a dimethylbenzanthracene-guanine conjugate. Additional structural aspects of these guanine derivatives are discussed.

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

Science.gov (United States)

Zrinyi, Nick; Pham, Anh Le-Tuan

2017-09-01

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

Acid-permanganate oxidation of potassium tetraphenylboron

International Nuclear Information System (INIS)

Smith, J.R.

1993-02-01

Scoping experiments have been performed which show that potassium tetraphenylboron (KTPB) is rapidly oxidized by permanganate in acidic solutions at room temperature. The main Products are CO 2 , highly oxidized organic compounds related to tartaric and tartronic acids, boric acid, and potassium phosphate (when phosphoric acid is used as the source of acid). One liter of 0.6M NaMnO 4 /2.5M H 3 PO 4 solution will destroy up to 8 grams of KTPB. The residual benzene concentration has been measured to be less than the RCRA limit of 0.5 ppm. Approximately 30% of the organic material is released as CO 2 (trace CO) and 0.16% as benzene vapor. The reaction is well behaved, no foaming or spattering. Tests were performed from .15M to near 1M permanganate. The phosphoric acid concentration was maintained at a concentration at least three times that of the permanganate since an excess of acid was desired and this is the ratio that these two reagents are consumed in the oxidation

[Studies on the oxidation reaction of octanol-2 with nitric acid by infrared spectroscopy].

Science.gov (United States)

Zhang, G; Zhao, G; Wang, Y; Zhang, Q; Zhang, S; Lu, F

1998-04-01

In this paper, the reaction process of oxidation of octanol-2 with nitric acid has been studied by IR spectroscopy. It is found that the main components of non-sapoifiable matter are different in different oxidation degrees. The relation between oxidation products and the amount of nitric acid are investigated,the reaction mechanism has also been studied. Experimental results show that the oxidation process of octanol-2 is as follows: first, octanol-2 is oxidated to octanone-2, or to nitrate, nitrite and nitrile copmpounds, then these compounds are reoxidated to caproic acid in the meantime some by-products, such as valeric, enanthic acids are also found in oxidated products.

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.

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...

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

Oxidative stability of fatty acid alkyl esters: a review.

Directory of Open Access Journals (Sweden)

Michal Angelovič

2015-12-01

Full Text Available The purpose of this study was to investigate and to process the current literary knowledge of the physico-chemical properties of vegetable oil raw used for biodiesel production in terms of its qualitative stability. An object of investigation was oxidative stability of biodiesel. In the study, we focused on the qualitative physico-chemical properties of vegetable oils used for biodiesel production, oxidative degradation and its mechanisms, oxidation of lipids, mechanisms of autooxidation, effectivennes of different synthetic antioxidants in relation to oxidative stability of biodiesel and methods of oxidative stability determination. Knowledge of the physical and chemical properties of vegetable oil as raw material and the factors affecting these properties is critical for the production of quality biodiesel and its sustainability. According to the source of oilseed, variations in the chemical composition of the vegetable oil are expressed by variations in the molar ratio among different fatty acids in the structure. The relative ratio of fatty acids present in the raw material is kept relatively constant after the transesterification reaction. The quality of biodiesel physico-chemical properties is influenced by the chain length and the level of unsaturation of the produced fatty acid alkyl esters. A biodiesel is thermodynamically stable. Its instability primarily occurs from contact of oxygen present in the ambient air that is referred to as oxidative instability. For biodiesel is oxidation stability a general term. It is necessary to distinguish ‘storage stability' and ‘thermal stability', in relation to oxidative degradation, which may occur during extended periods of storage, transportation and end use. Fuel instability problems can be of two related types, short-term oxidative instability and long-term storage instability. Storage instability is defined in terms of solid formation, which can plug nozzles, filters, and degrade engine

Omega-3 fatty acid oxidation products prevent vascular endothelial cell activation by coplanar polychlorinated biphenyls

International Nuclear Information System (INIS)

Majkova, Zuzana; Layne, Joseph; Sunkara, Manjula; Morris, Andrew J.; Toborek, Michal; Hennig, Bernhard

2011-01-01

Coplanar polychlorinated biphenyls (PCBs) may facilitate development of atherosclerosis by stimulating pro-inflammatory pathways in the vascular endothelium. Nutrition, including fish oil-derived long-chain omega-3 fatty acids, such as docosahexaenoic acid (DHA, 22:6ω-3), can reduce inflammation and thus the risk of atherosclerosis. We tested the hypothesis that cyclopentenone metabolites produced by oxidation of DHA can protect against PCB-induced endothelial cell dysfunction. Oxidized DHA (oxDHA) was prepared by incubation of the fatty acid with the free radical generator 2,2-azo-bis(2-amidinopropane) dihydrochloride (AAPH). Cellular pretreatment with oxDHA prevented production of superoxide induced by PCB77, and subsequent activation of nuclear factor-κB (NF-κB). A 4 /J 4 -neuroprostanes (NPs) were identified and quantitated using HPLC ESI tandem mass spectrometry. Levels of these NPs were markedly increased after DHA oxidation with AAPH. The protective actions of oxDHA were reversed by treatment with sodium borohydride (NaBH 4 ), which concurrently abrogated A 4 /J 4 -NP formation. Up-regulation of monocyte chemoattractant protein-1 (MCP-1) by PCB77 was markedly reduced by oxDHA, but not by un-oxidized DHA. These protective effects were proportional to the abundance of A 4 /J 4 NPs in the oxidized DHA sample. Treatment of cells with oxidized eicosapentaenoic acid (EPA, 20:5ω-3) also reduced MCP-1 expression, but less than oxDHA. Treatment with DHA-derived cyclopentenones also increased DNA binding of NF-E2-related factor-2 (Nrf2) and downstream expression of NAD(P)H:quinone oxidoreductase (NQO1), similarly to the Nrf-2 activator sulforaphane. Furthermore, sulforaphane prevented PCB77-induced MCP-1 expression, suggesting that activation of Nrf-2 mediates the observed protection against PCB77 toxicity. Our data implicate A 4 /J 4 -NPs as mediators of omega-3 fatty acid-mediated protection against the endothelial toxicity of coplanar PCBs.

Fatty acid oxidation and ketogenesis in astrocytes

International Nuclear Information System (INIS)

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 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 2 and labeled ketone bodies were produced from the oxidation of fatty acids labeled at carboxy- and ω-terminal carbons, indicating that fatty acids were oxidized by β-oxidation. The results from the radiolabeled tracer studies also indicated that a substantial proportion of the ω-terminal 4-carbon unit of the fatty acids bypassed the β-ketothiolase step of the β-oxidation pathway. The [ 14 C]acetoacetate formed from the [1- 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 [ 14 C]acetoacetate formed from the (ω-1)labeled fatty acids contained 90% of the label at carbon 3 and 10% at carbon 1

UV photodissociation spectroscopy of oxidized undecylenic acid films.

Science.gov (United States)

Gomez, Anthony L; Park, Jiho; Walser, Maggie L; Lin, Ao; Nizkorodov, Sergey A

2006-03-16

Oxidation of thin multilayered films of undecylenic (10-undecenoic) acid by gaseous ozone was investigated using a combination of spectroscopic and mass spectrometric techniques. The UV absorption spectrum of the oxidized undecylenic acid film is significantly red-shifted compared to that of the initial film. Photolysis of the oxidized film in the tropospheric actinic region (lambda > 295 nm) readily produces formaldehyde and formic acid as gas-phase products. Photodissociation action spectra of the oxidized film suggest that organic peroxides are responsible for the observed photochemical activity. The presence of peroxides is confirmed by mass-spectrometric analysis of the oxidized sample and an iodometric test. Significant polymerization resulting from secondary reactions of Criegee radicals during ozonolysis of the film is observed. The data strongly imply the importance of photochemistry in aging of atmospheric organic aerosol particles.

A Comparative Study of Basic, Amphoteric, and Acidic Catalysts in the Oxidative Coupling of Methanol and Ethanol for Acrolein Production.

Science.gov (United States)

Lilić, Aleksandra; Wei, Tiantian; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

2017-09-11

The impact of acid/base properties (determined by adsorption microcalorimetry) of various catalysts on the cross-aldolization of acetaldehyde and formaldehyde leading to acrolein was methodically studied in oxidizing conditions starting from a mixture of methanol and ethanol. The aldol condensation and further dehydration to acrolein were carried out on catalysts presenting various acid/base properties (MgO, Mg-Al oxides, Mg/SiO 2 , NbP, and heteropolyanions on silica, HPA/SiO 2 ). Thermodynamic calculations revealed that cross-aldolization is always favored compared with self-aldolization of acetaldehyde, which leads to crotonaldehyde formation. The presence of strong basic sites is shown to be necessary, but a too high amount drastically increases CO x production. On strong acid sites, production of acrolein and carbon oxides (CO x ) does not increase with temperature. The optimal catalyst for this process should be amphoteric with a balanced acid/base cooperation of medium strength sites and a small amount (150 kJ mol -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative production of xylonic acid using xylose in distillation stillage of cellulosic ethanol fermentation broth by Gluconobacter oxydans.

Science.gov (United States)

Zhang, Hongsen; Han, Xushen; Wei, Chengxiang; Bao, Jie

2017-01-01

An oxidative production process of xylonic acid using xylose in distillation stillage of cellulosic ethanol fermentation broth was designed, experimentally investigated, and evaluated. Dry dilute acid pretreated and biodetoxified corn stover was simultaneously saccharified and fermented into 59.80g/L of ethanol (no xylose utilization). 65.39g/L of xylose was obtained in the distillation stillage without any concentrating step after ethanol was distillated. Then the xylose was completely converted into 66.42g/L of xylonic acid by Gluconobacter oxydans. The rigorous Aspen Plus modeling shows that the wastewater generation and energy consumption was significantly reduced comparing to the previous xylonic acid production process using xylose in pretreatment liquid. This study provided a practical process option for xylonic acid production from lignocellulose feedstock with significant reduction of wastewater and energy consumption. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

The oxidation of acid azo dye AY 36 by a manganese oxide containing mine waste

International Nuclear Information System (INIS)

Clarke, Catherine E.; Kielar, Filip; Johnson, Karen L.

2013-01-01

Highlights: ► This study looks at the oxidative breakdown of the amine containing dye acid yellow 36 by a Mn oxide containing mine waste. ► The oxidation proceeds by successive one electron transfers between the dye molecule and the Mn oxide minerals. ► The initial decolorization of the dye is rapid, but does not involve the cleavage of the azo bond. -- Abstract: The oxidative breakdown of acid azo dye acid yellow 36 (AY 36) by a Mn oxide containing mine tailings is demonstrated. The oxidation reaction is pH dependent with the rate of decolorization increasing with decreasing pH. The oxidation reaction mechanism is initiated at the amino moiety and proceeds via successive, one electron transfers from the dye to the Mn oxide minerals. The reaction pathway involves the formation of a number of colorless intermediate products, some of which hydrolyze in a Mn oxide-independent step. Decolorization of the dye is rapid and is observed before the cleavage of the azo-bond, which is a slower process. The terminal oxidation products were observed to be p-benzoquinone and 3-hydroxybenzenesulfonate. The reaction order of the initial decolorization was determined to be pseudo fractional order with respect to pH and pseudo first order with respect to dye concentration and Mn tailings’ surface area

Branched Chain Amino Acid Oxidation in Cultured Rat Skeletal Muscle Cells

Science.gov (United States)

Pardridge, William M.; Casanello-Ertl, Delia; Duducgian-Vartavarian, Luiza

1980-01-01

Leucine metabolism in skeletal muscle is linked to protein turnover. Since clofibrate is known both to cause myopathy and to decrease muscle protein content, the present investigations were designed to examine the effects of acute clofibrate treatment on leucine oxidation. Rat skeletal muscle cells in tissue culture were used in these studies because cultivated skeletal muscle cells, like muscle in vivo, have been shown to actively utilize branched chain amino acids and to produce alanine. The conversion of [1-14C]leucine to 14CO2 or to the [1-14C]keto-acid of leucine (α-keto-isocaproate) was linear for at least 2 h of incubation; the production of 14CO2 from [1-14C]leucine was saturable with a Km = 6.3 mM and a maximum oxidation rate (Vmax) = 31 nmol/mg protein per 120 min. Clofibric acid selectively inhibited the oxidation of [1-14C]leucine (Ki = 0.85 mM) and [U-14C]isoleucine, but had no effect on the oxidation of [U-14C]glutamate, -alanine, -lactate, or -palmitate. The inhibition of [1-14C]leucine oxidation by clofibrate was also observed in the rat quarter-diaphragm preparation. Clofibrate primarily inhibited the production of 14CO2 and had relatively little effect on the production of [1-14C]keto-acid of leucine. A physiological concentration—3.0 g/100 ml—of albumin, which actively binds clofibric acid, inhibited but did not abolish the effects of a 2-mM concentration of clofibric acid on leucine oxidation. Clofibrate treatment stimulated the net consumption of pyruvate, and inhibited the net production of alanine. The drug also increased the cytosolic NADH/NAD+ ratio as reflected by an increase in the lactate/pyruvate ratio, in association with a decrease in cell aspartate levels. The changes in pyruvate metabolism and cell redox state induced by the drug were delayed compared with the nearly immediate inhibition of leucine oxidation. These studies suggest that clofibric acid, in concentrations that approximate high therapeutic levels of the drug

Nitroxyl-mediated oxidation of lignin and polycarboxylated products

Energy Technology Data Exchange (ETDEWEB)

Stahl, Shannon S.; Rafiee, Mohammad

2018-02-27

Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

Modifications of proteins by polyunsaturated fatty acid peroxidation products

DEFF Research Database (Denmark)

Refsgaard, Hanne; Tsai, Lin; Stadtman, Earl

2000-01-01

The ability of unsaturated fatty acid methyl esters to modify amino acid residues in bovine serum albumin (BSA), glutamine synthetase, and insulin in the presence of a metal-catalyzed oxidation system [ascorbate/Fe(lll)/O-2] depends on the degree of unsaturation of the fatty acid. The fatty acid......-dependent generation of carbonyl groups and loss of lysine residues increased in the order methyl linoleate fatty acids were oxidized in the presence...... in the formation of protein carbonyls, These results are consistent with the proposition that metal-catalyzed oxidation of polyunsaturated fatty acids can contribute to the generation of protein carbonyls by direct interaction of lipid oxidation products (alpha,beta-unsaturated aldehydes) with lysine residues...

Catalytic abatement of nitrous oxide from nitric and production

NARCIS (Netherlands)

Oonk, J.

1998-01-01

Nitric acid production is identified as a main source of nitrous oxide. Options for emission reduction however are not available. TNO and Hydro Agri studied the technological and economic feasibility of catalytic decomposition of nitrous oxide in nitric acid tail-gases. Although in literature

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.

Analysis of Chlorogenic Acid Oxidation Pathway in Simulated ...

African Journals Online (AJOL)

Purpose: To investigate the pathways involved in the oxidation of chlorogenic acid (CA) and phenol metabolism in honeysuckle buds. Methods: A model that mimics CA oxidation by honeysuckle polyphenol oxidase (PPO) by controlling the reaction temperature or reaction duration was employed, and the resulting products ...

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.

Aspirin increases mitochondrial fatty acid oxidation

International Nuclear Information System (INIS)

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

2017-01-01

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. - Highlights: • Aspirin increases mitochondrial—but inhibits peroxisomal—fatty acid oxidation. • Aspirin acetylates mitochondrial proteins including fatty acid oxidation enzymes. • SIRT3 does not influence the effect of aspirin on fatty acid oxidation. • Increased fatty acid oxidation is likely due to altered mitochondrial morphology and respiration.

Macrokinetics of magnesium sulfite oxidation inhibited by ascorbic acid

International Nuclear Information System (INIS)

Lidong, Wang; Yongliang, Ma; Wendi, Zhang; Qiangwei, Li; Yi, Zhao; Zhanchao, Zhang

2013-01-01

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 −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

Aerobic Oxidation of Xylose to Xylaric acid in Water over Pt Catalysts.

Science.gov (United States)

Saha, Basudeb; Sadula, Sunitha

2018-05-02

Energy-efficient catalytic conversion of biomass intermediates to functional chemicals can enable bio-products viable. Herein, we report an efficient and low temperature aerobic oxidation of xylose to xylaric acid, a promising bio-based chemical for the production of glutaric acid, over commercial catalysts in water. Among several heterogeneous catalysts investigated, Pt/C exhibits the best activity. Systematic variation of reaction parameters in the pH range of 2.5 to 10 suggests that the reaction is fast at higher temperatures but high C-C scission of intermediate C5-oxidized products to low carbon carboxylic acids undermines xylaric acid selectivity. The C-C cleavage is also high in basic solution. The oxidation at neutral pH and 60 C achieves the highest xylaric acid yield (64%). O2 pressure and Pt-amount have significant influence on the reactivity. Decarboxylation of short chain carboxylic acids results in formation of CO2, causing some carbon loss; however such decarboxylation is slow in the presence of xylose. The catalyst retained comparable activity, in terms of product selectivity, after five cycles with no sign of Pt leaching. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards Sustainable Production of Formic Acid.

Science.gov (United States)

Bulushev, Dmitri A; Ross, Julian R H

2018-03-09

Formic acid is a widely used commodity chemical. It can be used as a safe, easily handled, and transported source of hydrogen or carbon monoxide for different reactions, including those producing fuels. The review includes historical aspects of formic acid production. It briefly analyzes production based on traditional sources, such as carbon monoxide, methanol, and methane. However, the main emphasis is on the sustainable production of formic acid from biomass and biomass-derived products through hydrolysis and oxidation processes. New strategies of low-temperature synthesis from biomass may lead to the utilization of formic acid for the production of fuel additives, such as methanol; upgraded bio-oil; γ-valerolactone and its derivatives; and synthesis gas used for the Fischer-Tropsch synthesis of hydrocarbons. Some technological aspects are also considered. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selenium dioxide catalysed oxidation of acetic acid hydrazide

Indian Academy of Sciences (India)

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 ...

Aspects of the regulation of long-chain fatty acid oxidation in bovine liver

International Nuclear Information System (INIS)

Jesse, B.W.; Emery, R.S.; Thomas, J.W.

1986-01-01

Factors involved in regulation of bovine hepatic fatty acid oxidation were examined using liver slices. Fatty acid oxidation was measured as the conversion of l-[ 14 C] palmitate to 14 CO 2 and total [ 14 C] acid-soluble metabolites. Extended (5 to 7 d) fasting of Holstein cows had relatively little effect on palmitate oxidation to acid-soluble metabolites by liver slices, although oxidation to CO 2 was decreased. Feeding a restricted roughage, high concentrate ration to lactating cows resulted in inhibition of palmitate oxidation. Insulin, glucose, and acetate inhibited palmitate oxidation by bovine liver slices. The authors suggest the regulation of bovine hepatic fatty acid oxidation may be less dependent on hormonally induced alterations in enzyme activity as observed in rat liver and more dependent upon action of rumen fermentation products or their metabolites on enzyme systems involved in fatty acid oxidation

Determination of moxifloxacin and its oxidation products with kinetic evaluation under potassium permanganate treatment in acidic solution by ultra-performance liquid chromatography/tandem mass spectrometry.

Science.gov (United States)

Hubicka, Urszula; Zmudzki, Paweł; Zajdel, Paweł; Krzek, Jan

2013-01-01

A simple, sensitive, and reproducible ultra-performance LC method for the determination of moxifloxacin (MOXI) oxidation stability under permanganate treatment in acidic conditions (pH 3.0-6.0) was developed. Besides the MOXI peak [retention time (RT) = 2.58], four additional products (RT = 0.86, 0.91, 1.42, and 1.89) were observed in all conditions tested. The oxidation process followed second-order reaction kinetics and depended upon solution acidity. The highest reaction rate constant was observed at pH 3.0, and this value decreased as the pH was increased to 6.0. The oxidation products were characterized, and their fragmentation pathways, derived from MS/MS data, were proposed. Two of these products were identified as hydroxyl derivatives of MOXI and two others as their oxidation product analogs with molecular ions of 418.4 and 416.4 m/z, respectively.

Oxidative Decarboxylation of Levulinic Acid by Cupric Oxides

Directory of Open Access Journals (Sweden)

Lu Lin

2010-11-01

Full Text Available In this paper, cupric oxides was found to effectively oxidize levulinic acid (LA and lead to the decarboxylation of levulinic acid to 2-butanone. The effects of cupric oxide dosage, reaction time and initial pH value were investigated in batch experiments and a plausible mechanism was proposed. The results showed that LA decarboxylation over cupric oxides at around 300 °C under acidic conditions produced the highest yield of butanone (67.5%. In order to elucidate the catalytic activity of cupric oxides, XRD, AFM, XPS and H2-TPR techniques was applied to examine their molecular surfaces and their effects on the reaction process.

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

Science.gov (United States)

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

2009-12-30

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

Gluconic Acid: Properties, Applications and Microbial Production

Directory of Open Access Journals (Sweden)

Sumitra Ramachandran

2006-01-01

Full Text Available Gluconic acid is a mild organic acid derived from glucose by a simple oxidation reaction. The reaction is facilitated by the enzyme glucose oxidase (fungi and glucose dehydrogenase (bacteria such as Gluconobacter. Microbial production of gluconic acid is the preferred method and it dates back to several decades. The most studied and widely used fermentation process involves the fungus Aspergillus niger. Gluconic acid and its derivatives, the principal being sodium gluconate, have wide applications in food and pharmaceutical industry. This article gives a review of microbial gluconic acid production, its properties and applications.

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.

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

International Nuclear Information System (INIS)

Moradmand Jalali, Hamed; Bashiri, Hadis; Rasa, Hossein

2015-01-01

In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO 2 , ZnO and ZrO 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 2 (rutile and anatase), ZnO and ZrO 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

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

Science.gov (United States)

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

2017-08-10

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

Optimization of the nitrous vapors experimental conditions production by nitric acid electrochemical reduction; Optimisation des conditions operatoires de production de vapeurs nitreuses par reduction electrochimique d`acide nitrique

Energy Technology Data Exchange (ETDEWEB)

Lemaire, M.

1996-11-22

Gaseous nitrogen oxides (NO and NO{sub 2}) involved as oxidizing agents in nuclear fuel reprocessing can be produced by electrochemical reduction of nitric acid. This is an interesting alternative to the existing process because no wastes are generated. voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0,05 V{sub SHE} and between 0,5 V{sub SHE} and 1 V{sub SHE}. The highest potential region reduction mechanism was studied by: classical micro-electrolysis methods, macro-electrolysis methods, infrared spectroscopy coupled to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric reduction can also explained by an other chemical reaction. If the potential value of platinum electrode is above 0,8 V{sub SHE}, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author). 91 refs.

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

The extraction of trace amounts of tantalum(V) from different mineral acid solutions by 4-(5-nonyl) pyridine oxide and trioctylamine oxide

International Nuclear Information System (INIS)

Ejaz, M.; Carswell, D.J.

1976-01-01

Data are presented on the distribution of trace amounts of tantalum(V) between different mineral acid solutions and 0.1M solutions of N-oxides of 4-(5-nonyl) pyridine and trioctylamine. The optimal acidity is 0.01-0.5M, depending on the nature of the acid. Common anions have little effect on extraction. Possible mechanism of extraction are suggested making use of slope analysis data. Separation factors for a number of metal ions with respect to tantalum are reported for the 0.1M 4-(5-nonyl)pyridine oxide - 1M sulphuric acid extraction system. Separation from uranium(VI), thorium(IV) and a number of fission products is suggested. The conclusions are unique as follows: Amine oxides are as unique as oxygen-donor extractants in their extraction of tantalum(V) from weakly acid solutions; tantalum is almost completely extracted from weakly nitric, hydrochloric and sulphuric acid solutions by both of the amine oxides; the extraction in low acidity solutions is independent of the nature of the anion of the acids present, indicating the ability of amine oxides to extract the product of hydrolysis of hydrolysable elements. In this respect amine oxides are much better than tributyl phosphate. (T.G.)

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

Treatment of Fatty Acid Oxidation Disorders

Science.gov (United States)

... Treatment of fatty acid oxidation disorders Treatment of fatty acid oxidation disorders E-mail to a friend Please ... this page It's been added to your dashboard . Fatty acid oxidation disorders are rare health conditions that affect ...

Selective oxidation of glycerol to formic acid in highly concentrated aqueous solutions with molecular oxygen using V-substituted phosphomolybdic acids

KAUST Repository

Zhang, Jizhe

2014-01-01

Formic acid is an important commodity chemical as well as a promising medium for hydrogen storage and hydrogen production. In this paper, we report that formic acid can be produced through selective oxidation of glycerol, a low-cost by-product of biodiesel, by using vanadium-substituted phosphomolybdic acids as catalysts and molecular oxygen as the oxidant. Significantly, this catalytic system allows for high-concentration conversions and thus leads to exceptional efficiency. Specifically, 3.64 g of formic acid was produced from 10 g of glycerol/water (50/50 in weight) solution. © 2014 the Partner Organisations.

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.

Production of Valuables Organic Acids from Organic Wastes with Hydrothermal Treatment Process

Directory of Open Access Journals (Sweden)

Muhammad Faisal

2009-06-01

Full Text Available This article reports production of valuables organic acids from the hydrothermal treatment of representative organic wastes and compounds (i. e. domestic sludge, proteinaceous, cellulosic and plastic wastes with or without oxidant (H2O2. Organic acids such as acetic, formic, propionic, succinic and lactic acids were obtained in significant amounts. At 623 K (16.5 MPa, acetic acid of about 26 mg/g-dry waste fish entrails was obtained. This increased to 42 mg/g dry waste fish entrails in the presence of H2O2. Experiments on glucose to represent cellulosic wastes were also carried out, getting acetic acid of about 29 mg/g-glucose. The study was extended to terephthalic acid and glyceraldehyde, reaction intermediates of hydrothermal treatment of PET plastic wastes and glucose, respectively. Studies on temperature dependence of formation of organic acids showed thermal stability of acetic acid, whereas, formic acid decomposed readily under hydrothermal conditions. In general, results demonstrated that the presence of oxidants favored formation of organic acids with acetic acid being the major product. Keywords: hydrothermal treatment, organic acids, organic wastes, oxidant, supercritical water oxidation

Lipid and fatty acid metabolism in Ralstonia eutropha: relevance for the biotechnological production of value-added products.

Science.gov (United States)

Riedel, Sebastian L; Lu, Jingnan; Stahl, Ulf; Brigham, Christopher J

2014-02-01

Lipid and fatty acid metabolism has been well studied in model microbial organisms like Escherichia coli and Bacillus subtilis. The major precursor of fatty acid biosynthesis is also the major product of fatty acid degradation (β-oxidation), acetyl-CoA, which is a key metabolite for all organisms. Controlling carbon flux to fatty acid biosynthesis and from β-oxidation allows for the biosynthesis of natural products of biotechnological importance. Ralstonia eutropha can utilize acetyl-CoA from fatty acid metabolism to produce intracellular polyhydroxyalkanoate (PHA). R. eutropha can also be engineered to utilize fatty acid metabolism intermediates to produce different PHA precursors. Metabolism of lipids and fatty acids can be rerouted to convert carbon into other value-added compounds like biofuels. This review discusses the lipid and fatty acid metabolic pathways in R. eutropha and how they can be used to construct reagents for the biosynthesis of products of industrial importance. Specifically, how the use of lipids or fatty acids as the sole carbon source in R. eutropha cultures adds value to these biotechnological products will be discussed here.

HPLC-ESI-MS/MS analysis of oxidized di-caffeoylquinic acids generated by metalloporphyrin-catalyzed reactions

International Nuclear Information System (INIS)

Santos, Michel D.; Lopes, Norberto P.; Iamamoto, Yassuko

2008-01-01

This paper reports an HPLC-ESI-MS/MS investigation on the oxidation of 3,5- and 4,5- dicaffeoylquinic acid using iron(III) tetraphenylporphyrin chloride as catalyst. Two major mono-oxidised products of the quinic acid moiety have been identified for both compounds. However, only the 4,5-derivative afforded two different tri-oxo products. Thus, it seems that the oxidation pattern depends on the number and positions of the caffeic acid moieties present in caffeoylquinic acid molecules. (author)

HPLC-ESI-MS/MS analysis of oxidized di-caffeoylquinic acids generated by metalloporphyrin-catalyzed reactions

Energy Technology Data Exchange (ETDEWEB)

Santos, Michel D.; Lopes, Norberto P. [Universidade de Sao Paulo (USP), Ribeirao Preto, SP (Brazil). Faculdade de Ciencias Farmaceuticas. Dept. de Fisica e Quimica]. E-mail: npelopes@fcfrp.usp.br; Iamamoto, Yassuko [Universidade de Sao Paulo (USP), Ribeirao Preto, SP (Brazil). Faculdade de Ciencias Farmaceuticas. Dept. de Quimica

2008-07-01

This paper reports an HPLC-ESI-MS/MS investigation on the oxidation of 3,5- and 4,5- dicaffeoylquinic acid using iron(III) tetraphenylporphyrin chloride as catalyst. Two major mono-oxidised products of the quinic acid moiety have been identified for both compounds. However, only the 4,5-derivative afforded two different tri-oxo products. Thus, it seems that the oxidation pattern depends on the number and positions of the caffeic acid moieties present in caffeoylquinic acid molecules. (author)

Control of bovine hepatic fatty acid oxidation

International Nuclear Information System (INIS)

Jesse, B.W.; Emery, R.S.; Thomas, J.W.

1986-01-01

Fatty acid oxidation by bovine liver slices and mitochondria was examined to determine potential regulatory sites of fatty acid oxidation. Conversion of 1-[ 14 C]palmitate to 14 CO 2 and total [ 14 C]acid-soluble metabolites was used to measure fatty acid oxidation. Oxidation of palmitate (1 mM) was linear in both liver slice weight and incubation time. Carnitine stimulated palmitate oxidation; 2 mM dl-carnitine produced maximal stimulation of palmitate oxidation to both CO 2 and acid-soluble metabolites. Propionate (10 mM) inhibited palmitate oxidation by bovine liver slices. Propionate (.5 to 10 mM) had no effect on palmitate oxidation by mitochondria, but malonyl Coenzyme A, the first committed intermediate of fatty acid synthesis, inhibited mitochondrial palmitate oxidation (inhibition constant = .3 μM). Liver mitochonndrial carnitine palmitoyltransferase exhibited Michaelis constants for palmitoyl Coenzyme A and l-carnitine of 11.5 μM and .59 mM, respectively. Long-chain fatty acid oxidation in bovine liver is regulated by mechanisms similar to those in rats but adapted to the unique digestive physiology of the bovine

HPLC-ESI-MS/MS analysis of oxidized di-caffeoylquinic acids generated by metalloporphyrin-catalyzed reactions

Directory of Open Access Journals (Sweden)

Michel D. Santos

2008-01-01

Full Text Available This paper reports an HPLC-ESI-MS/MS investigation on the oxidation of 3,5- and 4,5- dicaffeoylquinic acid using iron(III tetraphenylporphyrin chloride as catalyst. Two major mono-oxidised products of the quinic acid moiety have been identified for both compounds. However, only the 4,5-derivative afforded two different tri-oxo products. Thus, it seems that the oxidation pattern depends on the number and positions of the caffeic acid moieties present in caffeoylquinic acid molecules.

Selective oxidation of glycerol to formic acid in highly concentrated aqueous solutions with molecular oxygen using V-substituted phosphomolybdic acids

KAUST Repository

Zhang, Jizhe; Sun, Miao; Han, Yu

2014-01-01

Formic acid is an important commodity chemical as well as a promising medium for hydrogen storage and hydrogen production. In this paper, we report that formic acid can be produced through selective oxidation of glycerol, a low-cost by-product

Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols

DEFF Research Database (Denmark)

Kristensen, Kasper; Enggrob, Kirsten L.; King, S. M.

2013-01-01

products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural...

Nickel Inhibits Mitochondrial Fatty Acid Oxidation

Science.gov (United States)

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

2015-01-01

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 hr), 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. PMID:26051273

Optimization of the nitrous vapors experimental conditions production by nitric acid electrochemical reduction

International Nuclear Information System (INIS)

Lemaire, M.

1996-01-01

Gaseous nitrogen oxides (NO and NO 2 ) involved as oxidizing agents in nuclear fuel reprocessing can be produced by electrochemical reduction of nitric acid. This is an interesting alternative to the existing process because no wastes are generated. voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0,05 V SHE and between 0,5 V SHE and 1 V SHE . The highest potential region reduction mechanism was studied by: classical micro-electrolysis methods, macro-electrolysis methods, infrared spectroscopy coupled to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric reduction can also explained by an other chemical reaction. If the potential value of platinum electrode is above 0,8 V SHE , products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author)

Utilisation of sugarcane trash and other cellulosic wastes for production of oxalic acid

Energy Technology Data Exchange (ETDEWEB)

Mane, J D; Modak, H M; Ramaiah, N A; Jadhav, S J

1988-01-01

The nitric acid oxidation process was developed for the production of oxalic acid from sugarcane trash, groundnut shells, corn cobs and rice husks. Good yields of oxalic acid from the above raw materials were obtained under optimum conditions, with sugarcane trash as the preferable raw material. The absorption of waste nitrogen oxide gases in aqueous NaOH to get a valuable by-product, sodium nitrite, was also successful.

PREPARATION OF METAL OXIDE POWDERS FROM METAL LOADED VERSATIC ACID

OpenAIRE

KAKIHATA, Takayuki; USAMI, Kensuke; YAMAMOTO, Hideki; SHIBATA, Junji

1998-01-01

A production process for metal oxide powders was developed using a solvent extraction method. Versatic Acid 10 and D2EHPA solutions containing copper, zinc and nickel were used for a precipitation-stripping process, where oxalic acid was added to the solution as a precipitation reagent.Copper, zinc and nickel oxalates were easily formed in an aqueous phase, and 99.9% of precipitation was obtained for each metal during this process. These metal oxalates were easily converted to metal oxides by...

Glucose-stimulated acrolein production from unsaturated fatty acids.

Science.gov (United States)

Medina-Navarro, R; Duran-Reyes, G; Diaz-Flores, M; Hicks, J J; Kumate, J

2004-02-01

Glucose auto-oxidation may be a significant source of reactive oxygen species (ROS), and also be important in the lipid peroxidation process, accompanied by the release of toxic reactive products. We wanted to demonstrate that acrolein can be formed directly and actively from free fatty acids in a hyperglycemic environment. A suspension of linoleic and arachidonic acids (2.5 mM) was exposed to different glucose concentrations (5, 10 and 15 mmol/L) in vitro. The samples were extracted with organic solvents, partitioned, followed at 255-267 nm, and analysed using capillary electrophoresis and mass spectroscopy. The total release of aldehydes significantly (P products, acrolein (5% of total) and its condensing product, 4-hydroxy-hexenal, were identified. From the results presented here, it was possible to demonstrate the production of acrolein, probably as a fatty acid product, due to free radicals generated from the glucose auto-oxidation process. The results led us to propose that acrolein, which is one of the most toxic aldehydes, is produced during hyperglycemic states, and may lead to tissue injury, as one of the initial problems to be linked to high levels of glucose in vivo.

The Kinetics and Mechanism for the Oxidation of Nicotinic Acid by Peroxomonosulfate in Acidic Aqueous Medium

Energy Technology Data Exchange (ETDEWEB)

Agrawal, Anju; Sailani, Riya; Gupta, Beena; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

2012-04-15

The kinetics of oxidation of nicotinic acid by peroxomonosulfate (PMS) has been studied in acetate buffers. Stoichiometry of the reaction corresponds to the reaction of one mole of the oxidant with a mole of nicotinic acid. N→O product has been confirmed both by UV visible and IR spectroscopy. The reaction is second order viz. first order with respect to each reactant. Activation parameters have also been evaluated. A plausible reaction mechanism is mentioned and the derived kinetic rate law accounts for experimental observations.

The Kinetics and Mechanism for the Oxidation of Nicotinic Acid by Peroxomonosulfate in Acidic Aqueous Medium

International Nuclear Information System (INIS)

Agrawal, Anju; Sailani, Riya; Gupta, Beena; Khandelwal, C. L.; Sharma, P. D.

2012-01-01

The kinetics of oxidation of nicotinic acid by peroxomonosulfate (PMS) has been studied in acetate buffers. Stoichiometry of the reaction corresponds to the reaction of one mole of the oxidant with a mole of nicotinic acid. N→O product has been confirmed both by UV visible and IR spectroscopy. The reaction is second order viz. first order with respect to each reactant. Activation parameters have also been evaluated. A plausible reaction mechanism is mentioned and the derived kinetic rate law accounts for experimental observations

Kinetics and mechanism of the oxidation of formic and oxalic acids ...

Indian Academy of Sciences (India)

Unknown

The organic acids were commercial products of the highest degree of purity .... reaction is not complete even at high concentration of ZnCl2, and that only the ... activation in the oxidation of oxalic acid suggests the involvement of both the ...

Production of superconducting ceramic oxides by coprecipitation

International Nuclear Information System (INIS)

Bizaio, L.R.; Lima, M.A.F. de; Figueiredo Jardim, R.de; Pinheiro, E.A.; Galembeck, F.

1988-01-01

An alternative method for production of ceramic oxides is described. The method consist in the coprecipitation reaction of metallic ions with oxalic acid. The obtainment samples present additional phases characterized by X-rays and optical microscopy. (C.G.C.) [pt

Characterization of the newly isolated ω-oxidizing yeast Candida sorbophila DS02 and its potential applications in long-chain dicarboxylic acid production.

Science.gov (United States)

Lee, Heeseok; Sugiharto, Yohanes Eko Chandra; Lee, Seunghoon; Park, Gyuyeon; Han, Changpyo; Jang, Hyeran; Jeon, Wooyoung; Park, Heejoon; Ahn, Jungoh; Kang, Kyungbo; Lee, Hongwoen

2017-08-01

α, ω-Dicarboxylic acids (DCAs) are multipurpose chemicals widely used in polymers, perfumes, plasticizers, lubricants, and adhesives. The biotransformation of DCAs from alkanes and fatty acids by microorganisms has attracted recent interest, since synthesis via chemical oxidation causes problems in terms of the environment and safety. We isolated an ω-oxidizing yeast from a wastewater disposal facility of a petrochemical factory by chemostat enrichment culture. The haploid strain identified as Candida sorbophila DS02 grew on glucose and dodecane, exhibiting greater cell shrinkage on the latter. In flask cultures with mixed alkanes (C10-16) and fatty acid methyl esters (C10-16), DS02 used mixed alkanes simultaneously unlike Candida tropicalis and Yarrowia lipolytica and showed high substrate resistance. In flask cultures with acrylic acid-a known inhibitor of β-oxidation-DS02 produced 0.28 g/l dodecanedioic acid (DDDA) from dodecane, similar to wild-type C. tropicalis ATCC 20336. In fed-batch fermentation, DS02 produced 9.87 g/l DDDA, which was 5.7-fold higher than wild-type C. tropicalis. These results suggest that C. sorbophila strain DS02 has potential applications for the large-scale production of DCA.

Nitric-phosphoric acid oxidation of solid and liquid organic materials

International Nuclear Information System (INIS)

Pierce, R.A.; Smith, J.R.; Poprik, D.C.

1995-01-01

Nitric-phosphoric acid oxidation has been developed specifically to address issues that face the Savannah River Site, other defense-related facilities, private industry, and small-volume generators such as university and medical laboratories. Initially tested to destroy and decontaminate SRS solid, Pu-contaminated job-control waste, the technology has also exhibited potential for remediating hazardous and mixed-hazardous waste forms. The process is unique to Savannah River and offers a valuable alternative to other oxidation processes that require extreme temperatures and/or elevated pressures. To address the broad categories of waste, many different organic compounds which represent a cross-section of the waste that must be treated have been successfully oxidized. Materials that have been quantitatively oxidized at atmospheric pressure below 180 degrees C include neoprene, cellulose, EDTA, tributylphosphate, and nitromethane. More stable compounds such as benzoic acid, polyethylene, oils, and resins have been completely decomposed below 200 degrees C and 10 psig. The process uses dilute nitric acid in a concentrated phosphoric acid media as the main oxidant for the organic compounds. Phosphoric acid allow nitric acid to be retained in solution well above its normal boiling point. The reaction forms NOx vapors which can be reoxidized and recycled using air and water. The addition of 0.001M Pd(II) reduces CO generation to near 1% of the released carbon gases. The advantages of this process are that it is straightforward, uses relatively inexpensive reagents, operates at relatively low temperature and pressure, and produces final solutions which are compatible with stainless steel equipment. For organic wastes, all carbon, hydrogen, and nitrogen are converted to gaseous products. If interfaced with an acid recovery system which converts NOx back to nitric acid, the net oxidizer would be oxygen from air

Oxidative degradation of ion-exchange resins in acid medium. Vol. 3

International Nuclear Information System (INIS)

Eskander, S.B.; Ghattas, N.K.

1996-01-01

Volume reduction of spent ion-exchange resins used in nuclear facilities receive increasing importance due to the increase in storage cost, unstable physical and chemical properties and their relatively high specific activity (in some cases up to 1 Ci per liter). The present study is part of research program on the treatment and immobilization of radioactive spent ion-exchange resins simulate; hydrogen peroxide was used for the oxidative degradation of spent ion-exchange resins simulate in sulphuric acid medium. Five liters ring digester developed in Karlsruhe nuclear research center-(KFK)- in germany was the chosen option to perform the oxidation process. The work reported focused on the kinetics and mechanism of the oxidation process. Heating the organic resins in sulphuric acid results in its carbonization and partial oxidation of only 1.7% of the carbon added. Results show that the oxidation reaction is a relatively slow process of first order with K value in the order of 10 -4 min -1 , and the main oxidation product was carbon dioxide. The production of carbon oxide in the off gas stream increased sharply by the addition of hydrogen peroxide to the hot sulphuric acid-resin mixture. The results obtained show that more than 97% of the carbon added was oxidized to carbon dioxide and carbon monoxide. The rate constant value (K) of this reaction was calculated to be (1.69±0.13) x 10 -2 min -1 . The results of gas chromatographic analysis indicate that no significant amounts of hazardous organic materials were detected in the off-gas streams. 6 figs., 4 tabs

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

Directory of Open Access Journals (Sweden)

Y. Tan

2012-01-01

Full Text Available Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA. Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

Pineapple by-product and canola oil as partial fat replacers in low-fat beef burger: Effects on oxidative stability, cholesterol content and fatty acid profile.

Science.gov (United States)

Selani, Miriam M; Shirado, Giovanna A N; Margiotta, Gregório B; Rasera, Mariana L; Marabesi, Amanda C; Piedade, Sonia M S; Contreras-Castillo, Carmen J; Canniatti-Brazaca, Solange G

2016-05-01

The effect of freeze-dried pineapple by-product and canola oil as fat replacers on the oxidative stability, cholesterol content and fatty acid profile of low-fat beef burgers was evaluated. Five treatments were performed: conventional (CN, 20% fat) and four low-fat formulations (10% fat): control (CT), pineapple by-product (PA), canola oil (CO), and pineapple by-product and canola oil (PC). Low-fat cooked burgers showed a mean cholesterol content reduction of 9.15% compared to the CN. Canola oil addition improved the fatty acid profile of the burgers, with increase in the polyunsaturated/saturated fatty acids ratio and decrease in the n-6/n-3 ratio, in the atherogenic and thrombogenic indexes. The oxidative stability of the burgers was affected by the vegetable oil addition. However, at the end of the storage time (120 days), malonaldehyde values of CO and PC were lower than the threshold for the consumer's acceptance. Canola oil, in combination with pineapple by-product, can be considered promising fat replacers in the development of healthier burgers. Copyright © 2016 Elsevier Ltd. All rights reserved.

Alkali production associated with malolactic fermentation by oral streptococci and protection against acid, oxidative, or starvation damage.

Science.gov (United States)

Sheng, Jiangyun; Baldeck, Jeremiah D; Nguyen, Phuong T M; Quivey, Robert G; Marquis, Robert E

2010-07-01

Alkali production by oral streptococci is considered important for dental plaque ecology and caries moderation. Recently, malolactic fermentation (MLF) was identified as a major system for alkali production by oral streptococci, including Streptococcus mutans. Our major objectives in the work described in this paper were to further define the physiology and genetics of MLF of oral streptococci and its roles in protection against metabolic stress damage. L-Malic acid was rapidly fermented to L-lactic acid and CO(2) by induced cells of wild-type S. mutans, but not by deletion mutants for mleS (malolactic enzyme) or mleP (malate permease). Mutants for mleR (the contiguous regulator gene) had intermediate capacities for MLF. Loss of capacity to catalyze MLF resulted in loss of capacity for protection against lethal acidification. MLF was also found to be protective against oxidative and starvation damage. The capacity of S. mutans to produce alkali from malate was greater than its capacity to produce acid from glycolysis at low pH values of 4 or 5. MLF acted additively with the arginine deiminase system for alkali production by Streptococcus sanguinis, but not with urease of Streptococcus salivarius. Malolactic fermentation is clearly a major process for alkali generation by oral streptococci and for protection against environmental stresses.

Alkali production associated with malolactic fermentation by oral streptococci and protection against acid, oxidative, or starvation damage

Science.gov (United States)

Sheng, Jiangyun; Baldeck, Jeremiah D.; Nguyen, Phuong T.M.; Quivey, Robert G.; Marquis, Robert E.

2011-01-01

Alkali production by oral streptococci is considered important for dental plaque ecology and caries moderation. Recently, malolactic fermentation (MLF) was identified as a major system for alkali production by oral streptococci, including Streptococcus mutans. Our major objectives in the work described in this paper were to further define the physiology and genetics of MLF of oral streptococci and its roles in protection against metabolic stress damage. l-Malic acid was rapidly fermented to l-lactic acid and CO2 by induced cells of wild-type S. mutans, but not by deletion mutants for mleS (malolactic enzyme) or mleP (malate permease). Mutants for mleR (the contiguous regulator gene) had intermediate capacities for MLF. Loss of capacity to catalyze MLF resulted in loss of capacity for protection against lethal acidification. MLF was also found to be protective against oxidative and starvation damage. The capacity of S. mutans to produce alkali from malate was greater than its capacity to produce acid from glycolysis at low pH values of 4 or 5. MLF acted additively with the arginine deiminase system for alkali production by Streptococcus sanguinis, but not with urease of Streptococcus salivarius. Malolactic fermentation is clearly a major process for alkali generation by oral streptococci and for protection against environmental stresses. PMID:20651853

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

Science.gov (United States)

Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

2016-03-10

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

Reciprocal effects of 5-(tetradecyloxy)-2-furoic acid on fatty acid oxidation.

Science.gov (United States)

Otto, D A; Chatzidakis, C; Kasziba, E; Cook, G A

1985-10-01

Under certain incubation conditions 5-(tetradecyloxy)-2-furoic acid (TOFA) stimulated the oxidation of palmitate by hepatocytes, as observed by others. A decrease in malonyl-CoA concentration accompanied the stimulation of oxidation. Under other conditions, however, TOFA inhibited fatty acid oxidation. The observed effects of TOFA depended on the TOFA and fatty acid concentrations, the cell concentration, the time of TOFA addition relative to the addition of fatty acid, and the nutritional state of the animal (fed or starved). The data indicate that only under limited incubation conditions may TOFA be used as an inhibitor of fatty acid synthesis without inhibition of fatty acid oxidation. When rat liver mitochondria were preincubated with TOFA, ketogenesis from palmitate was slightly inhibited (up to 20%) at TOFA concentrations that were less than that of CoA, but the inhibition became almost complete (up to 90%) when TOFA was greater than or equal to the CoA concentration. TOFA had only slight or no inhibitory effects on the oxidation of palmitoyl-CoA, palmitoyl(-)carnitine, or butyrate. Since TOFA can be converted to TOFyl-CoA, the data suggest that the inhibition of fatty acid oxidation from palmitate results from the decreased availability of CoA for extramitochondrial activation of fatty acids. These data, along with previous data of others, indicate that inhibition of fatty acid oxidation by CoA sequestration is a common mechanism of a group of carboxylic acid inhibitors. A general caution is appropriate with regard to the interpretation of results when using TOFA in studies of fatty acid oxidation.

Simulation Analysis of Sludge Disposal and Volatile Fatty Acids Production from Gravity Pressure Reactor via Wet Air Oxidation

Energy Technology Data Exchange (ETDEWEB)

Park, Gwon Woo [Biomass and Waste Energy Laboratory, KIER, Daejeon (Korea, Republic of); Seo, Tae Wan; Lee, Hong-Cheol; Hwang, In-Ju [Environmental and Plant Engineering Research Institute, KICT, Goyang (Korea, Republic of)

2016-04-15

Efficacious wastewater treatment is essential for increasing sewage sludge volume and implementing strict environmental regulations. The operation cost of sludge treatment amounts up to 50% of the total costs for wastewater treatment plants, therefore, an economical sludge destruction method is crucially needed. Amid several destruction methods, wet air oxidation (WAO) can efficiently treat wastewater containing organic pollutants. It can be used not only for sludge destruction but also for useful by-product production. Volatile fatty acids (VFAs), one of many byproducts, is considered to be an important precursor of biofuel and chemical materials. Its high reaction condition has instituted the study of gravity pressure reactor (GPR) for an economical process of WAO to reduce operation cost. Simulation of subcritical condition was conducted using Aspen Plus with predictive Soave-Redlich-Kwong (PSRK) equation of state. Conjointly, simulation analysis for GPR depth, oxidizer type, sludge flow rate and oxidizer injection position was carried out. At GPR depth of 1000m and flow rate of 2 ton/h, the conversion and yield of VFAs were 92.02% and 0.17g/g, respectively.

Simulation Analysis of Sludge Disposal and Volatile Fatty Acids Production from Gravity Pressure Reactor via Wet Air Oxidation

International Nuclear Information System (INIS)

Park, Gwon Woo; Seo, Tae Wan; Lee, Hong-Cheol; Hwang, In-Ju

2016-01-01

Efficacious wastewater treatment is essential for increasing sewage sludge volume and implementing strict environmental regulations. The operation cost of sludge treatment amounts up to 50% of the total costs for wastewater treatment plants, therefore, an economical sludge destruction method is crucially needed. Amid several destruction methods, wet air oxidation (WAO) can efficiently treat wastewater containing organic pollutants. It can be used not only for sludge destruction but also for useful by-product production. Volatile fatty acids (VFAs), one of many byproducts, is considered to be an important precursor of biofuel and chemical materials. Its high reaction condition has instituted the study of gravity pressure reactor (GPR) for an economical process of WAO to reduce operation cost. Simulation of subcritical condition was conducted using Aspen Plus with predictive Soave-Redlich-Kwong (PSRK) equation of state. Conjointly, simulation analysis for GPR depth, oxidizer type, sludge flow rate and oxidizer injection position was carried out. At GPR depth of 1000m and flow rate of 2 ton/h, the conversion and yield of VFAs were 92.02% and 0.17g/g, respectively

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.

Non-enzymatic lipid oxidation products in biological systems: assessment of the metabolites from polyunsaturated fatty acids.

Science.gov (United States)

Vigor, Claire; Bertrand-Michel, Justine; Pinot, Edith; Oger, Camille; Vercauteren, Joseph; Le Faouder, Pauline; Galano, Jean-Marie; Lee, Jetty Chung-Yung; Durand, Thierry

2014-08-01

Metabolites of non-enzymatic lipid peroxidation of polyunsaturated fatty acids notably omega-3 and omega-6 fatty acids have become important biomarkers of lipid products. Especially the arachidonic acid-derived F2-isoprostanes are the classic in vivo biomarker for oxidative stress in biological systems. In recent years other isoprostanes from eicosapentaenoic, docosahexaenoic, adrenic and α-linolenic acids have been evaluated, namely F3-isoprostanes, F4-neuroprostanes, F2-dihomo-isoprostanes and F1-phytoprostanes, respectively. These have been gaining interest as complementary specific biomarkers in human diseases. Refined extraction methods, robust analysis and elucidation of chemical structures have improved the sensitivity of detection in biological tissues and fluids. Previously the main reliable instrumentation for measurement was gas chromatography-mass spectrometry (GC-MS), but now the use of liquid chromatography-tandem mass spectrometry (LC-MS/MS) and immunological techniques is gaining much attention. In this review, the types of prostanoids generated from non-enzymatic lipid peroxidation of some important omega-3 and omega-6 fatty acids and biological samples that have been determined by GC-MS and LC-MS/MS are discussed. Copyright © 2014. Published by Elsevier B.V.

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.

Electrochemical degradation of clofibric acid in water by anodic oxidation

International Nuclear Information System (INIS)

Sires, Ignasi; Cabot, Pere Lluis; Centellas, Francesc; Garrido, Jose Antonio; Rodriguez, Rosa Maria; Arias, Conchita; Brillas, Enric

2006-01-01

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 (·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 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 ·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 2 with BDD. A reaction pathway for clofibric acid degradation involving all these intermediates is proposed

Recovery of vanadium (V) from used catalysts in sulfuric acid production units by oxalic acid

International Nuclear Information System (INIS)

Abdulbaki, M.; Shino, O.

2009-07-01

Vanadium penta oxide (V 2 O 5 ), is used, in large quantities as a catalyst for the oxidation of SO 2 to SO 3 in sulfuric acid production units, during the oxidation process the level of the oxidation declines with the time because of catalyst poisoning. So the spent catalyst is usually through out in a specified special places by General Fertilizer Company which causes a pollution of the land. The present paper, studies the recovery of vanadium from the spent catalyst by using the oxalic acid. The optimal conditions of spent catalyst leaching have been studied. It has been shown that 2%(w/w) of oxalic acid is the most suitable for leaching process at 70 degree centigrade. The precipitation of vanadium using some alkaline media NH 4 OH has been also studied, it has been shown that ammonium hydroxide was the best at 50 degree centigrade. (author)

Green reduction of graphene oxide by ascorbic acid

Science.gov (United States)

Khosroshahi, Zahra; Kharaziha, Mahshid; Karimzadeh, Fathallah; Allafchian, Alireza

2018-01-01

Graphene, a single layer of sp2-hybridized carbon atoms in a hexagonal (two-dimensional honey-comb) lattice, has attracted strong scientific and technological interest due to its novel and excellent optical, chemical, electrical, mechanical and thermal properties. The solution-processable chemical reduction of Graphene oxide (GO is considered as the most favorable method regarding mass production of graphene. Generally, the reduction of GO is carried out by chemical approaches using different reductants such as hydrazine and sodium borohydride. These components are corrosive, combustible and highly toxic which may be dangerous for personnel health and the environment. Hence, these reducing agents are not promising choice for reducing of graphene oxide (GO). As a consequence, it is necessary for further development and optimization of eco-friendly, natural reducing agent for clean and effective reduction of GO. Ascorbic acid, an eco-friendly and natural reducing agents, having a mild reductive ability and nontoxic property. So, the aim of this research was to green synthesis of GO with ascorbic acid. For this purpose, the required amount of NaOH and ascorbic acid were added to GO solution (0.5 mg/ml) and were heated at 95 °C for 1 hour. According to the X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electrochemical results, GO were reduced with ascorbic acid like hydrazine with better electrochemical properties and ascorbic acid is an ideal substitute for hydrazine in the reduction of graphene oxide process.

Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

Science.gov (United States)

Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

2018-01-01

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

Fatty acid omega-oxidation as a rescue pathway for fatty acid oxidation disorders in humans

NARCIS (Netherlands)

Wanders, Ronald J. A.; Komen, Jasper; Kemp, Stephan

2011-01-01

Fatty acids (FAs) can be degraded via different mechanisms including alpha-, beta- and omega-oxidation. In humans, a range of different genetic diseases has been identified in which either mitochondrial FA beta-oxidation, peroxisomal FA beta-oxidation or FA alpha-oxidation is impaired. Treatment

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

DEFF Research Database (Denmark)

Jacobsen, Charlotte; Hartvigsen, Karsten; Thomsen, Mikael Holm

2001-01-01

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...... 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...

Engineering the production of conjugated fatty acids in Arabidopsis thaliana leaves

Science.gov (United States)

The seeds of many non-domesticated plant species synthesize oils containing high amounts of a single unusual fatty acid, many of which have potential usage in industry. Despite the identification of enzymes for unusual oxidized fatty acid synthesis, the production of these fatty acids in engineered ...

DNAPL remediation with in situ chemical oxidation using potassium permanganate - Part I. Mineralogy of Mn oxide and its dissolution in organic acids

Science.gov (United States)

Li, X. David; Schwartz, Franklin W.

2004-01-01

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 Å. The chemical formula is K 0.854Mn 1.786O 4·1.55H 2O. It has a relatively small specific surface area at 23.6±0.82 m 2/g. Its point of zero charge (pzc) was measured as 3.7±0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m 2/h for citric acid, 1.35 mM/m 2/h for oxalic acid, and 5.176 mM/m 2/h for EDTA. These rates compare with 0.0025 mM/m 2/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant

Production of Odd-Carbon Dicarboxylic Acids in Escherichia coli Using an Engineered Biotin-Fatty Acid Biosynthetic Pathway.

Science.gov (United States)

Haushalter, Robert W; Phelan, Ryan M; Hoh, Kristina M; Su, Cindy; Wang, George; Baidoo, Edward E K; Keasling, Jay D

2017-04-05

Dicarboxylic acids are commodity chemicals used in the production of plastics, polyesters, nylons, fragrances, and medications. Bio-based routes to dicarboxylic acids are gaining attention due to environmental concerns about petroleum-based production of these compounds. Some industrial applications require dicarboxylic acids with specific carbon chain lengths, including odd-carbon species. Biosynthetic pathways involving cytochrome P450-catalyzed oxidation of fatty acids in yeast and bacteria have been reported, but these systems produce almost exclusively even-carbon species. Here we report a novel pathway to odd-carbon dicarboxylic acids directly from glucose in Escherichia coli by employing an engineered pathway combining enzymes from biotin and fatty acid synthesis. Optimization of the pathway will lead to industrial strains for the production of valuable odd-carbon diacids.

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.

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.

Fatty acid profile, color and lipid oxidation of organic fermented sausage during chilling storage as influenced by acid whey and probiotic strains addition

Directory of Open Access Journals (Sweden)

Karolina Maria Wójciak

2015-02-01

Full Text Available Organic fermented sausages typically spoil during long-term storage due to oxidative rancidity. The application of natural antioxidants to meat stuffing is a major practice intended to inhibit the oxidation process and color changes. This study aimed to assess the effect of two unusual starter cultures: three probiotic strains (Lactobacillus casei LOCK 0900, Lactobacillus casei LOCK 0908 and Lactobacillus paracasei LOCK 0919 and lactic acid bacteria from acid whey on model fermented sausage type products focusing on oxidative stability by measuring instrumental color (L*, a*, b* values, conjugated dienes (CD, TBARS immediately after 21 days of ripening (0 and after 90 and 180 days of refrigerated storage (4 ºC. Determination of fatty acid composition, in meat product was performed after ripening and after 180 days of storage. At the end of the storage period, the salted sausages were characterized by the same content of polyunsaturated fatty acids (PUFA compared to cured samples. The addition of acid whey and a mixture of probiotic strains to nitrite-free sausage formulation was barely able to protect lipids against oxidation in comparison to nitrite during vacuum storage. Surprisingly, the use of acid whey has an influence on the desired red-pinkish color of organic fermented sausage after ripening and after 180 days of storage period.

The Effect of Buckwheat Hull Extract on Lipid Oxidation in Frozen-Stored Meat Products.

Science.gov (United States)

Hęś, Marzanna; Szwengiel, Artur; Dziedzic, Krzysztof; Le Thanh-Blicharz, Joanna; Kmiecik, Dominik; Górecka, Danuta

2017-04-01

This study investigated the effect of antioxidants on lipid stability of frozen-stored meat products. Buckwheat hull extract was used to enrich fried meatballs made from ground pork. During 180-d storage of meat products, lipid oxidation (peroxide and 2-thiobarbituric acid reactive substances [TBARS] value) was periodically monitored. The results were compared with butylated hydroxytoluene (BHT). The addition of antioxidants decreased lipid oxidation in stored meatballs. The highest ability to control peroxide and TBARS values was demonstrated for buckwheat hull extract. Moreover, buckwheat hull extract showed a higher 2,2-diphenyl-1-picrylhydrazyl free radical scavenging activity as well as higher Fe(II) ion chelating ability, as compared with BHT. The total content of phenolic compounds are highly correlated to the individual polyphenols in extract of buckwheat hull, among which the following were assayed: 3,4-dihydroxybenzoic acid, 4-hydroxybenzoic acid, gallic acid, isovanillic acid and p-coumaric acid, and flavonoids: isoorientin, quercetin, quercetin 3-d-glucoside, rutin, and vitexin. These results indicate that plant extracts can be used to prolong shelf life of products by protecting them against lipid oxidation and deterioration of their nutritional quality. © 2017 Institute of Food Technologists®.

Production of hydroxyl radicals from abiotic oxidation of pyrite by oxygen under circumneutral conditions in the presence of low-molecular-weight organic acids

Science.gov (United States)

Zhang, Peng; Yuan, Songhu

2017-12-01

Besides acidic environments, pyrite oxidation also occurs in circumneutral environments, such as well-buffered marine and estuarine sediments and salt marshes where low-molecular-weight organic acids (LMWOAs) (e.g., citrate and oxalate) prevail. However, the production of hydroxyl radicals (radOH) from pyrite oxidation by oxygen (O2) in these circumneutral environments is poorly understood. In this study, radOH production was measured during the abiotic oxidation of pyrite by O2 under circumneutral conditions. A pyrite suspension (50 g/L pyrite) that was buffered at pH 6-8 was exposed to air for oxygenation in the dark. Benzoate (20 mM) was added into the suspension to trap radOH. At pH 7, the cumulative radOH reached 7.5 μM within 420 min in the absence of LMWOAs, whereas it increased to 14.8, 12 and 11.2 μM in the presence of 1 mM ethylenediaminotetraacetate, citrate and oxalate, respectively. When the citrate concentration, which serves as a LMWOAs model, was increased from 0.5 to 5 mM, the cumulative radOH increased from 10.3 to 27.3 μM within 420 min at pH 7. With the decrease in pH from 8 to 6, the cumulative radOH increased from 2.1 to 23.3 μM in the absence of LMWOAs, but it increased from 8.8 to 134.9 μM in the presence of 3 mM citrate. The presence of LMWOAs enhanced the radOH production from pyrite oxidation under circumneutral conditions. In the absence of LMOWAs, radOH is produced mostly from the oxidation of adsorbed Fe(II) by O2. In the presence of citrate, radOH production is attributed mainly to the oxidation of Fe(II)-citrate- by O2 and secondarily to the oxidation of H2O on surface-sulfur defects. The acceleration of pyrite oxidation by Fe(III)-citrate increases radOH production. Fe(II)-citrate- is generated mainly from the complexation of adsorbed Fe(II) by citrate and the reduction of Fe(III)-citrate, and the generation is suppressed by the oxidation of adsorbed Fe(II). Fe(III)-citrate is generated predominantly from Fe

Separation of caesium-137 from fission products using phosphotungstic acid

International Nuclear Information System (INIS)

Murthy, T.S.; Balasubramaniam, K.R.; Ananthakrishnan, M.; Varma, R.N.

1977-01-01

Separation of caesium 137 from fission products using phosphotungstic acid is reported. Phosphotungstate caesium is precipitated as caesium from fission product waste solution in acid medium and subsequently purified. Separation of phosphate and tungstate ions has been done using a typical hydrous oxide like alumina. The exchange capacity of alumina for phosphate and tungstate ions, and the purity of the product are determined. Results are discussed. Based on the findings a procedure is recommended for caesium 137 separation. (A.K.)

Degradation of the azo dye Acid Red 1 by anodic oxidation and indirect electrochemical processes based on Fenton's reaction chemistry. Relationship between decolorization, mineralization and products

International Nuclear Information System (INIS)

Florenza, Xavier; Solano, Aline Maria Sales; Centellas, Francesc; Martínez-Huitle, Carlos Alberto

2014-01-01

Highlights: • Degradation of Acid Red 1 by anodic oxidation, electro-Fenton and photoelectro-Fenton • Quicker and similar decolorization by electro-Fenton and photoelectro-Fenton due to oxidation with ● OH in the bulk • Almost total mineralization by photoelectro-Fenton with Pt or BDD due to fast photolysis of products by UVA light • Detection of 11 aromatic products, 15 hydroxylated compounds, 13 desulfonated derivatives and 7 carboxylic acids • Release of NH 4 + , NO 3 − and SO 4 2− ions, and generation of persistent N-products of low molecular mass - Abstract: Solutions of 236 mg dm −3 Acid Red 1 (AR1), an azo dye widely used in textile dying industries, at pH 3.0 have been comparatively treated by anodic oxidation with electrogenerated H 2 O 2 (AO-H 2 O 2 ), electro-Fenton (EF) and photoelectro-Fenton (PEF) at constant current density (j). Assays were performed with a stirred tank reactor equipped with a Pt or boron-doped diamond (BDD) anode and an air-diffusion cathode for H 2 O 2 generation from O 2 reduction. The main oxidizing agents were hydroxyl radicals produced at the anode from water oxidation in all methods and in the bulk from Fenton's reaction between generated H 2 O 2 and 0.5 mmol dm −3 Fe 2+ in EF and PEF. For each anode, higher oxidation power was found in the sequence AO-H 2 O 2 < EF < PEF. The oxidation ability of the BDD anode was always superior to that of Pt. Faster and similar decolorization efficiency was achieved in EF and PEF owing to the quicker destruction of aromatics with hydroxyl radicals produced in the bulk. The PEF process with BDD was the most potent method yielding almost total mineralization due to the additional rapid photolysis of recalcitrant intermediates like Fe(III)-carboxylate complexes under UVA irradiation. The increase in j always enhanced the decolorization and mineralization processes because of the greater production of hydroxyl radicals, but decreases the mineralization current efficiency

Repair of oxidative DNA damage by amino acids.

Science.gov (United States)

Milligan, J R; Aguilera, J A; Ly, A; Tran, N Q; Hoang, O; Ward, J F

2003-11-01

Guanyl radicals, the product of the removal of a single electron from guanine, are produced in DNA by the direct effect of ionizing radiation. We have produced guanyl radicals in DNA by using the single electron oxidizing agent (SCN)2-, itself derived from the indirect effect of ionizing radiation via thiocyanate scavenging of OH. We have examined the reactivity of guanyl radicals in plasmid DNA with the six most easily oxidized amino acids cysteine, cystine, histidine, methionine, tryptophan and tyrosine and also simple ester and amide derivatives of them. Cystine and histidine derivatives are unreactive. Cysteine, methionine, tyrosine and particularly tryptophan derivatives react to repair guanyl radicals in plasmid DNA with rate constants in the region of approximately 10(5), 10(5), 10(6) and 10(7) dm3 mol(-1) s(-1), respectively. The implication is that amino acid residues in DNA binding proteins such as histones might be able to repair by an electron transfer reaction the DNA damage produced by the direct effect of ionizing radiation or by other oxidative insults.

Volatile profile, lipid oxidation and protein oxidation of irradiated ready-to-eat cured turkey meat products

International Nuclear Information System (INIS)

Feng, Xi; Ahn, Dong Uk

2016-01-01

Irradiation had little effects on the thiobarbituric acid reactive substances (TBARS) values in ready-to-eat (RTE) turkey meat products, while it increased protein oxidation at 4.5 kGy. The volatile profile analyses indicated that the amount of sulfur compounds increased linearly as doses increased in RTE turkey meat products. By correlation analysis, a positive correlation was found between benzene/ benzene derivatives and alcohols with lipid oxidation, while aldehydes, ketones and alkane, alkenes and alkynes were positively correlated with protein oxidation. Principle component analysis showed that irradiated meat samples can be discriminated by two categories of volatile compounds: Strecker degradation products and radiolytic degradation products. The cluster analysis of volatile data demonstrated that low-dose irradiation had minor effects on the volatile profile of turkey sausages (<1.5 kGy). However, as the doses increased, the differences between the irradiated and non-irradiated cured turkey products became significant. - Highlights: • Irradiation had little effects on lipid oxidation of ready-to-eat cured turkey. • 4.5 kGy irradiation increased protein oxidation. • Irradiated samples were isolated due to Strecker/radiolytic degradation products. • 1.5 kGy irradiation had limited effects on the volatile profile of turkey sausages. • Dimethyl disulfide can be used as a potential marker for irradiated meat products.

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

Science.gov (United States)

Moradmand Jalali, Hamed; Bashiri, Hadis; Rasa, Hossein

2015-05-01

In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO2, ZnO and ZrO2) 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. Copyright © 2015 Elsevier B.V. All rights reserved.

Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

Science.gov (United States)

Flores, Rubia Gomes; Andersen, Silvia Layara Floriani; Maia, Leonardo Kenji Komay; José, Humberto Jorge; Moreira, Regina de Fatima Peralta Muniz

2012-11-30

Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Emulsifying Property and Antioxidative Activity of Cuttlefish Skin Gelatin Modified with Oxidized Linoleic Acid and Oxidized Tannic Acid

NARCIS (Netherlands)

Aewsiri, T.; Benjakul, S.; Visessanguan, W.; Wierenga, P.A.; Gruppen, H.

2013-01-01

Cuttlefish skin gelatins modified with oxidized linoleic acid (OLA) and oxidized tannic acid (OTA) were characterized and determined for emulsifying properties and antioxidative activity. Modification of gelatin with 5% OTA increased the total phenolic content and 1,1-diphenyl-2-picrylhydrazyl,

Effects of hypoxia and pyruvate infusion on myocardial fatty acid oxidation measured with 123I heptadecanoic acid

International Nuclear Information System (INIS)

Comans, E.F.I.; Visser, F.C.; Elzinga, Gijs

1993-01-01

Radio-iodinated fatty acids like 123 I heptadecanoic acid (HDA) can be used for the non-invasive delineation of myocardial non-esterified fatty acid (FA) metabolism. In this study the quantitative value of HDA was assessed for the measurement of myocardial FA oxidation. In an isolated saline perfused rat heart preparation myocardial time-activity curves were made during control perfusion and after inhibition of FA oxidation by hypoxia and infusion of 10.0 mM pyruvate, respectively. Control experiments were performed using 1- 14 C palmitate as the 'golden standard' for myocardial FA oxidation. Myocardial HDA oxidation was calculated from the amplitude of the third exponential term of the time-activity curve. During control perfusion no differences were observed between the calculated oxygen equivalents (from HDA oxidation) and the measured (A-V oxygen content difference) and the estimated ( 14 CO 2 production) values. Inhibition of palmitate oxidation with pyruvate was accurately detected with HDA. During hypoxic perfusion, an overestimation of palmitate oxidation was calculated on the basic of HDA oxidation. Infusion of pyruvate did not influence the time constants of the time-activity curves, whereas during hypoxic perfusion an increase of the time constant of the third exponential term was observed, probably caused by the presence of back-diffusion of non-metabolized HDA. We conclude that HDA can be used as a quantitative tool for the measurement of myocardial FA oxidation under various metabolic conditions. During periods of a decreased oxygen availability back-diffusion of FA needs to be taken into account for the interpretation of the myocardial time-activity curves. (author)

Oxidation of β-lactam antibiotics by peracetic acid: Reaction kinetics, product and pathway evaluation.

Science.gov (United States)

Zhang, Kejia; Zhou, Xinyan; Du, Penghui; Zhang, Tuqiao; Cai, Meiquan; Sun, Peizhe; Huang, Ching-Hua

2017-10-15

Peracetic acid (PAA) is a disinfection oxidant used in many industries including wastewater treatment. β-Lactams, a group of widely prescribed antibiotics, are frequently detected in wastewater effluents and surface waters. The reaction kinetics and transformation of seven β-lactams (cefalexin (CFX), cefadroxil (CFR), cefapirin (CFP), cephalothin (CFT), ampicillin (AMP), amoxicillin (AMX) and penicillin G (PG)) toward PAA were investigated to elucidate the behavior of β-lactams during PAA oxidation processes. The reaction follows second-order kinetics and is much faster at pH 5 and 7 than at pH 9 due to speciation of PAA. Reactivity to PAA follows the order of CFR ∼ CFX > AMP ∼ AMX > CFT ∼ CFP ∼ PG and is related to β-lactam's nucleophilicity. The thioether sulfur of β-lactams is attacked by PAA to generate sulfoxide products. Presence of the phenylglycinyl amino group on β-lactams can significantly influence electron distribution and the highest occupied molecular orbital (HOMO) location and energy in ways that enhance the reactivity to PAA. Reaction rate constants obtained in clean water matrix can be used to accurately model the decay of β-lactams by PAA in surface water matrix and only slightly overestimate the decay in wastewater matrix. Results of this study indicate that the oxidative transformation of β-lactams by PAA can be expected under appropriate wastewater treatment conditions. Copyright © 2017. Published by Elsevier Ltd.

Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural

Science.gov (United States)

Pacheco, Joshua J.; Davis, Mark E.

2014-01-01

Terephthalic acid (PTA), a monomer in the synthesis of polyethylene terephthalate (PET), is obtained by the oxidation of petroleum-derived p-xylene. There is significant interest in the synthesis of renewable, biomass-derived PTA. Here, routes to PTA starting from oxidized products of 5-hydroxymethylfurfural (HMF) that can be produced from biomass are reported. These routes involve Diels-Alder reactions with ethylene and avoid the hydrogenation of HMF to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with high pressure ethylene over a pure-silica molecular sieve containing framework tin (Sn-Beta) to produce the Diels-Alder dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with 31% selectivity at 61% HMFA conversion after 6 h at 190 °C. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of Sn-Beta for 2 h to produce methyl 4-(methoxymethyl)benzenecarboxylate (MMBC) with 46% selectivity at 28% MMFC conversion or in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) for 6 h to produce MMBC with 81% selectivity at 26% MMFC conversion. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the Diels-Alder dehydration product is observed. PMID:24912153

Activation of peroxisome proliferator-activated receptor-α enhances fatty acid oxidation in human adipocytes

International Nuclear Information System (INIS)

Lee, Joo-Young; Hashizaki, Hikari; Goto, Tsuyoshi; Sakamoto, Tomoya; Takahashi, Nobuyuki; Kawada, Teruo

2011-01-01

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

Assessment of myocardial metabolism with iodine-123 heptadecanoic acid: effect of decreased fatty acid oxidation on deiodination

International Nuclear Information System (INIS)

Luethy, P.C.; Chatelain, P.; Papageorgiou, I.; Schubiger, A.; Lerch, R.A.

1988-01-01

Terminally radioiodinated fatty acid analogs are of potential use for the noninvasive delineation of regional alterations of fatty acid metabolism by gamma imaging. Since radioactivity from extracted iodine-123 heptadecanoic acid [( 123I]HDA) is released from the myocardium in form of free radioiodide (123I-) the present study was performed to determine whether deiodination of [123I]HDA is related to free fatty acid metabolism. Myocardial production of free radioiodide was measured in rat hearts in vitro and in vivo both under control conditions and after inhibition of fatty acid oxidation. In isolated rat hearts perfused at constant flow with a medium containing [123I]HDA, release of 123I- was markedly reduced during cardioplegia and pharmacologic inhibition of mitochondrial fatty acid transfer with POCA by 67% (p less than 0.005) and 72% (p less than 0.005), respectively. In fasted rats in vivo, 1 min after i.v. injection of [123I]HDA, 51 +/- 5% of myocardial radioactivity was recovered in the aqueous phase, containing free iodide, of myocardial lipid extracts. Aqueous activity was significantly decreased in fed (20 +/- 2%; p less than 0.002) and POCA pretreated (30 +/- 3.7%; p less than 0.05) animals exhibiting reduced oxidation of [14C]palmitate. Thus, deiodination of [123I]HDA was consistently reduced during inhibition of fatty acid oxidation in vitro and in vivo. The results apply to the interpretation of myocardial clearance curves of terminally radioiodinated fatty acid analogs

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

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.

Formation of organic acids from trace carbon in acidic oxidizing media

International Nuclear Information System (INIS)

Terrassier, C.

2003-01-01

Carbon 14 does not fully desorb as CO 2 during the hot concentrated nitric acid dissolution step of spent nuclear fuel reprocessing: a fraction is entrained in solution into the subsequent process steps as organic species. The work described in this dissertation was undertaken to identify the compounds arising from the dissolution in 3 N nitric acid of uranium carbides (selected as models of the chemical form of carbon 14 in spent fuel) and to understand their formation and dissolution mechanism. The compounds were present at traces in solution, and liquid-solid extraction on a specific stationary phase (porous graphite carbon) was selected to concentrate the monoaromatic poly-carboxylic acids including mellitic acid, which is mentioned in the literature but has not been formally identified. The retention of these species and of oxalic acid - also cited in the literature - was studied on this stationary phase as a function of the mobile phase pH, revealing an ion exchange retention mechanism similar to the one observed for benzyltrimethylammonium polystyrene resins. The desorption step was then optimized by varying the eluent pH and ionic strength. Mass spectrometry analysis of the extracts identified acetic acid, confirmed the presence of mellitic acid, and revealed compounds of high molecular weight (about 200 g/mol); the presence of oxalic acid was confirmed by combining gas chromatography and mass spectrometry. Investigating the dissolution of uranium and zirconium carbides in nitric acid provided considerable data on the reaction and suggested a reaction mechanism. The reaction is self-catalyzing via nitrous acid, and the reaction rate de pends on the acidity and nitrate ion concentration in solution. Two uranium carbide dissolution mechanisms are proposed: one involves uranium at oxidation state +IV in solution, coloring the dissolution solution dark green, and the other assumes that uranium monocarbide is converted to uranium oxide. The carboxylic acid

Potential risk of coupling products between tetrahalobisphenol A and humic acid prepared via oxidation with a biomimetic catalyst.

Science.gov (United States)

Kodama, Ritsu; Sazawa, Kazuto; Miyamoto, Takafumi; Zhu, Qianqian; Igarashi, Mami; Oda, Kohki; Kuramitz, Hideki; Fukushima, Masami

2018-04-04

Tetrahalobisphenol A (TXPBAs, X = Br or Cl), TBBPA and TCBPA, which are widely used as flame retardants, ultimately disposed of in landfills. In landfills, enzymatically oxidized TXBPAs can be covalently incorporated into humic acids (HAs) to form coupling products (HA-TXBPAs). In the present study, HA-TXBPAs were prepared by catalytic oxidation with iron(III)-phthalocyanine-tetrasulfate as a model of oxidative enzymes. The stability of HA-TXBPAs was evaluated by incubating them under physicochemical conditions of landfills (pH 9 and 50 °C). For HA-TBBPA, 18-26% of TBBPA was released from HA-TBBPA, due to the acid dissociation of the loosely bound TBBPA. However, no additional release was observed, even after 30 days, indicating that 74-82% of the TBBPA was incorporated into the HA. For HA-TCBPA, 3-4% of TCBPA and a major byproduct, 4-(2-hydroxyisopropyl)-2,6-dichlorophenol, was found to be loosely incorporated into HA. For both TBBPA and TCBPA, covalently bound organo-halogens were not released during the 30 days of incubation. Inhibition of the growth of Chlamydomonas reinhardtii was indicated when trace levels of TXBPAs (approximately 0.1 μM) were present. These results suggest that HA-TXBPAs contain not only covalently incorporated TXBPAs but also loosely bound TXBPAs and halophenols. The latter in HA-TXBPAs have the potential to leach from landfills and affect aquatic ecosystems. Copyright © 2018 Elsevier Ltd. All rights reserved.

Optimization of conditions to produce nitrous gases by electrochemical reduction of nitric acid; Optimisation des conditions operatoires de production de vapeurs nitreuses par reduction electrochimique d`acide nitrique

Energy Technology Data Exchange (ETDEWEB)

Lemaire, M. [CEA Centre d`Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France)]|[CEA Centre d`Etudes de la Vallee du Rhone, 30 -Marcoule (France). Direction du Cycle du Combustible

1996-11-22

Gaseous nitrogen oxides (NO and NO{sub 2}) involved as oxidizing agents in nuclear fuel reprocessing can be an produced by electrochemical reduction of nitric acid. This could be an interesting alternative to the usual process because no wastes are generated. Voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0.05 V{sub S}HE and 0.3 V{sub S}HE and O.5 V{sub S}HE and 1 V{sub S}HE. The highest potential region reduction mechanism was studies by: classical micro-electrolysis methods; macro-electrolysis methods; infra-red spectroscopy couplet to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric acid reduction can also be explained by an other chemical reaction. In the potential value of platinum electrode is above 0.8 V{sub S}HE, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author). 91 refs.

Production of Odd-Carbon Dicarboxylic Acids in Escherichia coli Using an Engineered Biotin–Fatty Acid Biosynthetic Pathway

Energy Technology Data Exchange (ETDEWEB)

Haushalter, Robert W. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Bioscience Division; Phelan, Ryan M. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Bioscience Division; Hoh, Kristina M. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Bioscience Division; Su, Cindy [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Bioscience Division; Wang, George [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Bioscience Division; Baidoo, Edward E. K. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Bioscience Division; Keasling, Jay D. [Joint BioEnergy Inst. (JBEI), Emeryville, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Bioscience Division

2017-03-14

Dicarboxylic acids are commodity chemicals used in the production of plastics, polyesters, nylons, fragrances, and medications. Bio-based routes to dicarboxylic acids are gaining attention due to environmental concerns about petroleum-based production of these compounds. Some industrial applications require dicarboxylic acids with specific carbon chain lengths, including odd-carbon species. Biosynthetic pathways involving cytochrome P450-catalyzed oxidation of fatty acids in yeast and bacteria have been reported, but these systems produce almost exclusively even-carbon species. Here in this paper we report a novel pathway to odd-carbon dicarboxylic acids directly from glucose in Escherichia coli by employing an engineered pathway combining enzymes from biotin and fatty acid synthesis. Optimization of the pathway will lead to industrial strains for the production of valuable odd-carbon diacids.

Complementary sample preparation strategies for analysis of cereal β-glucan oxidation products by UPLC-MS/MS

Science.gov (United States)

Boulos, Samy; Nyström, Laura

2017-11-01

The oxidation of cereal (1→3,1→4)-β-D-glucan can influence the health promoting and technological properties of this linear, soluble homopolysaccharide by introduction of new functional groups or chain scission. Apart from deliberate oxidative modifications, oxidation of β-glucan can already occur during processing and storage, which is mediated by hydroxyl radicals (HO•) formed by the Fenton reaction. We present four complementary sample preparation strategies to investigate oat and barley β-glucan oxidation products by hydrophilic interaction ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), employing selective enzymatic digestion, graphitized carbon solid phase extraction (SPE), and functional group labeling techniques. The combination of these methods allows for detection of both lytic (C1, C3/4, C5) and non-lytic (C2, C4/3, C6) oxidation products resulting from HO•-attack at different glucose-carbons. By treating oxidized β-glucan with lichenase and β-glucosidase, only oxidized parts of the polymer remained in oligomeric form, which could be separated by SPE from the vast majority of non-oxidized glucose units. This allowed for the detection of oligomers with mid-chain glucuronic acids (C6) and carbonyls, as well as carbonyls at the non-reducing end from lytic C3/C4 oxidation. Neutral reducing ends were detected by reductive amination with anthranilic acid/amide as labeled glucose and cross-ring cleaved units (arabinose, erythrose) after enzyme treatment and SPE. New acidic chain termini were observed by carbodiimide-mediated amidation of carboxylic acids as anilides of gluconic, arabinonic, and erythronic acids. Hence, a full characterization of all types of oxidation products was possible by combining complementary sample preparation strategies. Differences in fine structure depending on source (oat vs. barley) translates to the ratio of observed oxidized oligomers, with in-depth analysis corroborating a random HO�

Reactivity of tributyl phosphate degradation products with nitric acid: Relevance to the Tomsk-7 accident

International Nuclear Information System (INIS)

Barney, G.S.; Cooper, T.D.

1995-01-01

The reaction of a degraded tributyl phosphate (TBP) solvent with nitric acid is thought to have caused the chemical explosion at the Tomsk-7 reprocessing plant at Tomsk, Russia in 1993. The estimated temperature of the organic layer was not high eneough to cause significant reaction of nitric acid with TBP or hydrocarbon diluent compounds. A more reactive organic compound was likely present in the organic layer that reacted with sufficient heat generation to raise the temperature to the point where an autocatalytic oxidation of the organic solvent was initiated. Two of the most likely reactive compounds that are present in degraded TBP solvents are n-butanol and n-butyl nitrate. The reactions of these compounds with nitric acid are the subject of this study. The objective of laboratory-scale tests was to identify chemical reactions that occur when n-butanol and n-butyl nitrate contact heated nitric acid solutions. Reaction products were identified and quantitified, the temperatures at which these reactions occur and heats of reaction were measured, and reaction variables (temperature, nitric acid concentration, organic concentration, and reaction time) were evaluated. Data showed that n-butyl nitrate is less reactive than n-butanol. An essentially complete oxidation reaction of n-butanol at 110-120 C produced four major reaction products. Mass spectrometry identified the major inorganic oxidation products for both n-butanol and n-butyl nitrate as nitric oxide and carbon dioxide. Calculated heats of reaction for n-butanol and n-butyl nitrate to form propionic acid, a major reaction product, are -1860 cal/g n-butanol and -953 cal/g n-butyl nitrate. These heats of reaction are significant and could have raised the temperature of the organic layer in the Tomsk-7 tank to the point where autocatalytic oxidation of other organic compounds present resulted in an explosion

Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

International Nuclear Information System (INIS)

Morss, L.R.

1992-01-01

The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

Taenia crassiceps: fatty acids oxidation and alternative energy source in in vitro cysticerci exposed to anthelminthic drugs.

Science.gov (United States)

Vinaud, Marina Clare; Ferreira, Cirlane Silva; Lino Junior, Ruy de Souza; Bezerra, José Clecildo Barreto

2009-07-01

Cysticerci metabolic studies demonstrate alternative pathways responsible for its survival, such as energy sources, fatty acids oxidation and excretion of beta-hydroxybutyrate, which indicates the capability of energy production from proteins. The aim of this study was to detect alternative metabolic pathways for energy production and its end products in Taenia crassiceps cysticerci in vitro exposed to praziquantel and albendazole, in sub-lethal doses. Spectrophotometer and chromatographic analysis were performed to detect: propionate, acetate, beta-hydroxybutyrate, total proteins, urea and creatinine, SE by cysticerci in vitro exposed to praziquantel and albendazole. The drugs influenced the metabolism by inducing the creatinine phosphate phosphorylation as an alternative energy source, inhibiting the use of proteins and amino acids in the acid nucleic synthesis; and preventing the budding and replication of the cysticerci. This study also highlights the description of urea excretion, which is an important metabolic pathway to excrete toxic products such as ammonia, and the fatty acid oxidation as an alternative energy source in cysticerci exposed to anthelmintic drugs.

Recovery of fission products from acidic waste solutions thereof

International Nuclear Information System (INIS)

Carlin, W.W.; Darlington, W.B.; Dubois, D.W.

1975-01-01

Fission products, e.g., palladium, ruthenium and technetium, are removed from aqueous, acidic waste solutions thereof. The acidic waste solution is electrolyzed in an electrolytic cell under controlled cathodic potential conditions and technetium, ruthenium, palladium and rhodium are deposited on the cathode. Metal deposit is removed from the cathode and dissolved in acid. Acid insoluble rhodium metal is recovered, dissolved by alkali metal bisulfate fusion and purified by electrolysis. In one embodiment, the solution formed by acid dissolution of the cathode metal deposit is treated with a strong oxidizing agent and distilled to separate technetium and ruthenium (as a distillate) from palladium. Technetium is separated from ruthenium by organic solvent extraction and then recovered, e.g., as an ammonium salt. Ruthenium is disposed of as waste by-product. Palladium is recovered by electrolysis of an acid solution thereof under controlled cathodic potential conditions. Further embodiments wherein alternate metal recovery sequences are used are described. (U.S.)

Continuous electrochemical oxidation of biomass derived 5-(hydroxymethyl)furfural into 2,5-furandicarboxylic acid

NARCIS (Netherlands)

Latsuzbaia, R.; Bisselink, R.; Anastasopol, A.; Meer, van der H.; Heck, van R.; Yagüe, M.S.; Zijlstra, M.; Roelands, M.; Crockatt, M.; Goetheer, E.; Giling, E.

2018-01-01

Abstract: A continuous electrochemical process with integrated product separation has been developed for production of 2,5-furandicarboxylic acid (FDCA) by oxidation of 5-(hydroxymethyl)furfural (HMF) in aqueous alkaline media on non-noble Ni/NiOOH foam electrodes at ambient conditions. Initially,

PEGylated single-walled carbon nanotubes activate neutrophils to increase production of hypochlorous acid, the oxidant capable of degrading nanotubes

Energy Technology Data Exchange (ETDEWEB)

Vlasova, Irina I., E-mail: irina.vlasova@yahoo.com [Research Institute for Physico-Chemical Medicine, Federal Medico-Biological Agency, Moscow (Russian Federation); Vakhrusheva, Tatyana V. [Research Institute for Physico-Chemical Medicine, Federal Medico-Biological Agency, Moscow (Russian Federation); Sokolov, Alexey V.; Kostevich, Valeria A. [Research Institute for Physico-Chemical Medicine, Federal Medico-Biological Agency, Moscow (Russian Federation); Research Institute for Experimental Medicine, Russian Academy of Medical Science, Saint Petersburg (Russian Federation); Gusev, Alexandr A.; Gusev, Sergey A. [Research Institute for Physico-Chemical Medicine, Federal Medico-Biological Agency, Moscow (Russian Federation); Melnikova, Viktoriya I. [Institute of Developmental Biology, Russian Academy of Science, Moscow (Russian Federation); Lobach, Anatolii S. [Institute of Problems of Chemical Physics, Russian Academy of Science, Chernogolovka (Russian Federation)

2012-10-01

Perspectives for the use of carbon nanotubes in biomedical applications depend largely on their ability to degrade in the body into products that can be easily cleared out. Carboxylated single-walled carbon nanotubes (c-SWCNTs) were shown to be degraded by oxidants generated by peroxidases in the presence of hydrogen peroxide. In the present study we demonstrated that conjugation of poly(ethylene glycol) (PEG) to c-SWCNTs does not interfere with their degradation by peroxidase/H{sub 2}O{sub 2} system or by hypochlorite. Comparison of different heme-containing proteins for their ability to degrade PEG-SWCNTs has led us to conclude that the myeloperoxidase (MPO) product hypochlorous acid (HOCl) is the major oxidant that may be responsible for biodegradation of PEG-SWCNTs in vivo. MPO is secreted mainly by neutrophils upon activation. We hypothesize that SWCNTs may enhance neutrophil activation and therefore stimulate their own biodegradation due to MPO-generated HOCl. PEG-SWCNTs at concentrations similar to those commonly used in in vivo studies were found to activate isolated human neutrophils to produce HOCl. Both PEG-SWCNTs and c-SWCNTs enhanced HOCl generation from isolated neutrophils upon serum-opsonized zymosan stimulation. Both types of nanotubes were also found to activate neutrophils in whole blood samples. Intraperitoneal injection of a low dose of PEG-SWCNTs into mice induced an increase in percentage of circulating neutrophils and activation of neutrophils and macrophages in the peritoneal cavity, suggesting the evolution of an inflammatory response. Activated neutrophils can produce high local concentrations of HOCl, thereby creating the conditions favorable for degradation of the nanotubes. -- Highlights: ► Myeloperoxidase (MPO) product hypochlorous acid is able to degrade CNTs. ► PEGylated SWCNTs stimulate isolated neutrophils to produce hypochlorous acid. ► SWCNTs are capable of activating neutrophils in blood samples. ► Activation of

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.

Catalytic decomposition of nitrous oxide from nitric acid production tail gases. Investigation of inhibition effects. Executive summary

International Nuclear Information System (INIS)

Mul, G.; Perez-Ramirez, J.; Xu, Xiaoding; Oonk, H.; Yakovlev, A.

2001-06-01

Nitric acid production is an important source of nitrous oxide, one of the green-house gases. Catalytic decomposition of N2O in nitric acid tail-gases might be a possibility for emission reduction, but technology is not yet available. As a part of development of suitable catalytic systems, research was performed, aiming at: gaining an improved understanding of catalytic decomposition of N2O and the inhibiting effects of NO, NO2, H2O and O2; and preparing a 'go-no go' decision whether or not to proceed with subsequent re-search and development and if yes, to indicate what technology further development should aim for. Due to the presence of NOx and water in the nitric acid tail gases, catalytic decomposition proves not to be feasible at temperatures below 350C. At higher temperatures possibilities do exist and a number of promising catalysts are identified. These are active (80 - 100 % conversion) in the temperature range of 400 - 500C and under simulated tail gas conditions. Considering process conditions only (temperatures and composition of the tail-gases), the catalysts studied (pref. the Rh/Al2O3 types) could be in principle applied successfully in all Dutch nitric acid plants

Effect of Oxidation Time on Humic Acid Yields

International Nuclear Information System (INIS)

Khin Thidar Cho; May Zin Lwin

2010-12-01

In this study,humic acids were produced from coal under controlled conditions by using different oxidation time. This research studies on the behaviour of coal during oxidation process. The coal used as raw material in this research was obtained from Ka Lay Wa, Sagaing Division . The coals were oxidized at the different oxidation times from 76 hr to 380 hr at the temperature 150 5C. The yields of humic acid, the ultimate analysis (percentage of carbon, hydrogen, nitrogen and oxygen) and the proximate analysis (percentage of volatile, ash and moisture) were done in this study. The functional groups and structural entities of the obtained humic acids were identified by using Fourier Transform Infrared Spectrophotometer (FTIR). The yield percentage of prepared humic acid in Ka Lay Wa coal was found to be 3%.

Hydrogen production by electrochemical decomposition of formic acid via solid polymer electrolyte

Energy Technology Data Exchange (ETDEWEB)

Kilic, Ebru Oender [KOSGEB Bursa Business Development Center, Besevler Kucuk Sanayi Sitesi 16149 Nilufer/Bursa (Turkey); Koparal, Ali Savas; Oeguetveren, Uelker Bakir [Anadolu University, Iki Eylul Campus, Applied Research Center for Environmental Problems 26555 Eskisehir (Turkey); Anadolu University, Iki Eylul Campus, Department of Environmental Engineering, 26555 Eskisehir (Turkey)

2009-01-15

The aim of this work is to investigate the feasibility of simultaneous hydrogen production by electrochemical decomposition of formic acid via solid polymer electrolyte (SPE) in an electrochemical reactor. Titanium oxide coated with iridium oxide as anode and carbon fibre with Pt catalyst as cathode were used in the experiments. Effects of applied current density, flow rates and temperature of formic acid solution, concentration of supporting electrolyte and pH of the solution on performance of the process have been investigated. The effect of membrane thickness has also been examined. The results suggest that electrolysis using SPE is a promising method for the treatment of organic pollutants. Hydrogen with purity of 99.999% at ambient temperature by using carbon fibre cathode with Pt catalyst can be produced simultaneously and COD removal efficiency of 95% has been achieved not requiring any chemical addition and temperature increase. Also complete electrochemical oxidation of formic acid at the original pH to CO{sub 2} and H{sub 2}O without production of intermediate has been proved by HPLC analysis. (author)

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

Cholesterol oxidation in meat products and its regulation by supplementation of sodium nitrite and apple polyphenol before processing.

Science.gov (United States)

Osada, K; Hoshina, S; Nakamura, S; Sugano, M

2000-09-01

The levels of cholesterol oxidation derivatives (OxChol) in eight commercial species of meat products were examined. These products contained more than 1 mg/100 g of OxChol, and 7beta-hydroxycholesterol + 5beta-epoxycholesterol (111-1092 microg/100 g), 5alpha-epoxycholesterol (80-712 microg/100 g), cholestanetriol (0-368 microg/100 g), and 7-ketocholesterol (708-1204 microg/100 g) were detected. To know the interaction of sodium nitrite supplementation against cholesterol oxidation in meat products, sausage was produced with or without varying levels of sodium nitrite and stored in the refrigerator for 15 days. As a result, cholesterol oxidation in sausage was inhibited by addition of sodium nitrite in a dose-dependent manner. This observation may be associated with inactivation of O(2)(-) radical and stabilization of polyunsaturated fatty acids (PUFAs). In fact, the levels of OxChol in sausage increased, accompanying the decrease of coexisting linoleic acid when sodium nitrite was not added to sausage meat. Thus, cholesterol oxidation in meat products seems to be considarably promoted by the oxidation of coexisting PUFAs. On the other hand, additive apple polyphenol also inhibited linoleic acid oxidation in sausage and then suppressed cholesterol oxidation through its radical scavenging effects. Therefore, apple polyphenol, having a large amount of an oligomer of catechin, may interfere with cholesterol oxidation in meat processing or storage of meat products through its antioxidative action and be useful as a new antioxitant for meat products when it is added to the original meat before processing.

Production and release of acylcarnitines by primary myotubes reflect the differences in fasting fat oxidation of the donors.

Science.gov (United States)

Wolf, Magnus; Chen, Shili; Zhao, Xinjie; Scheler, Mika; Irmler, Martin; Staiger, Harald; Beckers, Johannes; de Angelis, Martin Hrabé; Fritsche, Andreas; Häring, Hans-Ulrich; Schleicher, Erwin D; Xu, Guowang; Lehmann, Rainer; Weigert, Cora

2013-06-01

Acylcarnitines are biomarkers of incomplete β-oxidation and mitochondrial lipid overload but indicate also high rates of mitochondrial fatty acid oxidation. It is unknown whether the production of acylcarnitines in primary human myotubes obtained from lean, metabolically healthy subjects reflects the fat oxidation in vivo. Our objective was to quantify the acylcarnitine production in myotubes obtained from subjects with low and high fasting respiratory quotient (RQ). Fasting RQ was determined by indirect calorimetry. Muscle biopsies from the vastus lateralis muscle were taken from 6 subjects with low fasting RQ (mean 0.79 ± 0.03) and 6 with high fasting RQ (0.90 ± 0.03), and satellite cells were isolated, cultured, and differentiated to myotubes. Myotubes were cultivated with 125 μM (13)C-labeled palmitate for 30 minutes and 4 and 24 hours. Quantitative profiling of 42 intracellular and 31 extracellular acylcarnitines was performed by stable isotope dilution-based metabolomics analysis by liquid chromatography coupled to mass spectrometry. Myotubes from donors with high fasting RQ produced and released significant higher amounts of medium-chain acylcarnitines. High (13)C8 and (13)C10 acylcarnitine levels in the extracellular compartment correlated with high fasting RQ. The decreased expression of medium-chain acyl-coenzyme A dehydrogenase (MCAD) in these myotubes can explain the higher rate of incomplete fatty acid oxidation. A lower intracellular [(13)C]acetylcarnitine to carnitine and lower intracellular (13)C16/(13)C18 acylcarnitine to carnitine ratio indicate reduced fatty acid oxidation capacity in these myotubes. Mitochondrial DNA content was not different. Acylcarnitine production and release from primary human myotubes of donors with high fasting RQ indicate a reduced fatty acid oxidation capacity and a higher rate of incomplete fatty acid oxidation. Thus, quantitative profiling of acylcarnitine production in human myotubes can be a suitable tool to

Omega-3 Fatty Acid Supplementation is Associated With Oxidative Stress and Dyslipidemia, but Does not Contribute to Better Lipid and Oxidative Status on Hemodialysis Patients.

Science.gov (United States)

de Mattos, Andresa Marques; da Costa, José Abrão Cardeal; Jordão Júnior, Alceu Afonso; Chiarello, Paula Garcia

2017-09-01

The aim of the study was to explore the effects of n-3 polyunsaturated fatty acids (PUFA) supplementation in physiological doses on oxidative stress (OS) and dyslipidemia in patients on hemodialysis (HD). Randomized, double-blind, controlled, experimental trial. A total of 88 HD patients ≥18 years old and on HD for at least 6 months. A total of 43 patients received 1.28 g/day of n-3 PUFA, and 45 other patients received soybean oil for 12 weeks. Both oil supplements were vitamin E standardized. Routine tests, lipid profile, advanced oxidation protein products, isoprostanes, vitamins C and E, total antioxidant capacity, serum fatty acids, and adverse effects were evaluated. Supplementation was not able to alter lipid or OS profiles. There was an increase in the serum n-3 PUFA levels (eicosapentaenoic acid: +116%; docosahexaenoic acid: +100%) and an improvement in the n-6/n-3 ratio (-49%) in the supplemented group. Associations between n-3 PUFA and improvement in isoprostane and advanced oxidation protein product and HDL were observed. Treatment was well tolerated. Although the n-3 PUFA supplementation was associated with lower concentrations of isoprostane and advanced oxidation protein product and higher HDL levels, it was not sufficient for the improvement of highly prevalent risk factors, such as OS and dyslipidemia in HD patients. Copyright © 2017 National Kidney Foundation, Inc. Published by Elsevier Inc. All rights reserved.

Endogenous lycopene improves ethanol production under acetic acid stress in Saccharomyces cerevisiae.

Science.gov (United States)

Pan, Shuo; Jia, Bin; Liu, Hong; Wang, Zhen; Chai, Meng-Zhe; Ding, Ming-Zhu; Zhou, Xiao; Li, Xia; Li, Chun; Li, Bing-Zhi; Yuan, Ying-Jin

2018-01-01

Acetic acid, generated from the pretreatment of lignocellulosic biomass, is a significant obstacle for lignocellulosic ethanol production. Reactive oxidative species (ROS)-mediated cell damage is one of important issues caused by acetic acid. It has been reported that decreasing ROS level can improve the acetic acid tolerance of Saccharomyces cerevisiae . Lycopene is known as an antioxidant. In the study, we investigated effects of endogenous lycopene on cell growth and ethanol production of S. cerevisiae in acetic acid media. By accumulating endogenous lycopene during the aerobic fermentation of the seed stage, the intracellular ROS level of strain decreased to 1.4% of that of the control strain during ethanol fermentation. In the ethanol fermentation system containing 100 g/L glucose and 5.5 g/L acetic acid, the lag phase of strain was 24 h shorter than that of control strain. Glucose consumption rate and ethanol titer of yPS002 got to 2.08 g/L/h and 44.25 g/L, respectively, which were 2.6- and 1.3-fold of the control strain. Transcriptional changes of INO1 gene and CTT1 gene confirmed that endogenous lycopene can decrease oxidative stress and improve intracellular environment. Biosynthesis of endogenous lycopene is first associated with enhancing tolerance to acetic acid in S. cerevisiae . We demonstrate that endogenous lycopene can decrease intracellular ROS level caused by acetic acid, thus increasing cell growth and ethanol production. This work innovatively   puts forward a new strategy for second generation bioethanol production during lignocellulosic fermentation.

Myeloperoxidase-mediated protein lysine oxidation generates 2-aminoadipic acid and lysine nitrile in vivo.

Science.gov (United States)

Lin, Hongqiao; Levison, Bruce S; Buffa, Jennifer A; Huang, Ying; Fu, Xiaoming; Wang, Zeneng; Gogonea, Valentin; DiDonato, Joseph A; Hazen, Stanley L

2017-03-01

Recent studies reveal 2-aminoadipic acid (2-AAA) is both elevated in subjects at risk for diabetes and mechanistically linked to glucose homeostasis. Prior studies also suggest enrichment of protein-bound 2-AAA as an oxidative post-translational modification of lysyl residues in tissues associated with degenerative diseases of aging. While in vitro studies suggest redox active transition metals or myeloperoxidase (MPO) generated hypochlorous acid (HOCl) may produce protein-bound 2-AAA, the mechanism(s) responsible for generation of 2-AAA during inflammatory diseases are unknown. In initial studies we observed that traditional acid- or base-catalyzed protein hydrolysis methods previously employed to measure tissue 2-AAA can artificially generate protein-bound 2-AAA from an alternative potential lysine oxidative product, lysine nitrile (LysCN). Using a validated protease-based digestion method coupled with stable isotope dilution LC/MS/MS, we now report protein bound 2-AAA and LysCN are both formed by hypochlorous acid (HOCl) and the MPO/H 2 O 2 /Cl - system of leukocytes. At low molar ratio of oxidant to target protein N ε -lysine moiety, 2-AAA is formed via an initial N ε -monochloramine intermediate, which ultimately produces the more stable 2-AAA end-product via sequential generation of transient imine and semialdehyde intermediates. At higher oxidant to target protein N ε -lysine amine ratios, protein-bound LysCN is formed via initial generation of a lysine N ε -dichloramine intermediate. In studies employing MPO knockout mice and an acute inflammation model, we show that both free and protein-bound 2-AAA, and in lower yield, protein-bound LysCN, are formed by MPO in vivo during inflammation. Finally, both 2-AAA and to lesser extent LysCN are shown to be enriched in human aortic atherosclerotic plaque, a tissue known to harbor multiple MPO-catalyzed protein oxidation products. Collectively, these results show that MPO-mediated oxidation of protein lysyl

Enhanced 15-HPETE production during oxidant stress induces apoptosis of endothelial cells.

Science.gov (United States)

Sordillo, Lorraine M; Weaver, James A; Cao, Yu-Zhang; Corl, Chris; Sylte, Matt J; Mullarky, Isis K

2005-05-01

Oxidant stress plays an important role in the etiology of vascular diseases by increasing rates of endothelial cell apoptosis, but few data exist on the mechanisms involved. Using a unique model of oxidative stress based on selenium deficiency (-Se), the effects of altered eicosanoid production on bovine aortic endothelial cells (BAEC) apoptosis was evaluated. Oxidant stress significantly increased the immediate oxygenation product of arachidonic acid metabolized by the 15-lipoxygenase pathway, 15-hydroxyperoxyeicosatetraenoic acid (15-HPETE). Treatment of -Se BAEC with TNFalpha/cyclohexamide (CHX) exhibited elevated levels of apoptosis, which was significantly reduced by the addition of a specific 15-lipoxygenase inhibitor PD146176. Furthermore, the addition of 15-HPETE to PD146176-treated BAEC, partially restored TNF/CHX-induced apoptosis. Increased exposure to 15-HPETE induced apoptosis, as determined by internucleosomal DNA fragmentation, chromatin condensation, caspase-3 activation, and caspase-9 activation, which suggests mitochondrial dysfunction. The expression of Bcl-2 protein also was decreased in -Se BAEC. Addition of a caspase-9 inhibitor (LEHD-fmk) completely blocked 15-HPETE-induced chromatin condensation in -Se BAEC, suggesting that 15-HPETE-induced apoptosis is caspase-9 dependent. Increased apoptosis of BAEC as a result of oxidant stress and subsequent production of 15-HPETE may play a critical role in a variety of inflammatory based diseases.

Integrated production of cellulosic bioethanol and succinic acid from industrial hemp in a biorefinery concept

DEFF Research Database (Denmark)

Kuglarz, Mariusz; Alvarado-Morales, Merlin; Karakashev, Dimitar Borisov

2016-01-01

The aim of this study was to develop integrated biofuel (cellulosic bioethanol) and biochemical (succinic acid) production from industrial hemp (Cannabis sativa L.) in a biorefinery concept. Two types of pretreatments were studied (dilute-acid and alkaline oxidative method). High cellulose recovery...... productivity. With respect to succinic acid production, the highest productivity was obtained after liquid fraction fermentation originated from steam treatment with 1.5% of acid. The mass balance calculations clearly showed that 149 kg of EtOH and 115 kg of succinic acid can be obtained per 1 ton of dry hemp....... Results obtained in this study clearly document the potential of industrial hemp for a biorefinery....

Inhibiting mitochondrial β-oxidation selectively reduces levels of nonenzymatic oxidative polyunsaturated fatty acid metabolites in the brain.

Science.gov (United States)

Chen, Chuck T; Trépanier, Marc-Olivier; Hopperton, Kathryn E; Domenichiello, Anthony F; Masoodi, Mojgan; Bazinet, Richard P

2014-03-01

Schönfeld and Reiser recently hypothesized that fatty acid β-oxidation is a source of oxidative stress in the brain. To test this hypothesis, we inhibited brain mitochondrial β-oxidation with methyl palmoxirate (MEP) and measured oxidative polyunsaturated fatty acid (PUFA) metabolites in the rat brain. Upon MEP treatment, levels of several nonenzymatic auto-oxidative PUFA metabolites were reduced with few effects on enzymatically derived metabolites. Our finding confirms the hypothesis that reduced fatty acid β-oxidation decreases oxidative stress in the brain and β-oxidation inhibitors may be a novel therapeutic approach for brain disorders associated with oxidative stress.

Oxidation of trimethoprim by ferrate(VI): kinetics, products, and antibacterial activity.

Science.gov (United States)

Anquandah, George A K; Sharma, Virender K; Knight, D Andrew; Batchu, Sudha Rani; Gardinali, Piero R

2011-12-15

Kinetics, stoichiometry, and products of the oxidation of trimethoprim (TMP), one of the most commonly detected antibacterial agents in surface waters and municipal wastewaters, by ferrate(VI) (Fe(VI)) were determined. The pH dependent second-order rate constants of the reactions of Fe(VI) with TMP were examined using acid-base properties of Fe(VI) and TMP. The kinetics of reactions of diaminopyrimidine (DAP) and trimethoxytoluene (TMT) with Fe(VI) were also determined to understand the reactivity of Fe(VI) with TMP. Oxidation products of the reactions of Fe(VI) with TMP and DAP were identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Reaction pathways of oxidation of TMP by Fe(VI) are proposed to demonstrate the cleavage of the TMP molecule to ultimately result in 3,4,5,-trimethoxybenzaldehyde and 2,4-dinitropyrimidine as among the final identified products. The oxidized products mixture exhibited no antibacterial activity against E. coli after complete consumption of TMP. Removal of TMP in the secondary effluent by Fe(VI) was achieved.

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...... 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...

Regularities of praseodymium oxide dissolution in acids

International Nuclear Information System (INIS)

Savin, V.D.; Elyutin, A.V.; Mikhajlova, N.P.; Eremenko, Z.V.; Opolchenova, N.L.

1989-01-01

The regularities of Pr 2 O 3 , Pr 2 O 5 and Pr(OH) 3 interaction with inorganic acids are studied. pH of the solution and oxidation-reduction potential registrated at 20±1 deg C are the working parameters of studies. It is found that the amount of all oxides dissolved increase in the series of acids - nitric, hydrochloric and sulfuric, in this case for hydrochloric and sulfuric acid it increases in the series of oxides Pr 2 O 3 , Pr 2 O 5 and Pr(OH) 3 . It is noted that Pr 2 O 5 has a high value of oxidation-reduction potential with a positive sign in the whole disslolving range. A low positive value of a redox potential during dissolving belongs to Pr(OH) 3 and in the case of Pr 2 O 3 dissloving redox potential is negative. The schemes of dissolving processes which do not agree with classical assumptions are presented

Calcium-dependent nitric oxide production is involved in the cytoprotective properties of n-acetylcysteine in glycochenodeoxycholic acid-induced cell death in hepatocytes

International Nuclear Information System (INIS)

Gonzalez-Rubio, Sandra; Linares, Clara I.; Bello, Rosario I.; Gonzalez, Raul; Ferrin, Gustavo; Hidalgo, Ana B.; Munoz-Gomariz, Elisa; Rodriguez, Blanca A.; Barrera, Pilar; Ranchal, Isidora; Duran-Prado, Mario; Aguilar-Melero, Patricia; De la Mata, Manuel; Muntane, Jordi

2010-01-01

The intracellular oxidative stress has been involved in bile acid-induced cell death in hepatocytes. Nitric oxide (NO) exerts cytoprotective properties in glycochenodeoxycholic acid (GCDCA)-treated hepatocytes. The study evaluated the involvement of Ca 2+ on the regulation of NO synthase (NOS)-3 expression during N-acetylcysteine (NAC) cytoprotection against GCDCA-induced cell death in hepatocytes. The regulation of Ca 2+ pools (EGTA or BAPTA-AM) and NO (L-NAME or NO donor) production was assessed during NAC cytoprotection in GCDCA-treated HepG2 cells. The stimulation of Ca 2+ entrance was induced by A23187 in HepG2. Cell death, Ca 2+ mobilization, NOS-1, -2 and -3 expression, AP-1 activation, and NO production were evaluated. GCDCA reduced intracellular Ca 2+ concentration and NOS-3 expression, and enhanced cell death in HepG2. NO donor prevented, and L-NAME enhanced, GCDCA-induced cell death. The reduction of Ca 2+ entry by EGTA, but not its release from intracellular stores by BAPTA-AM, enhanced cell death in GCDCA-treated cells. The stimulation of Ca 2+ entrance by A23187 reduced cell death and enhanced NOS-3 expression in GCDCA-treated HepG2 cells. The cytoprotective properties of NAC were related to the recovery of intracellular Ca 2+ concentration, NOS-3 expression and NO production induced by GCDCA-treated HepG2 cells. The increase of NO production by Ca 2+ -dependent NOS-3 expression during NAC administration reduces cell death in GCDCA-treated hepatocytes.

Calcium-dependent nitric oxide production is involved in the cytoprotective properties of n-acetylcysteine in glycochenodeoxycholic acid-induced cell death in hepatocytes

Energy Technology Data Exchange (ETDEWEB)

Gonzalez-Rubio, Sandra; Linares, Clara I; Bello, Rosario I [Liver Research Unit, Reina Sofia University Hospital, Cordoba (Spain); Gonzalez, Raul; Ferrin, Gustavo [Liver Research Unit, Reina Sofia University Hospital, Cordoba (Spain); Centro de Investigacion Biomedica en Red de Enfermedades Hepaticas y Digestivas (CIBEREH o Ciberehd) (Spain); Hidalgo, Ana B [Liver Research Unit, Reina Sofia University Hospital, Cordoba (Spain); Munoz-Gomariz, Elisa [Department of Biostatistics, Reina Sofia University Hospital, Cordoba (Spain); Rodriguez, Blanca A [Liver Research Unit, Reina Sofia University Hospital, Cordoba (Spain); Barrera, Pilar; Ranchal, Isidora [Liver Research Unit, Reina Sofia University Hospital, Cordoba (Spain); Centro de Investigacion Biomedica en Red de Enfermedades Hepaticas y Digestivas (CIBEREH o Ciberehd) (Spain); Duran-Prado, Mario [Instituto de Parasitologia y Biomedicina Lopez Neyra, CSIC, Granada (Spain); CIBER Fisiopatologia de la Obesidad y Nutricion CB06/03, Instituto de Salud Carlos III, Ministerio de Sanidad y Consumo (Spain); Aguilar-Melero, Patricia [Liver Research Unit, Reina Sofia University Hospital, Cordoba (Spain); De la Mata, Manuel [Liver Research Unit, Reina Sofia University Hospital, Cordoba (Spain); Centro de Investigacion Biomedica en Red de Enfermedades Hepaticas y Digestivas (CIBEREH o Ciberehd) (Spain); Muntane, Jordi [Liver Research Unit, Reina Sofia University Hospital, Cordoba (Spain); Centro de Investigacion Biomedica en Red de Enfermedades Hepaticas y Digestivas (CIBEREH o Ciberehd) (Spain)

2010-01-15

The intracellular oxidative stress has been involved in bile acid-induced cell death in hepatocytes. Nitric oxide (NO) exerts cytoprotective properties in glycochenodeoxycholic acid (GCDCA)-treated hepatocytes. The study evaluated the involvement of Ca{sup 2+} on the regulation of NO synthase (NOS)-3 expression during N-acetylcysteine (NAC) cytoprotection against GCDCA-induced cell death in hepatocytes. The regulation of Ca{sup 2+} pools (EGTA or BAPTA-AM) and NO (L-NAME or NO donor) production was assessed during NAC cytoprotection in GCDCA-treated HepG2 cells. The stimulation of Ca{sup 2+} entrance was induced by A23187 in HepG2. Cell death, Ca{sup 2+} mobilization, NOS-1, -2 and -3 expression, AP-1 activation, and NO production were evaluated. GCDCA reduced intracellular Ca{sup 2+} concentration and NOS-3 expression, and enhanced cell death in HepG2. NO donor prevented, and L-NAME enhanced, GCDCA-induced cell death. The reduction of Ca{sup 2+} entry by EGTA, but not its release from intracellular stores by BAPTA-AM, enhanced cell death in GCDCA-treated cells. The stimulation of Ca{sup 2+} entrance by A23187 reduced cell death and enhanced NOS-3 expression in GCDCA-treated HepG2 cells. The cytoprotective properties of NAC were related to the recovery of intracellular Ca{sup 2+} concentration, NOS-3 expression and NO production induced by GCDCA-treated HepG2 cells. The increase of NO production by Ca{sup 2+}-dependent NOS-3 expression during NAC administration reduces cell death in GCDCA-treated hepatocytes.

Influence of oxalic acid on the dissolution kinetics of manganese oxide

Science.gov (United States)

Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

2012-11-01

The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

Impact of primary amine group from aminophospholipids and amino acids on marine phospholipids stability: Non-enzymatic browning and lipid oxidation

DEFF Research Database (Denmark)

Lu, Henna Fung Sieng; Nielsen, Nina Skall; Baron, Caroline P.

2013-01-01

The main objective of this study was to investigate the oxidative stability and non-enzymatic browning reactions of marine PL in the presence or in the absence of primary amine group from aminophospholipids and amino acids. Marine phospholipids liposomal dispersions were prepared from two authentic......) Strecker derived volatiles, (ii) yellowness index (YI), (iii) hydrophobic and (iv) hydrophilic pyrroles content. The oxidative stability of the samples was assessed through measurement of secondary lipid derived volatile oxidation products. The result showed that the presence of PE and amino acids caused...... the formation of pyrroles, generated Strecker derived volatiles, decreased the YI development and lowered lipid oxidation. The lower degree of lipid oxidation in liposomal dispersions containing amino acids might be attributed to antioxidative properties of pyrroles or amino acids....

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

International Nuclear Information System (INIS)

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

2014-01-01

The degradation of clofibric acid induced by hydroxyl radical, hydrated electron and O 2 −∙ /HO 2 ∙ reactive species was studied in aqueous solutions. Clofibric acid was decomposed more effectively by hydroxyl radical than by hydrated electron or O 2 −∙ /HO 2 ∙ . Various hydroxylated, dechlorinated and fragmentation products have been identified and quantified. A new LC–MS method was developed based on 18 O isotope labeling to follow the formation of hydroxylated derivatives of clofibric acid. Possible degradation pathways have been proposed. The overall degradation was monitored by determination of sum parameters like COD, TOC and AOX. It was found that the organic chlorine degrades very effectively prior to complete mineralization. After the treatment no toxic effect was found according to Vibrio fischeri tests. However, at early stages some of the reaction products were more harmful than clofibric acid. - Highlights: • Clofibric acid is effectively degraded by OH radical. • Main primary and secondary products are hydroxylated and dihydroxylated phenyl type derivatives of clofibric acid. • In air saturated aqueous solutions O 2 plays an important role in decomposition of the aromatic structure. • A new LC–MS method with 18 O-labeling was developed. • Early stage reaction products are more toxic to bacteria Vibrio fischeri than clofibric acid

'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

COMPARISON OF METHODS FOR ETHYLHEXYL 4-METHOXYCINNAMATE ACID ESTER OXIDATION IN WATER MEDIUM

Directory of Open Access Journals (Sweden)

Waldemar Studziński

2017-07-01

Full Text Available The aim of studies was to compare an impact of oxidizing agents on degradation of ethylhexyl 4-methoxycinnamate acid (EHMC. The oxidation reaction was carried out in the presence of sodium hypochlorite, hydrogen peroxide and ozone with/without UV radiation. EHMC degradation and analysis of products were performed using gas chromatograph coupled with mass spectrometry detector. The most effective method of EHMC degradation turned out to be ozonation with participation of UV radiation. In this system, degradation proceeded the most quickly and generated formation of small amount of by-products (2-propyl-1-pentanol; 4-metoxybenzaldehyde and Z-EHMC. Under the influence of sodium hypochlorite, the numerous chloroorganic products were formed, which can cause secondary contamination of water. Application of appropriate oxidation processes can contribute to degradation of micropollutants and thus to improvement of water quality.

Defective (U-14 C) palmitic acid oxidation in Duchenne muscular dystrophy

Energy Technology Data Exchange (ETDEWEB)

Carroll, J.E.; Norris, B.J.; Brooke, M.H.

1985-01-01

Compared with normal skeletal muscle, muscle from patients with Duchenne dystrophy had decreased (U-14 C) palmitic acid oxidation. (1-14 C) palmitic acid oxidation was normal. These results may indicate a defect in intramitochondrial fatty acid oxidation.

Defective [U-14 C] palmitic acid oxidation in Duchenne muscular dystrophy

International Nuclear Information System (INIS)

Carroll, J.E.; Norris, B.J.; Brooke, M.H.

1985-01-01

Compared with normal skeletal muscle, muscle from patients with Duchenne dystrophy had decreased [U-14 C] palmitic acid oxidation. [1-14 C] palmitic acid oxidation was normal. These results may indicate a defect in intramitochondrial fatty acid oxidation

Oxidative modifications of conjugated and unconjugated linoleic acid during heating.

Science.gov (United States)

Giua, L; Blasi, F; Simonetti, M S; Cossignani, L

2013-10-15

The oxidative stability of conjugated linoleic (CLA) and linoleic (LA) acids in different chemical forms (free acids, methyl esters and homogeneous triacylglycerols) was compared. All model systems were heated at 180°C for different times (15, 30, 45 and 60min). The primary oxidation products were evaluated by spectrophometric analysis, while the volatile compounds were determined by solid phase micro-extraction (SPME), coupled with gas chromatography-mass spectrometry (HRGC-MS). The isomer profile modifications were investigated by silver-ion high performance liquid chromatography (Ag(+)-HPLC) equipped with an UV detector. Generally, peroxide values decreased during the heating time. Among the volatiles, saturated aldehydes were the most represented compounds. Isomerization of cis,trans and trans,cis CLA to trans,trans isomers was observed mainly for the methyl form of CLA. The three different chemical forms of LA never showed isomerization phenomena. Copyright © 2012 Elsevier Ltd. All rights reserved.

Nitric-phosphoric acid oxidation of organic waste materials

International Nuclear Information System (INIS)

Pierce, R.A.; Smith, J.R.

1995-01-01

A wet chemical oxidation technology has been developed to address issues facing defense-related facilities, private industry, and small-volume generators such as university and medical laboratories. Initially tested to destroy and decontaminate a heterogenous mixture of radioactive-contaminated solid waste, the technology can also remediate other hazardous waste forms. The process, unique to Savannah River, offers a valuable alternative to incineration and other high-temperature or high-pressure oxidation processes. The process uses nitric acid in phosphoric acid; phosphoric acid allows nitric acid to be retained in solution well above its normal boiling point. The reaction converts organics to carbon dioxide and water, and generates NO x vapors which can be recycled using air and water. Oxidation is complete in one to three hours. In previous studies, many organic compounds were completely oxidized, within experimental error, at atmospheric pressure below 180 degrees C; more stable compounds were decomposed at 200 degrees C and 170 kPa. Recent studies have evaluated processing parameters and potential throughputs for three primary compounds: EDTA, polyethylene, and cellulose. The study of polyvinylchloride oxidation is incomplete at this time

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...

Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock.

Science.gov (United States)

Mello, Paola de A; Duarte, Fábio A; Nunes, Matheus A G; Alencar, Mauricio S; Moreira, Elizabeth M; Korn, Mauro; Dressler, Valderi L; Flores, Erico M M

2009-08-01

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9min of ultrasonic irradiation (20kHz, 750W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.

Production of α-keto acids Part I. Immobilized cells ofTrigonopsis variabilis containing D-amino acid oxidase.

Science.gov (United States)

Brodelius, P; Nilsson, K; Mosbach, K

1981-12-01

Whole cells ofTrigonopsis variabilis were immobilized by entrapment in Ca(2+)-alginate and used for the production of α-keto acids from the corresponding D-amino acids. The D-amino acid oxidase within the immobilized cells has a broad substrate specificity. Hydrogen peroxide formed in the enzymatic reaction was efficiently hydrolyzed by manganese oxide co-immobilized with the cells. The amino acid oxidase activity was assayed with a new method based on reversed-phase HPLC. Oxygen requirements, bead size, concentration of cells in the beads, flow rate, and other factors were investigated in a " trickle-bed " reactor.

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

Improving oxidative stability of olive oil: Incorporation of Spirulina and evaluation of its synergism with citric acid

International Nuclear Information System (INIS)

Alavi, N.; Golmakani, M.T.

2017-01-01

The effects of different Spirulina concentrations used alone and in combination with citric acid on the oxidative stability of olive oil were assessed. The amounts of primary and secondary oxidation products produced in Spirulina samples were lower than that of the control. The improved oxidative stability indices of Spirulina samples with and without citric acid were in the range of 85.20–94.47% and 258.10–260.21%, respectively. In comparison with the control, Spirulina samples manifested significantly higher carotenoid and chlorophyll contents at the beginning and end of the storage period. The presence of these bioactive compounds results from the presence of Spirulina in the medium and can thus retard the oxidation of olive oil. A higher oxidative stability was reached using BHT in comparison with Spirulina samples. Furthermore, no synergistic action was observed in possible connections between citric acid and Spirulina. In conclusion, Spirulina can enhance oxidative stability and improve the shelf life of olive oil. [es

Effects of Uric Acid on Exercise-induced Oxidative Stress

OpenAIRE

平井, 富弘

2001-01-01

We studied effects of uric acid on exercise― induced oxidative stress in humans based on a hypothesis that uric acid acts as an antioxidant to prevent from exercise―induced oxidative stress. Relation between uric acid level in plasma and increase of thiobarbituric acid reactive substance (TBARS)after the cycle ergometer exercise was examined. Thiobarbituricacid reactive substance in plasma increased after the ergometer exercise. High uric acid in plasma did not result in low increase of TBARS...

Studies on the biological oxidation - The oxidation of ascorbic acid (vitamin C) in biological fluids

OpenAIRE

Guzmán Barrón, E. S.; Guzmán Barrón, Alberto; Klemperer, Friedrich

2014-01-01

Biological fluids can be divided according to their behavior toward ascorbic acid into two groups: those having an inhibitory mechanism that protects the ascorbic acid oxidation, and those lacking this mechanism. Animal fluids and some of vegetable origin (those containing dosables amounts of ascorbic acid) corresponding to the first group. Ascorbic acid is protected from oxidation in the fluids by the action of copper catalyst. Fluids from plants (those that contain very little ascorbic acid...

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

Impaired fatty acid oxidation as a cause for lipotoxicity in cardiomyocytes

International Nuclear Information System (INIS)

Haffar, T.; Bérubé-Simard, F.; Bousette, N.

2015-01-01

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 "1"4C–CO_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 attenuated

Natively oxidized amino acid residues in the spinach cytochrome b 6 f complex.

Science.gov (United States)

Taylor, Ryan M; Sallans, Larry; Frankel, Laurie K; Bricker, Terry M

2018-01-29

The cytochrome b 6 f complex of oxygenic photosynthesis produces substantial levels of reactive oxygen species (ROS). It has been observed that the ROS production rate by b 6 f is 10-20 fold higher than that observed for the analogous respiratory cytochrome bc 1 complex. The types of ROS produced (O 2 •-, 1 O 2 , and, possibly, H 2 O 2 ) and the site(s) of ROS production within the b 6 f complex have been the subject of some debate. Proposed sources of ROS have included the heme b p , PQ p •- (possible sources for O 2 •- ), the Rieske iron-sulfur cluster (possible source of O 2 •- and/or 1 O 2 ), Chl a (possible source of 1 O 2 ), and heme c n (possible source of O 2 •- and/or H 2 O 2 ). Our working hypothesis is that amino acid residues proximal to the ROS production sites will be more susceptible to oxidative modification than distant residues. In the current study, we have identified natively oxidized amino acid residues in the subunits of the spinach cytochrome b 6 f complex. The oxidized residues were identified by tandem mass spectrometry using the MassMatrix Program. Our results indicate that numerous residues, principally localized near p-side cofactors and Chl a, were oxidatively modified. We hypothesize that these sites are sources for ROS generation in the spinach cytochrome b 6 f complex.

Replacement of two amino acids of 9R-dioxygenase-allene oxide synthase of Aspergillus niger inverts the chirality of the hydroperoxide and the allene oxide.

Science.gov (United States)

Sooman, Linda; Wennman, Anneli; Hamberg, Mats; Hoffmann, Inga; Oliw, Ernst H

2016-02-01

The genome of Aspergillus niger codes for a fusion protein (EHA25900), which can be aligned with ~50% sequence identity to 9S-dioxygenase (DOX)-allene oxide synthase (AOS) of Fusarium oxysporum, homologues of the Fusarium and Colletotrichum complexes and with over 62% sequence identity to homologues of Aspergilli, including (DOX)-9R-AOS of Aspergillus terreus. The aims were to characterize the enzymatic activities of EHA25900 and to identify crucial amino acids for the stereospecificity. Recombinant EHA25900 oxidized 18:2n-6 sequentially to 9R-hydroperoxy-10(E),12(Z)-octadecadienoic acid (9R-HPODE) and to a 9R(10)-allene oxide. 9S- and 9R-DOX-AOS catalyze abstraction of the pro-R hydrogen at C-11, but the direction of oxygen insertion differs. A comparison between twelve 9-DOX domains of 9S- and 9R-DOX-AOS revealed conserved amino acid differences, which could contribute to the chirality of products. The Gly616Ile replacement of 9R-DOX-AOS (A. niger) increased the biosynthesis of 9S-HPODE and the 9S(10)-allene oxide, whereas the Phe627Leu replacement led to biosynthesis of 9S-HPODE and the 9S(10)-allene oxide as main products. The double mutant (Gly616Ile, Phe627Leu) formed over 90% of the 9S stereoisomer of HPODE. 9S-HPODE was formed by antarafacial hydrogen abstraction and oxygen insertion, i.e., the original H-abstraction was retained but the product chirality was altered. We conclude that 9R-DOX-AOS can be altered to 9S-DOX-AOS by replacement of two amino acids (Gly616Ile, Phe627Leu) in the DOX domain. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydrothermal Treatment of Cellulose in Hot-Pressurized Water for the Production of Levulinic Acid

Directory of Open Access Journals (Sweden)

ASLI YUKSEL

2016-12-01

Full Text Available In this paper, hot-pressurized water, operating above boiling point and below critical point of water (374. 15 °C and 22.1 MPa, was used as a reaction medium for the decomposition of cellulose to high-value chemicals, such levulinic acid. Effects of reaction temperature, pressure, time, external oxidant type and concentration on the cellulose degradation and product distribution were evaluated. In order to compare the cellulose decomposition and yields of levulinic acid, experiments were performed with and without addition of oxidizing agents (H2SO4 and H2O2. Analysis of the liqueur was monitored by HPLC and GC-MS at different temperatures (150 - 280 °C, pressures (5-64 bars and reaction times (30 - 120 mins. Levulinic acid, 5-HMF and formic acid were detected as main products. 73% cellulose conversion was achieved with 38% levulinic acid yield when 125 mM of sulfuric acid was added to the reaction medium at 200 °C for 60 min reaction time.

Caffeic acid, a phenol found in white wine, modulates endothelial nitric oxide production and protects from oxidative stress-associated endothelial cell injury.

Directory of Open Access Journals (Sweden)

Massimiliano Migliori

Full Text Available Several studies demonstrated that endothelium dependent vasodilatation is impaired in cardiovascular and chronic kidney diseases because of oxidant stress-induced nitric oxide availability reduction. The Mediterranean diet, which is characterized by food containing phenols, was correlated with a reduced incidence of cardiovascular diseases and delayed progression toward end stage chronic renal failure. Previous studies demonstrated that both red and white wine exert cardioprotective effects. In particular, wine contains Caffeic acid (CAF, an active component with known antioxidant activities.The aim of the present study was to investigate the protective effect of low doses of CAF on oxidative stress-induced endothelial injury.CAF increased basal as well as acetylcholine-induced NO release by a mechanism independent from eNOS expression and phosphorylation. In addition, low doses of CAF (100 nM and 1 μM increased proliferation and angiogenesis and inhibited leukocyte adhesion and endothelial cell apoptosis induced by hypoxia or by the uremic toxins ADMA, p-cresyl sulfate and indoxyl sulfate. The biological effects exerted by CAF on endothelial cells may be at least in part ascribed to modulation of NO release and by decreased ROS production. In an experimental model of kidney ischemia-reperfusion injury in mice, CAF significantly decreased tubular cell apoptosis, intraluminal cast deposition and leukocyte infiltration.The results of the present study suggest that CAF, at very low dosages similar to those observed after moderate white wine consumption, may exert a protective effect on endothelial cell function by modulating NO release independently from eNOS expression and phosphorylation. CAF-induced NO modulation may limit cardiovascular and kidney disease progression associated with oxidative stress-mediated endothelial injury.

COMPARISON OF METHODS FOR ETHYLHEXYL 4-METHOXYCINNAMATE ACID ESTER OXIDATION IN WATER MEDIUM

OpenAIRE

Waldemar Studziński; Alicja Gackowska

2017-01-01

The aim of studies was to compare an impact of oxidizing agents on degradation of ethylhexyl 4-methoxycinnamate acid (EHMC). The oxidation reaction was carried out in the presence of sodium hypochlorite, hydrogen peroxide and ozone with/without UV radiation. EHMC degradation and analysis of products were performed using gas chromatograph coupled with mass spectrometry detector. The most effective method of EHMC degradation turned out to be ozonation with participation of UV radiation. In this...

Activation of peroxisome proliferator-activated receptor-α (PPARα) suppresses postprandial lipidemia through fatty acid oxidation in enterocytes

International Nuclear Information System (INIS)

Kimura, Rino; Takahashi, Nobuyuki; Murota, Kaeko; Yamada, Yuko; Niiya, Saori; Kanzaki, Noriyuki; Murakami, Yoko; Moriyama, Tatsuya; Goto, Tsuyoshi; Kawada, Teruo

2011-01-01

Highlights: → PPARα activation increased mRNA expression levels of fatty acid oxidation-related genes in human intestinal epithelial Caco-2 cells. → PPARα activation also increased oxygen consumption rate and CO 2 production and decreased secretion of triglyceride and ApoB from Caco-2 cells. → Orally administration of bezafibrate increased mRNA expression levels of fatty acid oxidation-related genes and CO 2 production in small intestinal epithelial cells. → Treatment with bezafibrate decreased postprandial serum concentration of triglyceride after oral injection of olive oil in mice. → It suggested that intestinal lipid metabolism regulated by PPARα activation suppresses postprandial lipidemia. -- Abstract: Activation of peroxisome proliferator-activated receptor (PPAR)-α which regulates lipid metabolism in peripheral tissues such as the liver and skeletal muscle, decreases circulating lipid levels, thus improving hyperlipidemia under fasting conditions. Recently, postprandial serum lipid levels have been found to correlate more closely to cardiovascular diseases than fasting levels, although fasting hyperlipidemia is considered an important risk of cardiovascular diseases. However, the effect of PPARα activation on postprandial lipidemia has not been clarified. In this study, we examined the effects of PPARα activation in enterocytes on lipid secretion and postprandial lipidemia. In Caco-2 enterocytes, bezafibrate, a potent PPARα agonist, increased mRNA expression levels of fatty acid oxidation-related genes, such as acyl-CoA oxidase, carnitine palmitoyl transferase, and acyl-CoA synthase, and oxygen consumption rate (OCR) and suppressed secretion levels of both triglycerides and apolipoprotein B into the basolateral side. In vivo experiments revealed that feeding high-fat-diet containing bezafibrate increased mRNA expression levels of fatty acid oxidation-related genes and production of CO 2 and acid soluble metabolites in enterocytes. Moreover

Glufosinate ammonium stimulates nitric oxide production through N-methyl D-aspartate receptors in rat cerebellum.

Science.gov (United States)

Nakaki, T; Mishima, A; Suzuki, E; Shintani, F; Fujii, T

2000-09-01

Glufosinate ammonium, a structural analogue of glutamate, is an active herbicidal ingredient. The neuronal activities of this compound were investigated by use of a microdialysis system that allowed us to measure nitric oxide production in the rat cerebellum in vivo. Kainate (0.3-30 nmol/10 microliter), N-methyl-D-aspartate (NMDA) (3-300 nmol/10 microliter) and glufosinate ammonium (30-3000 nmol/10 microliter), which were administered through the microdialysis probe at a rate of 1 microliter/min for 10 min, stimulated nitric oxide production. The glufosinate ammonium-elicited increase in nitric oxide production was suppressed by an inhibitor of nitric oxide synthase and was antagonized by NMDA receptor antagonists, but not by a kainate/(+/-)-alphaamino-3-hydroxy-5-methylisoxazole-4-propionic acid receptor antagonist. These results suggest that glufosinate ammonium stimulates nitric oxide production through NMDA receptors.

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.

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)

Oxidation-extraction of uranium from wet-process phosphoric acid

International Nuclear Information System (INIS)

Lawes, B.C.

1985-01-01

The invention involves an improvement to the reductive stripping process for recovering uranium values from wet-process phosphoric acid solution, where uranium in the solution is oxidized to uranium (VI) oxidation state and then extracted from the solution by contact with a water immiscible organic solvent, by adding sufficient oxidant, hydrogen peroxide, to obtain greater than 90 percent conversion of the uranium to the uranium (VI) oxidation state to the phosphoric acid solution and simultaneously extracting the uranium (VI)

AMPK-independent pathways regulate skeletal muscle fatty acid oxidation

DEFF Research Database (Denmark)

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

2008-01-01

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...... dead (KD) AMPK alpha2. In wild-type (WT) mice, AICAR and contraction increased AMPK alpha2 and alpha1 activities, the phosphorylation of ACC2 and rates of fatty acid oxidation while tending to reduce malonyl-CoA levels. Despite no activation of AMPK in KD mice, ACC2 phosphorylation was maintained...

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...

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.

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.

Investigation of the direct and indirect electrochemical oxidation of hydrazine in nitric acid medium on platinum

International Nuclear Information System (INIS)

Cames, B.

1997-01-01

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

Effect of Acid Oxidation on the Dispersion Property of Multiwalled Carbon Nanotubes

Science.gov (United States)

Goh, P. S.; Ismail, A. F.; Aziz, M.

2009-06-01

A means of dispersion of multiwalled carbon nanotube (MWCNT) via mixed acid (HNO3 and H2SO4) oxidation with different treatment durations was investigated through the solubility study of the treated carbon nanotubes in some common solvents. Fourier transformed infrared (FTIR) characterization of the reaction products revealed that the surface of MWCNTs was successfully functionalized with surface acidic groups. The acid-base titration demonstrated that the amount of surface acidic groups increased in parallel with the refluxing duration. The acid modified MWCNTs were found to be well dispersed in polar solvents, such as ethanol and water due to the presence of the hydrophilic acid functional groups on the surface of raw MWCNTs. Such chemical modification of carbon nanotube properties will pave the way towards the realistic applications in the nanotechnology world.

Procedure of Destructive Chemical Recovery of Precious Metals in Nitric Acid Production

Directory of Open Access Journals (Sweden)

Ljubičić, M.

2012-07-01

Full Text Available The heart of the nitric acid production process is the chemical reactor containing a platinum-based catalyst pack and an associated catchment system, which allows the ammonia oxidation reaction to take place efficiently. Under the severe operating conditions imposed by the high-pressure ammonia oxidation process, the catalyst gauzes experience progressive deterioration, as shown by the restricted surface of the catalyst wires, the loss of catalytic activity and the loss of catalytic materials. The higher the pressure of gaseous ammonia oxidation, the greater the loss of platinum group metals from the surface of the applied selective heterogeneous catalysts. Total losses for one batch over the whole period of using selective heterogeneous catalysts may account in the range from 20 to 40 % of the total installed quantity of precious metals. An important part of the platinum removed from the platinum-rhodium alloy wires can be recovered at the outlet of the reactor by means of palladium catchment gauzes. However, this catchment process, which is based on the great ability of palladium to alloy with platinum, is not 100 % effective and a fraction of the platinum and practically all of the rhodium lost by the catalyst wires, evades the catchment package and is then deposited in other parts of the plant, especially heat exchangers. From the above mentioned operating equipment, the retained mass of precious metals can be recovered by the technical procedure of non-destructive and destructive chemical solid-liquid extraction.Shown is the technical procedure of destructive chemical recovery of preheater and boiler for preheating and production of steam by applying sulfuric acid (w = 20 % and subsequent procedure of raffination of derived sludge, to the final recovery of precious metals. The technical procedure of destructive chemical recovery of precious metals from preheater and boiler for preheating and production of steam in nitric acid production is

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...... 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....

Riboflavin enhances photo-oxidation of amino acids under simulated clinical conditions

International Nuclear Information System (INIS)

Bhatia, J.; Stegink, L.D.; Ziegler, E.E.

1983-01-01

In neonatal nurseries, solutions of amino acids with added vitamins may be exposed to relatively intense light from phototherapy units. Light, especially in the presence of photosensitizers such as certain vitamins, is capable of destroying amino acids. In the present study, the effect of riboflavin on amino acid concentrations in solutions exposed to light was studied. Solutions of crystalline amino acids with and without added riboflavin were infused into shielded collecting vessels for 24 hr under conditions simulating those occurring during phototherapy. Decreases in concentrations of some amino acids were observed with light exposure alone. Decreases in concentrations of methionine, proline, tryptophan, and tyrosine were significantly greater in the presence of riboflavin that in its absence. Riboflavin concentrations were also significantly reduced after light exposure. Although the losses of amino acids are probably not nutritionally significant, the photo-oxidation products are largely unknown and may be toxic

Effect of nanoparticles binding ß-amyloid peptide on nitric oxide production by cultured endothelial cells and macrophages

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Orlando A

2013-04-01

Full Text Available Antonina Orlando,1 Francesca Re,1 Silvia Sesana,1 Ilaria Rivolta,1 Alice Panariti,1 Davide Brambilla,2 Julien Nicolas,2 Patrick Couvreur,2 Karine Andrieux,2 Massimo Masserini,1 Emanuela Cazzaniga1 1Department of Health Sciences, University of Milano-Bicocca, Monza, Italy; 2Institut Galien Paris Sud, University Paris-Sud, Châtenay-Malabry, France Background: As part of a project designing nanoparticles for the treatment of Alzheimer’s disease, we have synthesized and characterized a small library of nanoparticles binding with high affinity to the β-amyloid peptide and showing features of biocompatibility in vitro, which are important properties for administration in vivo. In this study, we focused on biocompatibility issues, evaluating production of nitric oxide by cultured human umbilical vein endothelial cells and macrophages, used as models of cells which would be exposed to nanoparticles after systemic administration. Methods: The nanoparticles tested were liposomes and solid lipid nanoparticles carrying phosphatidic acid or cardiolipin, and PEGylated poly(alkyl cyanoacrylate nanoparticles (PEG-PACA. We measured nitric oxide production using the Griess method as well as phosphorylation of endothelial nitric oxide synthase and intracellular free calcium, which are biochemically related to nitric oxide production. MTT viability tests and caspase-3 detection were also undertaken. Results: Exposure to liposomes did not affect the viability of endothelial cells at any concentration tested. Increased production of nitric oxide was detected only with liposomes carrying phosphatidic acid or cardiolipin at the highest concentration (120 µg/mL, together with increased synthase phosphorylation and intracellular calcium levels. Macrophages exposed to liposomes showed a slightly dose-dependent decrease in viability, with no increase in production of nitric oxide. Exposure to solid lipid nanoparticles carrying phosphatidic acid decreased viability in

The ultrasound-assisted oxidative scission of monoenic fatty acids by ruthenium tetroxide catalysis: influence of the mixture of solvents.

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Rup, Sandrine; Zimmermann, François; Meux, Eric; Schneider, Michel; Sindt, Michele; Oget, Nicolas

2009-02-01

Carboxylic acids and diacids were synthesized from monoenic fatty acids by using RuO4 catalysis, under ultrasonic irradiation, in various mixtures of solvents. Ultrasound associated with Aliquat 336 have promoted in water, the quantitative oxidative cleavage of the CH=CH bond of oleic acid. A design of experiment (DOE) shows that the optimal mixture of solvents (H2O/MeCN, ratio 1/1, 2.2% RuCl3/4.1 eq. NaIO4) gives 81% azelaic acid and 97% pelargonic acid. With the binary heterogeneous mixture H2O/AcOEt, the oxidation of the oleic acid leads to a third product, the alpha-dione 9,10-dioxostearic acid.

Importance of relative humidity in the oxidative ageing of organic aerosols: case study of the ozonolysis of maleic acid aerosol

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P. J. Gallimore

2011-12-01

Full Text Available Many important atmospheric aerosol processes depend on the chemical composition of the aerosol, e.g. water uptake and particle cloud interactions. Atmospheric ageing processes, such as oxidation reactions, significantly and continuously change the chemical composition of aerosol particles throughout their lifetime. These ageing processes are often poorly understood. In this study we utilize an aerosol flow tube set up and an ultra-high resolution mass spectrometer to explore the effect of relative humidity (RH in the range of <5–90% on the ozonolysis of maleic acid aerosol which is employed as model organic aerosol system. Due to the slow reaction kinetics relatively high ozone concentrations of 160–200 ppm were used to achieve an appreciable degree of oxidation of maleic acid. The effect of oxidative ageing on the hygroscopicity of maleic acid particles is also investigated using an electrodynamic balance and thermodynamic modelling. RH has a profound effect on the oxidation of maleic acid particles. Very little oxidation is observed at RH < 50% and the only observed reaction products are glyoxylic acid and formic acid. In comparison, when RH > 50% there are about 15 oxidation products identified. This increased oxidation was observed even when the particles were exposed to high humidities long after a low RH ozonolysis reaction. This result might have negative implications for the use of water as an extraction solvent for the analysis of oxidized organic aerosols. These humidity-dependent differences in the composition of the ozonolyzed aerosol demonstrate that water is both a key reactant in the oxidation scheme and a determinant of particle phase and hence diffusivity. The measured chemical composition of the processed aerosol is used to model the hygroscopic growth, which compares favourably with water uptake results from the electrodynamic balance measurements. A reaction mechanism is presented which takes into account the RH dependent

CD36 Mediated Fatty Acid-Induced Podocyte Apoptosis via Oxidative Stress.

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Wei Hua

Full Text Available Hyperlipidemia-induced apoptosis mediated by fatty acid translocase CD36 is associated with increased uptake of ox-LDL or fatty acid in macrophages, hepatocytes and proximal tubular epithelial cells, leading to atherosclerosis, liver damage and fibrosis in obese patients, and diabetic nephropathy (DN, respectively. However, the specific role of CD36 in podocyte apoptosis in DN with hyperlipidemia remains poorly investigated.The expression of CD36 was measured in paraffin-embedded kidney tissue samples (Ctr = 18, DN = 20 by immunohistochemistry and immunofluorescence staining. We cultured conditionally immortalized mouse podocytes (MPC5 and treated cells with palmitic acid, and measured CD36 expression by real-time PCR, Western blot analysis and immunofluorescence; lipid uptake by Oil red O staining and BODIPY staining; apoptosis by flow cytometry assay, TUNEL assay and Western blot analysis; and ROS production by DCFH-DA fluorescence staining. All statistical analyses were performed using SPSS 21.0 statistical software.CD36 expression was increased in kidney tissue from DN patients with hyperlipidemia. Palmitic acid upregulated CD36 expression and promoted its translocation from cytoplasm to plasma membrane in podocytes. Furthermore, palmitic acid increased lipid uptake, ROS production and apoptosis in podocytes, Sulfo-N-succinimidyloleate (SSO, the specific inhibitor of the fatty acid binding site on CD36, decreased palmitic acid-induced fatty acid accumulation, ROS production, and apoptosis in podocytes. Antioxidant 4-hydroxy-2,2,6,6- tetramethylpiperidine -1-oxyl (tempol inhibited the overproduction of ROS and apoptosis in podocytes induced by palmitic acid.CD36 mediated fatty acid-induced podocyte apoptosis via oxidative stress might participate in the process of DN.

Citric acid-modified Fenton's reaction for the oxidation of chlorinated ethylenes in soil solution systems.

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Seol, Yongkoo; Javandel, Iraj

2008-06-01

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 H2O2 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 H2O2 relative to iron catalysts (Fe2+/H2O2<1/330) would result in lowering the efficiency of contaminant removal by iron chelation in the citric acid system. Column tests confirmed that citric acid could provide suitable acidic conditions to achieve higher than 55% contaminant removal rates.

catalyzed oxidation of some amino acids by acid bromate

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ABSTRACT: Kinetic investigations on Pd(II) catalyzed oxidation of dl-serine and dl- ... A suitable mechanism in agreement with observed kinetics has been ..... In acidic solution of potassium bromate quick .... Annual Review of Biochemistry.

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

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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.

New oxidation and photo-oxidation products of tryptophan

International Nuclear Information System (INIS)

Savige, W.E.

1975-01-01

Dye-sensitized photo-oxidation of tryptophan in water gives N'-formylkynurenine and (+-)-3a-hydroxy-1,2,3a,8,8a-hexahydropyrrolo[2,3-b] indole-2-carboxylic acid. The latter rearranges to oxindolyl-3-alanine on irradiation with UV light and reacts with thiols, including cysteine, in warm 20% acetic acid to give the corresponding 2-tryptophyl sulphides. (orig.) [de

Amino Acid and Peptide Immobilization on Oxidized Nanocellulose: Spectroscopic Characterization

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Barazzouk, Saïd; Daneault, Claude

2012-01-01

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. PMID:28348303

Amino Acid and Peptide Immobilization on Oxidized Nanocellulose: Spectroscopic Characterization

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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.

Photocatalytic ozonation of terephthalic acid: a by-product-oriented decomposition study.

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Fuentes, Iliana; Rodríguez, Julia L; Poznyak, Tatyana; Chairez, Isaac

2014-11-01

Terephthalic acid (TA) is considered as a refractory model compound. For this reason, the TA degradation usually requires a prolonged reaction time to achieve mineralization. In this study, vanadium oxide (VxOy) supported on titanium oxide (TiO2) served as a photocatalyst in the ozonation of the TA with light-emitting diodes (LEDs), having a bandwidth centered at 452 nm. The modified catalyst (VxOy/TiO2) in combination with ozone and LEDs improved the TA degradation and its by-products. The results obtained by this system were compared with photolysis, single ozonation, catalytic ozonation, and photocatalytic ozonation of VxOy/TiO2 with UV lamp. The LED-based photocatalytic ozonation showed almost the same decomposition efficiency of the TA, but it was better in comparison with the use of UV lamp. The oxalic acid accumulation, as the final product of the TA decomposition, was directly influenced by either the presence of VxOy or/and the LED irradiation. Several by-products formed during the TA degradation, such as muconic, fumaric, and oxalic acids, were identified. Besides, two unidentified by-products were completely removed during the observed time (60 min). It was proposed that the TA elimination in the presence of VxOy/TiO2 as catalyst was carried out by the combination of different mechanisms: molecular ozone reaction, indirect mechanism conducted by ·OH, and the surface complex formation.

Cooking methods employing natural anti-oxidant food additives effectively reduced concentration of nephrotoxic and carcinogenic aristolochic acids in contaminated food grains.

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Li, Weiwei; Chan, Chi-Kong; Wong, Yee-Lam; Chan, K K Jason; Chan, Ho Wai; Chan, Wan

2018-10-30

Emerging evidence suggests that aristolochic acids (AA) produced naturally by a common weed Aristolochia clematitis in the cultivation fields is contaminating the food products in Balkan Peninsula and acting as the etiological agent in the development of Balkan endemic nephropathy. In this study, we investigated the combined use of natural anti-oxidative "food additives" and different cooking methods to find a solution for the widespread contamination of AA in food products. The results indicated that the addition of healthy dietary supplements (such as cysteine, glutathione, ascorbic acid, citric acid and magnesium) during cooking, is a highly efficient method in lowering the concentration of AA in the final food products. Because previous observation indicated one of the toxicological mechanisms by which AA exert its toxicity is to induce oxidative stress in internal organs, it is anticipated that these added anti-oxidants will also help to attenuate the nephrotoxicity of AA. Copyright © 2018 Elsevier Ltd. All rights reserved.

Oxidation of urate by a therapeutic nitric oxide/air mixture

International Nuclear Information System (INIS)

Hicks, M.; Nguyen, L.; Day, R.; Rogers, P.

1996-01-01

Full text: Little is known about the potential toxicological consequences of therapeutic exposure of lung tissue to inhaled nitric oxide (NO). This route of administration is currently being successfully employed for the treatment of pulmonary hypertension and other lung pathologies including acute reperfusion injury in lung transplant patients. The toxicity of NO lies in its ability to act as an oxidant either in its own right or in concert with oxygen or with the superoxide free radical. One important interaction may be the reaction of these products with protective antioxidants in the lung epithelial lining fluid. One such antioxidant found in significant concentrations in both upper and lower airways is uric acid. In the present study, urate solutions (30μM) were exposed to a therapeutic concentration of NO gas, (35 ppm in air), for up to 90 minutes. Oxidative changes were followed spectrophotometrically and by HPLC. Significant loss of uric acid was observed with a concomitant formation of nitrite and allantoin, the stable oxidation product of NO and the major oxidation product of uric acid, respectively. No oxidation of urate was observed in the presence of air alone or when urate was incubated with nitrite. Uric acid oxidation could also be prevented by passing the NO / air stream through 10% KOH before the uric acid solution. This strategy removed trace amounts of higher oxides of nitrogen, (especially NO 2 ), from the NO / air stream. Thus, therapeutic inhalation of NO may deplete soluble antioxidants such as uric acid, especially during long-term chronic exposure unless care is taken to minimise formation of higher oxides of nitrogen

Oxidative stability of dark chicken meat through frozen storage: influence of dietary fat and alpha-tocopherol and ascorbic acid supplementation.

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Grau, A; Guardiola, F; Grimpa, S; Barroeta, A C; Codony, R

2001-11-01

We used factorial design to ascertain the influence of dietary fat source (linseed, sunflower and oxidized sunflower oils, and beef tallow) and the dietary supplementation with alpha-tocopheryl acetate (alpha-TA) (225 mg/kg of feed) and ascorbic acid (AA) (110 mg/kg) on dark chicken meat oxidation (lipid hydroperoxide and TBA values and cholesterol oxidation product content). alpha-TA greatly protected ground and vacuum-packaged raw or cooked meat from fatty acid and cholesterol oxidation after 0, 3.5, or 7 mo of storage at -20 C. In contrast, AA provided no protection, and no synergism between alpha-TA and AA was observed. Polyunsaturated fatty acid-enriched diets (those containing linseed, sunflower, or oxidized sunflower oils) increased meat susceptibility to oxidation. Cooking always involved more oxidation, especially in samples from linseed oil diets. The values of all the oxidative parameters showed a highly significant negative correlation with the alpha-tocopherol content of meat.

Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

International Nuclear Information System (INIS)

Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

1984-01-01

The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

Oxidative modification of lipoic acid by HNE in Alzheimer disease brain

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Sarita S. Hardas

2013-01-01

Full Text Available Alzheimer disease (AD is an age-related neurodegenerative disease characterized by the presence of three pathological hallmarks: synapse loss, extracellular senile plaques (SP and intracellular neurofibrillary tangles (NFTs. The major component of SP is amyloid β-peptide (Aβ, which has been shown to induce oxidative stress. The AD brain shows increased levels of lipid peroxidation products, including 4-hydroxy-2-nonenal (HNE. HNE can react covalently with Cys, His, or Lys residues on proteins, altering structure and function of the latter. In the present study we measured the levels of the HNE-modified lipoic acid in brain of subjects with AD and age-matched controls. Lipoic acid is a key co-factor for a number of proteins including pyruvate dehydrogenase and α-ketoglutarate dehydrogenase, key complexes for cellular energetics. We observed a significant decrease in the levels of HNE-lipoic acid in the AD brain compared to that of age-matched controls. To investigate this phenomenon further, the levels and activity of lipoamide dehydrogenase (LADH were measured in AD and control brains. Additionally, LADH activities were measured after in-vitro HNE-treatment to mice brains. Both LADH levels and activities were found to be significantly reduced in AD brain compared to age-matched control. HNE-treatment also reduced the LADH activity in mice brain. These data are consistent with a two-hit hypothesis of AD: oxidative stress leads to lipid peroxidation that, in turn, causes oxidative dysfunction of key energy-related complexes in mitochondria, triggering neurodegeneration. This study is consonant with the notion that lipoic acid supplementation could be a potential treatment for the observed loss of cellular energetics in AD and potentiate the antioxidant defense system to prevent or delay the oxidative stress in and progression of this devastating dementing disorder.

Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products.

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Olvera-Vargas, Hugo; Oturan, Nihal; Aravindakumar, C T; Paul, M M Sunil; Sharma, Virender K; Oturan, Mehmet A

2014-01-01

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.

Kinetics and Mechanism of Oxidation of Aromatic Aldehydes by Imidazolium Dichromate in Aqueous Acetic Acid Medium

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S. Sheik Mansoor

2009-01-01

Full Text Available The kinetics of oxidation of benzaldehyde (BA and para-substituted benzaldehydes by imidazolium dichromate (IDC has been studied in aqueous acetic acid medium in the presence of perchloric acid. The reaction is first order each in [IDC], [Substrate] and [H+]. The reaction rates have been determined at different temperatures and the activation parameters calculated. Electron withdrawing substituents are found to increase the reaction and electron releasing substituents are found to retard the rate of the reaction and the rate data obey the Hammett relationship. The products of the oxidation are the corresponding acids. The rate decreases with the increase in the water content of the medium. A suitable mechanism is proposed.

Investigations on the oxidation of nitric acid plutonium solutions with ozone

International Nuclear Information System (INIS)

Boehm, M.

1983-01-01

The reaction of ozone with nitric acid Pu solutions was studied as a function of reaction time, acid concentration and Pu concentration. Strong nitric acid Pu solutions are important in nuclear fuel element production and reprocessing. The Pu must be converted into hexavalent Pu before precipitation from the homogeneous solution together with uranium-IV, ammonia and CO 2 in the form of ammonium uranyl/plutonyl carbonate (AUPuC). Formation of a solid phase during ozonation was observed for the first time. The proneness to solidification increases with incrasing plutonium concentrations and with decreasing acid concentrations. If the formation of a solid phase during ozonation of nitric acid Pu solutions cannot be prevented, the PU-IV oxidation process described is unsuitable for industrial purposes as Pu solutions in industrial processes have much higher concentrations than the solutions used in the present investigation. (orig./EF) [de

[Enhanced electro-chemical oxidation of Acid Red 3R solution with phosphotungstic acid supported on gamma-Al2O3].

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Yue, Lin; Wang, Kai-Hong; Guo, Jian-Bo; Yang, Jing-Liang; Liu, Bao-You; Lian, Jing; Wang, Tao

2013-03-01

Supported phosphotungstic acid catalysts on gamma-Al2O3 (HPW/gamma-Al2O3) were prepared by solution impregnation and characterized by FTIR, XRD, TG-DTA and SEM. The heteropolyanion shows a Keggin structure. Electro-chemical oxidation of Acid Red 3R was investigated in the presence of HPW supported on gamma-Al2O3 as packing materials in the reactor. The results show that HPW/gamma-Al2O3 has a good catalytic activity for decolorization of Acid Red 3R. When HPW loading was 4.6%, pH value of Acid Red 3R was 3, the voltage was 25.0 V, air-flow was 0.04 m3 x h(-1), and electrode span was 3.0 cm, the decolorization efficiency of Acid Red 3R can reach 97.6%. The removal rate of color had still about 80% in this electro-chemical oxidation system, after HPW/gamma-Al2O3 was used for 10 times, but active component loss existed. The interim product was analyzed by means of Vis-UV absorption spectrum. It shows that the conjugated structure of dye is destroyed primarily.

Extra Virgin Olive Oil Reduced Polyunsaturated Fatty Acid and Cholesterol Oxidation in Rodent Liver: Is This Accounted for Hydroxytyrosol-Fatty Acid Conjugation?

Science.gov (United States)

Lee, Yiu Yiu; Crauste, Céline; Wang, Hualin; Leung, Ho Hang; Vercauteren, Joseph; Galano, Jean-Marie; Oger, Camille; Durand, Thierry; Wan, Jennifer Man-Fan; Lee, Jetty Chung-Yung

2016-10-17

The effects of extra virgin olive oil (EVOO) and carbon tetrachloride (CCl 4 ) induced oxidative stress in rats were determined by the generation of isoprostanoids. These are known to be robust biomarkers to evaluate nonenzymatic and free radical related oxidation. Other oxidative stress biomarkers such as hydroxyeicosatetraenoic acid products (HETEs) and cholesterol oxidation products (COPs) were also determined. The rodents received a control diet, high-fat diet (20% w/w) composed of extra virgin olive oil (EVOO), corn oil (CO), or lard, and high-fat diets with CCl 4 insult throughout the experimental period. The EVOO diet was found to suppress the formation of isoprostanoids and COPs compared to that of the control. EVOO also had a high total phenolic content and antioxidant activity compared to those of CO and lard and may be contributed to by the hydroxytyrosol component conjugated to fatty acids (HT-FA). This is the first study to identify HT-FA in EVOO, and it was 4-fold higher than that of olive oil, whereas none was found in corn oil. Furthermore, the EVOO diet showed reduced liver lipid vesicles in CCl 4 treated rats compared to that of the control. However, liver toxicity measurements of AST (aspartate transaminase) and ALT (alanine transaminase) activities showed augmentation with CCl 4 treatment but were not alleviated by the diets given. Our findings suggest that EVOO is a daily functional food capable of enhancing the antioxidant system for liver protection; the effect is potentially attributed to the phenolic and lipophenolic (phenol conjugated by fatty acids) content.

Study on mechanism for oxidation of N,N-dimethylhydroxylamine by nitrous acid

International Nuclear Information System (INIS)

Li Gaoliang; He Hui

2011-01-01

The oxidation of N,N-dimethylhydroxylamine (DMHAN) by nitrous acid is investigated in perchloric acid and nitric acid medium, respectively. The effects of H + , DMHAN, ionic strength and temperature on the reaction are studied. The rate equation in perchloric acid medium has been determined to be -d[HNO 2 ]/dt = k[DMHAN][HNO 2 ], where k = 12.8 ± 1.0 (mol/L) -1 min -1 when the temperature is 18.5 deg C and the ionic strength is 0.73 mol/L with an activation energy about 41.5 kJ mol -1 . The reaction becomes complicated when it is performed in nitric acid medium. When the molarity of HNO 3 is higher than 1.0 mol/L, nitrous acid will be produced via the reaction between nitric acid and DMHAN. The reaction products are analyzed and the reaction mechanism is discussed in this paper. (author)

Syntrophic acetate oxidation in two-phase (acid-methane) anaerobic digesters.

Science.gov (United States)

Shimada, T; Morgenroth, E; Tandukar, M; Pavlostathis, S G; Smith, A; Raskin, L; Kilian, R E

2011-01-01

The microbial processes involved in two-phase anaerobic digestion were investigated by operating a laboratory-scale acid-phase (AP) reactor and analyzing two full-scale, two-phase anaerobic digesters operated under mesophilic (35 °C) conditions. The digesters received a blend of primary sludge and waste activated sludge (WAS). Methane levels of 20% in the laboratory-scale reactor indicated the presence of methanogenic activity in the AP. A phylogenetic analysis of an archaeal 16S rRNA gene clone library of one of the full-scale AP digesters showed that 82% and 5% of the clones were affiliated with the orders Methanobacteriales and Methanosarcinales, respectively. These results indicate that substantial levels of aceticlastic methanogens (order Methanosarcinales) were not maintained at the low solids retention times and acidic conditions (pH 5.2-5.5) of the AP, and that methanogenesis was carried out by hydrogen-utilizing methanogens of the order Methanobacteriales. Approximately 43, 31, and 9% of the archaeal clones from the methanogenic phase (MP) digester were affiliated with the orders Methanosarcinales, Methanomicrobiales, and Methanobacteriales, respectively. A phylogenetic analysis of a bacterial 16S rRNA gene clone library suggested the presence of acetate-oxidizing bacteria (close relatives of Thermacetogenium phaeum, 'Syntrophaceticus schinkii,' and Clostridium ultunense). The high abundance of hydrogen consuming methanogens and the presence of known acetate-oxidizing bacteria suggest that acetate utilization by acetate oxidizing bacteria in syntrophic interaction with hydrogen-utilizing methanogens was an important pathway in the second-stage of the two-phase digestion, which was operated at high ammonium-N concentrations (1.0 and 1.4 g/L). A modified version of the IWA Anaerobic Digestion Model No. 1 (ADM1) with extensions for syntrophic acetate oxidation and weak-acid inhibition adequately described the dynamic profiles of volatile acid production

Integrated production of cellulosic bioethanol and succinic acid from industrial hemp in a biorefinery concept.

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Kuglarz, Mariusz; Alvarado-Morales, Merlin; Karakashev, Dimitar; Angelidaki, Irini

2016-01-01

The aim of this study was to develop integrated biofuel (cellulosic bioethanol) and biochemical (succinic acid) production from industrial hemp (Cannabis sativa L.) in a biorefinery concept. Two types of pretreatments were studied (dilute-acid and alkaline oxidative method). High cellulose recovery (>95%) as well as significant hemicelluloses solubilization (49-59%) after acid-based method and lignin solubilization (35-41%) after alkaline H2O2 method were registered. Alkaline pretreatment showed to be superior over the acid-based method with respect to the rate of enzymatic hydrolysis and ethanol productivity. With respect to succinic acid production, the highest productivity was obtained after liquid fraction fermentation originated from steam treatment with 1.5% of acid. The mass balance calculations clearly showed that 149kg of EtOH and 115kg of succinic acid can be obtained per 1ton of dry hemp. Results obtained in this study clearly document the potential of industrial hemp for a biorefinery. Copyright © 2015 Elsevier Ltd. All rights reserved.

Contribution of the activated catalase to oxidative stress resistance and γ-aminobutyric acid production in Lactobacillus brevis.

Science.gov (United States)

Lyu, Changjiang; Hu, Sheng; Huang, Jun; Luo, Maiqi; Lu, Tao; Mei, Lehe; Yao, Shanjing

2016-12-05

Lactic acid bacteria (LAB) are generally sensitive to H 2 O 2 , a compound which can paradoxically produce themselves and lead to the growth arrest and cell death. To counteract the potentially toxic effects of this compound, the gene katE encoding a heme-dependent catalase (CAT) belonging to the family of monofunctional CATs was cloned from Lactobacillus brevis CGMCC1306. The enhanced homologous CAT expression was achieved using the NICE system. L. brevis cells with overexpressed CAT showed 685-fold and 823-fold higher survival when exposed to 30mmol/L of H 2 O 2 and long-term aerated stress (after 72h), respectively, than that of the wild type cells. Furtherly, the effects of activated CAT on GABA production in L. brevis were investigated. A GABA production level of 66.4g/L was achieved using two-step biotransformation that successively employed the growing and resting cells derived from engineering L. brevis CAT. These results demonstrated clearly that overexpression of the KatE gene in L. brevis led to a marked increased survival in oxidizing environment, and shed light on a novel feasible approach to enhance the GABA production level by improving the antioxidative properties. Copyright © 2016 Elsevier B.V. All rights reserved.

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

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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.

Arachidonic acid triggers an oxidative burst in leukocytes

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Pompeia C.

2003-01-01

Full Text Available The change in cellular reducing potential, most likely reflecting an oxidative burst, was investigated in arachidonic acid- (AA stimulated leukocytes. The cells studied included the human leukemia cell lines HL-60 (undifferentiated and differentiated into macrophage-like and polymorphonuclear-like cells, Jurkat and Raji, and thymocytes and macrophages from rat primary cultures. The oxidative burst was assessed by nitroblue tetrazolium reduction. AA increased the oxidative burst until an optimum AA concentration was reached and the burst decreased thereafter. In the leukemia cell lines, optimum concentration ranged from 200 to 400 µM (up to 16-fold, whereas in rat cells it varied from 10 to 20 µM. Initial rates of superoxide generation were high, decreasing steadily and ceasing about 2 h post-treatment. The continuous presence of AA was not needed to stimulate superoxide generation. It seems that the NADPH oxidase system participates in AA-stimulated superoxide production in these cells since the oxidative burst was stimulated by NADPH and inhibited by N-ethylmaleimide, diphenyleneiodonium and superoxide dismutase. Some of the effects of AA on the oxidative burst may be due to its detergent action. There apparently was no contribution of other superoxide-generating systems such as xanthine-xanthine oxidase, cytochromes P-450 and mitochondrial electron transport chain, as assessed by the use of inhibitors. Eicosanoids and nitric oxide also do not seem to interfere with the AA-stimulated oxidative burst since there was no systematic effect of cyclooxygenase, lipoxygenase or nitric oxide synthase inhibitors, but lipid peroxides may play a role, as indicated by the inhibition of nitroblue tetrazolium reduction promoted by tocopherol.

Chlorination and chloramination of aminophenols in aqueous solution: oxidant demand and by-product formation.

Science.gov (United States)

Mehrez, O Abou; Dossier-Berne, F; Legube, B

2015-01-01

Chlorination and monochloramination of aminophenols (AP) were carried out in aqueous solution at 25°C and at pH 8.5. Oxidant demand and disinfection by-product formation were determined in excess of oxidant. Experiments have shown that chlorine consumption of AP was 40-60% higher than monochloramine consumption. Compared with monochloramination, chlorination of AP formed more chloroform and haloacetic acids (HAA). Dichloroacetic acid was the major species of HAA. Chloroform and HAA represented, respectively, only 1-8% and 14-15% of adsorbable organic halides (AOX) by monochloramination but up to 29% and 39% of AOX by chlorination.

Hydrodeoxygenation of oxidized distilled bio-oil for the production of gasoline fuel type

International Nuclear Information System (INIS)

Luo, Yan; Guda, Vamshi Krishna; Hassan, El Barbary; Steele, Philip H.; Mitchell, Brian; Yu, Fei

2016-01-01

Highlights: • Oxidation had more influence on the yield of total hydrocarbons than distillation. • The highest total hydrocarbon yield was obtained from oxidized distilled bio-oil. • The 2nd-stage hydrocarbons were in the range of gasoline fuel boiling points. • The main products for upgrading of oxidized bio-oil were aliphatic hydrocarbons. • The main products for upgrading of non-oxidized bio-oil were aromatic hydrocarbons. - Abstract: Distilled and oxidized distilled bio-oils were subjected to 1st-stage mild hydrodeoxygenation and 2nd-stage full hydrodeoxygenation using nickel/silica–alumina catalyst as a means to enhance hydrocarbon yield. Raw bio-oil was treated for hydrodeoxygenation as a control to which to compare study treatments. Following two-stage hydrodeoxygenation, four types of hydrocarbons were mainly comprised of gasoline and had water contents, oxygen contents and total acid numbers of nearly zero and higher heating values of 44–45 MJ/kg. Total hydrocarbon yields for raw bio-oil, oxidized raw bio-oil, distilled bio-oil and oxidized distilled bio-oil were 11.6, 16.2, 12.9 and 20.5 wt.%, respectively. The results indicated that oxidation had the most influence on increasing the yield of gasoline fuel type followed by distillation. Gas chromatography/mass spectrometry characterization showed that 66.0–76.6% of aliphatic hydrocarbons and 19.5–31.6% of aromatic hydrocarbons were the main products for oxidized bio-oils while 35.5–38.7% of aliphatic hydrocarbons and 58.2–63.1% of aromatic hydrocarbons were the main products for non-oxidized bio-oils. Both aliphatic and aromatic hydrocarbons are important components for liquid transportation fuels and chemical products.

Intensity of lipid oxidation and formation of cholesterol oxidation products during frozen storage of raw and cooked chicken

OpenAIRE

Conchillo, A. (Ana); Ansorena, D. (Diana); Astiasarán, I. (Iciar)

2004-01-01

Raw and cooked chicken breasts were stored at −18 °C for 3 months under aerobic and vacuum conditions, and the intensity of lipid oxidation and the formation of COP (cholesterol oxidation products) were studied. Raw samples showed low COP levels (4.60–7.40 µg g−1 fat), TBARS (thiobarbituric acid reactive substances) levels (0.01–0.03 mg kg−1) and peroxide values (not detected) under both aerobic and vacuum conditions. Cooked samples (grilled and roasted) showed TBARS levels of 0.36–0.99 mg kg...

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.

Biodegradation of photo-oxidized lignite and characterization of the products

Science.gov (United States)

Li, Jiantao; Liu, Xiangrong; Yue, Zilin; Zhang, Yaowen

2018-01-01

Biodegradation of photo-oxidized Inner Mongolia lignite by pseudomonas aeruginosa was studied and the degradation percentage reached 56.27%, while the corresponding degradation percentage of the strain degrading raw Inner Mongolia lignite is only 23.16%. The degradation products were characterized. Proximate and ultimate analyses show that the higher oxygen content increased by photo-oxidation pretreatment maybe promoted the degradation process. Ultraviolet spectroscopy (UV) analysis of the liquid product reveals that it contains unsaturated structures and aromatic rings are the main structure units. Gas chromatography-mass spectrometry (GC-MS) analysis indicates that the main components of the ethyl acetate extracts are low molecular weight organic compounds, such as ketones, acids, hydrocarbons, esters and alcohols. Infrared spectroscopy (IR) analysis of raw lignite, photo-oxidized lignite and residual lignite demonstrates that the absorption peaks of functional groups in residual lignite disappeared or weakened obviously. Scanning electron microscopy (SEM) analysis manifests that small holes appear in photo-oxidized lignite surface, which may be promote the degradation process and this is only from the physical morphology aspects, so it can be inferred from the tests and analyses results that the more important reason of the high degradation percentage is mostly that the photo-oxidation pretreatment changes the chemical structures of lignite.

Effect of sulfonylureas on hepatic fatty acid oxidation

International Nuclear Information System (INIS)

Patel, T.B.

1986-01-01

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 μM 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- 1 $C]oleic acid (0.1 mM) increased the rate of 14 C 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

Chiral lewis Acid catalysis in nitrile oxide cycloadditions.

Science.gov (United States)

Sibi, Mukund P; Itoh, Kennosuke; Jasperse, Craig P

2004-05-05

We describe examples of highly regio- and enantioselective nitrile oxide cycloadditions to unsaturated alkenes using substoichiometric amounts of a chiral Lewis acid. Pyrazolidinones proved to be effective achiral templates in the cycloadditions providing C-adducts typically in >30:1 selectivity and 80-99% ee. To avoid potential problems involving coordination of the Lewis acid by amine bases, we have devised a novel method for the generation of unstable nitrile oxides from hydroximinoyl chlorides using Amberlyst 21 as the base.

Ultrasensitive determination of DNA oxidation products by gas chromatography-tandem mass spectrometry and the role of antioxidants in the prevention of oxidative damage.

Science.gov (United States)

Dawbaa, Sam; Aybastıer, Önder; Demir, Cevdet

2017-04-15

Oxidative stress is considered as one of the significant causes of DNA damage which in turn contributes to cell death through a series of intermediate processes such as cancer formation, mutation, and aging. Natural sources such as plant and fruit products have provided us with interesting substances of antioxidant activity that could be recruited in protecting the genetic materials of the cells. This study is an effort to discover some of those antioxidants effects in their standard and natural forms by performing an ultrasensitive determination of the products of DNA oxidation using GC-MS/MS. Experiments were used to determine the direct antioxidant activity of the substances contained in the tendrils of Vitis vinifera (var. alphonse) by extracting them and achieving Folin-Ciocalteau and CHROMAC analyses to determine the total phenolic content (TPC) and the antioxidant capacity of the extract, respectively; results revealed a phenolic content of 11.39±0.30mg Gallic Acid Equivalent (GAE)/g of the plant's fresh weight (FW) by Folin-Ciocalteau and 8.17±0.49mg Trolox Equivalent (TE)/g FW by CHROMAC assays. The qualitative analysis of the plant extract by HPLC-DAD technique revealed that two flavonoid glycosides namely rutin and isoquercitrin in addition to chlorogenic acid were contained in the extract. The determination of the DNA oxidation products was performed after putting DNA, rutin and isoquercitrin standard samples with different concentration, and the extract's sample under oxidative stress. Eighteen DNA oxidation products were traced using GC-MS/MS with ultra-sensitivity and the experiments proved a significant decrease in the concentration of the DNA oxidation products when the extract was used as a protectant against the oxidative stress. It is believed by conclusion that the extract of V. vinifera's (var. alphonse) tendrils has a good antioxidant activity; hence it is recommended to be used as a part of the daily healthy food list if possible

Kinetic and Mechanistic Studies of Oxidation of an Antiallergic Drug with Bromamine-T in Acid and Alkaline Media

International Nuclear Information System (INIS)

Puttaswamy; Anu Sukhdev

2012-01-01

Cetrizine dihydrochloride (CTZH) is widely used as an anti-allergic drug. Sodium N-bromo-p-toluenesulfonamide or bromamine-T (BAT) is the bromine analogue of chloramine-T (CAT) and is found to be a better oxidizing agent than CAT. In the present research, the kinetics of oxidation of CTZH with BAT in acid and alkaline media was studied at 313 K. The experimental rate laws obtained are: -d[BAT]/dt = k[BAT] [CTZH] 0.80 [H + ] -0.48 in acid medium and -d[BAT]/dt = k[BAT][CTZH] 0.48 [OH - ] 0.52 [PTS] -0.40 in alkaline medium where PTS is p-toluenesulfonamide. Activation parameters and reaction constants were evaluated. The solvent isotope effect was studied using D 2 O. The dielectric effect is positive. The stoichiometry of the reaction was found to be 1:1 and the oxidation products were identified as 4-chlorobenzophenone and (2-piperazin-1-yl-ethoxy)-acetic acid in both media. The rate of oxidation of CTZH is faster in acid medium. Suitable mechanisms and related rate laws have been worked out

Oleic, Linoleic and Linolenic Acids Increase ROS Production by Fibroblasts via NADPH Oxidase Activation

Science.gov (United States)

Hatanaka, Elaine; Dermargos, Alexandre; Hirata, Aparecida Emiko; Vinolo, Marco Aurélio Ramirez; Carpinelli, Angelo Rafael; Newsholme, Philip; Armelin, Hugo Aguirre; Curi, Rui

2013-01-01

The effect of oleic, linoleic and γ-linolenic acids on ROS production by 3T3 Swiss and Rat 1 fibroblasts was investigated. Using lucigenin-amplified chemiluminescence, a dose-dependent increase in extracellular superoxide levels was observed during the treatment of fibroblasts with oleic, linoleic and γ-linolenic acids. ROS production was dependent on the addition of β-NADH or NADPH to the medium. Diphenyleneiodonium inhibited the effect of oleic, linoleic and γ-linolenic acids on fibroblast superoxide release by 79%, 92% and 82%, respectively. Increased levels of p47phox phosphorylation due to fatty acid treatment were detected by Western blotting analyses of fibroblast proteins. Increased p47phox mRNA expression was observed using real-time PCR. The rank order for the fatty acid stimulation of the fibroblast oxidative burst was as follows: γ-linolenic > linoleic > oleic. In conclusion, oleic, linoleic and γ-linolenic acids stimulated ROS production via activation of the NADPH oxidase enzyme complex in fibroblasts. PMID:23579616

Oleic, linoleic and linolenic acids increase ros production by fibroblasts via NADPH oxidase activation.

Directory of Open Access Journals (Sweden)

Elaine Hatanaka

Full Text Available The effect of oleic, linoleic and γ-linolenic acids on ROS production by 3T3 Swiss and Rat 1 fibroblasts was investigated. Using lucigenin-amplified chemiluminescence, a dose-dependent increase in extracellular superoxide levels was observed during the treatment of fibroblasts with oleic, linoleic and γ-linolenic acids. ROS production was dependent on the addition of β-NADH or NADPH to the medium. Diphenyleneiodonium inhibited the effect of oleic, linoleic and γ-linolenic acids on fibroblast superoxide release by 79%, 92% and 82%, respectively. Increased levels of p47 (phox phosphorylation due to fatty acid treatment were detected by Western blotting analyses of fibroblast proteins. Increased p47 (phox mRNA expression was observed using real-time PCR. The rank order for the fatty acid stimulation of the fibroblast oxidative burst was as follows: γ-linolenic > linoleic > oleic. In conclusion, oleic, linoleic and γ-linolenic acids stimulated ROS production via activation of the NADPH oxidase enzyme complex in fibroblasts.

Two-Step Electrochemical Intercalation and Oxidation of Graphite for the Mass Production of Graphene Oxide.

Science.gov (United States)

Cao, Jianyun; He, Pei; Mohammed, Mahdi A; Zhao, Xin; Young, Robert J; Derby, Brian; Kinloch, Ian A; Dryfe, Robert A W

2017-12-06

Conventional chemical oxidation routes for the production of graphene oxide (GO), such as the Hummers' method, suffer from environmental and safety issues due to their use of hazardous and explosive chemicals. These issues are addressed by electrochemical oxidation methods, but such approaches typically have a low yield due to inhomogeneous oxidation. Herein we report a two-step electrochemical intercalation and oxidation approach to produce GO on the large laboratory scale (tens of grams) comprising (1) forming a stage 1 graphite intercalation compound (GIC) in concentrated sulfuric acid and (2) oxidizing and exfoliating the stage 1 GIC in an aqueous solution of 0.1 M ammonium sulfate. This two-step approach leads to GO with a high yield (>70 wt %), good quality (>90%, monolayer), and reasonable oxygen content (17.7 at. %). Moreover, the as-produced GO can be subsequently deeply reduced (3.2 at. % oxygen; C/O ratio 30.2) to yield highly conductive (54 600 S m -1 ) reduced GO. Electrochemical capacitors based on the reduced GO showed an ultrahigh rate capability of up to 10 V s -1 due to this high conductivity.

Natural resistance to ascorbic acid induced oxidative stress is mainly mediated by catalase activity in human cancer cells and catalase-silencing sensitizes to oxidative stress

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Klingelhoeffer Christoph

2012-05-01

against oxidative stress mediated by ascorbic acid induced hydrogen peroxide production. The antioxidative enzyme catalase is important to protect cancer cells against cytotoxic hydrogen peroxide. Silenced catalase expression increased the susceptibility of the formerly resistant cancer cell line BT-20 to oxidative stress.

Involvement of Acetobacter orientalis in the production of lactobionic acid in Caucasian yogurt ("Caspian Sea yogurt") in Japan.

Science.gov (United States)

Kiryu, T; Kiso, T; Nakano, H; Ooe, K; Kimura, T; Murakami, H

2009-01-01

Lactobionic acid was first found in a Caucasian fermented milk product popularly known as "Caspian Sea yogurt" in Japan. The presence of lactobionic acid in the fermented milk was indicated by the results of both high-performance anion-exchange chromatographic analysis with pulsed amperometric detection and mass spectrometric analysis. Thereafter, the acid was purified from the yogurt and analyzed by nuclear magnetic resonance. A substantial amount of lactobionic acid was found to be accumulated in the upper layer of the yogurt, especially within 10 mm from the surface. A total of 45 mg of lactobionic acid per 100 g of the upper yogurt layer was collected after 4 d of fermentation. The annual intake of lactobionic acid in individuals consuming 100 g of the yogurt every day would be 0.5 to 1.0 g. A lactose-oxidizing bacterium was isolated from the fermented milk and was identified as Acetobacter orientalis. Washed A. orientalis cells oxidized monosaccharides such as d-glucose at considerable rates, although their activities for substrates such as lactose, maltose, and cellobiose were much lower. When A. orientalis cells were cultivated in cow's milk, they exhibited lactose-oxidizing activity, suggesting that this bacterium was the main organism involved in the production of lactobionic acid in the yogurt.

Preferential oxidation of linolenic acid compared to linoleic acid in the liver of catfish (Heteropneustes fossilis and Clarias batrachus)

International Nuclear Information System (INIS)

Bandyopadhyay, G.K.; Dutta, J.; Ghosh, S.

1982-01-01

The fate of [1(- 14 C] linoleic acid and [1( 14 C] linolenic acid in the liver slices and also in the liver tissues of live carnivorous catfish, Heteropneustes fossilis and Clarias batrachus, was studied. Incorporation of the fatty acids into different lipid classes in the live fish differed greatly from the tissue slices, indicating certain physiological control operative in vivo. The extent of desaturation and chain elongation of linoleic and linolenic acids into long-chain polyunsaturated fatty acids was low. Linolenic acid was oxidized (thus labeling the saturated fatty acid with liberated 14 C-acetyl-CoA) in preference to linoleic acid, and this oxidation also seemed to be under physiological control since both of the fatty acids were poorly oxidized in the tissue slices and in the killed fish. These fish can therefore recognize the difference in the acyl chain structures of linoleate and linolenate. The higher oxidation of linolenic acid and poor capacity for its conversion to longer chain, highly unsaturated derivatives indicates a higher demand for the dietary supply of these essential fatty acids in these two species

Kinetics of oxidic phase dissolution in acids

International Nuclear Information System (INIS)

Gorichev, I.G.; Kipriyanov, N.A.

1981-01-01

The critical analysis of the experimental data on dissolution kinetics of metal oxides (BeO, V 2 O 5 , UO 2 , Nb 2 O 5 , Ta 2 O 5 etc.) in acid media is carried out. Kinetic peculiarities of oxide dissolution are explained on the basis of the notions of electron- proton theory. It is established that the surface nonstoichiometric ccomposition of oxide phase and potential jump, appearing on the interface of the oxide-electrolyte phase are the important factors, determining the dissolution rate of a solid phase. The dissolution rate of metal oxides is limited by the transition of protons into the solid oxide phase. Morphological models of heterogeneous kinetics are used when explaining kinetic regularities of oxide dissolution process [ru

Nitrous Acid as an Oxidant in Acidic Media

Science.gov (United States)

1979-09-25

current work is the account of Ogsts and Sawski3 who studied the oxidation of benzyl ethers at 90C in acidic, aqueous dioxane. They found an increase in...and G. Tobin, Chem. Com., 180 (1978); (b) J. Hoggett , R. Moodie, and K. Schofield, Chem. Comm., 605 (1969). 15. (a) B. Challis and A. Lawson. J. Chem

Mechanism of catalytic action of oxide systems in reactions of aldehyde oxidation to carboxylic acids

International Nuclear Information System (INIS)

Andrushkevich, T.V.

1997-01-01

Mechanism of selective action of oxide catalysts (on the base of V 2 O 4 , MoO 3 ) of aldehyde oxidation to acids is considered, reaction acrolein oxidation to acrylic acid is taken as an example. Multistage mechanism of the process is established; it involves consequent transformation of coordination-bonded aldehyde into carbonyl-bonded aldehyde and symmetric carboxylate. Principles of active surface construction are formulated, they take into account the activity of stabilization center of concrete intermediate compound and bond energy of oxygen with surface. (author)

Application of acid whey and set milk to marinate beef with reference to quality parameters and product safety.

Science.gov (United States)

Wójciak, Karolina M; Krajmas, Paweł; Solska, Elżbieta; Dolatowski, Zbigniew J

2015-01-01

The aim of the study was to evaluate the potential of acid whey and set milk as a marinade in the traditional production of fermented eye round. Studies involved assaying pH value, water activity (aw), oxidation-reduction potential and TBARS value, colour parameters in CIE system (L*, a*, b*), assaying the number of lactic acid bacteria and certain pathogenic bacteria after ripening process and after 60-day storing in cold storage. Sensory analysis and analysis of the fatty acids profile were performed after completion of the ripening process. Analysis of pH value in the products revealed that application of acid whey to marinate beef resulted in increased acidity of ripening eye round (5.14). The highest value of the colour parameter a* after ripening process and during storage was observed in sample AW (12.76 and 10.07 respectively), the lowest on the other hand was observed in sample SM (10.06 and 7.88 respectively). The content of polyunsaturated fatty acids (PUFA) was higher in eye round marinated in acid whey by approx. 4% in comparison to other samples. Application of acid whey to marinade beef resulted in increased share of red colour in general colour tone as well as increased oxidative stability of the product during storage. It also increased the content of polyunsaturated fatty acids (PUFA) in the product. All model products had high content of lactic acid bacteria and there were no pathogenic bacteria such as: L. monocytogenes, Y. enterocolitica, S. aureus, Clostridium sp.

Activation of peroxisome proliferator-activated receptor-{alpha} (PPAR{alpha}) suppresses postprandial lipidemia through fatty acid oxidation in enterocytes

Energy Technology Data Exchange (ETDEWEB)

Kimura, Rino [Laboratory of Molecular Function of Food, Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Uji, Kyoto 611-0011 (Japan); Takahashi, Nobuyuki, E-mail: nobu@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); Murota, Kaeko [Department of Life Science, School of Science and Engineering, Kinki University, Osaka 770-8503 (Japan); Yamada, Yuko [Laboratory of Physiological Function of Food, Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Uji, Kyoto 611-0011 (Japan); Niiya, Saori; Kanzaki, Noriyuki; Murakami, Yoko [Laboratory of Molecular Function of Food, Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Uji, Kyoto 611-0011 (Japan); Moriyama, Tatsuya [Department of Applied Cell Biology, Graduate School of Agriculture, Kinki University, Nara 631-8505 (Japan); Goto, Tsuyoshi; Kawada, Teruo [Laboratory of Molecular Function of Food, Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Uji, Kyoto 611-0011 (Japan)

2011-06-24

Highlights: {yields} PPAR{alpha} activation increased mRNA expression levels of fatty acid oxidation-related genes in human intestinal epithelial Caco-2 cells. {yields} PPAR{alpha} activation also increased oxygen consumption rate and CO{sub 2} production and decreased secretion of triglyceride and ApoB from Caco-2 cells. {yields} Orally administration of bezafibrate increased mRNA expression levels of fatty acid oxidation-related genes and CO{sub 2} production in small intestinal epithelial cells. {yields} Treatment with bezafibrate decreased postprandial serum concentration of triglyceride after oral injection of olive oil in mice. {yields} It suggested that intestinal lipid metabolism regulated by PPAR{alpha} activation suppresses postprandial lipidemia. -- Abstract: Activation of peroxisome proliferator-activated receptor (PPAR)-{alpha} which regulates lipid metabolism in peripheral tissues such as the liver and skeletal muscle, decreases circulating lipid levels, thus improving hyperlipidemia under fasting conditions. Recently, postprandial serum lipid levels have been found to correlate more closely to cardiovascular diseases than fasting levels, although fasting hyperlipidemia is considered an important risk of cardiovascular diseases. However, the effect of PPAR{alpha} activation on postprandial lipidemia has not been clarified. In this study, we examined the effects of PPAR{alpha} activation in enterocytes on lipid secretion and postprandial lipidemia. In Caco-2 enterocytes, bezafibrate, a potent PPAR{alpha} agonist, increased mRNA expression levels of fatty acid oxidation-related genes, such as acyl-CoA oxidase, carnitine palmitoyl transferase, and acyl-CoA synthase, and oxygen consumption rate (OCR) and suppressed secretion levels of both triglycerides and apolipoprotein B into the basolateral side. In vivo experiments revealed that feeding high-fat-diet containing bezafibrate increased mRNA expression levels of fatty acid oxidation-related genes and

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

Science.gov (United States)

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

2014-09-01

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

Kinetics and mechanism of the oxidation of formic and oxalic acids ...

Indian Academy of Sciences (India)

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 ...

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.

Mineralization of phthalic acid by solar photoelectro-Fenton with a stirred boron-doped diamond/air-diffusion tank reactor: Influence of Fe3+ and Cu2+ catalysts and identification of oxidation products

International Nuclear Information System (INIS)

Garcia-Segura, Sergi; Salazar, Ricardo; Brillas, Enric

2013-01-01

and six short-linear carboxylic acids were identified as oxidation products. A plausible reaction sequence for phthalic acid mineralization involving all the detected products was finally proposed

Synthesis of acetic acid by catalytic oxidation of butenes-2. Synthesis of acetic acid from sec. -butyl alcohol and methyl ethyl ketone in vapor-phase catalytic oxidation

Energy Technology Data Exchange (ETDEWEB)

Yamashita, T.; Matsuzawa, Y.; Ninagawa, S.

1977-11-01

Eleven binary catalysts containing vanadium pentoxide (V/sub 2/O/sub 5/), 17 binary catalysts containing cobalt oxide (Co/sub 3/O/sub 4/), and 18 ternary catalysts containing both V/sub 2/O/sub 5/ and Co/sub 3/O/sub 4/ were screened for the stepwise conversion of sec.-butanol to methyl ethyl ketone (MEK) and acetic acid. Of the binary catalysts, 4:1 Rh/V and Co/V binary oxides gave the best acetic acid yields. With the Co/V catalyst, the selectivity for MEK increased rapidly as the cobalt content of the catalyst increased above 50%, reaching 81% at 226/sup 0/C and 90% conversion on 9:1 Co/V oxide. The 9:1 Co/V catalyst also yielded acetaldehyde from ethanol with 98% selectivity at 210/sup 0/C and acetone from isopropanol with 98% selectivity at 200/sup 0/C, but dehydrated tert.-butanol to isobutene. V/Cr and V/Sb binary oxides were the most effective catalysts for the oxidation of MEK to acetic acid, with 78-88% selectivities at 100% conversion at 260/sup 0/C. Of the ternary oxides tested for the one-step conversion of sec.-butanol to acetic acid, a 6:2:2 Co/V/Al catalyst gave best results, (i.e., 34% selectivity for acetic acid (45% for total acids) at 100% conversion and 68% selectivity (90% for total acids) at 50Vertical Bar3< conversion). Graphs, tables, and 21 references.

CuO and Ag2O/CuO Catalyzed Oxidation of Aldehydes to the Corresponding Carboxylic Acids by Molecular Oxygen

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Yaowu Sha

2008-04-01

Full Text Available Furfural was oxidized to furoic acid by molecular oxygen under catalysis by 150nm-sized Ag2O/CuO (92% or simply CuO (86.6%. When 30 nm-size catalyst was used,the main product was a furfural Diels-Alder adduct. Detailed reaction conditions andregeneration of catalysts were investigated. Under optimal conditions, a series of aromaticand aliphatic aldehydes were oxidized to the corresponding acids in good yields.

Phosphor investigation in the production of Syrian phosphoric acid using Nuclear Magnetic Resonance

International Nuclear Information System (INIS)

Al-Hassanieh, O.; Al-Hameish, M.

2009-06-01

Nuclear magnetic resonance spectroscopy (NMR) was applied in this work to the industrial process of extraction of uranium from phosphoric acid and to the process of the purification of the phosphoric acid for food proposes. The structural changes of used extraction materials and the organic content of the final product was studied. 13 C , 1 H and 32 P-spectra of all material during the process were recorded. The spectra of the three used extraction materials Bis(2-ethylhexyl Phosphoric Acid)) DEHPA, TriOctyl Phosphine Oxide (TOPO) (C 8 H 1 7) 3 P=O and TriButyl Phosphate (TBP) (C 4 H 9 O) 3 P=O show a partial degradation during the process. The final product ( Phosphoric acid for Food proposes) doesn't contain any organic solvents or extraction material. (author)

Enzymatic production of α-ketoglutaric acid from l-glutamic acid via l-glutamate oxidase.

Science.gov (United States)

Niu, Panqing; Dong, Xiaoxiang; Wang, Yuancai; Liu, Liming

2014-06-10

In this study, a novel strategy for α-ketoglutaric acid (α-KG) production from l-glutamic acid using recombinant l-glutamate oxidase (LGOX) was developed. First, by analyzing the molecular structure characteristics of l-glutamic acid and α-KG, LGOX was found to be the best catalyst for oxidizing the amino group of l-glutamic acid to a ketonic group without the need for exogenous cofactor. Then the LGOX gene was expressed in Escherichia coli BL21 (DE3) in a soluble and active form, and the recombinant LGOX activity reached to a maximum value of 0.59U/mL at pH 6.5, 30°C. Finally, the maximum α-KG concentration reached 104.7g/L from 110g/L l-glutamic acid in 24h, under the following optimum conditions: 1.5U/mL LGOX, 250U/mL catalase, 3mM MnCl2, 30°C, and pH 6.5. Copyright © 2014. Published by Elsevier B.V.

Oxidation of phenolic acid derivatives by soil and its relevance to allelopathic activity.

Science.gov (United States)

Ohno, T

2001-01-01

Previous studies have suggested that phenolic acids from legume green manures may contribute to weed control through allelopathy. The objectives of this study were to investigate the oxidation reactions of phenolic acids in soil and to determine the subsequent effects of oxidation upon phytotoxicity. Soils were reacted for 18 h with 0.25 mmol L(-1) benzoic and cinnamic acid derivative solutions and Mn release from the suspension was used as a marker for phenolic acid oxidation. The extent of oxidation in soil suspensions was in the order of 3,4dihydroxy- > 4-hydroxy-3-methoxy- > 4-hydroxy-approximately 2-hydroxy-substituted benzoic and cinnamic acids. The same ranking was observed for cyclic voltammetry peak currents of the cinnamic acid derivatives. This suggests that the oxidation of phenolic acids is controlled by the electron transfer step from the sorbed phenolic acid to the metal oxide. A bioassay experiment showed that the 4-hydroxy-, 4-hydroxy-3-methoxy-, and 3,4-dihydroxy-substituted cinnamic acids were bioactive at 0.25 mmol L(-1) concentration. Reaction with soil for 18 h resulted in the elimination of bioactivity of these three cinnamic acids at the 5% significance level. The oxidative reactivity of phenolic acids may limit the potential of allelopathy as a component of an integrated weed management system. However, the initial phytotoxicity after soil incorporation may coincide with the early, critical stage of weed emergence and establishment, so that allelopathic phenolic acids may still play a role in weed management despite their reactivity in soil systems.

Formic acid

Energy Technology Data Exchange (ETDEWEB)

Nielsen, H; Laing, B

1921-12-03

The production of formic acid by the oxidation of methane with a metallic oxide or by the interaction of carbon monoxide and water vapor in the presence of a catalyst, preferably a metallic oxide, is described along with the destructive distillation of carbonaceous material in the preesnce of formic acid vapor for the purpose of increasing the yield of condensible hydrocarbons.

Characterization of the limonene oxidation products with liquid chromatography coupled to the tandem mass spectrometry

Science.gov (United States)

Witkowski, Bartłomiej; Gierczak, Tomasz

2017-04-01

Composition of the secondary organic aerosol (SOA) generated during ozonolysis of limonene was investigated with liquid chromatography coupled to the negative electrospray ionization (ESI), quadrupole tandem mass spectrometry (MS/MS) as well as high resolution Time-of-Flight mass spectrometry. Aerosol was generated in the flow-tube reactor. HR-MS/MS analysis allowed for proposing structures for the several up-to-date unknown limonene oxidation products. In addition to the low MW limonene oxidation products, significant quantities of oligomers characterized by elemental compositions: C19H30O5, C18H28O6, C19H28O7, C19H30O7 and C20H34O9 were detected in the SOA samples. It was concluded that these compounds are most likely esters, aldol reaction products and/or hemiacetals. In addition to detailed study of the limonene oxidation products, the reaction time as well as initial ozone concentration impact on the limonene SOA composition was investigated. The relative intensities of the two esters of the limonic acid and 7-hydroxy limononic acid increased as a result of lowering the initial ozone concentration and shortening the reaction time, indicating that esterification may be an important oligomerization pathway during limonene SOA formation.

Bezafibrate in skeletal muscle fatty acid oxidation disorders

DEFF Research Database (Denmark)

Ørngreen, Mette Cathrine; Madsen, Karen Lindhardt; Preisler, Nicolai

2014-01-01

OBJECTIVE: To assess whether bezafibrate increases fatty acid oxidation (FAO) and lowers heart rate (HR) during exercise in patients with carnitine palmitoyltransferase (CPT) II and very long-chain acyl-CoA dehydrogenase (VLCAD) deficiencies. METHODS: This was a 3-month, randomized, double......, triglyceride, and free fatty acid concentrations; however, there were no changes in palmitate oxidation, FAO, or HR during exercise. CONCLUSION: Bezafibrate does not improve clinical symptoms or FAO during exercise in patients with CPT II and VLCAD deficiencies. These findings indicate that previous in vitro...

Kinetics of the oxidative hydroxylation of tetraphosphorus in the presence of copper(II chloride modified by humic (fulvo- acid

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Zhaksyntay Kairbekov

2012-12-01

Full Text Available It was established that in mild conditions (50-70 oC, РО2= 1 atm white phosphorus effectively is oxidized by oxygen in water-toluene solutions of copper(II chloride modified by humic (fulvo- acid to give mainly phosphoric acid. Humic (fulvo- acid was extracted from brown coal of domestic deposit Kiyakty. For determination of optimum parameters of fulvo-acid extraction the laboratory experiments were carried out using the method of experiment planning. The kinetics, intermediate and final products, optimum conditions of new catalytic reaction of P4 oxidation by oxygen in water medium were defined by kinetics, volumometry, redox-potentiometry, 31Р{1Н} NMR spectroscopy and  titration. 

Essential fatty acid-rich diets protect against striatal oxidative damage induced by quinolinic acid in rats.

Science.gov (United States)

Morales-Martínez, Adriana; Sánchez-Mendoza, Alicia; Martínez-Lazcano, Juan Carlos; Pineda-Farías, Jorge Baruch; Montes, Sergio; El-Hafidi, Mohammed; Martínez-Gopar, Pablo Eliasib; Tristán-López, Luis; Pérez-Neri, Iván; Zamorano-Carrillo, Absalom; Castro, Nelly; Ríos, Camilo; Pérez-Severiano, Francisca

2017-09-01

Essential fatty acids have an important effect on oxidative stress-related diseases. The Huntington's disease (HD) is a hereditary neurologic disorder in which oxidative stress caused by free radicals is an important damage mechanism. The HD experimental model induced by quinolinic acid (QUIN) has been widely used to evaluate therapeutic effects of antioxidant compounds. The aim of this study was to test whether the fatty acid content in olive- or fish-oil-rich diet prevents against QUIN-related oxidative damage in rats. Rats were fed during 20 days with an olive- or a fish-oil-rich diet (15% w/w). Posterior to diet period, rats were striatally microinjected with QUIN (240 nmol/µl) or saline solution. Then, we evaluated the neurological damage, oxidative status, and gamma isoform of the peroxisome proliferator-activated receptor (PPARγ) expression. Results showed that fatty acid-rich diet, mainly by fish oil, reduced circling behavior, prevented the fall in GABA levels, increased PPARγ expression, and prevented oxidative damage in striatal tissue. In addition none of the enriched diets exerted changes neither on triglycerides or cholesterol blood levels, nor or hepatic function. This study suggests that olive- and fish-oil-rich diets exert neuroprotective effects.

Elucidation of oxidation and degradation products of oxygen containing fuel components by combined use of a stable isotopic tracer and mass spectrometry.

Science.gov (United States)

Frauscher, Marcella; Besser, Charlotte; Allmaier, Günter; Dörr, Nicole

2017-11-15

In order to reveal the degradation products of oxygen-containing fuel components, in particular fatty acid methyl esters, a novel approach was developed to characterize the oxidation behaviour. Combination of artificial alteration under pressurized oxygen atmosphere, a stable isotopic tracer, and gas chromatography electron impact mass spectrometry (GC-EI-MS) was used to obtain detailed information on the formation of oxidation products of (9Z), (12Z)-octadecadienoic acid methyl ester (C18:2 ME). Thereby, biodiesel simulating model compound C18:2 ME was oxidized in a rotating pressurized vessel standardized for lubricant oxidation tests (RPVOT), i.e., artificially altered, under 16 O 2 as well as 18 O 2 atmosphere. Identification of the formed degradation products, mainly carboxylic acids of various chain lengths, alcohols, ketones, and esters, was performed by means of GC-EI-MS. Comparison of mass spectra of compounds under both atmospheres revealed not only the degree of oxidation and the origin of oxygen atoms, but also the sites of oxidative attack and bond cleavage. Hence, the developed and outlined strategy based on a gas-phase stable isotopic tracer and mass spectrometry provides insight into the degradation of oxygen-containing fuels and fuel components by means of the accurate differentiation of oxygen origin in a degradation product. Copyright © 2017 Elsevier B.V. All rights reserved.

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. Copyright © 2015 Elsevier B.V. All rights reserved.

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

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Cassiano Felippe Gonçalves-de-Albuquerque

Full Text Available 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.

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.

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

Kinetics of Oxidation of Cobalt(III Complexes of a Acids by Hydrogen Peroxide in the Presence of Surfactants

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Mansur Ahmed

2008-01-01

Full Text Available Hydrogen peroxide oxidation of pentaamminecobalt(III complexes of α-hydroxy acids at 35°C in micellar medium has been attempted. In this reaction the rate of oxidation shows first order kinetics each in [cobalt(III] and [H2O2]. Hydrogen peroxide induced electron transfer in [(NH35 CoIII-L]2+ complexes of α-hydroxy acids readily yields 100% of cobalt(II with nearly 100% of C-C bond cleavage products suggesting that it behaves mainly as one equivalent oxidant in micellar medium. With unbound ligand also it behaves only as C-C cleavage agent rather than C-H cleavage agent. With increasing micellar concentration an increase in the rate is observed.

Integrative device and process of oxidization, degassing, acidity adjustment of 1BP from APOR process

Energy Technology Data Exchange (ETDEWEB)

Zuo, Chen; Zheng, Weifang, E-mail: wfazh@ciae.ac.cn; Yan, Taihong; He, Hui; Li, Gaoliang; Chang, Shangwen; Li, Chuanbo; Yuan, Zhongwei

2016-02-15

Graphical abstract: Previous (left) and present (right) device of oxidation, degassing, acidity adjustment of 1BP. - Highlights: • We designed an integrative device and process. • The utilization efficiency of N{sub 2}O{sub 4} is increased significantly. • Our work results in considerable simplification of the device. • Process parameters are determined by experiments. - Abstract: Device and process of oxidization, degassing, acidity adjustment of 1BP (The Pu production feed from U/Pu separation section) from APOR process (Advanced Purex Process based on Organic Reductants) were improved through rational design and experiments. The device was simplified and the process parameters, such as feed position and flow ratio, were determined by experiments. Based on this new device and process, the reductants N,N-dimethylhydroxylamine (DMHAN) and methylhydrazine (MMH) in 1BP solution could be oxidized with much less N{sub 2}O{sub 4} consumption.

Analysis of Chlorogenic Acid Oxidation Pathway in Simulated ...

African Journals Online (AJOL)

Keywords: Honeysuckle, Chlorogenic acid, Enzymatic browning, Mimic system, Oxidation pathway, ... enzymatic oxidation of CA is the major cause of ..... to the concentration of catechol, o-quinone and current at PPO-modified microcylinder biosensor for diffusion- kinetic model. J Electroanal Chem 2011; 660: 200-208.

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.

Production of carboxylic acid and salt co-products

Science.gov (United States)

Hanchar, Robert J.; Kleff, Susanne; Guettler, Michael V.

2014-09-09

This invention provide processes for producing carboxylic acid product, along with useful salts. The carboxylic acid product that is produced according to this invention is preferably a C.sub.2-C.sub.12 carboxylic acid. Among the salts produced in the process of the invention are ammonium salts.

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

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ethylene oxide adduct of fatty acid... 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) is...

Uric Acid Induces Hepatic Steatosis by Generation of Mitochondrial Oxidative Stress

Science.gov (United States)

Lanaspa, Miguel A.; Sanchez-Lozada, Laura G.; Choi, Yea-Jin; Cicerchi, Christina; Kanbay, Mehmet; Roncal-Jimenez, Carlos A.; Ishimoto, Takuji; Li, Nanxing; Marek, George; Duranay, Murat; Schreiner, George; Rodriguez-Iturbe, Bernardo; Nakagawa, Takahiko; Kang, Duk-Hee; Sautin, Yuri Y.; Johnson, Richard J.

2012-01-01

Metabolic syndrome represents a collection of abnormalities that includes fatty liver, and it currently affects one-third of the United States population and has become a major health concern worldwide. Fructose intake, primarily from added sugars in soft drinks, can induce fatty liver in animals and is epidemiologically associated with nonalcoholic fatty liver disease in humans. Fructose is considered lipogenic due to its ability to generate triglycerides as a direct consequence of the metabolism of the fructose molecule. Here, we show that fructose also stimulates triglyceride synthesis via a purine-degrading pathway that is triggered from the rapid phosphorylation of fructose by fructokinase. Generated AMP enters into the purine degradation pathway through the activation of AMP deaminase resulting in uric acid production and the generation of mitochondrial oxidants. Mitochondrial oxidative stress results in the inhibition of aconitase in the Krebs cycle, resulting in the accumulation of citrate and the stimulation of ATP citrate lyase and fatty-acid synthase leading to de novo lipogeneis. These studies provide new insights into the pathogenesis of hepatic fat accumulation under normal and diseased states. PMID:23035112

Oil-in-water emulsions as a delivery system for n-3 fatty acids in meat products.

Science.gov (United States)

Salminen, Hanna; Herrmann, Kurt; Weiss, Jochen

2013-03-01

The oxidative and physical stabilities of oil-in-water emulsions containing n-3 fatty acids (25 wt.% oil, 2.5 wt.% whey protein, pH 3.0 or pH 6.0), and their subsequent incorporation into meat products were investigated. The physical stability of fish oil emulsions was excellent and neither coalescence nor aggregation occurred during storage. Oxidative stability was better at pH 6.0 compared to pH 3.0 likely due to antioxidative continuous phase proteins. Incorporation of fish oil emulsions into pork sausages led to an increase in oxidation compared to sausages without the added fish oil emulsion. Confocal microscopy of pork sausages with fish oil emulsions revealed that droplets had coalesced in the meat matrix over time which may have contributed to the decreased oxidative stability. Results demonstrate that although interfacial engineering of n-3 fatty acids containing oil-in-water emulsions provides physical and oxidative stability of the base-emulsion, their incorporation into complex meat matrices is a non-trivial undertaking and products may incur changes in quality over time. Copyright © 2012 Elsevier Ltd. All rights reserved.

Influence of pH-control in phosphoric acid treatment of zinc oxide

Energy Technology Data Exchange (ETDEWEB)

Onoda, H., E-mail: onoda@kpu.ac.jp [Department of Informatics and Environmental Sciences, Kyoto Prefectural University (Japan); Chemel, M. [Ecole de Biologie Industrielle, CERGY Cedex (France)

2017-04-15

Zinc oxide is often used as a white pigment for cosmetics; however, it shows photocatalytic activity that causes decomposition of sebum on the skin when exposed to the ultraviolet radiation in sunlight. In this work, zinc oxide was reacted with phosphoric acid at various pH values to synthesize a novel white pigment for cosmetics. The chemical composition, powder properties, photocatalytic activities, colors, and smoothness of these pigments were studied. The obtained materials exhibited X-ray diffraction peaks relating to zinc oxide and phosphate after phosphoric acid treatment. The ratio of zinc phosphate to zinc oxide was estimated from inductively coupled plasma - atomic emission spectroscopy results. Samples treated at pH 4-7 yielded small particles with sub-micrometer sizes. The photocatalytic activity of zinc oxide became lower after phosphoric acid treatment. Samples treated at pH 4-7 showed the same reflectance as zinc oxide in both the ultraviolet and visible ranges. Adjustment of the pH was found to be important in the phosphoric acid treatment of zinc oxide. (author)

Hepatic Fatty Acid Oxidation Restrains Systemic Catabolism during Starvation

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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.

Kinetic and Mechanistic Studies of Oxidation of an Antiallergic Drug with Bromamine-T in Acid and Alkaline Media

Energy Technology Data Exchange (ETDEWEB)

Puttaswamy; Anu Sukhdev [Bangalore Univ., Bangalore (India)

2012-11-15

Cetrizine dihydrochloride (CTZH) is widely used as an anti-allergic drug. Sodium N-bromo-p-toluenesulfonamide or bromamine-T (BAT) is the bromine analogue of chloramine-T (CAT) and is found to be a better oxidizing agent than CAT. In the present research, the kinetics of oxidation of CTZH with BAT in acid and alkaline media was studied at 313 K. The experimental rate laws obtained are: -d[BAT]/dt = k[BAT] [CTZH]{sup 0.80}[H{sup +}]{sup -0.48} in acid medium and -d[BAT]/dt = k[BAT][CTZH]{sup 0.48}[OH{sup -}]{sup 0.52}[PTS]{sup -0.40} in alkaline medium where PTS is p-toluenesulfonamide. Activation parameters and reaction constants were evaluated. The solvent isotope effect was studied using D{sub 2}O. The dielectric effect is positive. The stoichiometry of the reaction was found to be 1:1 and the oxidation products were identified as 4-chlorobenzophenone and (2-piperazin-1-yl-ethoxy)-acetic acid in both media. The rate of oxidation of CTZH is faster in acid medium. Suitable mechanisms and related rate laws have been worked out.

Application of Primary Abatement Technology for Reduction of N2O Emmision in Petrokemija Nitric Acid Production

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Ćosić, L.

2013-01-01

Full Text Available Industrial nitric acid production by oxidation of gaseous ammonia with Ostwald procedure produces an unwanted by-product – colorless nitrous oxide, N2O. As emission of N2O represents a very serious problem due of its huge contribution to global warming, certain measures focused on its maximum reduction should be undertaken. Minimization of N2O emission in nitric acid production can be achieved in different parts of the process flow, depending on the applied available technologies. For the abatement of N2O emissions in Petrokemija's nitric acid production processes from the list of the best available technologies chosen were primary and secondary abatement technologies. The mentioned ensures reduction of N2O by use of improved selective heterogeneous catalysts in the step of gaseous ammonia oxidation. Precious metals in the shape of gauzes are used as selective heterogeneous catalyst in primary technology, while in the case of secondary technology the Fe2 O3 catalyst on Al2O3 support in the shape of spherical pellets is chosen. Shown is the application of primary technology for the abatement of N2O in both nitric acid production facilities and their comparison with classical heterogeneous catalyst and preparation for the installation of secondary selective catalyst. N2O emissions with the application of primary technology in both production facilities were reduced from 12 kg of N2O to 7 kg of N2O per ton of pure HNO3. With the primary reduction in N2O emissions the foundation was established for further reduction with the secondary technology to the final value of 0.7 kg of N2O per ton of pure HNO3, which represents mass concentration in the tail gas below 200 mg m-3 (at n. c.. With the applied technologies for the abatement of N2O emissions in Petrokemija's nitric acid production the future prescribed emission limit value will be satisfied.

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

2016-09-08

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.

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. Copyright © 2016 Elsevier Inc. All rights reserved.

Potential inhibitors from wet oxidation of wheat straw and their effect on ethanol production of Saccharomyces cerevisiae

DEFF Research Database (Denmark)

Klinke, Helene Bendstrup; Olsson, Lisbeth; Thomsen, A.B.

2003-01-01

Alkaline wet oxidation (WO) (using water, 6.5 g/L sodium carbonate and 12 bar oxygen at 195degreesC) was used as pretreatment method for wheat straw (60 g/L), resulting in a hydrolysate and a cellulosic solid fraction. The hydrolysate consisted of soluble hemicellulose (8 g/L), low......-molecular-weight carboxylic acids (3.9 g/L), phenols (0.27 g/L = 1.7 mM) and 2-furoic acid (0.007 g/L). The wet oxidized wheat straw hydrolysate caused no inhibition of ethanol production by Saccharomyces cerevisiae ATCC 96581. Nine phenols and 2-furoic acid, identified to be present in the hydrolysate, were each tested...

Lactic acid production from wheat straw hemicellulose hydrolysate by Lactobacillus pentosus and Lactobacillus brevis

DEFF Research Database (Denmark)

Garde, Arvid; Jonsson, Gunnar Eigil; Schmidt, A. S.

2002-01-01

Lactic acid production by Lactobacillus brevis and Lactobacillus pentosus on a hemicellulose hydrolysate (HH) of wet-oxidized wheat straw was evaluated. The potential of 11-12 g/l fermentable sugars was released from the HH through either enzymatic or acidic pretreatment. Fermentation of added......% of the theoretical maximum yield after enzymatic, or acid treatment of HH, respectively. Individually, neither of the two strains were able to fully utilize the relatively broad spectra of sugars released by the acid and enzyme treatments; however, lactic acid production increased to 95% of the theoretical maximum...... yield by co-inoculation of both strains. Xylulose was the main sugar released after enzymatic treatment of HH with Celluclast(R). Lb. brevis was able to degrade xylobiose, but was unable to assimilate xylulose, whereas Lb. pentosus was able to assimilate xylulose but unable to degrade xylobiose. (C...

Omega-3 fatty acids alter behavioral and oxidative stress parameters in animals subjected to fenproporex administration.

Science.gov (United States)

Model, Camila S; Gomes, Lara M; Scaini, Giselli; Ferreira, Gabriela K; Gonçalves, Cinara L; Rezin, Gislaine T; Steckert, Amanda V; Valvassori, Samira S; Varela, Roger B; Quevedo, João; Streck, Emilio L

2014-03-01

Studies have consistently reported the participation of oxidative stress in bipolar disorder (BD). Evidences indicate that omega-3 (ω3) fatty acids play several important roles in brain development and functioning. Moreover, preclinical and clinical evidence suggests roles for ω3 fatty acids in BD. Considering these evidences, the present study aimed to investigate the effects of ω3 fatty acids on locomotor behavior and oxidative stress parameters (TBARS and protein carbonyl content) in brain of rats subjected to an animal model of mania induced by fenproporex. The fenproporex treatment increased locomotor behavior in saline-treated rats under reversion and prevention model, and ω3 fatty acids prevented fenproporex-related hyperactivity. Moreover, fenproporex increased protein carbonyls in the prefrontal cortex and cerebral cortex, and the administration of ω3 fatty acids reversed this effect. Lipid peroxidation products also are increased in prefrontal cortex, striatum, hippocampus and cerebral after fenproporex administration, but ω3 fatty acids reversed this damage only in the hippocampus. On the other hand, in the prevention model, fenproporex increased carbonyl content only in the cerebral cortex, and administration of ω3 fatty acids prevented this damage. Additionally, the administration of fenproporex resulted in a marked increased of TBARS in the prefrontal cortex, hippocampus, striatum and cerebral cortex, and prevent this damage in the prefrontal cortex, hippocampus and striatum. In conclusion, we are able to demonstrate that fenproporex-induced hyperlocomotion and damage through oxidative stress were prevented by ω3 fatty acids. Thus, the ω3 fatty acids may be important adjuvant therapy of bipolar disorder.

The effect of natural antioxidants on the rate of accumulation of oxidation products in the fat phase of butter cream

Directory of Open Access Journals (Sweden)

M. S. Voronina

2016-01-01

Full Text Available Describes the main finishing prefabricated pastries and cakes-cream. Researched range of cream depending on the fruit components and method of production. Aim: to study the degree of oxidation cream with natural antioxidants from fruits and berries processing products, namely in the form of concentrated juice of fruits and berries. Outlines the process of oxidation of lipids, one of the fundamental processes of loss of quality food products. Describes the action of antioxidants as antioxidants on accumulation intensity concentrations of primary and secondary oxidation products, making the final product unsuitable for the consumer and the bounding its shelf life. Presents the results of a study of the contents of primary and secondary oxidation products in butter cream immediately after cooking, as well as samples, stored for five days with the addition of antioxidants in the form of concentrated juice of fruits and berries in the amount of 2–7% by weight of cream. As a control sample has been used cream with no additives. Quality indicators to characterize the degree of oxidation of the product: acid, peroxide, anizidin and tioburbit number. The study found that adding a concentrated juice of fruits and berries as antioxidant in recipe cream reduces the growth rate of the concentration of free fatty acids on the fifth day, as compared with the reference sample. Adding concentrated juice of fruits and berries slows down the process of dissolution of the fat molecules in fat fraction of cream with the formation of free fatty acids; intensity decay reaction of peroxides and hydroxides slows down and, consequently, decreases the formation of aldehydes, deteriorating the taste and smell of the cream; quantitatively reduced the growth of education malondial′degida.

Preparation and characterization of dialdehyde starch by one-step acid hydrolysis and oxidation.

Science.gov (United States)

Zuo, Yingfeng; Liu, Wenjie; Xiao, Junhua; Zhao, Xing; Zhu, Ying; Wu, Yiqiang

2017-10-01

Dialdehyde starch was prepared by one-step synthesis of acid hydrolysis and oxidation, using corn starch as the raw material, sodium periodate (NaIO 4 ) as the oxidant, and hydrochloric acid (HCl) as the acid solution. The prepared dialdehyde starch was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and gel permeation chromatography (GPC). The results confirmed that oxidation occurred between the starch and NaIO 4 . The acid hydrolysis reaction reduced the molecular weight of starch and effectively improved the aldehyde group contents (92.7%). Scanning electron microscope (SEM) analysis indicated that the average particle size decreased after acid hydrolysis and oxidation reaction. X-ray diffraction (XRD) and thermal gravimetric analyzer (TGA) analysis demonstrated that the crystallinity of the obtained dialdehyde starch showed a downward trend and a decelerated thermal decomposition rate. The starch after acid hydrolysis and oxidation exhibited lower hot paste viscosity and higher reactivity. Copyright © 2017. Published by Elsevier B.V.

Acid-catalyzed kinetics of indium tin oxide etching

Energy Technology Data Exchange (ETDEWEB)

Choi, Jae-Hyeok; Kim, Seong-Oh; Hilton, Diana L. [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); Cho, Nam-Joon, E-mail: njcho@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, 637459 (Singapore)

2014-08-28

We report the kinetic characterization of indium tin oxide (ITO) film etching by chemical treatment in acidic and basic electrolytes. It was observed that film etching increased under more acidic conditions, whereas basic conditions led to minimal etching on the time scale of the experiments. Quartz crystal microbalance was employed in order to track the reaction kinetics as a function of the concentration of hydrochloric acid and accordingly solution pH. Contact angle measurements and atomic force microscopy experiments determined that acid treatment increases surface hydrophilicity and porosity. X-ray photoelectron spectroscopy experiments identified that film etching is primarily caused by dissolution of indium species. A kinetic model was developed to explain the acid-catalyzed dissolution of ITO surfaces, and showed a logarithmic relationship between the rate of dissolution and the concentration of undisassociated hydrochloric acid molecules. Taken together, the findings presented in this work verify the acid-catalyzed kinetics of ITO film dissolution by chemical treatment, and support that the corresponding chemical reactions should be accounted for in ITO film processing applications. - Highlights: • Acidic conditions promoted indium tin oxide (ITO) film etching via dissolution. • Logarithm of the dissolution rate depended linearly on the solution pH. • Acid treatment increased ITO surface hydrophilicity and porosity. • ITO film etching led to preferential dissolution of indium species over tin species.

Microbial Propionic Acid Production

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R. Axayacatl Gonzalez-Garcia

2017-05-01

Full Text Available Propionic acid (propionate is a commercially valuable carboxylic acid produced through microbial fermentation. Propionic acid is mainly used in the food industry but has recently found applications in the cosmetic, plastics and pharmaceutical industries. Propionate can be produced via various metabolic pathways, which can be classified into three major groups: fermentative pathways, biosynthetic pathways, and amino acid catabolic pathways. The current review provides an in-depth description of the major metabolic routes for propionate production from an energy optimization perspective. Biological propionate production is limited by high downstream purification costs which can be addressed if the target yield, productivity and titre can be achieved. Genome shuffling combined with high throughput omics and metabolic engineering is providing new opportunities, and biological propionate production is likely to enter the market in the not so distant future. In order to realise the full potential of metabolic engineering and heterologous expression, however, a greater understanding of metabolic capabilities of the native producers, the fittest producers, is required.

Effect of water content on thermal oxidation of oleic acid investigated by combination of EPR spectroscopy and SPME-GC-MS/MS.

Science.gov (United States)

Chen, Hongjian; Cao, Peirang; Li, Bo; Sun, Dewei; Wang, Yong; Li, Jinwei; Liu, Yuanfa

2017-04-15

Promotion of water to the thermal oxidation of oleic acid was detected by the combination of EPR, SPME-GC-MS/MS and GC. Spin-trapping technique was used to identify and quantify the radical species formed during thermal oxidation of oleic acid by using DMPO as electron spin trap. The most abundant radical species were identified as DMPO-alkyl radical adducts. EPR intensity plateau of the samples with 5% water content was 140% higher than the samples without water. It implies oleic acid samples with high water content had high level of oxidation rates. The proportion of aldehydes of the samples with 2% water content was the maximum about 59.97%. Among the formed products, (E,E)-2,4-decadienal has genotoxic and cytotoxic effects, whose percentage was nearly twice comparing with that of 5-0% water content. This study demonstrated that higher water content in frying systems would contribute to seriously oxidation and degradation of oleic acids. Copyright © 2016 Elsevier Ltd. All rights reserved.

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

Directory of Open Access Journals (Sweden)

M. M. Chim

2017-12-01

Full Text Available Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4 droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5 hydroxyl functionalization product (C5H8O5 and a C4 fragmentation product (C4H6O3. These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from

Formic Acid Oxidation at Platinum-Bismuth Clusters

DEFF Research Database (Denmark)

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

2014-01-01

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....... Catalysts prepared in this way exhibit about 10 times higher activity for formic acid oxidation in comparison to pure Pt, as revealed both by potentiodynamic and quasy-potentiostatic measurements. This high activity is the result of well-balanced ensemble effect induced by Bi-oxide species interrupting Pt...

Impact of Air Frying on Cholesterol and Fatty Acids Oxidation in Sardines: Protective Effects of Aromatic Herbs.

Science.gov (United States)

Ferreira, Fernanda S; Sampaio, Geni R; Keller, Laura M; Sawaya, Alexandra C H F; Chávez, Davy W H; Torres, Elizabeth A F S; Saldanha, Tatiana

2017-12-01

The high temperatures used to fry fish may induce thermo-oxidation of cholesterol, forming cholesterol oxidation products (COPs). COPs have been associated to coronary heart diseases, atherosclerosis, and other chronic diseases. Air fryers are an alternative thermal process technology to fry foods without oil, and are considered a healthier cooking method. This study is the 1st to evaluate the formation of COPs and the degradation of polyunsaturated fatty acids (PUFAs) in air-fried sardine fillets. Furthermore, we evaluated the effect of fresh herbs added as natural antioxidants to sardines subjected to air frying. Parsley (Petroselinum crispum), chives (Allium schoenoprasum L.), and a mixture of both herbs (cheiro-verde) were added in quantities of 0%, 2%, and 4%. Air frying significantly decreased the content of essential PUFAs, and increased the levels of COPs from 61.2 (raw) to 283 μg/g (P addition of 4% of cheiro-verde in air-fried sardines presented the best protective effect against lipid oxidation. Fish is an important source of essential lipids. However, oxidized cholesterol products, which are formed during thermal processing, are potential hazards to human health. Air fryers present an alternative thermal process for frying food without oil, and this method of cooking is considered to be more convenient and healthier This study shows that the air frying increased the formation of cholesterol oxidation products and decreased the essential polyunsaturated fatty acids in sardine fillets. However, the lipid oxidation is significantly reduced by adding fresh herbs, such as parsley (Petroselinum crispum), chives (Allium schoenoprasum L.), or a mixture of both herbs (cheiro-verde) that are natural antioxidants. © 2017 Institute of Food Technologists®.

Oxidative dehydration of glycerol to acrylic acid over vanadium-impregnated zeolite beta

Energy Technology Data Exchange (ETDEWEB)

Pestana, Carolina F.M.; Guerra, Antonio C.O.; Turci, Cassia C. [Universidade Federal do Rio de Janeiro, RJ (Brazil). Inst. de Quimica; Ferreira, Glaucio B. [Universidade Federal Fluminense, Niteroi, RJ (Brazil). Inst. de Quimica; Mota, Claudio J.A., E-mail: cmota@iq.ufrj.br [INCT Energia e Ambiente, Universidade Federal do Rio de Janeiro, RJ (Brazil)

2013-01-15

The oxidative dehydration of glycerol to acrylic acid was studied over vanadium-impregnated zeolite Beta. Catalysts were prepared by wet impregnation of ammonium metavanadate over ammonium-exchanged zeolite Beta, followed by air calcination at 823 K. Impregnation reduced the specific surface area, but did not significantly affected the acidity (Bronsted and Lewis) of the zeolites. The catalytic evaluation was carried out in a fixed bed flow reactor using air as the carrier and injecting glycerol by means of a syringe pump. Acrolein was the main product, with acetaldehyde and hydroxy-acetone (acetol) being also formed. Acrylic acid was formed with approximately 25% selectivity at 548 K over the impregnated zeolites. The result can be explained by XPS (X-ray photoelectron spectroscopy) measurements, which indicated a good dispersion of the vanadium inside the pores. (author)

Oxidative dehydration of glycerol to acrylic acid over vanadium-impregnated zeolite beta

International Nuclear Information System (INIS)

Pestana, Carolina F.M.; Guerra, Antonio C.O.; Turci, Cassia C.

2013-01-01

The oxidative dehydration of glycerol to acrylic acid was studied over vanadium-impregnated zeolite Beta. Catalysts were prepared by wet impregnation of ammonium metavanadate over ammonium-exchanged zeolite Beta, followed by air calcination at 823 K. Impregnation reduced the specific surface area, but did not significantly affected the acidity (Bronsted and Lewis) of the zeolites. The catalytic evaluation was carried out in a fixed bed flow reactor using air as the carrier and injecting glycerol by means of a syringe pump. Acrolein was the main product, with acetaldehyde and hydroxy-acetone (acetol) being also formed. Acrylic acid was formed with approximately 25% selectivity at 548 K over the impregnated zeolites. The result can be explained by XPS (X-ray photoelectron spectroscopy) measurements, which indicated a good dispersion of the vanadium inside the pores. (author)

Clarithromycin, trimethoprim, and penicillin and oxidative nucleic acid modifications in humans

DEFF Research Database (Denmark)

Larsen, Emil List; Cejvanovic, Vanja; Kjaer, Laura Kofoed

2017-01-01

, phenoxymethylpenicillin (penicillin V), or placebo. Oxidative modifications were measured as 24-h urinary excretion of 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxodG) and 8-oxo-7,8-dihydroguanosine (8-oxoGuo), and plasma levels of malondialdehyde before and after treatment as a measurement of DNA oxidation, RNA oxidation.......7% (95% CI: 5.8–37.6%), but did not influence urinary excretion of 8-oxoGuo. Penicillin V did not influence urinary excretion of 8-oxodG or 8-oxoGuo. None of the antibiotic drugs influenced plasma levels of malondialdehyde. Conclusion Clarithromycin significantly increases oxidative nucleic acid...... modifications. Increased oxidative modifications might explain some of clarithromycin's known adverse reactions. Trimethoprim significantly lowers DNA oxidation but not RNA oxidation. Penicillin V had no effect on oxidative nucleic acid modifications....

Identification of the Products of Oxidation of Quercetin by Air Oxygenat Ambient Temperature

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Viktor A Utsal

2007-03-01

Full Text Available Oxidation of quercetin by air oxygen takes place in water and aqueous ethanol solutions under mild conditions, namely in moderately-basic media (pH ∼ 8-10 at ambient temperature and in the absence of any radical initiators, without enzymatic catalysis or irradiation of the reaction media by light. The principal reaction products are typical of other oxidative degradation processes of quercetin, namely 3,4-dihydroxy-benzoic (proto-catechuic and 2,4,6-trihydroxybenzoic (phloroglucinic acids, as well as the decarboxylation product of the latter – 1,3,5-trihydroxybenzene (phloroglucinol. In accordance with the literature data, this process involves the cleavage of the γ-pyrone fragment (ring C of the quercetin molecule by oxygen, with primary formation of 4,6-dihydroxy-2-(3,4-dihydroxybenzoyloxybenzoic acid (depside. However under such mild conditions the accepted mechanism of this reaction (oxidative decarbonylation with formation of carbon monoxide, CO should be reconsidered as preferably an oxidative decarboxylation with formation of carbon dioxide, CO2. Direct head-space analysis of the gaseous components formed during quercetin oxidation in aqueous solution at ambient temperature indicates that the ratio of carbon dioxide/carbon monoxide in the gas phase after acidification of the reaction media is ca. 96:4 %. Oxidation under these mild conditions is typical for other flavonols having OH groups at C3 (e.g., kaempferol, but it is completely suppressed if this hydroxyl group is substituted by a glycoside fragment (as in rutin, or a methyl substituent. An alternative oxidation mechanism involving the direct cleavage of the C2-C3 bond in the diketo-tautomer of quercetin is proposed.

Spectra investigation on surface characteristics of graphene oxide nanosheets treated with tartaric, malic and oxalic acids.

Science.gov (United States)

Teng, Xiyao; Yan, Manqing; Bi, Hong

2014-01-24

The surface characteristics of graphene oxide nanosheets (GO) treated respectively with tartaric acid, malic acid and oxalic acid, have been investigated by mainly using optical spectroscopic methods including Fourier transform infrared spectroscopy (FT-IR), Ultraviolet-visible (UV-Vis) absorption and Raman spectroscopy. Additionally, the electrochemical property of the products has also been studied. The data revealed that oxygen-containing groups such as OH, COOH and CO on the GO surface have been almost removed and thus reduced graphene oxide nanosheets (RGN) were obtained. Interestingly, the number of sp(2) domains of RGN increases as treated by tartaric acidacidacid whereas the steric hindrance (SH) decreases and the ionization constant (IC) differs among these three acids. Furthermore, the specific capacitances (Cs) of GO have been greatly promoted from 2.4 F g(-1) to 100.8, 112.4, and 147 F g(-1) after treated with tartaric, malic and oxalic acids, respectively. This finding agrees well with the spectra result of the tendency of surface conjugated degree alteration. We claim that the difference in both SH and IC among these acids is the main reason for the diverse surface characteristics as well as the improved Cs of the RGN. Copyright © 2013 Elsevier B.V. All rights reserved.

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....

Ferrous Iron Oxidation by Thiobacillus ferrooxidans: Inhibition with Benzoic Acid, Sorbic Acid, and Sodium Lauryl Sulfate

OpenAIRE

Onysko, Steven J.; Kleinmann, Robert L. P.; Erickson, Patricia M.

1984-01-01

Benzoic acid, sorbic acid, and sodium lauryl sulfate at low concentrations (5 to 10 mg/liter) each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of Thiobacillus ferrooxidans. The rate of chemical oxidation of ferrous iron in low-pH, sterile batch reactors was not substantially affected at the tested concentrations (5 to 50 mg/liter) of any of the compounds.

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. Copyright © 2011 Elsevier Ltd. All rights reserved.

Oxidation of indole-3-acetic acid to oxindole-3-acetic acid by etiolated and green corn tissues

International Nuclear Information System (INIS)

Reinecke, D.

1989-01-01

Etiolated corn tissues oxidase indole-3-acetic acid (IAA) to oxindole-3-acetic acid (OxIAA). This oxidation results in loss of auxin activity and may plant a role in regulating IAA-stimulated growth. The enzyme has been partially purified and characterized and shown to require O 2 , and a heat-stable lipid-soluble corn factor which can be replaced by linolenic or linoleic acids in the oxidation of IAA. Corn oil was tested as a cofactor in the IAA oxidation reaction. Corn oil stimulated enzyme activity by 30% while trilinolein was inactive. The capacity of green tissue to oxidize IAA was examined by incubating leaf sections from 2 week old light-grown corn seedlings with 14 C-IAA. OxIAA and IAA were separated from other IAA metabolites on a 3 ml anion exchange column. Of the IAA taken up by the sections, 13% was oxidized to OxIAA. This is the first evidence that green tissue of corn may also regulate IAA levels by oxidizing IAA to OxIAA

Effects of garlic extract on color, lipid oxidation and oxidative breakdown products in raw ground beef during refrigerated storage

Directory of Open Access Journals (Sweden)

XINZHUANG ZHANG

2016-03-01

Full Text Available The study aims to investigate the effects of garlic extracts on color, lipid oxidation, and oxidative breakdown products in raw ground beef during refrigerated storage. The two treatments were:control group (C, with no addition and experiment group (D, 50 mg garlic extracts added to 100 g beef. Adding garlic extracts significant increased a* value (PA ≤ 0.05, and significant decreased TBARS and PV values (PA ≤ 0.05. The pH and –SH value of D group had a decreasing tendency (PA=0.0522 and an increasing tendency (PA=0.0636 respectively compared to C group. Garlic extracts protected phospholipids, fatty acids and polypeptides from oxidation. The results indicatethat garlic extracts have the antioxidant activity, helping maintain the meat color, inhibiting lipid oxidation and protein degradation of raw ground beef during refrigerated storage.

Fatty acids oxidation and alternative energy sources detected in Taenia crassiceps cysticerci after host treatment with antihelminthic drugs.

Science.gov (United States)

Fraga, Carolina Miguel; Costa, Tatiane Luiza; Bezerra, José Clecildo Barreto; de Souza Lino Junior, Ruy; Vinaud, Marina Clare

2012-05-01

Human cysticercosis caused by Taenia crassiceps is rare however it is considered of zoonotic risk. The treatment of the infected patients was successful when using albendazole or praziquantel. The active forms of albendazole inhibit the glucose uptake and the active forms of praziquantel alter glycogen levels and nutrients absorption. The aim of this study was to analyze the production of organic acids that indicate the oxidation of fatty acids and the use of alternative energy sources from T. crassiceps cysticerci removed from the peritoneal cavity of mice treated with low dosages of albendazole (5.75 and 11.5mg/kg) or praziquantel (3.83 and 7.67 mg/kg). The beta-hydroxibutyrate production was higher by the larval stage cysticerci in all treated groups and the propionate production was higher in final stage cysticerci treated with 11.5mg/kg of albendazole when compared to the control group. The larval stages of cysticerci from the groups treated with 5.75 mg/kg of albendazole and 3.83 mg/kg of praziquantel produced more urea than the initial and final stages which indicate amino acids breakdown. We conclude that it was possible to detect the fatty acid oxidation and amino acids breakdown which indicate the use of alternative energy production sources as the used dosages only cause a partial blockage of the glucose uptake and leads to metabolic alterations in the cysticerci. The metabolic behavior observed after host treatment was different from former descriptions of the in vitro one which indicates great host-parasite interaction. Copyright © 2012 Elsevier Inc. All rights reserved.

Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

Energy Technology Data Exchange (ETDEWEB)

Ji, Yuefei [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China); Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)

2016-08-05

Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

Energy Technology Data Exchange (ETDEWEB)

Johnson, Gregory R.; Bell, Alexis T. (LBNL); (UCB)

2016-06-17

Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH₄ and increase the selectivity toward C₅₊ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becoming insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C₅₊ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and

Phytanic acid alpha-oxidation: decarboxylation of 2-hydroxyphytanoyl-CoA to pristanic acid in human liver

NARCIS (Netherlands)

Verhoeven, N. M.; Wanders, R. J.; Schor, D. S.; Jansen, G. A.; Jakobs, C.

1997-01-01

The degradation of the first intermediate in the alpha-oxidation of phytanic acid, 2-hydroxyphytanoyl-CoA, was investigated. Human liver homogenates were incubated with 2-hydroxyphytanoyl-CoA or 2-hydroxyphytanic acid, after which formation of 2-ketophytanic acid and pristanic acid were studied.

Oxidative stability during storage of fish oil from filleting by-products of rainbow trout (Oncorhynchus mykiss) is largely independent of the processing and production temperature

DEFF Research Database (Denmark)

Honold, Philipp; Nouard, Marie-Louise; Jacobsen, Charlotte

2016-01-01

Rainbow trout (Oncorhynchus mykiss) is the main fish species produced in Danish fresh water farming. Large amounts of fileting by-products like heads, bones, tails (HBT), and intestines are produced when rainbow trout is processed to smoked rainbow trout filets. The filleting by-products can...... be used to produce high quality fish oil. In this study, the oxidative stability of fish oil produced from filleting by-products was evaluated. The oil was produced from conventional or organic fish (low and high omega-3 fatty acid content) at different temperatures (70 and 90°C). The oxidative stability...

Relative levels of dietary EPA and DHA impact gastric oxidation and essential fatty acid uptake.

Science.gov (United States)

Dasilva, Gabriel; Boller, Matthew; Medina, Isabel; Storch, Judith

2018-05-01

Previous research showed that increasing the proportion of docosahexaenoic acid (DHA) in marine lipid supplements significantly reduces associated health benefits compared with balanced eicosapentaenoic acid (EPA):DHA supplementation Dasilva et al., 2015 [1]. It was therefore hypothesized that the EPA and DHA molecules might have differential resistance to oxidation during gastric digestion and that the oxidation level achieved could be inversely correlated with intestinal absorption and, hence, with the resultant health benefits. Accordingly, we tested this proposed mechanism of action by investigating the degree of oxidation in the stomach, and the levels of bioaccessible lipids, of varying molar proportions of DHA and EPA (2:1, 1:1 and 1:2) using the dynamic gastrointestinal tract model TIM-1. In addition, small intestine enterocyte absorption and metabolism were simulated by Caco-2 cell monolayers that were incubated with these same varying proportions of DHA and EPA, and comparing oxidized and nonoxidized polyunsaturated fatty acids (PUFAs). The results show an inverse correlation between lipid oxidation products in the stomach and the levels of bioaccessible lipids. The balanced 1:1 EPA:DHA diet resulted in lower oxidation of PUFAs during stomach digestion relative to the other ratios tested. Finally, cell-based studies showed significantly lower assimilation of oxidized EPA and DHA substrates compared to nonoxidized PUFAs, as well as significant differences between the net uptake of EPA and DHA. Overall, the present work suggests that the correct design of diets and/or supplements containing marine lipids can strongly influence the stability and bioaccessibility of PUFAs during gastrointestinal digestion and subsequent absorption. This could modulate their health benefits related with inflammation, oxidative stress and metabolic disorders. Copyright © 2017 Elsevier Inc. All rights reserved.

Carbohydrate metabolism during prolonged exercise and recovery: interactions between pyruvate dehydrogenase, fatty acids, and amino acids

DEFF Research Database (Denmark)

Mourtzakis, Marina; Saltin, B.; Graham, T.

2006-01-01

During prolonged exercise, carbohydrate oxidation may result from decreased pyruvate production and increased fatty acid supply and ultimately lead to reduced pyruvate dehydrogenase (PDH) activity. Pyruvate also interacts with the amino acids alanine, glutamine, and glutamate, whereby the decline...... amino acid taken up during exercise and recovery. Alanine and glutamine were also associated...... with pyruvate metabolism, and they comprised 68% of total amino-acid release during exercise and recovery. Thus reduced pyruvate production was primarily associated with reduced carbohydrate oxidation, whereas the greatest production of pyruvate was related to glutamate, glutamine, and alanine metabolism...

Effect of acid on the aggregation of poly(ethylene xide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers.

Science.gov (United States)

Yang, Bin; Guo, Chen; Chen, Shu; Ma, Junhe; Wang, Jing; Liang, Xiangfeng; Zheng, Lily; Liu, Huizhou

2006-11-23

The acid effect on the aggregation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers EO(20)PO(70)EO(20) has been investigated by transmission electron microscopy (TEM), particle size analyzer (PSA), Fourier transformed infrared, and fluorescence spectroscopy. The critical micellization temperature for Pluronic P123 in different HCl aqueous solutions increases with the increase of acid concentration. Additionally, the hydrolysis degradation of PEO blocks is observed in strong acid concentrations at higher temperatures. When the acid concentration is low, TEM and PSA show the increase of the micelle mean diameter and the decrease of the micelle polydispersity at room temperature, which demonstrate the extension of EO corona and tendency of uniform micelle size because of the charge repulsion. When under strong acid conditions, the aggregation of micelles through the protonated water bridges was observed.

Metaproteomics and ultrastructure characterization of Komagataeibacter spp. involved in high-acid spirit vinegar production.

Science.gov (United States)

Andrés-Barrao, Cristina; Saad, Maged M; Cabello Ferrete, Elena; Bravo, Daniel; Chappuis, Marie-Luise; Ortega Pérez, Ruben; Junier, Pilar; Perret, Xavier; Barja, François

2016-05-01

Acetic acid bacteria (AAB) are widespread microorganisms in nature, extensively used in food industry to transform alcohols and sugar alcohols into their corresponding organic acids. Specialized strains are used in the production of vinegar through the oxidative transformation of ethanol into acetic acid. The main AAB involved in the production of high-acid vinegars using the submerged fermentation method belong to the genus Komagataeibacter, characterized by their higher ADH stability and activity, and higher acetic acid resistance (15-20%), compared to other AAB. In this work, the bacteria involved in the production of high-acid spirit vinegar through a spontaneous acetic acid fermentation process was studied. The analysis using a culture-independent approach revealed a homogeneous bacterial population involved in the process, identified as Komagataeibacter spp. Differentially expressed proteins during acetic acid fermentation were investigated by using 2D-DIGE and mass spectrometry. Most of these proteins were functionally related to stress response, the TCA cycle and different metabolic processes. In addition, scanning and transmission electron microscopy and specific staining of polysaccharide SDS-PAGE gels confirmed that Komagataeibacter spp. lacked the characteristic polysaccharide layer surrounding the outer membrane that has been previously reported to have an important role in acetic acid resistance in the genus Acetobacter. Copyright © 2015 Elsevier Ltd. All rights reserved.

Potential of Rhodococcus strains for biotechnological vanillin production from ferulic acid and eugenol.

Science.gov (United States)

Plaggenborg, Rainer; Overhage, Jörg; Loos, Andrea; Archer, John A C; Lessard, Philip; Sinskey, Anthony J; Steinbüchel, Alexander; Priefert, Horst

2006-10-01

The potential of two Rhodococcus strains for biotechnological vanillin production from ferulic acid and eugenol was investigated. Genome sequence data of Rhodococcus sp. I24 suggested a coenzyme A-dependent, non-beta-oxidative pathway for ferulic acid bioconversion, which involves feruloyl-CoA synthetase (Fcs), enoyl-CoA hydratase/aldolase (Ech), and vanillin dehydrogenase (Vdh). This pathway was proven for Rhodococcus opacus PD630 by physiological characterization of knockout mutants. However, expression and functional characterization of corresponding structural genes from I24 suggested that degradation of ferulic acid in this strain proceeds via a beta-oxidative pathway. The vanillin precursor eugenol facilitated growth of I24 but not of PD630. Coniferyl aldehyde was an intermediate of eugenol degradation by I24. Since the genome sequence of I24 is devoid of eugenol hydroxylase homologous genes (ehyAB), eugenol bioconversion is most probably initiated by a new step in this bacterium. To establish eugenol bioconversion in PD630, the vanillyl alcohol oxidase gene (vaoA) from Penicillium simplicissimum CBS 170.90 was expressed in PD630 together with coniferyl alcohol dehydrogenase (calA) and coniferyl aldehyde dehydrogenase (calB) genes from Pseudomonas sp. HR199. The recombinant strain converted eugenol to ferulic acid. The obtained data suggest that genetically engineered strains of I24 and PD630 are suitable candidates for vanillin production from eugenol.

Dietary phenolic acids reverse insulin resistance, hyperglycaemia, dyslipidaemia, inflammation and oxidative stress in high-fructose diet-induced metabolic syndrome rats.

Science.gov (United States)

Ibitoye, Oluwayemisi B; Ajiboye, Taofeek O

2017-12-20

This study investigated the influence of caffeic, ferulic, gallic and protocatechuic acids on high-fructose diet-induced metabolic syndrome in rats. Oral administration of the phenolic acids significantly reversed high-fructose diet-mediated increase in body mass index and blood glucose. Furthermore, phenolic acids restored high-fructose diet-mediated alterations in metabolic hormones (insulin, leptin and adiponectin). Similarly, elevated tumour necrosis factor-α, interleukin-6 and -8 were significantly lowered. Administration of phenolic acids restored High-fructose diet-mediated increase in the levels of lipid parameters and indices of atherosclerosis, cardiac and cardiovascular diseases. High-fructose diet-mediated decrease in activities of antioxidant enzymes (superoxide dismutase, catalase, glutathione peroxidase, glutathione reductase and glucose 6-phosphate dehydrogenase) and increase in oxidative stress biomarkers (reduced glutathione, lipid peroxidation products, protein oxidation and fragmented DNA) were significantly restored by the phenolic acids. The result of this study shows protective influence of caffeic acid, ferulic acid, gallic acid and protocatechuic acid in high-fructose diet-induced metabolic syndrome.

Kinetics of the oxidative hydroxylation of sodium hypophosphite in the presence of copper (II chloride modified by humic (fulvo- acid

Directory of Open Access Journals (Sweden)

Zhaksyntay Kairbekov

2012-12-01

Full Text Available It was established that in soft conditions (50-70oC, PO2 = 1 atm sodium hypophosphite effectively is oxidized by oxygen in water solutions of copper(II chloride  to give mainly a phosphorous acid. Humic (fulvo- acid was extracted from brown coal of domestic deposit Kiyakty. For determination of optimum parameters of fulvo-acid extraction the laboratory experiments were carried out using the method of experiment planning. The kinetics, the intermediate and final products, optimal conditions of new catalytic reaction of NaH2PO2 oxidation by oxygen in water solution were defined by kinetics, volumometry, redox-potentiometry and a titration.

Ferrous Iron Oxidation by Thiobacillus ferrooxidans: Inhibition with Benzoic Acid, Sorbic Acid, and Sodium Lauryl Sulfate

Science.gov (United States)

Onysko, Steven J.; Kleinmann, Robert L. P.; Erickson, Patricia M.

1984-01-01

Benzoic acid, sorbic acid, and sodium lauryl sulfate at low concentrations (5 to 10 mg/liter) each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of Thiobacillus ferrooxidans. The rate of chemical oxidation of ferrous iron in low-pH, sterile batch reactors was not substantially affected at the tested concentrations (5 to 50 mg/liter) of any of the compounds. PMID:16346592

Lipid oxidation. Part 2. Oxidation products of olive oil methyl esters.

Science.gov (United States)

Pokorný, J; Tài, P; Parízková, H; Smidrkalová, E; El-Tarras, M F; Janícek, G

1976-01-01

Olive oil was converted into methyl esters which were autoxidized at 60 degrees C. The composition of oxidized products was determined by the comparison of infrared spectra and NMR spectra of the original and acetylated samples, the sample reduced with potassium iodide and the acetylated reduced sample. Oxidized products were separated by preparative thin layer chromatography on silica gel and characterized by selective detection and by infrared spectrometry of the fractions. The oxidation products consisted of hydroperoxido butyl oleate, substituted hydroperoxides, mono- and disubstituted monomeric derivatives and a small amount of oligomers.

Studies of Tc oxidation states in humic acid solutions

International Nuclear Information System (INIS)

Wang Bo; Liu Dejun; Yao Jun

2011-01-01

The oxidation state of Tc is an important aspect of the speciation in groundwater which contained organic substances due to it control the precipitation, complexation, sorption and colloid formation behavior of the Tc under HWL geological disposal conditions. In present work, the oxidation states of Tc were investigated using the LaCl 3 coagulation method and solution extraction method in aqueous solutions in which the humic acid concentration range is from 0 to 20 mg/L and the Tc (VII) concentration is about 10 -8 mol/L. The radiocounting of 99 Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99 Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl 3 coagulation method was carried out for the investigation of Tc oxidation states in humic acid aqueous systems at about pH 8. The tetraphenylarsonium chloride (TPA)-chloroform extraction method was used also simultaneously to investigation the concentrations of Tc (IV) and Tc (VII) for the availability of the LaCl 3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl 3 precipitation method. These two experimental results demonstrated that Tc (VII) is very stable in the Tc (VII)-humic acid system during a 350 days experimental period, and the Tc (IV) concentrations are very lower, that is indicate that there didn't oxidizing reactions between the Fluka humic acid and Tc (VII) in aqueous solutions under anaerobic conditions. That means the presence of humic acids even in anaerobic groundwater is disadvantage for the retardance of radionuclides. (authors)

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

International Nuclear Information System (INIS)

Hsieh, Chien-Te; Hsiao, Han-Tsung; Tzou, Dong-Ying; Yu, Po-Yuan; Chen, Po-Yen; Jang, Bi-Sheng

2015-01-01

Herein reported is an atomic layer deposition (ALD) process of platinum (Pt) from (methylcyclopentadienyl) trimethylplatinum (MeCpPtMe 3 ) and oxygen (O 2 ) for synthesizing the Pt electrocatalysts toward methanol and formic acid oxidation. The as-synthesized Pt catalysts are thermally reduced in 5 vol% H 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 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 ads and Pt–(OH) 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

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Production of oceanic nitrous oxide by ammonia-oxidizing archaea

Directory of Open Access Journals (Sweden)

C. R. Löscher

2012-07-01

Full Text Available The recent finding that microbial ammonia oxidation in the ocean is performed by archaea to a greater extent than by bacteria has drastically changed the view on oceanic nitrification. The numerical dominance of archaeal ammonia-oxidizers (AOA over their bacterial counterparts (AOB in large parts of the ocean leads to the hypothesis that AOA rather than AOB could be the key organisms for the oceanic production of the strong greenhouse gas nitrous oxide (N₂O that occurs as a by-product of nitrification. Very recently, enrichment cultures of marine ammonia-oxidizing archaea have been reported to produce N₂O.

Here, we demonstrate that archaeal ammonia monooxygenase genes (amoA were detectable throughout the water column of the eastern tropical North Atlantic (ETNA and eastern tropical South Pacific (ETSP Oceans. Particularly in the ETNA, comparable patterns of abundance and expression of archaeal amoA genes and N₂O co-occurred in the oxygen minimum, whereas the abundances of bacterial amoA genes were negligible. Moreover, selective inhibition of archaea in seawater incubations from the ETNA decreased the N₂O production significantly. In studies with the only cultivated marine archaeal ammonia-oxidizer Nitrosopumilus maritimus SCM1, we provide the first direct evidence for N₂O production in a pure culture of AOA, excluding the involvement of other microorganisms as possibly present in enrichments. N. maritimus showed high N₂O production rates under low oxygen concentrations comparable to concentrations existing in the oxycline of the ETNA, whereas the N₂O production from two AOB cultures was comparably low under similar conditions. Based on our findings, we hypothesize that the production of N₂O in tropical ocean areas results mainly from archaeal nitrification and will be affected by the predicted decrease in dissolved

The oxidation of uranium(IV) ions by nitrous acid in 30% tri-butyl phosphate

International Nuclear Information System (INIS)

Koltunov, V.S.; Marchenko, V.I.; Savilova, O.A.; Dvoeglazov, K.N.; Taylor, R.J.

2004-01-01

The kinetics of the oxidation of U(IV) ions by nitrous acid in a 30% TBP solution have been determined. The rate equation was found to be: - d[U(IV)] / dt = k 2a [U(IV)][HNO 2 ][HNO 3 ][H 2 O] / [HNO 3 ] 2 + β 3 [HNO 3 ][H 2 O] + β 4 [H 2 O] 2 , where, k 2a = 0.405 ± 0.055 M -1 min -1 at 55 C (β 3 ∼ 0.08; β 4 ∼ 0.007) and the activation energy was E = 112 ± 17 kJ mol -1 . The reaction mechanism appeared to involve interaction with the 1 st hydrolysis product of U(IV)-UOH 3+ . The data is compared with a previous study of the nitric acid oxidation of U(IV) in 30% TBP. This reaction is autocatalytic due to the formation of nitrous acid during the reaction. The kinetics of the decomposition of HNO 2 in 30% TBP (in the absence of U(IV)) have also been reported. (orig.)

Simple quantification of surface carboxylic acids on chemically oxidized multi-walled carbon nanotubes

Science.gov (United States)

Gong, Hyejin; Kim, Seong-Taek; Lee, Jong Doo; Yim, Sanggyu

2013-02-01

The surface of multi-walled carbon nanotube (MWCNT) was chemically oxidized using nitric acid and sulfuric-nitric acid mixtures. Thermogravimetric analysis, transmission electron microscopy and infrared spectroscopy revealed that the use of acid mixtures led to higher degree of oxidation. More quantitative identification of surface carboxylic acids was carried out using X-ray photoelectron spectroscopy (XPS) and acid-base titration. However, these techniques are costly and require very long analysis times to promptly respond to the extent of the reaction. We propose a much simpler method using pH measurements and pre-determined pKa value in order to estimate the concentration of carboxylic acids on the oxidized MWCNT surfaces. The results from this technique were consistent with those obtained from XPS and titration, and it is expected that this simple quantification method can provide a cheap and fast way to monitor and control the oxidation reaction of MWCNT.

Photo-oxidation of gaseous ethanol on photocatalyst prepared by acid leaching of titanium oxide/hydroxyapatite composite

International Nuclear Information System (INIS)

Ono, Y.; Rachi, T.; Yokouchi, M.; Kamimoto, Y.; Nakajima, A.; Okada, K.

2013-01-01

Highlights: ► Photocatalyst powder was prepared by acid leaching of TiO 2 /apatite composite. ► The photocatalytic activity was evaluated from in situ FT-IR study using ethanol. ► Apatite in the composite had positive effect for the photo-oxidation of ethanol. ► The enhanced oxidation rate was explained by the difference in deactivation rate. - Abstract: Highly active photocatalysts were synthesized by leaching of heat-treated titanium dioxide (TiO 2 )/hydroxyapatite (HAp) powder with hydrochloric acid at 0.25, 0.50, 0.75 mol/l, and their photocatalytic activities were evaluated from in situ Fourier transform infrared (FT-IR) study of photo-oxidation of gaseous ethanol. By changing the acid concentration, the TiO 2 /HAp composite had different atomic ratios of Ca/Ti (0.0–2.8) and P/Ti (0.3–2.1). It was found that phosphate group remained on the surface of TiO 2 particle even in the sample treated with concentrated acid (0.75 mol/l). These acid-treated samples showed higher rates for ethanol photo-oxidation than the commercial TiO 2 powder, Degussa P25. The highest rate was obtained in the TiO 2 /HAp composite treated with the dilute (0.25 mol/l) acid in spite of its low content of TiO 2 photocatalyst. This enhanced photocatalytic activity was attributed to the result that the deactivation with repeated injections of ethanol gas was suppressed in the TiO 2 /HAp composites compared with the TiO 2 powders

N2O production pathways in the subtropical acid forest soils in China

International Nuclear Information System (INIS)

Zhang Jinbo; Cai Zucong; Zhu Tongbin

2011-01-01

To date, N 2 O production pathways are poorly understood in the humid subtropical and tropical forest soils. A 15 N-tracing experiment was carried out under controlled laboratory conditions to investigate the processes responsible for N 2 O production in four subtropical acid forest soils (pH 2 O emission in the subtropical acid forest soils, being responsible for 56.1%, 53.5%, 54.4%, and 55.2% of N 2 O production, in the GC, GS, GB, and TC soils, respectively, under aerobic conditions (40%-52%WFPS). The heterotrophic nitrification (recalcitrant organic N oxidation) accounted for 27.3%-41.8% of N 2 O production, while the contribution of autotrophic nitrification was little in the studied subtropical acid forest soils. The ratios of N 2 O-N emission from total nitrification (heterotrophic+autotrophic nitrification) were higher than those in most previous references. The soil with the lowest pH and highest organic-C content (GB) had the highest ratio (1.63%), suggesting that soil pH-organic matter interactions may exist and affect N 2 O product ratios from nitrification. The ratio of N 2 O-N emission from heterotrophic nitrification varied from 0.02% to 25.4% due to soil pH and organic matter. Results are valuable in the accurate modeling of N2O production in the subtropical acid forest soils and global budget. - Highlights: → We studied N 2 O production pathways in subtropical acid forest soil under aerobic conditions. → Denitrification was the main source of N 2 O production in subtropical acid forest soils. → Heterotrophic nitrification accounted for 27.3%-41.8% of N 2 O production. → While, contribution of autotrophic nitrification to N 2 O production was little. → Ratios of N 2 O-N emission from nitrification were higher than those in most previous references.

Nitrous Oxide Production by Abundant Benthic Macrofauna

DEFF Research Database (Denmark)

Stief, Peter; Schramm, Andreas

of the short-term metabolic induction of gut denitrification is the preferential production of nitrous oxide rather than dinitrogen. On a large scale, gut denitrification in, for instance, Chironomus plumosus larvae can increase the overall nitrous oxide emission of lake sediment by a factor of eight. We...... screened more than 20 macrofauna species for nitrous oxide production and identified filter-feeders and deposit-feeders that occur ubiquitously and at high abundance (e.g., chironomids, ephemeropterans, snails, and mussels) as the most important emitters of nitrous oxide. In contrast, predatory species...... that do not ingest large quantities of microorganisms produced insignificant amounts of nitrous oxide. Ephemera danica, a very abundant mayfly larva, was monitored monthly in a nitrate-polluted stream. Nitrous oxide production by this filter-feeder was highly dependent on nitrate availability...

Preparation and use of nitrogen (2) oxide of special purity for production of oxygen and nitrogen isotopes

International Nuclear Information System (INIS)

Polevoj, A.S.

1989-01-01

Problems related with production of oxygen and nitrogen isotopes by means of low-temperature rectification of nitrogen (2) oxide are analyzed. Special attention, in particular, is payed to the techniques of synthesis and high purification of initial NO, utilization of waste flows formed during isotope separation. Ways to affect the initial isotope composition of nitrogen oxide and the rate of its homogeneous-isotope exchange, which provide for possibility of simultaneous production of oxygen and nitrogen isotopes by means of NO rectification, are considered. Description of a new technique for high purification of nitrogen oxide, prepared at decomposition of nitric acid by sulfurous anhydride, suggested by the author is presented

Enhancing lipid productivity of Chlorella vulgaris using oxidative stress by TiO2 nanoparticles

International Nuclear Information System (INIS)

Kang, Nam Kyu; Lee, Bongsoo; Choi, Gang-Guk; Moon, Myounghoon; Park, Min S.; Yang, Ji-Won; Lim, JitKang

2014-01-01

Ability to increase the lipid production in microalgae is one of the heavily sought-after ideas to improve the economic feasibility of microalgae-derived transportation fuels for commercial applications. We used the oxidative stress by TiO 2 nanoparticles, a well-known photocatalyst, to induce lipid production in microalgae. Chlorella vulgaris UTEX 265 was cultivated under various concentrations of TiO 2 ranging from 0.1 to 5 g/L under UV-A illumination. Maximum specific growth rate was affected in responding to TiO 2 concentrations. In the presence of UV-A, chlorophyll concentration was decreased at the highest concentration of TiO 2 (5 g/L TiO 2 ) by oxidative stress. The fatty acid methyl ester (FAME) composition analysis suggested that oxidative stress causes the accumulation and decomposition of lipids. The highest FAME productivity was 18.2 g/L/d under low concentrations of TiO 2 (0.1 g/L) and a short induction time (two days). The controlled condition of TiO 2 /UV-A inducing oxidative stress (0.1 g/L TiO 2 and two days induction) could be used to increase the lipid productivity of C. vulgaris UTEX 265. Our results show the possibility of modulating the lipid induction process through oxidative stress with TiO 2 /UV-A

Relevance of Alternative Routes of Kynurenic Acid Production in the Brain

Directory of Open Access Journals (Sweden)

L. A. Ramos-Chávez

2018-01-01

Full Text Available The catabolism of tryptophan has gained great importance in recent years due to the fact that the metabolites produced during this process, with neuroactive and redox properties, are involved in physiological and pathological events. One of these metabolites is kynurenic acid (KYNA, which is considered as a neuromodulator since it can interact with NMDA, nicotinic, and GPR35 receptors among others, modulating the release of neurotransmitters as glutamate, dopamine, and acetylcholine. Kynureninate production is attributed to kynurenine aminotransferases. However, in some physiological and pathological conditions, its high production cannot be explained just with kynurenine aminotransferases. This review focuses on the alternative mechanism whereby KYNA can be produced, either from D-amino acids or by means of other enzymes as D-amino acid oxidase or by the participation of free radicals. It is important to mention that an increase in KYNA levels in processes as brain development, aging, neurodegenerative diseases, and psychiatric disorders, which share common factors as oxidative stress, inflammation, immune response activation, and participation of gut microbiota that can also be related with the alternative routes of KYNA production, has been observed.

β-oxidation and rapid metabolism, but not uptake regulate brain eicosapentaenoic acid levels.

Science.gov (United States)

Chen, Chuck T; Bazinet, Richard P

2015-01-01

The brain has a unique polyunsaturated fatty acid composition, with high levels of arachidonic and docosahexaenoic acids (DHA) while levels of eicosapentaenoic acid (EPA) are several orders of magnitude lower. As evidence accumulated that fatty acid entry into the brain was not selective and, in fact, that DHA and EPA enter the brain at similar rates, new mechanisms were required to explain their large concentration differences in the brain. Here we summarize recent research demonstrating that EPA is rapidly and extensively β-oxidized upon entry into the brain. Although the ATP generated from the β-oxidation of EPA is low compared to the use of glucose, fatty acid β-oxidation may serve to regulate brain fatty acid levels in the absence of selective transportation. Furthermore, when β-oxidation of EPA is blocked, desaturation of EPA increases and Land׳s recycling decreases to maintain low EPA levels. Copyright © 2014 Elsevier Ltd. All rights reserved.

Differential intracellular calcium influx, nitric oxide production, ICAM-1 and IL8 expression in primary bovine endothelial cells exposed to nonesterified fatty acids.

Science.gov (United States)

Loaiza, Anitsi; Carretta, María D; Taubert, Anja; Hermosilla, Carlos; Hidalgo, María A; Burgos, Rafael A

2016-02-25

Nonesterified fatty acids (NEFAs) are involved in proinflammatory processes in cattle, including in the increased expression of adhesion molecules in endothelial cells. However, the mechanisms underlying these effects are still unknown. The aim of this study was to assess the effects of NEFAs on the intracellular calcium (Ca(2+) i) influx, nitric oxide production, and ICAM-1 and IL-8 expression in primary bovine umbilical vein endothelial cells (BUVECs). Myristic (MA), palmitic (PA), stearic (SA), oleic (OA) and linoleic acid (LA) rapidly increased Ca(2+) i. The calcium response to all tested NEFAs showed an extracellular calcium dependence and only the LA response was significantly inhibited until the intracellular calcium was chelated. The EC50 values for MA and LA were 125 μM and 37 μM, respectively, and the MA and LA effects were dependent on calcium release from the endoplasmic reticulum stores and on the L-type calcium channels. Only the calcium response to MA was significantly reduced by GW1100, a selective G-protein-coupled free fatty acid receptor (GPR40) antagonist. We also detected a functional FFAR1/GPR40 protein in BUVECs by using western blotting and the FFAR1/GPR40 agonist TAK-875. Only LA increased the cellular nitric oxide levels in a calcium-dependent manner. LA stimulation but not MA stimulation increased ICAM-1 and IL-8-expression in BUVECs. This effect was inhibited by GW1100, an antagonist of FFAR1/GPR40, but not by U-73122, a phospholipase C inhibitor. These findings strongly suggest that each individual NEFA stimulates endothelial cells in a different way, with clearly different effects on intracellular calcium mobilization, NO production, and IL-8 and ICAM-1 expression in primary BUVECs. These findings not only extend our understanding of NEFA-mediated diseases in ruminants, but also provide new insight into the different molecular mechanisms involved during endothelial cell activation by NEFAs.

Modeling of nitrous oxide production by autotrophic ammonia-oxidizing bacteria with multiple production pathways.

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Ni, Bing-Jie; Peng, Lai; Law, Yingyu; Guo, Jianhua; Yuan, Zhiguo

2014-04-01

Autotrophic ammonia oxidizing bacteria (AOB) have been recognized as a major contributor to N2O production in wastewater treatment systems. However, so far N2O models have been proposed based on a single N2O production pathway by AOB, and there is still a lack of effective approach for the integration of these models. In this work, an integrated mathematical model that considers multiple production pathways is developed to describe N2O production by AOB. The pathways considered include the nitrifier denitrification pathway (N2O as the final product of AOB denitrification with NO2(-) as the terminal electron acceptor) and the hydroxylamine (NH2OH) pathway (N2O as a byproduct of incomplete oxidation of NH2OH to NO2(-)). In this model, the oxidation and reduction processes are modeled separately, with intracellular electron carriers introduced to link the two types of processes. The model is calibrated and validated using experimental data obtained with two independent nitrifying cultures. The model satisfactorily describes the N2O data from both systems. The model also predicts shifts of the dominating pathway at various dissolved oxygen (DO) and nitrite levels, consistent with previous hypotheses. This unified model is expected to enhance our ability to predict N2O production by AOB in wastewater treatment systems under varying operational conditions.

Protective effects of gallic acid against spinal cord injury-induced oxidative stress.

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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.

Comparison studies of propylene oxide addition to phenyloctadecanol and phenyloctadecanoic acid and the surface activity studies of their sulphated products

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Ahmed, M. H.M.

2001-10-01

Full Text Available Phenyloctadecanol and phenyloctadecanoic acid were produced via Lewis acid catalyzed reaction of benzene and oleyl alcohol (60 ºC or oleic acid at (80 ºC respectively. A comparison study was achieved for the addition of propylene oxide to both substrates in the presence of base (KOH and Lewis acid (SbCl5 catalysts. It was found that, the hydroxypropylation of both substrates at low temperature via Lewis acid catalyst is more preferable than via the base catalyst. The surface activity of the sulphated products was determined. The results revealed that, the samples produced from alcohol (phenyloctadecanol show a better surface activity than that from acid (phenyloctadecanoic acid. On the other hand the samples produced from both substrates using Lewis acid catalyst have a better surface activity than that produced with the base catalyst.Se ha obtenido feniloctadecanol y ácido feniloctadecanoico vía reacción catalizada ácido de Lewis a partir de benceno y alcohol oleílico (60º C o ácido oleico (80º C respectivamente. Se ha llevado a cabo un estudio comparativo por adición de óxido de propileno a ambos sustratos en presencia de base (KOH y ácido de Lewis (SbCl5 como catalizadores. Se encontró que la hidroxipropilación de ambos sustratos a baja temperatura mediante catálisis ácido de Lewis es preferible a la catálisis básica. Se determinó la actividad superficial de los productos sulfatados. Los resultados mostraron que las muestras producidas a partir de alcohol (feniloctadecanol tenían una mejor actividad superficial que las producidas a partir de ácido (ácido feniloctadecanoico. Por otro lado, las muestras producidas a partir de ambos sustratos utilizando catalizador ácido de Lewis tuvieron una actividad superficial mejor que las producidas con catálisis básica.

Increasing fatty acid oxidation remodels the hypothalamic neurometabolome to mitigate stress and inflammation.

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Joseph W McFadden

Full Text Available Modification of hypothalamic fatty acid (FA metabolism can improve energy homeostasis and prevent hyperphagia and excessive weight gain in diet-induced obesity (DIO from a diet high in saturated fatty acids. We have shown previously that C75, a stimulator of carnitine palmitoyl transferase-1 (CPT-1 and fatty acid oxidation (FAOx, exerts at least some of its hypophagic effects via neuronal mechanisms in the hypothalamus. In the present work, we characterized the effects of C75 and another anorexigenic compound, the glycerol-3-phosphate acyltransferase (GPAT inhibitor FSG67, on FA metabolism, metabolomics profiles, and metabolic stress responses in cultured hypothalamic neurons and hypothalamic neuronal cell lines during lipid excess with palmitate. Both compounds enhanced palmitate oxidation, increased ATP, and inactivated AMP-activated protein kinase (AMPK in hypothalamic neurons in vitro. Lipidomics and untargeted metabolomics revealed that enhanced catabolism of FA decreased palmitate availability and prevented the production of fatty acylglycerols, ceramides, and cholesterol esters, lipids that are associated with lipotoxicity-provoked metabolic stress. This improved metabolic signature was accompanied by increased levels of reactive oxygen species (ROS, and yet favorable changes in oxidative stress, overt ER stress, and inflammation. We propose that enhancing FAOx in hypothalamic neurons exposed to excess lipids promotes metabolic remodeling that reduces local inflammatory and cell stress responses. This shift would restore mitochondrial function such that increased FAOx can produce hypothalamic neuronal ATP and lead to decreased food intake and body weight to improve systemic metabolism.

[Fatty acids in confectionery products].

Science.gov (United States)

Daniewski, M; Mielniczuk, E; Jacórzyński, B; Pawlicka, M; Balas, J; Filipek, A; Górnicka, M

2000-01-01

The content of fat and fatty acids in 144 different confectionery products purchased on the market in Warsaw region during 1997-1999 have been investigated. In examined confectionery products considerable variability of both fat and fatty acids content have been found. The content of fat varied from 6.6% (coconut cookies) up to 40% (chocolate wafers). Saturated fatty acids were present in both cis and trans form. Especially trans fatty acids reach (above 50%) were fats extracted from nut wafers, coconuts wafers.

The role of calcium ions in the photocatalytic oxidation of humic acid at neutral pH.

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Mariquit, Eden G; Salim, Chris; Hinode, Hirofumi

2008-10-01

Humic acids (HAs) are natural organic matter derived from the decomposition of plant, algal, and microbial materials. They belong to the group of the most predominant type of natural organic matter present in ground and surface waters. HAs affect the mobility and bioavailability of aquatic contaminants. However, if they are left unremoved from the water before water treatment processes, they can form carcinogenic disinfection by-products, such as trihalomethanes, haloacetic acids, and other halogenated disinfection by-products, that can pose a threat to human beings. An advanced oxidation process using UV light and a commercially available titanium dioxide was used to oxidize HA at a pH that is similar to that of natural water. The effect of adding calcium ions to the adsorption and the photocatalytic oxidation of HAs was studied. The effect of varying the TiO(2) load was also investigated. The experiment was done using a photochemical batch reactor equipped with a mercury lamp emitting light with wavelengths of 310-580 nm. The absorbances by the samples were determined at wavelengths of 254 nm and 436 nm, which represent the aromatic-compound content of and the color of the solution, respectively. Results indicated calcium ions have an effect on both the adsorption and the photocatalytic oxidation of HA at a pH within 8.0 +/- 0.5. Calcium ions facilitated adsorption of HA onto the surface of TiO(2) and resulted to faster photocatalytic oxidation. The data were plotted with respect to the normalized absorbances and irradiation time.

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.

Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

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Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

2017-08-30

One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

Method of making metal oxide ceramic powders by using a combustible amino acid compound

Science.gov (United States)

Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

1992-01-01

This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

Chlorogenic acid ameliorates endotoxin-induced liver injury by promoting mitochondrial oxidative phosphorylation

Energy Technology Data Exchange (ETDEWEB)

Zhou, Yan [State Key Laboratory of Food Science and Technology and School of Food Science, Nanchang University, Nanchang 330047 (China); College of Food Safety, Guizhou Medical University, Guiyang 550025 (China); Ruan, Zheng, E-mail: ruanzheng@ncu.edu.cn [State Key Laboratory of Food Science and Technology and School of Food Science, Nanchang University, Nanchang 330047 (China); Zhou, Lili; Shu, Xugang [State Key Laboratory of Food Science and Technology and School of Food Science, Nanchang University, Nanchang 330047 (China); Sun, Xiaohong [College of Food Safety, Guizhou Medical University, Guiyang 550025 (China); Mi, Shumei; Yang, Yuhui [State Key Laboratory of Food Science and Technology and School of Food Science, Nanchang University, Nanchang 330047 (China); Yin, Yulong, E-mail: yinyulong@isa.ac.cn [State Key Laboratory of Food Science and Technology and School of Food Science, Nanchang University, Nanchang 330047 (China); Institute of Subtropical Agriculture, Chinese Academy of Sciences, Changsha 410125 (China)

2016-01-22

Acute or chronic hepatic injury is a common pathology worldwide. Mitochondrial dysfunction and the depletion of adenosine triphosphate (ATP) play important roles in liver injury. Chlorogenic acids (CGA) are some of the most abundant phenolic acids in human diet. This study was designed to test the hypothesis that CGA may protect against chronic lipopolysaccharide (LPS)-induced liver injury by modulating mitochondrial energy generation. CGA decreased the activities of serum alanine aminotransferase, aspartate aminotransferase and alkaline phosphatase. The contents of ATP and adenosine monophosphate (AMP), as well as the ratio of AMP/ATP, were increased after CGA supplementation. The activities of enzymes that are involved in glycolysis were reduced, while those of enzymes involved in oxidative phosphorylation were increased. Moreover, phosphorylated AMP-activated protein kinase (AMPK), and mRNA levels of AMPK-α, peroxisome proliferator-activated receptor-gamma coactivator 1α (PGC-1α), nuclear respiratory factor 1, and mitochondrial DNA transcription factor A were increased after CGA supplementation. Collectively, these findings suggest that the hepatoprotective effect of CGA might be associated with enhanced ATP production, the stimulation of mitochondrial oxidative phosphorylation and the inhibition of glycolysis. - Highlights: • Dietary supplementation with chlorogenic acid (CGA) improved endotoxin-induced liver injury. • Chlorogenic acid enhances ATP increase and shifts energy metabolism, which is correlated with up-regulation AMPK and PGC-1α. • The possible mechanism of CGA on mitochondrial biogenesis was correlated with up-regulation AMPK and PGC-1α.

Chlorogenic acid ameliorates endotoxin-induced liver injury by promoting mitochondrial oxidative phosphorylation

International Nuclear Information System (INIS)

Zhou, Yan; Ruan, Zheng; Zhou, Lili; Shu, Xugang; Sun, Xiaohong; Mi, Shumei; Yang, Yuhui; Yin, Yulong

2016-01-01

Acute or chronic hepatic injury is a common pathology worldwide. Mitochondrial dysfunction and the depletion of adenosine triphosphate (ATP) play important roles in liver injury. Chlorogenic acids (CGA) are some of the most abundant phenolic acids in human diet. This study was designed to test the hypothesis that CGA may protect against chronic lipopolysaccharide (LPS)-induced liver injury by modulating mitochondrial energy generation. CGA decreased the activities of serum alanine aminotransferase, aspartate aminotransferase and alkaline phosphatase. The contents of ATP and adenosine monophosphate (AMP), as well as the ratio of AMP/ATP, were increased after CGA supplementation. The activities of enzymes that are involved in glycolysis were reduced, while those of enzymes involved in oxidative phosphorylation were increased. Moreover, phosphorylated AMP-activated protein kinase (AMPK), and mRNA levels of AMPK-α, peroxisome proliferator-activated receptor-gamma coactivator 1α (PGC-1α), nuclear respiratory factor 1, and mitochondrial DNA transcription factor A were increased after CGA supplementation. Collectively, these findings suggest that the hepatoprotective effect of CGA might be associated with enhanced ATP production, the stimulation of mitochondrial oxidative phosphorylation and the inhibition of glycolysis. - Highlights: • Dietary supplementation with chlorogenic acid (CGA) improved endotoxin-induced liver injury. • Chlorogenic acid enhances ATP increase and shifts energy metabolism, which is correlated with up-regulation AMPK and PGC-1α. • The possible mechanism of CGA on mitochondrial biogenesis was correlated with up-regulation AMPK and PGC-1α.

OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products-A gamma radiolysis study

Energy Technology Data Exchange (ETDEWEB)

Krimmel, Birgit; Swoboda, Friederike [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology (Austria); Solar, Sonja, E-mail: sonja.solar@univie.ac.a [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology (Austria); Reznicek, Gottfried [Department of Pharmacognosy, Althanstrasse 14, A-1090 Vienna (Austria)

2010-12-15

The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH{sub 3} by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

Photo-oxidation of gaseous ethanol on photocatalyst prepared by acid leaching of titanium oxide/hydroxyapatite composite

Energy Technology Data Exchange (ETDEWEB)

Ono, Y., E-mail: ono-y@kanagawa-iri.go.jp [Mechanical and Material Engineering Division, Kanagawa Industrial Technology Center, Ebina, Kanagawa 243-0435 (Japan); Rachi, T.; Yokouchi, M.; Kamimoto, Y. [Mechanical and Material Engineering Division, Kanagawa Industrial Technology Center, Ebina, Kanagawa 243-0435 (Japan); Nakajima, A. [Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, Meguro, Tokyo 152-8552 (Japan); Okada, K. [Materials and Structures Laboratory, Tokyo Institute of Technology, Midori, Yokohama, Kanagawa 226-8503 (Japan)

2013-06-01

Highlights: ► Photocatalyst powder was prepared by acid leaching of TiO{sub 2}/apatite composite. ► The photocatalytic activity was evaluated from in situ FT-IR study using ethanol. ► Apatite in the composite had positive effect for the photo-oxidation of ethanol. ► The enhanced oxidation rate was explained by the difference in deactivation rate. - Abstract: Highly active photocatalysts were synthesized by leaching of heat-treated titanium dioxide (TiO{sub 2})/hydroxyapatite (HAp) powder with hydrochloric acid at 0.25, 0.50, 0.75 mol/l, and their photocatalytic activities were evaluated from in situ Fourier transform infrared (FT-IR) study of photo-oxidation of gaseous ethanol. By changing the acid concentration, the TiO{sub 2}/HAp composite had different atomic ratios of Ca/Ti (0.0–2.8) and P/Ti (0.3–2.1). It was found that phosphate group remained on the surface of TiO{sub 2} particle even in the sample treated with concentrated acid (0.75 mol/l). These acid-treated samples showed higher rates for ethanol photo-oxidation than the commercial TiO{sub 2} powder, Degussa P25. The highest rate was obtained in the TiO{sub 2}/HAp composite treated with the dilute (0.25 mol/l) acid in spite of its low content of TiO{sub 2} photocatalyst. This enhanced photocatalytic activity was attributed to the result that the deactivation with repeated injections of ethanol gas was suppressed in the TiO{sub 2}/HAp composites compared with the TiO{sub 2} powders.

Electrochemical oxidation of methanol and formic acid in fuel cell processes

Energy Technology Data Exchange (ETDEWEB)

Seland, Frode

2005-07-01

The main objectives of the thesis work were: (1), to study the oxidation of methanol and formic acid on platinum electrodes by employing conventional and advanced electrochemical methods, and (2), to develop membrane electrode assemblies based on polybenzimidazole membranes that can be used in fuel cells up to 200 C. D.c. voltammetry and a.c. voltammetry studies of methanol and formic acid on polycrystalline platinum in sulphuric acid electrolyte were performed to determine the mechanism and kinetics of the oxidation reactions. A combined potential step and fast cyclic voltammetry experiment was employed to investigate the time dependence primarily of methanol oxidation on platinum. Charge measurements clearly demonstrated the existence of a parallel path at low potentials and short times without formation of adsorbed CO. Furthermore, experimental results showed that only the serial path, via adsorbed CO, exists during continuous cycling, with the first step being diffusion controlled dissociative adsorption of methanol directly from the bulk electrolyte. The saturation charge of adsorbed CO derived from methanol was found to be significantly lower than CO derived from formic acid or dissolved CO. This was attributed to the site requirements of the dehydrogenation steps, and possibly different compositions of linear, bridged or multiply bonded CO. The coverage of adsorbed CO from formic acid decreased significantly at potentials just outside of the hydrogen region (0.35 V vs. RHE), while it did not start to decrease significantly until about 0.6 V vs. RHE for methanol. Adsorbed CO from dissolved CO rapidly oxidized at potentials above about 0.75 V due to formation of platinum oxide. Data from a.c. voltammograms from 0.5 Hz up to 30 kHz were assembled into electrochemical impedance spectra (EIS) and analyzed using equivalent circuits. The main advantages of collecting EIS spectra from a.c. voltammetry experiments are the ability to directly correlate the impedance

Cholesterol and fatty acids oxidation in meat from three muscles of Massese suckling lambs slaughtered at different weights

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Andrea Serra

2014-09-01

Full Text Available Eighteen Massese male lambs fed mainly with maternal milk were slaughtered at 11, 14 and 17 kg. Samples of Longissimus dorsi (LD, Triceps brachii (TB and Semimembranosus (Sm muscles were collected. Total intramuscular lipids were extracted by means of a mixture of chloroform methanol 2/1. Cholesterol content and its oxidation product (COP were determined by a gas chromatography apparatus equipped with an apolar 30 m column. Fatty acid oxidation was evaluated by means of thiobarbituric acid reactive substances (TBARS extracting the sample with aqueous acidic solution. The effect of slaughter weight on oxidation of intramuscular lipids was found only in TB muscles. In this muscle the cholesterol content showed a decreasing trend, while the content of COPs significantly increased with the age of animals. Among the COPs, the 7-ketocholesterol and 7β-hydroxycholesterol were the most abundant, followed by α- and β- epoxy-cholesterol and cholestan-triol. The content of TBARS did not vary owing to a similar fatty acid composition of intramuscular fat across weight of slaughter. In any case, the values of TBARS did not reach the threshold of the detection of off-flavour in meat.

Mechanistic studies of formic acid oxidation at polycarbazole supported Pt nanoparticles

International Nuclear Information System (INIS)

Moghaddam, Reza B.; Pickup, Peter G.

2013-01-01

Highlights: •A polycarbazole support decreases the accumulation of adsorbed intermediates on Pt during formic acid oxidation. •Polycarbazole causes a bilayer of Cu to form on Pt nanoparticles during Cu underpotential deposition. •XPS suggests that both of these effects are due to electron donation from the metal (Pt or Cu) into the polymer π-system. -- Abstract: Mechanistic aspects of the promotion of formic acid oxidation at Pt nanoparticles supported on a thin layer of polycarbazole (PCZ) have been investigated by voltammetry and X-ray photoelectron spectroscopy (XPS). The Pt nanoparticles were drop coated onto a glassy carbon (GC) electrode coated with a ca. 9 nm layer of electrochemically deposited polycarbazole. After 500 s of formic acid oxidation at 0 V vs. SCE, the current at a GC/PCZ/Pt electrode was 25 times higher than at a GC/Pt electrode. Voltammetry in formic acid free H 2 SO 4 following potentiostatic oxidation of formic acid revealed that there was less accumulation of adsorbed intermediates for the polycarbazole supported Pt nanoparticles than for those deposited directly onto the glassy carbon with, 50% more Pt sites remaining available for the GC/PCZ/Pt electrode relative to the GC/Pt electrode. Independent CO stripping experiments revealed only slight differences, while Cu underpotential deposition surprisingly resulted in the deposition of a ca. two-fold excess of Cu on the polycarbazole supported particles. This observation was supported by XPS which also revealed a second Cu signal at a higher binding energy, suggesting electron donation into the conjugated π system of the polymer. Such an interaction of Pt with the polycarbazole may be responsible for its higher activity for formic acid oxidation

The effect of valinomycin in fibroblasts from patients with fatty acid oxidation disorders

International Nuclear Information System (INIS)

Ndukwe Erlingsson, Uzochi Chimdinma; Iacobazzi, Francesco; Liu, Aiping; Ardon, Orly; Pasquali, Marzia; Longo, Nicola

2013-01-01

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 + ) at low concentrations due to the dissipation of the mitochondrial membrane potential. At higher doses, valinomycin increased TPP + accumulation due to the increased potassium permeability of the plasma membrane and subsequent cellular hyperpolarization. The incubation of normal fibroblasts with valinomycin increased [ 14 C]-palmitate oxidation (measured as [ 14 C]O 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

Glutamic acid and folic acid production in aerobic and anaerobic probiotics

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Zohre Taghi Abadi

2018-03-01

Full Text Available Introduction:From an industrial application or commercial point of view, glutamic acid is one of the most important amino acids and its microbial production has been reported from some bacteria. Regarding the role of probiotics to modulate human health and the ever-increasing demand of prebiotics in the food industry, in the current study, production of glutamic acid and folic acid from three probiotic bacteria (Bifidobacterium, Bifidobacterium bifidum, Sporolactobacillus was evaluated for the first time. Materials and methods: MRS broth and exclusive media was used for probiotic culture. The glutamic acid was identified using thin-layer chromatography and folic acid production was measured by folate kit. Each bacterium in terms of quality and quantity were measured by high pressure liquid chromatography. Results: Production of glutamic acid confirmed is based on the thin layer chromatography analysis and high pressure liquid chromatography results. In addition, it was observed that all three probiotics produce folic acid. The prevalence of folate in Bifidobacterium was measured as 315 mg/ml that was more than two other bacteria. Discussion and conclusion: To the best of our knowledge, this is the first report of microbial production of glutamic acid and folate from the probiotic bacteria. These beneficial bacteria can be used as a good source for mass production of these valuable compounds.

Kinetic Studies on the Oxidation of Some para and meta-Substituted Cinnamic Acids by Pyridinium Bromochromate in the Presence of Oxalic Acid (A Co-oxidation Study

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G. Vanangamudi

2009-01-01

Full Text Available The kinetics of oxidation of cinnamic acids by pyridinium bromochromate (PBC in the presence of oxalic acid has been studied in acetic acid-water (60:40% medium. The reaction shows unit order dependence each with respect to oxidant as well as oxalic acid [OX], the order with respect to [H+] and [CA] are fractional. The reaction is acid catalyzed and a low dielectric constant favours the reaction. Increase the ionic strength has no effect on the reaction rate. In the case of substituted cinnamic acids the order with respect to substrate vary depending upon the nature of the substituent present in the ring. In general, the electron withdrawing substituents retard the rate while the electron releasing substituents enhance the rate of reaction. From the kinetic data obtained the activation parameters have been computed and a suitable mechanism has been proposed.

Orphan drugs in development for long-chain fatty acid oxidation disorders: challenges and progress

OpenAIRE

Merritt II, J Lawrence; Sun,Angela

2015-01-01

Angela Sun, J Lawrence Merritt II Department of Pediatrics, University of Washington, Seattle, WA, USA Abstract: Fatty acid oxidation disorders are inborn errors of metabolism resulting in failure of ß-oxidation within or transport of fatty acids into the mitochondria. The long-chain fatty acid oxidation disorders are characterized by variable presentations ranging from newborn cardiomyopathy, to infantile hypoketotic hypoglycemia resulting from liver involvement, to skeletal myopa...

Formation of iron oxides from acid mine drainage and magnetic separation of the heavy metals adsorbed iron oxides

Energy Technology Data Exchange (ETDEWEB)

Kwon, Hee Won; Kim, Jeong Jin; Kim, Young Hun [Andong National University, Andong (Korea, Republic of); Ha, Dong Woo [Korea Electrotechnology Research Institute, Changwon (Korea, Republic of)

2016-03-15

There are a few thousand abandoned metal mines in South Korea. The abandoned mines cause several environmental problems including releasing acid mine drainage (AMD), which contain a very high acidity and heavy metal ions such as Fe, Cu, Cd, Pb, and As. Iron oxides can be formed from the AMD by increasing the solution pH and inducing precipitation. Current study focused on the formation of iron oxide in an AMD and used the oxide for adsorption of heavy metals. The heavy metal adsorbed iron oxide was separated with a superconducting magnet. The duration of iron oxide formation affected on the type of mineral and the degree of magnetization. The removal rate of heavy metal by the adsorption process with the formed iron oxide was highly dependent on the type of iron oxide and the solution pH. A high gradient magnetic separation (HGMS) system successfully separated the iron oxide and harmful heavy metals.

Transparent conducting oxides and production thereof

Science.gov (United States)

Gessert, Timothy A.; Yoshida, Yuki; Coutts, Timothy J.

2014-06-10

Transparent conducting oxides and production thereof are disclosed. An exemplary method of producing a transparent conducting oxide (TCO) material may comprise: providing a TCO target doped with either a high-permittivity oxide or a low-permittivity oxide in a process chamber. The method may also comprise depositing a metal oxide on the target in the process chamber to form a thin film having enhanced optical properties without substantially decreasing electrical quality.

Oxidation of C18 Hydroxy-Polyunsaturated Fatty Acids to Epoxide or Ketone by Catalase-Related Hemoproteins Activated with Iodosylbenzene.

Science.gov (United States)

Teder, Tarvi; Boeglin, William E; Brash, Alan R

2017-07-01

Small catalase-related hemoproteins with a facility to react with fatty acid hydroperoxides were examined for their potential mono-oxygenase activity when activated using iodosylbenzene. The proteins tested were a Fusarium graminearum 41 kD catalase hemoprotein (Fg-cat, gene FGSG_02217), a Pseudomonas fluorescens Pfl01 catalase (37.5 kD, accession number WP_011333788.1), and a Mycobacterium avium ssp. paratuberculosis 33 kD catalase (gene MAP-2744c). 13-Hydroxy-octadecenoic acids (which are normally unreactive) were selected as substrates because these enzymes react specifically with the corresponding 13S-hydroperoxides (Pakhomova et al. 18:2559-2568, 5; Teder et al. 1862:706-715, 14). In the presence of iodosylbenzene Fg-cat converted 13S-hydroxy-fatty acids to two products: the 15,16-double bond of 13S-hydroxy α-linolenic acid was oxidized stereospecifically to the 15S,16R-cis-epoxide or the 13-hydroxyl was oxidized to the 13-ketone. Products were identified by UV, HPLC, LC-MS, NMR and by comparison with authentic standards prepared for this study. The Pfl01-cat displayed similar activity. MAP-2744c oxidized 13S-hydroxy-linoleic acid to the 13-ketone, and epoxidized the double bonds to form the 9,10-epoxy-13-hydroxy, 11,12-epoxy-13-hydroxy, and 9,10-epoxy-13-keto derivatives; equivalent transformations occurred with 9S-hydroxy-linoleic acid as substrate. In parallel incubations in the presence of iodosylbenzene, human catalase displayed no activity towards 13S-hydroxy-linoleic acid, as expected from the highly restricted access to its active site. The results indicated that with suitable transformation to Compound I, monooxygenase activity can be demonstrated by these catalase-related hemoproteins with tyrosine as the proximal heme ligand.

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