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Sample records for acid oxidation defects

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

    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

  2. Defects at oxide surfaces

    Thornton, Geoff

    2015-01-01

    This book presents the basics and characterization of defects at oxide surfaces. It provides a state-of-the-art review of the field, containing information to the various types of surface defects, describes analytical methods to study defects, their chemical activity and the catalytic reactivity of oxides. Numerical simulations of defective structures complete the picture developed. Defects on planar surfaces form the focus of much of the book, although the investigation of powder samples also form an important part. The experimental study of planar surfaces opens the possibility of applying the large armoury of techniques that have been developed over the last half-century to study surfaces in ultra-high vacuum. This enables the acquisition of atomic level data under well-controlled conditions, providing a stringent test of theoretical methods. The latter can then be more reliably applied to systems such as nanoparticles for which accurate methods of characterization of structure and electronic properties ha...

  3. A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects

    Choi, Sang; Herron, Jeffrey A.; Scaranto, Jessica; Huang, Hongwen; Wang, Yi; Xia, Xiaohu; Lv, Tian; Park, Jinho; Peng, Hsin-Chieh; Mavrikakis, Manos; Xia, Younan

    2015-07-13

    Palladium has been recognized as the best anodic, monometallic electrocatalyst for the formic acid oxidation (FAO) reaction in a direct formic acid fuel cell. Here we report a systematic study of FAO on a variety of Pd nanocrystals, including cubes, right bipyramids, octahedra, tetrahedra, decahedra, and icosahedra. These nanocrystals were synthesized with approximately the same size, but different types of facets and twin defects on their surfaces. Our measurements indicate that the Pd nanocrystals enclosed by {1 0 0} facets have higher specific activities than those enclosed by {1 1 1} facets, in agreement with prior observations for Pd single-crystal substrates. If comparing nanocrystals predominantly enclosed by a specific type of facet, {1 0 0} or {1 1 1}, those with twin defects displayed greatly enhanced FAO activities compared to their single-crystal counterparts. To rationalize these experimental results, we performed periodic, self-consistent DFT calculations on model single-crystal substrates of Pd, representing the active sites present in the nanocrystals used in the experiments. The calculation results suggest that the enhancement of FAO activity on defect regions, represented by Pd(2 1 1) sites, compared to the activity of both Pd(1 0 0) and Pd(1 1 1) surfaces, could be attributed to an increased flux through the HCOO-mediated pathway rather than the COOH-mediated pathway on Pd(2 1 1). Since COOH has been identified as a precursor to CO, a site-poisoning species, a lower coverage of CO at the defect regions will lead to a higher activity for the corresponding nanocrystal catalysts, containing those defect regions.

  4. THYROID HORMONE REVERSES AGING-INDUCED MYOCARDIAL FATTY ACID OXIDATION DEFECTS AND IMPROVES THE RESPONSE TO ACUTELY INCREASED AFTERLOAD

    Ledee, Dolena; Portman, Michael A.; Kajimoto, Masaki; Isern, Nancy G.; Olson, Aaron

    2013-06-07

    Background: Subclinical hypothyroidism occurs during aging in humans and mice and may contribute to development of heart failure. Aging also impairs myocardial fatty acid oxidation, causing increased reliance on flux through pyruvate dehydrogenase (PDH) to maintain function. We hypothesize that the metabolic changes in aged hearts make them less tolerant to acutely increased work and that thyroid hormone reverses these defects. Methods: Studies were performed on young (Young, 4-6 months) and aged (Old, 22-24 months) C57/BL6 mice at standard (50 mmHg) and high afterload (80 mmHg). Another aged group received thyroid hormone for 3 weeks (Old-TH, high afterload only). Function was measured in isolated working hearts along with substrate fractional contributions (Fc) to the citric acid cycle (CAC) using perfusate with 13C labeled lactate, pyruvate, glucose and unlabeled palmitate and insulin. Results: Cardiac function was similar between Young and Old mice at standard afterload. Palmitate Fc was reduced but no individual carbohydrate contributions differed. CAC and individual substrate fluxes decreased in aged. At high afterload, -dP/dT was decreased in Old versus Young. Similar to low afterload, palmitate Fc was decreased in Old. Thyroid hormone reversed aging-induced changes in palmitate Fc and flux while significantly improving cardiac function. Conclusion: The aged heart shows diminished ability to increase cardiac work due to substrate limitations, primarily impaired fatty acid oxidation. The heart accommodates slightly by increasing efficiency through oxidation of carbohydrate substrates. Thyroid hormone supplementation in aged mice significantly improves cardiac function potentially through restoration of fatty acid oxidation.

  5. Genetic defects in fatty acid beta-oxidation and acyl-CoA dehydrogenases. Molecular pathogenesis and genotype-phenotype relationships

    Gregersen, Niels; Bross, Peter; Andresen, Brage S

    2004-01-01

    Mitochondrial fatty acid oxidation deficiencies are due to genetic defects in enzymes of fatty acid beta-oxidation and transport proteins. Genetic defects have been identified in most of the genes where nearly all types of sequence variations (mutation types) have been associated with disease. In...... on biogenesis, stability and kinetic properties for this variant enzyme will be discussed in detail and used as a paradigm for the study of other mis-sense variant proteins. We conclude that the total effect of mis-sense sequence variations may comprise an invariable--sequence variation specific...

  6. Antisite defects at oxide interfaces

    Chen, Hanghui; Millis, Andrew

    2016-03-01

    We use ab initio calculations to estimate the formation energies of cation (transition-metal) antisite defects at oxide interfaces and to understand the basic physical effects that drive or suppress the formation of these defects. Antisite defects are found to be favored in systems with substantial charge transfer across the interface, while Jahn-Teller distortions and itinerant ferromagnetism can prevent antisite defects and help stabilize atomically sharp interfaces. Our results enable identification of classes of systems that may be more and less susceptible to the formation of antisite defects, and they motivate experimental studies and further theoretical calculations to elucidate the local structure and stability of oxide interface systems.

  7. Impurity-defect structure of anodic aluminum oxide produced by two-sided anodizing in tartaric acid

    Chernyakova, K. V.; Vrublevsky, I. A.; Ivanovskaya, M. I.; Kotsikau, D. A.

    2012-03-01

    Porous aluminum oxide is prepared in a 0.4 M aqueous solution of tartaric acid by two-sided anodizing. Fourier Transform IR spectroscopy (FTIR) data reveal the presence, in the alumina, of unoxidized tartarate ions, as well as products of their partial (radical organic products and CO) and complete (CO2) oxidation. Carboxylate ions and elemental carbon contained in the anodic oxide impart a gray color to the films.

  8. Atomistic stimulation of defective oxides

    Minervini, L

    2000-01-01

    defect processes. The predominant intrinsic disorder reaction and the mechanism by which excess oxygen is accommodated are established. Furthermore, the most favourable migration mechanism and pathway for oxygen ions is predicted. Chapters 7 and 8 investigate pyrochlore oxides. These materials are candidates for solid oxide fuel cell components and as actinide host phases. Such applications require a detailed understanding of the defect processes. The defect energies, displayed as contour maps, are able to account for structure stability and, given an appropriate partial charge potential model, to accurately determine the oxygen positional parameter. In particular, the dependence of the positional parameter on intrinsic disorder is predicted. It is demonstrated, by radiation damage experiments, that these results are able to predict the radiation performance of pyrochlore oxides. Atomistic simulation calculations based on energy minimization techniques and classical pair potentials are used to study several i...

  9. Folic acid and birth defect prevention

    ... of certain birth defects. These include spina bifida, anencephaly, and some heart defects. Experts recommend women who ... Women who have had a baby with a neural tube defect may need a higher dose of folic acid. ...

  10. Heterologous expression of human carnitine palmitoyltransferase (CPT) II in yeast: A model for the molecular analysis of mitochondrial fatty acid oxidation defects

    Cavadini, P.; Invernizzi, F.; Baratta, S. [Istituto Nazionale Neurologico Carlo Besta, Milano (Italy)] [and others

    1994-09-01

    The CPT enzyme system, which is composed of two distinct mitochondrial membrane-bound proteins (CPT I and CPT II), provides the mechanism whereby long-chain fatty acids are transferred from the cytosol to the mitochondrial matrix to undergo {beta}-oxidation. Here, we report the development of an expression system for investigating genotype/phenotype correlations in CPT II deficiency and, potentially, other mitochondrial fatty acid oxidation defects. To explore yeast as an expression system, we introduced a cDNA encoding the entire human CPT II precursor into Saccharomyces cerevisiae. Expression was programmed by using an inducible galactose operon promoter (GAL1). Following induction, human CPT II was expressed at high levels, with activity 4- to 16-fold greater than in human fibroblasts. Levels of expression paralleled those of respiration, being higher in cells grown on a nonfermentable carbon source than in those grown on glucose. Immunoprecipitation of pulse-labeled transformed cells demonstrated that human CPT II expressed in yeast was targeted to mitochondria with correct proteolytic processing of its 25-residue mitochondrial leader sequence. Preliminary results on the expression of a number of mutant CPT II alleles associated with different clinical phenotypes demonstrated the value of this system for examining the functional consequences of disease-causing mutations and investigating genotype/phenotype correlations in patients with CPT II deficiency.

  11. Modelling the oxidation of defected fuel elements

    Interim dry storage of used fuel is an economical alternative to storage in water pools. The fuel must remain intact during the dry-storage period, otherwise future handling of the fuel will be expensive. Oxidation of defected fuel elements can lead to fuel disintegration. Thus it is important to be able to predict the extent of oxidation of defected fuel elements in a dry-storage facility. In this report, a model is developed for predicting the extent or rate of oxidation of defected fuel elements stored at temperatures up to 170 C. The model employs equivalent porous medium representation of the fuel and described the oxygen concentration in the fuel element using a reaction-diffusion equation. The one- and two-dimensional reaction-diffusion equations are solved on the assumption that the oxygen-fuel reaction is either zeroth or first order in the oxygen concentration. Dimensional analysis of the model equations shows that the solution depends explicitly on a single parameter p. The value of p can be calculated using data from the literature, or it can be estimated from the results of the CEX-1 experiments being carried out at Whiteshell Laboratories. The value of p, estimated from the CEX-1 results, is more than two orders of magnitude larger than the value of p calculated from literature data. Although some reasons for this large difference are suggested, further work is needed to resolve this discrepancy. (author). 16 refs., 2 tabs., 11 figs

  12. Hyaluronic acid in calves defects correction

    Lorenzo Rosset; Mario Goisis

    2014-01-01

    Aim: Since the advent of fillers, new techniques are continuously developed for different uses. In this study, we evaluated the use of hyaluronic acid for calf augmentation. Methods: A total of 42 patients were enrolled in this study. All of them underwent augmentation procedure in our centers under local anesthesia, the operations were completed within 1 h with a prompt correction of the defects. Results: Thirty-nine patients were satisfied with the treatment (93%), while three had complicat...

  13. Neural Tube Defects, Folic Acid and Methylation

    Henk J. Blom

    2013-09-01

    Full Text Available Neural tube defects (NTDs are common complex congenital malformations resulting from failure of the neural tube closure during embryogenesis. It is established that folic acid supplementation decreases the prevalence of NTDs, which has led to national public health policies regarding folic acid. To date, animal studies have not provided sufficient information to establish the metabolic and/or genomic mechanism(s underlying human folic acid responsiveness in NTDs. However, several lines of evidence suggest that not only folates but also choline, B12 and methylation metabolisms are involved in NTDs. Decreased B12 vitamin and increased total choline or homocysteine in maternal blood have been shown to be associated with increased NTDs risk. Several polymorphisms of genes involved in these pathways have also been implicated in risk of development of NTDs. This raises the question whether supplementation with B12 vitamin, betaine or other methylation donors in addition to folic acid periconceptional supplementation will further reduce NTD risk. The objective of this article is to review the role of methylation metabolism in the onset of neural tube defects.

  14. Hyaluronic acid in calves defects correction

    Lorenzo Rosset

    2014-09-01

    Full Text Available Aim: Since the advent of fillers, new techniques are continuously developed for different uses. In this study, we evaluated the use of hyaluronic acid for calf augmentation. Methods: A total of 42 patients were enrolled in this study. All of them underwent augmentation procedure in our centers under local anesthesia, the operations were completed within 1 h with a prompt correction of the defects. Results: Thirty-nine patients were satisfied with the treatment (93%, while three had complications, local infection, and lumps, that were resolved quickly (7%. Conclusion: Macrofillers can be injected into the calf to correct any defects. The advantages include short duration of treatment; the procedure performed under local anesthesia and limited side-effects that resolve promptly. This study suggests the use of biocompatible macrofillers for the augmentation of not only calves, but also for augmentation of breast and buttocks.

  15. Regularities of radiation defects build up on oxide materials surface

    Analysis of experimental data by radiation defects study on different oxide elements (silicon, beryllium, aluminium, rare earth elements) irradiated by the photo-, gamma-, neutron-, alpha- radiation, protons and helium ions show, that gas adsorption process on the surface centers and radiation defects build up in metal oxide correlated between themselves. These processes were described by the equivalent kinetic equations for analysis of radiation defects build up in the different metal oxides. It was revealed in the result of the analysis: number of radiation defects are droningly increasing up to limit value with the treatment temperature growth. Constant of radicals death at ionizing radiation increases as well. Amount of surface defects in different oxides defining absorbing activity of these materials looks as: silicon oxide→beryllium oxide→aluminium oxide. So it was found, that most optimal material for absorbing system preparation is silicon oxide by it power intensity and berylium oxide by it adsorption efficiency

  16. Defect Engineering in Plasmonic Metal Oxide Nanocrystals.

    Runnerstrom, Evan L; Bergerud, Amy; Agrawal, Ankit; Johns, Robert W; Dahlman, Clayton J; Singh, Ajay; Selbach, Sverre M; Milliron, Delia J

    2016-05-11

    Defects may tend to make crystals interesting but they do not always improve performance. In doped metal oxide nanocrystals with localized surface plasmon resonance (LSPR), aliovalent dopants and oxygen vacancies act as centers for ionized impurity scattering of electrons. Such electronic damping leads to lossy, broadband LSPR with low quality factors, limiting applications that require near-field concentration of light. However, the appropriate dopant can mitigate ionized impurity scattering. Herein, we report the synthesis and characterization of a novel doped metal oxide nanocrystal material, cerium-doped indium oxide (Ce:In2O3). Ce:In2O3 nanocrystals display tunable mid-infrared LSPR with exceptionally narrow line widths and the highest quality factors observed for nanocrystals in this spectral region. Drude model fits to the spectra indicate that a drastic reduction in ionized impurity scattering is responsible for the enhanced quality factors, and high electronic mobilities reaching 33 cm(2)V(-1) s(-1) are measured optically, well above the optical mobility for tin-doped indium oxide (ITO) nanocrystals. We investigate the microscopic mechanisms underlying this enhanced mobility with density functional theory calculations, which suggest that scattering is reduced because cerium orbitals do not hybridize with the In orbitals that dominate the bottom of the conduction band. Ce doping may also reduce the equilibrium oxygen vacancy concentration, further enhancing mobility. From the absorption spectra of single Ce:In2O3 nanocrystals, we determine the dielectric function and by simulation predict strong near-field enhancement of mid-IR light, especially around the vertices of our synthesized nanocubes. PMID:27111427

  17. Delay Testing Viability of Gate Oxide Short Defects

    J. M. Gallière; M. Renovell; F.Aza(i)s; Y. Bertrand

    2005-01-01

    Gate Oxide Short (GOS) defects are becoming predominant as technology is scaling down. Boolean and IDDQ testing of this defect has been widely studied but there is no paper dedicated to delay testing of this defect. So, this paper studies the delay behavior of Gate Oxide Short faults due to pinhole in the gate oxide. The objective of this paper is to give a detailed analysis of the behavior of the GOS defect taking into account the random parameter of the defect such as the GOS resistance and the GOS location. Because an accurate analysis is desired, the bi-dimensional array will be used.Because a complete analysis is desired, we derive the dynamic characteristic of the GOS as a function of the GOS resistance and location. It is demonstrated that i) GOS has a significant impact on gate delay, ii) GOS located close to the source of the transistor and with small resistance has very high impact.

  18. Structure, defects, and strain in silicon-silicon oxide interfaces

    Kovačević, Goran; Pivac, Branko

    2014-01-01

    The structure of the interfaces between silicon and silicon-oxide is responsible for proper functioning of MOSFET devices while defects in the interface can deteriorate this function and lead to their failure. In this paper we modeled this interface and characterized its defects and strain. MD simulations were used for reconstructing interfaces into a thermodynamically stable configuration. In all modeled interfaces, defects were found in the form of three-coordinated silicon atom, f...

  19. Partial thermodynamic properties and defective structure of oxide phases

    Partial thermodynamic properties and defective structure of oxide phases have been considered and evaluation of the properties is made, using various correlations to create a correct statisticothermodynamic model of the defective structure. The dependences OEHsub(Osub(2)) deg, ΔSsub(Osub(2)) deg and ΔSsub(Osub(2)) deg (ΔHsub(Osub(2)) deg) are presented for such oxides as VOsub(1+-x), VOsub(3/2+x), VOsub(2+-x), ZrOsub(2-x), HfOsub(2-x), WOsub(2+x), Wosub(3-x). Ways to evaluate the type of defects using the thermodynamic dependences are shown: 1) the use of thermodynamic data in the method of quasichemical equilibrium of defects; 2) the method, based on the establishment of defective structure according to linear dependence of oxygen activity on x in MOsub(s+-x) in the case of certain types of defects; 3) the method of model selection of a compound defective structure comparing the reduced dependences of partial thermodynamic functions of the phase composition with the ones, obtained experimentally. Models of complex types of defective structure during partial ordering of the defects for CeOsub(2-x) and UOsub(2+x) are analyzed. Despite the multiplicity of assumptions and insufficiency of application limits study the model of energy levels is admitted to be the most perpective statistical model to determine partial thermodynamic properties of nonstoichiometric compounds with a complex defective structure, experimental determination of which is hampered

  20. Metastable defects in beryllium oxide crystals

    The metastable luminescence centers of regular lattice are investigated in binary beryllium oxide crystals. Beryllium oxide hexagonal crystals are the simplest among low-symmetry oxide scintillators and serve as a model system. The anisotropy of energy transformation and transfer is analyzed

  1. Genetics Home Reference: congenital bile acid synthesis defect type 2

    ... DEFECT, CONGENITAL, 2 Sources for This Page Clayton PT. Disorders of bile acid synthesis. J Inherit Metab ... J, Duran M, Overmars H, Scambler PJ, Clayton PT. Mutations in SRD5B1 (AKR1D1), the gene encoding delta( ...

  2. The primary prevention of birth defects: Multivitamins or folic acid?

    2004-03-01

    Full Text Available Periconceptional use of folic acid alone or in multivitamin supplements is effective for the primary prevention of neural-tube defects. The Hungarian randomized and two-cohort controlled trials showed that periconceptional multivitamin supplementation can reduce the occurrence of some other structural birth defects, i.e. congenital abnormalities. These findings were supported by many, but not all observational studies. Recently there have been two main debated questions. The first one is whether the use of folic acid alone or folic acid-containing multivitamins is better. The second one is connected with the dilemma of whether high dose of folic acid (e.g. 5 mg might be better than a daily multivitamin with 0.4 – 0.8 mg of folic acid. Comparison of the pooled data of two Hungarian trials using a multivitamin containing 0.8 mg folic acid and the data of the Hungarian Case-Control Surveillance of Congenital Abnormalities using high dose of folic acid seemed to be appropriate to answer these questions. Multivitamins containing 0.4 – 0.8 mg of folic acid were more effective for the reduction of neural-tube defects than high dose of folic acid. Both multivitamins and folic acid can prevent some part of congenital cardiovascular malformations. Only multivitamins were able to reduce the prevalence at birth of obstructive defects of urinary tract, limb deficiencies and congenital pyloric stenosis. However, folic acid was effective in preventing some part of rectal/anal stenosis/atresia, and high dose of folic acid had effect in preventing some orofacial clefts. The findings are consistent that periconceptional multivitamin and folic acid supplementation reduce the overall occurrence of congenital abnormalities in addition to the demonstrated effect on neural-tube defects.

  3. The primary prevention of birth defects: Multivitamins or folic acid?

    Czeizel, Andrew E

    2004-01-01

    Periconceptional use of folic acid alone or in multivitamin supplements is effective for the primary prevention of neural-tube defects. The Hungarian randomized and two-cohort controlled trials showed that periconceptional multivitamin supplementation can reduce the occurrence of some other structural birth defects, i.e. congenital abnormalities. These findings were supported by many, but not all observational studies. Recently there have been two main debated questions. The first one is whether the use of folic acid alone or folic acid-containing multivitamins is better. The second one is connected with the dilemma of whether high dose of folic acid (e.g. 5 mg) might be better than a daily multivitamin with 0.4 - 0.8 mg of folic acid. Comparison of the pooled data of two Hungarian trials using a multivitamin containing 0.8 mg folic acid and the data of the Hungarian Case-Control Surveillance of Congenital Abnormalities using high dose of folic acid seemed to be appropriate to answer these questions. Multivitamins containing 0.4 - 0.8 mg of folic acid were more effective for the reduction of neural-tube defects than high dose of folic acid. Both multivitamins and folic acid can prevent some part of congenital cardiovascular malformations. Only multivitamins were able to reduce the prevalence at birth of obstructive defects of urinary tract, limb deficiencies and congenital pyloric stenosis. However, folic acid was effective in preventing some part of rectal/anal stenosis/atresia, and high dose of folic acid had effect in preventing some orofacial clefts. The findings are consistent that periconceptional multivitamin and folic acid supplementation reduce the overall occurrence of congenital abnormalities in addition to the demonstrated effect on neural-tube defects. PMID:15912190

  4. Diffusion of Point Defects in Non-Stoichiometric Oxides

    The defect structure and properties of non-stoichiometric oxides are inter-related by thermodynamic equilibria which exist at the interfaces between oxides and adjacent phases as well as within the oxides themselves. The purpose of this paper is to show that diffusive mass transport in non-stoichiometric oxides may be related specifically to (a) the equilibria between oxides and metallic phases, (b) the equilibria between oxides and the vapour phase, and (c) internal equilibria between various crystal defects within the oxide phase. Model equilibria for high temperature oxidation, diffusion of radioisotopes and crystal defects, and extrinsic electrical conductivity are described in detail for chromic oxide, Cr2O3, and strontium titanate, SrTiO3, Experimental measurements of diffusive mass transfer in Cr2O3 are shown to be in substantial agreement with predicted thermodynamic equilibria. The kinetics of oxidation of high-purity electrolytic chromium in damp hydrogen were studied using a torsion microbalance. A range of temperatures from 700 to 1000°C and hydrogen dew points from - 48 to 23°C were investigated. Damp hydrogen permitted the exploration of oxidizing conditions which were just perceptibly oxidizing with respect to the over-all equilibrium between Cr, Cr2O3 and the vapour phase. Samples, freshly abraded with 4/0 metailographic polish, exhibited a brief period of linear oxidation (∼20 min) followed by a lengthy period of diffusion-controlled parabolic oxidation (∼400 min.). The variation of the parabolic rate constant with H2O/H2 pressure ratio was found to agree with the pressure dependence predicted for Cr2O3 having a defect structure of cation vacancies and electron holes. The results were confirmed by self diffusion studies in single crystals of Cr2O3. Crystals and damp hydrogen vapour were equilibrated and Cr51 was used as a tracer. The results show that the tracer diffusion coefficient varies as the three-eighths power of the H2O/H2 pressure

  5. Differential diagnosis in patients with suspected bile acid synthesis defects

    Dorothea Haas; Hongying Gan-Schreier; Claus-Dieter Langhans; Tilman Rohrer; Guido Engelmann; Maura Heverin; David W Russell

    2012-01-01

    AIM:To investigate the clinical presentations associated with bile acid synthesis defects and to describe identification of individual disorders and diagnostic pitfalls.METHODS:Authors describe semiquantitative determination of 16 urinary bile acid metabolites by electrospray ionization-tandem mass spectrometry.Sample preparation was performed by solid-phase extraction.The total analysis time was 2 min per sample.Authors determined bile acid metabolites in 363 patients with suspected defects in bile acid metabolism.RESULTS:Abnormal bile acid metabolites were found in 36 patients.Two patients had bile acid synthesis defects but presented with atypical presentations.In 2 other patients who were later shown to be affected by biliary atresia and cystic fibrosis the profile of bile acid metabolites was initially suggestive of a bile acid synthesis defect.Three adult patients suffered from cerebrotendinous xanthomatosis.Nineteen patients had peroxisomal disorders,and 10 patients had cholestatic hepatopathy of other cause.CONCLUSION:Screening for urinary cholanoids should be done in every infant with cholestatic hepatopathy as well as in children with progressive neurological disease to provide specific therapy.

  6. The primary prevention of birth defects: Multivitamins or folic acid?

    Andrew E. Czeizel

    2004-01-01

    Periconceptional use of folic acid alone or in multivitamin supplements is effective for the primary prevention of neural-tube defects. The Hungarian randomized and two-cohort controlled trials showed that periconceptional multivitamin supplementation can reduce the occurrence of some other structural birth defects, i.e. congenital abnormalities. These findings were supported by many, but not all observational studies. Recently there have been two main debated questions. The first one is whet...

  7. Defects generated by oxidation of BF2+ implanted silicon

    Oxidation of silicon implanted with doses of 1014 BF2+ cm-2 and above generated a high density (about 108 cm-2) of stacking faults and dislocations. There is a critical BF2+ dose between 5 x 1013 and 1014 cm-2 for stacking fault generation. The density of stacking faults generated during 950 deg C oxidation was found to be lower than that from 900 deg C oxidation. TEM studies revealed this to be due to fault annihilation by the interaction of orthogonal stacking faults. EBIC studies showed the implantation induced defects to be electrically active. Pre-oxidation annealing was found to be effective in reducing the density of implantation induced defects. (author)

  8. Nitrogen defects in wide band gap oxides: defect equilibria and electronic structure from first principles calculations.

    Polfus, Jonathan M; Bjørheim, Tor S; Norby, Truls; Haugsrud, Reidar

    2012-09-01

    The nitrogen related defect chemistry and electronic structure of wide band gap oxides are investigated by density functional theory defect calculations of N(O)(q), NH(O)(×), and (NH2)(O)(·) as well as V(O)(··) and OH(O)(·) in MgO, CaO, SrO, Al(2)O(3), In(2)O(3), Sc(2)O(3), Y(2)O(3), La(2)O(3), TiO(2), SnO(2), ZrO(2), BaZrO(3), and SrZrO(3). The N(O)(q) acceptor level is found to be deep and the binding energy of NH(O)(×) with respect to N(O)' and (OH(O)(·) is found to be significantly negative, i.e. binding, in all of the investigated oxides. The defect structure of the oxides was found to be remarkably similar under reducing and nitriding conditions (1 bar N(2), 1 bar H(2) and 1 × 10(-7) bar H(2)O): NH(O)(×) predominates at low temperatures and [N(O)'] = 2[V(O)(··) predominates at higher temperatures (>900 K for most of the oxides). Furthermore, we evaluate how the defect structure is affected by non-equilibrium conditions such as doping and quenching. In terms of electronic structure, N(O)' is found to introduce isolated N-2p states within the band gap, while the N-2p states of NH(O)(×) are shifted towards, or overlap with the VBM. Finally, we assess the effect of nitrogen incorporation on the proton conducting properties of oxides and comment on their corrosion resistance in nitriding atmospheres in light of the calculated defect structures. PMID:22828729

  9. Radiation defects and metal ions of iron group in oxides

    The effect of transition ion impurities (iron group) upon optical properties and radiation defect production has been studied for alkaline earth metal oxides. Basic physical and chemical properties of the latters have been compared to those of transition metal (iron group) oxides. Original results of magnesium oxide monocrystal growth have been obtained by the method of chemical transport reactions in a narrow gap for various cobalt, nickel and manganese ion concentrations. For transition metal ions the dependences of optical absorption, luminescence and ESR on ion concentration in magnesium oxide have been found. Basing on those dependences and in terms of the ligand field theory the crystal field parameters have been calculated for cobalt and nickel ions. Characteristics of electron and hole center creation in oxides of alkaline earth metals stated for various concentrations of transition metal ions are the following: the change of the ions' electron state, their participation in the radiation defect creation and decay, the interaction between transition metal ions and radiation defects

  10. Modelling of fuel oxidation behaviour in operating defective fuel rods

    A fuel oxidation model is proposed for operating defective nuclear fuel rods. The present model is based on adsorption theory and accounts for high pressure effects. This model is in agreement with the fuel oxidation kinetics observed in high temperature annealing experiments conducted at 1 473 to 1 623 K in steam over a range of pressure from 0.001 to 0.1 MPa. Using a Freundlich adsorption isotherm, the current model is also consistent with recent experiments conducted at a higher pressure of 7 MPa. The model also considers radiolytic effects as a consequence of fission fragment bombardment in the fuel-to-clad gap. This treatment suggests that radiolysis-assisted oxidation is insignificant in operating defective rods (as compared to thermal effects), as supported by limited in-reactor data. The effects of diffusion of the interstitial oxygen ions in the solid in the operating rod is further discussed. (authors)

  11. Oxide-based protonic conductors: Point defects and transport properties

    Bonanos, N.

    , hydrogen pumps, fuel cells, etc. The extent to which protonic defects form depends mainly on the partial pressure of water vapour, temperature and basicity of the constituent oxides, while their mobility depends, among other factors, on the metal-oxygen bond length and bond energy. The defect equilibria...... that determine the protonic concentrations are considered, with emphasis on the regime of low oxygen partial pressure. The measurement of the thermoelectric power (TEP) and of the H+/D+ isotope effect in conductivity are discussed as a means of characterising the conduction process. (C) 2001 Elsevier...

  12. Oxide-based protonic conductors: Point defects and transport properties

    Bonanos, N.

    2001-01-01

    , hydrogen pumps, fuel cells, etc. The extent to which protonic defects form depends mainly on the partial pressure of water vapour, temperature and basicity of the constituent oxides, while their mobility depends, among other factors, on the metal-oxygen bond length and bond energy. The defect equilibria...... that determine the protonic concentrations are considered, with emphasis on the regime of low oxygen partial pressure. The measurement of the thermoelectric power (TEP) and of the H+/D+ isotope effect in conductivity are discussed as a means of characterising the conduction process. (C) 2001 Elsevier...

  13. Defects and properties of cadmium oxide based transparent conductors

    Yu, Kin Man; Detert, D. M.; Chen, Guibin; Zhu, Wei; Liu, Chaoping; Grankowska, S.; Hsu, L.; Dubon, O. D.; Walukiewicz, Wladek

    2016-05-01

    Transparent conductors play an increasingly important role in a number of semiconductor technologies. This paper reports on the defects and properties of Cadmium Oxide, a transparent conducting oxide which can be potentially used for full spectrum photovoltaics. We carried out a systematic investigation on the effects of defects in CdO thin films undoped and intentionally doped with In and Ga under different deposition and annealing conditions. We found that at low growth temperatures (1 Ω cm due to incorporation of excess O in the form of O-related acceptor defects, likely to be O interstitials. Intentional doping with In and Ga donors leads to an increase of both the electron concentration and the mobility. With proper doping CdO films with electron concentration of more than 1021 cm-3 and electron mobility higher than 120 cm2/V s can be achieved. Thermal annealing of doped CdO films in N2 ambient can further improve the electrical properties by removing native acceptors and improving film crystallinity. Furthermore, the unique doping behavior and electrical properties of CdO were explored via simulations based on the amphoteric defect model. A comparison of the calculations and experimental results show that the formation energy of native donors and acceptors at the Fermi stabilization energy is ˜1 eV and that the mobility of sputtered deposited CdO is limited by a background acceptor concentration of ˜5-6 × 1020/cm3. The calculations offer an insight into understanding of the effects of defects on electrical properties of undoped and doped CdO and offer a potential to use similar methods to analyze doping and defect properties of other semiconductor materials.

  14. Folic acid sensitive birth defects in association with intrauterine exposure to folic acid antagonists

    Meijer, W.M.; Walle, H.E.K.de; Kerstjens-Frederikse, W.S; de Jong-van den Berg, Lolkje Theodora Wilhelmina

    2005-01-01

    Since the protective effect of folic acid (FA) on birth defects is well known, it is reasonable to assume intrauterine exposure to FA antagonists increases the risk on these defects. We have therefore performed case-control analyses to investigate the risk of intrauterine exposure to FA antagonists,

  15. Mitochondrial respiratory control and early defects of oxidative phosphorylation in the failing human heart.

    Lemieux, Hélène; Semsroth, Severin; Antretter, Herwig; Höfer, Daniel; Gnaiger, Erich

    2011-12-01

    Heart failure is a consequence of progressive deterioration of cardiac performance. Little is known about the role of impaired oxidative phosphorylation in the progression of the disease, since previous studies of mitochondrial injuries are restricted to end-stage chronic heart failure. The present study aimed at evaluating the involvement of mitochondrial dysfunction in the development of human heart failure. We measured the control of oxidative phosphorylation with high-resolution respirometry in permeabilized myocardial fibres from donor hearts (controls), and patients with no or mild heart failure but presenting with heart disease, or chronic heart failure due to dilated or ischemic cardiomyopathy. The capacity of the phosphorylation system exerted a strong limitation on oxidative phosphorylation in the human heart, estimated at 121 pmol O(2)s(-1)mg(-1) in the healthy left ventricle. In heart disease, a specific defect of the phosphorylation system, Complex I-linked respiration, and mass-specific fatty acid oxidation were identified. These early defects were also significant in chronic heart failure, where the capacities of the oxidative phosphorylation and electron transfer systems per cardiac tissue mass were decreased with all tested substrate combinations, suggesting a decline of mitochondrial density. Oxidative phosphorylation and electron transfer system capacities were higher in ventricles compared to atria, but the impaired mitochondrial quality was identical in the four cardiac chambers of chronic heart failure patients. Coupling was preserved in heart disease and chronic heart failure, in contrast to the mitochondrial dysfunction observed after prolonged cold storage of cardiac tissue. Mitochondrial defects in the phosphorylation system, Complex I respiration and mass-specific fatty acid oxidation occurred early in the development of heart failure. Targeting these mitochondrial injuries with metabolic therapy may offer a promising approach to delay

  16. Understanding the defect structure of solution grown zinc oxide

    Zinc oxide (ZnO) is a wide bandgap semiconducting oxide with many potential applications in various optoelectronic devices such as light emitting diodes (LEDs) and field effect transistors (FETs). Much effort has been made to understand the ZnO structure and its defects. However, one major issue in determining whether it is Zn or O deficiency that provides ZnO its unique properties remains. X-ray absorption spectroscopy (XAS) is an ideal, atom specific characterization technique that is able to probe defect structure in many materials, including ZnO. In this paper, comparative studies of bulk and aqueous solution grown (≤90 °C) ZnO powders using XAS and x-ray pair distribution function (XPDF) techniques are described. The XAS Zn–Zn correlation and XPDF results undoubtedly point out that the solution grown ZnO contains Zn deficiency, rather than the O deficiency that were commonly reported. This understanding of ZnO short range order and structure will be invaluable for further development of solid state lighting and other optoelectronic device applications. - Graphical abstract: Highlights: ► ZnO powders have been synthesized through an aqueous solution method. ► Defect structure studied using XAS and XPDF. ► Zn–Zn correlations are less in the ZnO powders synthesized in solution than bulk. ► Zn vacancies are present in the powders synthesized. ► EXAFS and XPDF, when used complementary, are useful characterization techniques.

  17. Space charges and defect concentration profiles at complex oxide interfaces

    Gunkel, Felix; Waser, Rainer; Ramadan, Amr H. H.; De Souza, Roger A.; Hoffmann-Eifert, Susanne; Dittmann, Regina

    2016-06-01

    We discuss electronic and ionic defect concentration profiles at the conducting interface between the two wide-band-gap insulators LaAlO3 and SrTiO3 (STO). The profiles are deduced from a thermodynamic model considering a local space charge layer (SCL) originating from charge transfer to the interface region, thus combining electronic and ionic reconstruction mechanisms. We show that the electrical potential confining the two-dimensional electron gas (2DEG) at the interface modifies the equilibrium defect concentrations in the SCL. For the n -conducting interface, positively charged oxygen vacancies are depleted within the SCL, while negatively charged strontium vacancies accumulate. Charge compensation within the SCL is achieved by a mixed ionic-electronic interface reconstruction, while the competition between 2DEG and localized ionic defects is controlled by ambient p O2 . The concentration of strontium vacancies increases drastically in oxidizing conditions and exhibits a steep depth profile towards the interface. Accounting for the low cation diffusivity in STO, we also discuss kinetic limitations of cation defect formation and the effect of a partial equilibration of the cation sublattice. We discuss the resulting implications for low temperature transport.

  18. Theoretical studies of defects in binary and ternary oxides

    In the past decade, there has been an explosive development of computational techniques utilizing high-speed computers to study the electronic and atomic structural properties of solids. These techniques form an important compliment to laboratory experiments for providing a better understanding of spectroscopic properties, as well as the energetics of the solid systems. For ideal metallic and semiconducting crystal lattice with translational symmetry, the conventional energy band structure approaches are capable to provide a good degree of precision in both electronic structure and system energies. On the other hand the molecular-cluster model represents a convenient method of studying those properties that are primarily a function of the local environment of the system, such as vacancy, substitutional and interstitial defects. In this paper, the authors present some preliminary results of electronic structure of substitutional defects and vacancy in binary and ternary cubic zirconium oxides obtained by the embedded molecular-cluster model calculation. The importance of electronic charge redistribution in the solids where the defect is introduced into the perfect lattice is highlighted and the effect of electron polarization of the surrounding ions of the defect is discussed

  19. Towards precise defect control in layered oxide structures by using oxide molecular beam epitaxy

    Federico Baiutti

    2014-05-01

    Full Text Available In this paper we present the atomic-layer-by-layer oxide molecular beam epitaxy (ALL-oxide MBE which has been recently installed in the Max-Planck Institute for Solid State Research and we report on its present status, providing some examples that demonstrate its successful application in the synthesis of different layered oxides, with particular reference to superconducting La2CuO4 and insulator-to-metal La2−xSrxNiO4. We briefly review the ALL-oxide MBE technique and its unique capabilities in the deposition of atomically smooth single-crystal thin films of various complex oxides, artificial compounds and heterostructures, introducing our goal of pursuing a deep investigation of such systems with particular emphasis on structural defects, with the aim of tailoring their functional properties by precise defects control.

  20. A metal-oxide-semiconductor radiation dosimeter with a thick and defect-rich oxide layer

    Enhancing the density of defects in the oxide layer is the main factor in improving the sensitivity of a metal-oxide-semiconductor (MOS) radiation dosimeter. This paper reports a novel MOS dosimeter with a very thick and defect-rich oxide layer fabricated by MEMS technology. The category of defects in SiO2 and their possible effect on the radiation dose sensing was analyzed. Then, we proposed combining deep-reactive-ion etching, thermal oxidation and low pressure chemical vapor deposition to realize an oxide layer containing multiple and large interfaces which can increase defects significantly. The trench-and-beam structure of silicon was considered in detail. The fabrication process was developed for obtaining a thick and compact MEMS-made SiO2. Our devices were irradiated by γ-rays of 60Co at 2 Gy per minute for 2 h and a thermally stimulated current (TSC) method was used to determine the readout of the dosimeters. Results show that there is a peak current of about 450 nA, indicating a total TSC charge of 158 μC and sensitivity of 1.1 μC mm−3·Gy, which is 40 times the sensitivity of previous MOS dosimeters. (paper)

  1. Control of bovine hepatic fatty acid oxidation

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

    1986-09-01

    Fatty acid oxidation by bovine liver slices and mitochondria was examined to determine potential regulatory sites of fatty acid oxidation. Conversion of 1-(/sup 14/C)palmitate to /sup 14/CO/sub 2/ and total (/sup 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/sup 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 ..mu..M). Liver mitochonndrial carnitine palmitoyltransferase exhibited Michaelis constants for palmitoyl Coenzyme A and l-carnitine of 11.5 ..mu..M 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.

  2. Control of bovine hepatic fatty acid oxidation

    Fatty acid oxidation by bovine liver slices and mitochondria was examined to determine potential regulatory sites of fatty acid oxidation. Conversion of 1-[14C]palmitate to 14CO2 and total [14C]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 CO2 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

  3. Controlled Defects of Zinc Oxide Nanorods for Efficient Visible Light Photocatalytic Degradation of Phenol

    Jamal Al-Sabahi

    2016-03-01

    Full Text Available Environmental pollution from human and industrial activities has received much attention as it adversely affects human health and bio-diversity. In this work we report efficient visible light photocatalytic degradation of phenol using supported zinc oxide (ZnO nanorods and explore the role of surface defects in ZnO on the visible light photocatalytic activity. ZnO nanorods were synthesized on glass substrates using a microwave-assisted hydrothermal process, while the surface defect states were controlled by annealing the nanorods at various temperatures and were characterized by photoluminescence and X-ray photoelectron spectroscopy. High performance liquid chromatography (HPLC was used for the evaluation of phenol photocatalytic degradation. ZnO nanorods with high surface defects exhibited maximum visible light photocatalytic activity, showing 50% degradation of 10 ppm phenol aqueous solution within 2.5 h, with a degradation rate almost four times higher than that of nanorods with lower surface defects. The mineralization process of phenol during degradation was also investigated, and it showed the evolution of different photocatalytic byproducts, such as benzoquinone, catechol, resorcinol and carboxylic acids, at different stages. The results from this study suggest that the presence of surface defects in ZnO nanorods is crucial for its efficient visible light photocatalytic activity, which is otherwise only active in the ultraviolet region.

  4. Ursodeoxycholic acid improves gastrointestinal motility defects in gallstone patients

    A Colecchia; G Mazzella; L Sandri; F Azzaroli; M Magliuolo; P Simoni; ML Bacchi-Reggiani; E Roda; D Festi

    2006-01-01

    AIM: To simultaneously evaluate the presence of defects in gallbladder and gastric emptying, as well as in intestinal transit in gallstone patients (GS) and the effect of chronic ursodeoxycholic acid (UDCA) administration on these parameters and on serum bile acids and clinical outcome in GS and controls (CTR).METHODS: After a standard liquid test meal, gallbladder and gastric emptying (by ultrasound), oroileal transit time (OI∏) (by an immunoenzymatic technique)and serum bile acids (by HPLC) were evaluated before and after 3 mo of UDCA (12 mg/kg bw/d) or placebo administration in 10 symptomatic GS and 10 matched healthy CTR.RESULTS: OI∏ was longer in GS than in CTR (P <0.0001); UDCA significantly reduced OI∏ in GS (P <0.0001), but not in CTR. GS had longer gastric halfemptying time (t1/2) than CTR (P < 0.0044) at baseline;after UDCA, t1/2 significantly decreased (P < 0.006) in GS but not in CTR. Placebo administration had no effect on gastric emptying and intestinal transit in both GS and CTR.CONCLUSION: The gallstone patient has simultaneous multiple impairments of gallbladder and gastric emptying, as well as of intestinal transit. UDCA administration restores these defects in GS, without any effect in CTR. These results confirm the pathogenetic role of gastrointestinal motility in gallstone disease and suggest an additional mechanism of action for UDCA in reducing bile cholesterol supersaturation.

  5. Defect controlled ferromagnetism in xenon ion irradiated zinc oxide

    Satyarthi, P.; Ghosh, S. [Nanostech Laboratory, Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016 (India); Mishra, P.; Sekhar, B.R. [Institute of Physics, Bhubaneswar 751005 (India); Singh, F.; Kumar, P.; Kanjilal, D. [Inter University Accelerator Centre, Aruna Asaf Ali Marg, New Delhi 110067 (India); Dhaka, R.S. [Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016 (India); Srivastava, P., E-mail: pankajs@physics.iitd.ac.in [Nanostech Laboratory, Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016 (India)

    2015-07-01

    We report evolution of magnetic properties in zinc oxide (ZnO) single crystals and polycrystalline films induced by 500 KeV xenon ion (Xe{sup 3+}) irradiation. Room temperature ferromagnetism (RT-FM) behavior is observed in as deposited polycrystalline ZnO film and strength of FM enhances with ion fluence up to 2×10{sup 17} ions/cm{sup 2} and then decreases. However, RT-FM is not observed in ZnO single crystals even after irradiation with fluence up to 3.5×10{sup 17} ions/cm{sup 2}. The X-ray diffraction (XRD) and Raman measurements of ZnO single crystal reveal slightly disordered hexagonal wurtzite structure after irradiation. However, as deposited and irradiated polycrystalline ZnO films indicate excessive lattice defects in the wurtzite structure. X-ray photoelectron spectroscopy (XPS) reveals that Zn vacancy/interstitial defects are absent in all samples, although oxygen vacancy lattice defects are present. Density of oxygen vacancies is much higher in as deposited and irradiated polycrystalline ZnO films as compared to single crystals. This seems to be the determining factor for the presence and absence of RT-FM in ZnO films and single crystals respectively. The observed FM behavior in as deposited and irradiated polycrystalline ZnO films is explained on the basis of spin split impurity band formation from singly and doubly occupied oxygen vacancies which initiates d{sup 0} ferromagnetism. - Highlights: • We report defect controlled ferromagnetism in inert xenon ion irradiated ZnO. • Threshold concentration of O vacancies is essential to trigger ferromagnetism. • Spin imbalance of singly and doubly occupied oxygen vacancies induces ferromagnetism. • We reveal importance of d{sup 0} ferromagnetism in ZnO for future spintronics devices.

  6. Folate Deficiency and Folic Acid Supplementation: The Prevention of Neural-Tube Defects and Congenital Heart Defects

    Andrew E. Czeizel

    2013-11-01

    Full Text Available Diet, particularly vitamin deficiency, is associated with the risk of birth defects. The aim of this review paper is to show the characteristics of common and severe neural-tube defects together with congenital heart defects (CHD as vitamin deficiencies play a role in their origin. The findings of the Hungarian intervention (randomized double-blind and cohort controlled trials indicated that periconceptional folic acid (FA-containing multivitamin supplementation prevented the major proportion (about 90% of neural-tube defects (NTD as well as a certain proportion (about 40% of congenital heart defects. Finally the benefits and drawbacks of three main practical applications of folic acid/multivitamin treatment such as (i dietary intake; (ii periconceptional supplementation; and (iii flour fortification are discussed. The conclusion arrived at is indeed confirmation of Benjamin Franklin’s statement: “An ounce of prevention is better than a pound of care”.

  7. The Arabidopsis male-sterile mutant dde2-2 is defective in the ALLENE OXIDE SYNTHASE gene encoding one of the key enzymes of the jasmonic acid biosynthesis pathway

    von Malek, Bernadette; van der Graaff, Eric; Schneitz, Kay; Keller, Beat

    2002-01-01

    The Arabidopsis thaliana (L.) Heynh. mutant delayed-dehiscence2-2 (dde2-2) was identified in an En1/Spm1 transposon-induced mutant population screened for plants showing defects in fertility. The dde2-2 mutant allele is defective in the anther dehiscence process and filament elongation and thus e...

  8. Acid monolayer functionalized iron oxide nanoparticle catalysts

    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

  9. Direct Oxidation of Ethene to Acetic Acid

    2001-01-01

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

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

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

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

  11. Fatty acid oxidation and ketogenesis in astrocytes

    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 CO2 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 CO2 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 [14C]acetoacetate formed from the [1-14C]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 [14C]acetoacetate formed from the (ω-1)labeled fatty acids contained 90% of the label at carbon 3 and 10% at carbon 1

  12. Folic acid and primary prevention of birth defects.

    Taruscio, Domenica; Carbone, Pietro; Granata, Orietta; Baldi, Francesca; Mantovani, Alberto

    2011-01-01

    Birth defects (BDs) are an important public health problem, due to their overall incidence, occurring in 2-3% of live births in European Union. Neural tube defects (NTDs) are among major NTDs, due to their severity and relatively high incidence; in the meanwhile NTDs are also the most effectively preventable BDs to date. In particular, an adequate folic acid (FA) intake reduces both the occurrence and the recurrence of NTDs; FA is the synthetic form of folates, naturally occurring vitamins in a number of foods, especially vegetables. The daily intake of 0.4 mg of FA should be recommended to all women of childbearing age who plan to become pregnant. The Italian Network for Primary Prevention of BDs through FA Promotion has achieved a significant improvement in FA awareness and use in the periconceptional period. Nevertheless, primary prevention of BDs needs to make further progress; the Italian National Centre for Rare Diseases participates in european sureveillance of congenital anomalies (EUROCAT) Joint Action as coordinator of activities on the effectiveness of BDs prevention. Mandatory food fortification with FA has not been introduced in any European country. The health benefits of FA in reducing the risk of NTDs are undisputed; however mechanistic and animal studies suggest a relationship between high FA intakes and increased cancer promotion, while human studies are still inconsistent and inconclusive. A Working Group organized by the European Food Safety Authority pointed out significant uncertainties about fortification safety and the need for more studies; currently, FA intake from fortified foods and supplements should not exceed 1 mg/day in adults. In conclusion, based on up-to-date scientific evidence, the Italian Network strategy pivots on periconceptional supplementation integrated with promotion of healthy eating habits, support to health education, enhancing the role of women in managing life choices about their health and pregnancy and increasing

  13. Formation and dissolution behaviour of niobium oxide in phosphoric acid solutions

    The effect of phosphoric acid concentration and temperature on the formation and dissolution process of niobium oxide was investigated using capacitance, potential and galvanostatic measurements. The formation rate of the niobium oxide increases with increasing phosphoric acid concentration and decreases with increasing temperature. The dissolution rate of the niobium oxide is accelerated by increasing phosphoric acid concentration and temperature. The activation energy was calculated for both the formation and dissolution process and found to be 8.93 and 16.65 kJ/mol respectively. The effect of formation voltage on the dissolution process of niobium oxide was also investigated. The oxide film formed at high-formation voltage has a more defective character than that formed at lower voltage. This enhances the dissolution process of the oxide. The effect of current density on the formation rate and the thickness during the oxide film growth was measured. (orig.)

  14. Acid-permanganate oxidation of potassium tetraphenylboron

    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 CO2, 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 NaMnO4/2.5M H3PO4 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 CO2 (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

  15. Salmonella typhimurium mutants defective in acetohydroxy acid synthases I and II.

    Shaw, K J; Berg, C M; Sobol, T J

    1980-01-01

    An analysis of transposon-induced mutants shows that Salmonella typhimurium possesses two major isozymes of acetohydroxy acid synthase, the enzymes which mediate the first common step in isoleucine and valine biosynthesis. A third (minor) acetohydroxy acid synthase is present, but its significance in isoleucine and valine synthesis may be negligible. Mutants defective in acetohydroxy acid synthase II (ilvG::Tn10) require isoleucine, alpha-ketobutyrate, or threonine for growth, a mutant defect...

  16. Oxide film defects in Al alloys and the formation of hydrogen- related porosity

    Griffiths, W. D.; Gerrard, A. J.; Yue, Y.

    2016-03-01

    Double oxide film defects have also been held responsible for the origins of hydrogen porosity, where hydrogen dissolved in the Al melt passes into the interior atmosphere of the double oxide film defect causing it to inflate. However, this is in opposition to long- established evidence that H cannot readily diffuse through aluminium oxide. To investigate this further, samples of commercial purity Al were first degassed to remove their initial H content, and then heated to above their melting point and held in atmospheres of air and nitrogen respectively, to determine any differences in H pick-up. The experiment showed that samples held in an oxidising atmosphere, and having an oxide skin, picked up significantly less H than when the samples were held in a nitrogen atmosphere, which resulted in the formation of AlN in cracks in the oxide skin of the sample. It is suggested that double oxide film defects can give rise to hydrogen-related porosity, but this occurs more quickly when the oxygen in the original oxide film defect has been consumed by reaction with the surrounding melt and nitrogen reacts to form AlN, which is more permeable to H than alumina, more easily allowing the oxide film defect to give rise to a hydrogen pore. This is used to interpret results from an earlier synchrotron experiment, in which a small pore was seen to grow into a larger pore, while an adjacent large pore remained at a constant size.

  17. Neural tube defects in Costa Rica, 1987-2012: origins and development of birth defect surveillance and folic acid fortification.

    Barboza-Argüello, María de la Paz; Umaña-Solís, Lila M; Azofeifa, Alejandro; Valencia, Diana; Flores, Alina L; Rodríguez-Aguilar, Sara; Alfaro-Calvo, Thelma; Mulinare, Joseph

    2015-03-01

    Our aim was to provide a descriptive overview of how the birth defects surveillance and folic acid fortification programs were implemented in Costa Rica-through the establishment of the Registry Center for Congenital Anomalies (Centro de Registro de Enfermedades Congénitas-CREC), and fortification legislation mandates. We estimated the overall prevalence of neural tube defects (i.e., spina bifida, anencephaly and encephalocele) before and after fortification captured by CREC. Prevalence was calculated by dividing the total number of infants born with neural tube defects by the total number of live births in the country (1987-2012).A total of 1,170 newborns with neural tube defects were identified from 1987 to 2012 (1992-1995 data excluded); 628 were identified during the baseline pre-fortification period (1987-1991; 1996-1998); 191 during the fortification period (1999-2002); and 351 during the post-fortification time period (2003-2012). The overall prevalence of neural tube defects decreased from 9.8 per 10,000 live-births (95 % CI 9.1-10.5) for the pre-fortification period to 4.8 per 10,000 live births (95 % CI 4.3-5.3) for the post-fortification period. Results indicate a statistically significant (P < 0.05) decrease of 51 % in the prevalence of neural tube defects from the pre-fortification period to the post-fortification period. Folic acid fortification via several basic food sources has shown to be a successful public health intervention for Costa Rica. Costa Rica's experience can serve as an example for other countries seeking to develop and strengthen both their birth defects surveillance and fortification programs. PMID:24952876

  18. Defect Mediated Ferromagnetism in Zinc Oxide Thin Film Heterostructures

    Mal, Siddhartha

    Recent developments in the field of spintronics (spin based electronics) have led to an extensive search for materials in which semiconducting properties can be integrated with magnetic properties to realize the objective of successful fabrication of spin-based devices. Since zinc oxide (ZnO) posits a promising player, it is important to elucidate the critical issues regarding the origin and nature of magnetism in ZnO thin film heterostructures. Another critical issue in the development of practical devices based on metal oxides is the integration of high quality epitaxial thin films on the existing technology based on Si (100) substrates, which requires appropriate substrate templates. The present research work is focused on the study of room temperature ferromagnetism (RTFM) caused by intrinsic defects and precise control of RTFM using thermal treatments and laser and ion irradiation. We performed a systematic study of the structural, chemical, electrical, optical and magnetic properties of undoped ZnO films grown under different conditions as well as the films that were annealed in various environments. Oxygen annealed films displayed a sequential transition from ferromagnetism to diamagnetism as a function of the annealing temperature. An increase in the green band intensity has been observed in oxygen annealed ZnO films. Reversible switching of room-temperature ferromagnetism and n-type conductivity have been demonstrated by oxygen and vacuum annealing. Detailed electron energy loss spectroscopy and secondary ion mass spectroscopy studies have been presented to rule out the possibility of external source of magnetism. Electron-Paramagnetic Resonance (EPR) measurements indicate the presence of a broad peak at g=2.01. This would be most consistent with the magnetic moment arising from the oxygen vacancies (g=1.996), although the possible contribution from Zn vacancies (g=2.013) cannot be entirely ruled out. The magnetic moment in these films may arise from the

  19. The prevention of neural tube defects by folic acid supplementation

    H. W. Hitzeroth

    1993-05-01

    Full Text Available Neural tube defects, in particular spina bifida and anencephaly, are serious and relatively common congenital abnormalities worldwide. They also occur in South Africa and affect all population groups to varying degrees. The overall incidence in South Africa is approximately 1-2 per 1000 newborns. Higher incidences, up to 6 per 1000 newborns have been recorded in certain parts, especially in some rural areas of the country. In total as many as 1500 newborns could be affected by a neural tube defect each year. The precise aetiology of neural tube defects is still unknown.

  20. Defect engineering of the electronic transport through cuprous oxide interlayers

    Fadlallah, Mohamed M.; Eckern, Ulrich; Schwingenschlögl, Udo

    2016-06-01

    The electronic transport through Au–(Cu2O)n–Au junctions is investigated using first-principles calculations and the nonequilibrium Green’s function method. The effect of varying the thickness (i.e., n) is studied as well as that of point defects and anion substitution. For all Cu2O thicknesses the conductance is more enhanced by bulk-like (in contrast to near-interface) defects, with the exception of O vacancies and Cl substitutional defects. A similar transmission behavior results from Cu deficiency and N substitution, as well as from Cl substitution and N interstitials for thick Cu2O junctions. In agreement with recent experimental observations, it is found that N and Cl doping enhances the conductance. A Frenkel defect, i.e., a superposition of an O interstitial and O substitutional defect, leads to a remarkably high conductance. From the analysis of the defect formation energies, Cu vacancies are found to be particularly stable, in agreement with earlier experimental and theoretical work.

  1. Defect engineering of the electronic transport through cuprous oxide interlayers

    Fadlallah, Mohamed M.

    2016-06-03

    The electronic transport through Au–(Cu2O)n–Au junctions is investigated using first-principles calculations and the nonequilibrium Green’s function method. The effect of varying the thickness (i.e., n) is studied as well as that of point defects and anion substitution. For all Cu2O thicknesses the conductance is more enhanced by bulk-like (in contrast to near-interface) defects, with the exception of O vacancies and Cl substitutional defects. A similar transmission behavior results from Cu deficiency and N substitution, as well as from Cl substitution and N interstitials for thick Cu2O junctions. In agreement with recent experimental observations, it is found that N and Cl doping enhances the conductance. A Frenkel defect, i.e., a superposition of an O interstitial and O substitutional defect, leads to a remarkably high conductance. From the analysis of the defect formation energies, Cu vacancies are found to be particularly stable, in agreement with earlier experimental and theoretical work.

  2. Adding Folic Acid to Corn Masa Flour May Prevent Birth Defects

    ... For Consumers Consumer Updates Adding Folic Acid to Corn Masa Flour May Prevent Birth Defects Share Tweet ... mainstay of their regular diets—which often are corn masa-based.” This could be a reason why ...

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

    B. Syama Sundar; P.S.Radhakrishna murti

    2014-01-01

    Kinetics of oxidation of phenyl acetic acid and DL- Mandelic acid by potassium permanganate in aqueous acetic acid and perchloric acid mixture reveals that the kinetic orders are first order in oxidant, first order in H+ and zero order in substrate for phenyl acetic acid. DL-Mandelic acid exhibits first order in oxidant and zero order in substrate. The results are rationalised by a mechanism involving intermediate formation of mandelic acid in case of Phenyl acetic acid and ester formation wi...

  4. Interplay between strain, defect charge state, and functionality in complex oxides

    Aschauer, Ulrich; Spaldin, Nicola A.

    2016-07-01

    We use first-principles calculations to investigate the interplay between strain and the charge state of point defect impurities in complex oxides. Our work is motivated by recent interest in using defects as active elements to provide novel functionality in coherent epitaxial films. Using oxygen vacancies as model point defects, and CaMnO3 and MnO as model materials, we calculate the changes in internal strain caused by changing the charge state of the vacancies, and conversely the effect of strain on charge-state stability. Our results show that the charge state is a degree of freedom that can be used to control the interaction of defects with strain and hence the concentration and location of defects in epitaxial films. We propose the use of field-effect gating to reversibly change the charge state of defects and hence the internal strain and corresponding strain-induced functionalities.

  5. Final report. Defects and transport in mixed oxides

    Dieckmann, R{umlt u}diger

    2001-12-13

    New results on the point defect chemistry of (Ni{sub x}Fe{sub 1-x}){sub 3-delta}O{sub 4} and on the cation tracer diffusion in this spinel solid solution are presented and discussed. The equation system for the defect chemistry of perovskites of the type A{sub 1-x}B{sub 1+x}O{sub 3-delta} have been worked out and used to derive Kr{umlt o}ger-Vink diagrams. The deviation from stoichiometry, delta, in LA{sub 1-x}Mn{sub 1+x}O{sub 3-delta} has been measured at 1100, 1200, and 1300 degrees Celsius as a function of the oxygen activity and the composition variable x. At high and low oxygen activities, the data were fit by taking into account the electrostatic interaction between the charge defects by making use of the Debye H{umlt u}ckel theory.

  6. The influence of initial defects on mechanical stress and deformation distribution in oxidized silicon

    Kulinich O. A.

    2008-10-01

    Full Text Available The near-surface silicon layers in silicon – dioxide silicon systems with modern methods of research are investigated. It is shown that these layers have compound structure and their parameters depend on oxidation and initial silicon parameters. It is shown the influence of initial defects on mechanical stress and deformation distribution in oxidized silicon.

  7. Complex oxide scintillators: material defects and scintillation performace

    Nikl, Martin; Laguta, Valentyn; Vedda, A.

    2008-01-01

    Roč. 245, č. 9 (2008), 1701-1722. ISSN 0370-1972 R&D Projects: GA AV ČR IAA100100810 Institutional research plan: CEZ:AV0Z10100521 Keywords : scintillator * structural defects * impurities * trapping states * electron paramagnetic resonance * thermoluminescence Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.166, year: 2008

  8. Fatty acid oxidation in skeletal and cardiac muscle

    The biochemical investigations described in this thesis deal with two aspects of fatty acid oxidation in muscle: a comparison of the use of cell-free and cellular systems for oxidation measurements, and studies on the assay and the role of the fatty acid binding protein in fatty acid metabolism. The fatty acid oxidation rates are determined radiochemically by the sum of 14CO2 and 14C-labeled acid-soluble products formed during oxidation of [14C]-fatty acids. A radiochemical procedure for the assay of fatty acid binding by proteins is described. (Auth.)

  9. International retrospective cohort study of neural tube defects in relation to folic acid recommendations : are the recommendations working?

    Botto, LD; Lisi, A; Robert-Gnansia, E; Erickson, JD; Vollset, SE; Mastroiacovo, P; Botting, B; Cocchi, G; de Vigan, C; de Walle, H; Feijoo, M; Irgens, LM; McDonnell, B; Merlob, P; Ritvanen, A; Scarano, G; Siffel, C; Metneki, J; Stoll, C; Smithells, R; Goujard, J

    2005-01-01

    Objective To evaluate the effectiveness of policies and recommendations on folic acid aimed at reducing the occurrence of neural tube defects. Design Retrospective cohort study of births monitored by birth defect registries. Setting 13 birth defects registries monitoring rates of neural tube defects

  10. Defect structure of indium tin oxide and its relationship to conductivity

    Gonzalez, G. B.; Cohen, J. B.; Hwang, J.-H.; Mason, T. O.; Hodges, J. P.; Jorgensen, J. D.

    2000-05-09

    Doping In{sub 2}O{sub 3} with tin results in an improved transparent conducting oxide (TCO). Although indium tin oxide (ITO) is the most frequently used commercial TCO, its defect structure is still uncertain. Previously, its defect chemistry has been inferred based on the conductivity of the material. To directly study the defect structure of ITO, the authors prepared powders under different processing environments and performed neutron powder diffraction. Structural information was obtained by performing Rietveld analysis. The results include positions of the atoms, their thermal displacements, the fractional occupancy of the defect oxygen site, and the fractional occupancies of Sn on each of the two nonequivalent cation sites, showing a strong preference for the b site. These structural results are correlated with the measured electrical properties of the same samples.

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

    Yan Gong; Lu Lin; Zhipei Yan

    2011-01-01

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

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

    Yan Gong

    2011-02-01

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

  13. Methanol adsorption on magnesium oxide surface with defects: a DFT study

    Branda, M. M.; Ferullo, R. M.; Belelli, P. G.; Castellani, N. J.

    2003-03-01

    The methanol adsorption on several defects of the magnesium oxide surface were studied. Structural and electronic study with geometrical optimization and natural bond orbital (NBO) analysis were performed using a density functional theory (DFT) method. Oxygen and magnesium with different coordination numbers have very different reactivity in this surface producing dissociated and non-dissociated species. These results are in agreement with infrared spectroscopy observations where CH 3OH, OCH 3 and OH species were found in defective MgO surfaces.

  14. Multivitamins, Folic Acid and Birth Defects: Knowledge, Beliefs and Behaviors of Hispanic Women in North Carolina

    deRosset, Leslie; Mullenix, Amy; Zhang, Lei

    2009-01-01

    Background: Consumption of folic acid prior to conception can prevent up to 70% of neural tube defect (NTD)-affected pregnancies. In 1992, the U.S. Public Health Service (USPHS) issued a recommendation that all women of childbearing age capable of becoming pregnant consume 400 [mu]g of folic acid daily to reduce their risk for a NTD-affected…

  15. How surface reparation prevents catalytic oxidation of carbon monoxide on atomic gold at defective magnesium oxide surfaces.

    Töpfer, Kai; Tremblay, Jean Christophe

    2016-07-21

    In this contribution, we study using first principles the co-adsorption and catalytic behaviors of CO and O2 on a single gold atom deposited at defective magnesium oxide surfaces. Using cluster models and point charge embedding within a density functional theory framework, we simulate the CO oxidation reaction for Au1 on differently charged oxygen vacancies of MgO(001) to rationalize its experimentally observed lack of catalytic activity. Our results show that: (1) co-adsorption is weakly supported at F(0) and F(2+) defects but not at F(1+) sites, (2) electron redistribution from the F(0) vacancy via the Au1 cluster to the adsorbed molecular oxygen weakens the O2 bond, as required for a sustainable catalytic cycle, (3) a metastable carbonate intermediate can form on defects of the F(0) type, (4) only a small activation barrier exists for the highly favorable dissociation of CO2 from F(0), and (5) the moderate adsorption energy of the gold atom on the F(0) defect cannot prevent insertion of molecular oxygen inside the defect. Due to the lack of protection of the color centers, the surface becomes invariably repaired by the surrounding oxygen and the catalytic cycle is irreversibly broken in the first oxidation step. PMID:27345190

  16. Defects in the oxidative killing of microorganisms by phagocytic leukocytes.

    Roos, D; Weening, R S

    One of the most important mechanisms of phagocytic killing of ingested microorganisms by leukocytes is the generation of toxic oxygen products. During phagocytosis, neutrophils, as well as monocytes and macrophages, display a strongly increased cell respiration. Quantitatively the most important product of this reaction is hydrogen peroxide. Superoxide is also generated in large amounts, probably as an intermediate in the formation of hydrogen peroxide. Indications exist that singlet oxygen and hydroxyl radicals are also formed in this process. Some of these oxygen products have microbicidal properties by themselves. The effect of hydrogen peroxide is greatly enhanced by the enzyme myeloperoxidase. Several dysfunctions of this sytem are known. In chronic granulomatous disease the enzyme system that produces superoxide is not operative. Thus, no superoxide or hydrogen peroxide is generated, leading to a severely decreased bacterial killing capacity. The exact molecular defects in the X-linked and the autosomal form are as yet undefined. Two variants are also known: lipochrome histiocytosis, with different clinical and histological manifestations, and a 'triggering defect' where only strongly opsonized particles trigger the respiratory burst. Myeloperoxidase deficiency leads to slightly decreased killing capacity, especially for yeasts. In glucose-6-phosphate dehydrogenase deficiency no oxygen radicals or hydrogen peroxide are produced because no equivalents for oxygen reduction can be generated in the hexose-monophosphate shunt. Deficiencies in the glutathione redox system also result in impaired phagocyte function, probably because the cells have to be protected against their own toxic oxygen products. PMID:225141

  17. Study of defect generated visible photoluminescence in zinc oxide nano-particles prepared using PVA templates

    Oudhia, A. [Department of Physics, Government V.Y.T. PG. Autonomous College, Durg, 491001 C.G. (India); Choudhary, A., E-mail: aarti.bhilai@gmail.com [Department of Physics, Government V.Y.T. PG. Autonomous College, Durg, 491001 C.G. (India); Sharma, S.; Aggrawal, S. [Department of Physics, Government V.Y.T. PG. Autonomous College, Durg, 491001 C.G. (India); Dhoble, S.J. [RTM University Nagpur, Maharashtra (India)

    2014-10-15

    Intrinsic defect generated photoluminescence (PL) in zinc oxide nanoparticles (NPs) obtained by a PVA template based wet-chemical process has been studied. A good controllability was achieved on the surface defects, structure and the morphology of ZnO NPs through the variation of solvents used in synthesis. The PL emission strongly depended on the defect structure and morphology. SEM, XRD, annealing and PL excitation studies were used to analyze the types of defects involved in the visible emission as well as the defect concentration. The mechanism for the blue, green and yellow emissions was proposed. The spectral content of the visible emission was controlled through generation/removal of defects through the shape transformation or annealing by focusing on defect origins and broad controls. - Highlights: • ZnO nanoparticles were synthesized using poly-vinyl alcohol template in various solvents. • The structure and morphology of ZnO nanoparticles were depended on dielectric constant and boiling point of solvents. • Photoluminescence properties of ZnO nanoparticles were studied. • Maximum optical absorbance and Photoluminescence intensity were found in ethanolic preparation. • ZnO nanoparticles were annealed at different temperatures for detection of defect emission.

  18. Study of defect generated visible photoluminescence in zinc oxide nano-particles prepared using PVA templates

    Intrinsic defect generated photoluminescence (PL) in zinc oxide nanoparticles (NPs) obtained by a PVA template based wet-chemical process has been studied. A good controllability was achieved on the surface defects, structure and the morphology of ZnO NPs through the variation of solvents used in synthesis. The PL emission strongly depended on the defect structure and morphology. SEM, XRD, annealing and PL excitation studies were used to analyze the types of defects involved in the visible emission as well as the defect concentration. The mechanism for the blue, green and yellow emissions was proposed. The spectral content of the visible emission was controlled through generation/removal of defects through the shape transformation or annealing by focusing on defect origins and broad controls. - Highlights: • ZnO nanoparticles were synthesized using poly-vinyl alcohol template in various solvents. • The structure and morphology of ZnO nanoparticles were depended on dielectric constant and boiling point of solvents. • Photoluminescence properties of ZnO nanoparticles were studied. • Maximum optical absorbance and Photoluminescence intensity were found in ethanolic preparation. • ZnO nanoparticles were annealed at different temperatures for detection of defect emission

  19. Genetic defects in the oxidative phosphorylation (OXPHOS) system.

    Janssen, R.J.R.J.; Heuvel, L.P.W.J. van den; Smeitink, J.A.M.

    2004-01-01

    The oxidative phosphorylation (OXPHOS) system consists of five multiprotein complexes and two mobile electron carriers embedded in the lipid bilayer of the mitochondrial inner membrane. With the exception of complex II and the mobile carriers, the other parts of the OXPHOS system are under dual gene

  20. Slow Replication Fork Velocity of Homologous Recombination-Defective Cells Results from Endogenous Oxidative Stress

    Magdalou, Indiana; Machon, Christelle; Dardillac, Elodie; Técher, Hervé; Guitton, Jérôme; Debatisse, Michelle; Lopez, Bernard S.

    2016-01-01

    Replications forks are routinely hindered by different endogenous stresses. Because homologous recombination plays a pivotal role in the reactivation of arrested replication forks, defects in homologous recombination reveal the initial endogenous stress(es). Homologous recombination-defective cells consistently exhibit a spontaneously reduced replication speed, leading to mitotic extra centrosomes. Here, we identify oxidative stress as a major endogenous source of replication speed deceleration in homologous recombination-defective cells. The treatment of homologous recombination-defective cells with the antioxidant N-acetyl-cysteine or the maintenance of the cells at low O2 levels (3%) rescues both the replication fork speed, as monitored by single-molecule analysis (molecular combing), and the associated mitotic extra centrosome frequency. Reciprocally, the exposure of wild-type cells to H2O2 reduces the replication fork speed and generates mitotic extra centrosomes. Supplying deoxynucleotide precursors to H2O2-exposed cells rescued the replication speed. Remarkably, treatment with N-acetyl-cysteine strongly expanded the nucleotide pool, accounting for the replication speed rescue. Remarkably, homologous recombination-defective cells exhibit a high level of endogenous reactive oxygen species. Consistently, homologous recombination-defective cells accumulate spontaneous γH2AX or XRCC1 foci that are abolished by treatment with N-acetyl-cysteine or maintenance at 3% O2. Finally, oxidative stress stimulated homologous recombination, which is suppressed by supplying deoxynucleotide precursors. Therefore, the cellular redox status strongly impacts genome duplication and transmission. Oxidative stress should generate replication stress through different mechanisms, including DNA damage and nucleotide pool imbalance. These data highlight the intricacy of endogenous replication and oxidative stresses, which are both evoked during tumorigenesis and senescence initiation

  1. Quinolinic Acid: Neurotoxin or Oxidative Stress Modulator?

    Lenka Kubicova

    2013-10-01

    Full Text Available Quinolinic acid (2,3-pyridinedicarboxylic acid, QUIN is a well-known neurotoxin. Consequently, QUIN could produce reactive oxygen species (ROS. ROS are generated in reactions catalyzed by transition metals, especially iron (Fe. QUIN can form coordination complexes with iron. A combination of differential pulse voltammetry, deoxyribose degradation and Fe(II autoxidation assays was used for explorating ROS formation in redox reactions that are catalyzed by iron in QUIN-Fe complexes. Differential pulse voltammetry showed an anodic shift of the iron redox potential if iron was liganded by QUIN. In the H2O2/FeCl3/ascorbic acid variant of the deoxyribose degradation assay, the dose-response curve was U-shaped. In the FeCl3/ascorbic acid variant, QUIN unambiguously showed antioxidant effects. In the Fe(II autoxidation assay, QUIN decreased the rate of ROS production caused by Fe(II oxidation. Our study confirms that QUIN toxicity may be caused by ROS generation via the Fenton reaction. This, however, applies only for unnaturally high concentrations that were used in attempts to provide support for the neurotoxic effect. In lower concentrations, we show that by liganding iron, QUIN affects the Fe(II/Fe(III ratios that are beneficial to homeostasis. Our results support the notion that redox chemistry can contribute to explaining the hormetic dose-response effects.

  2. Point defects and irradiation in oxides: simulations at the atomic scale

    The studies done by Jean-Paul Crocombette between 1996 and 2005 in the Service de Recherches de Metallurgie Physique of the Direction de l'Energie Nucleaire in Saclay are presented in this Habilitation thesis. These works were part of the material science researches on the ageing, especially under irradiation, of oxides of interest for the nuclear industry. In this context simulation studies at the atomic scale were performed on two elementary components of ageing under irradiation : point defects and displacement cascades ; using two complementary simulation techniques : ab initio electronic structure calculations and empirical potential molecular dynamics. The first part deals with point defects : self defects (vacancies or interstitials) or hetero-atomic dopants. One first recalls the energetics of such defects in oxides, the specific features of defects calculations and the expected accuracy of these calculations. Then one presents the results obtained on uranium dioxide, oxygen in silver and amorphous silica. The second part tackles the modelling of disintegration recoil nuclei in various?displacement cascades created by crystalline matrices for actinide waste disposal. Cascade calculations give access to the amorphization mechanisms under irradiation of these materials. One thus predicts that the amorphization in zircon takes place directly in the tracks whereas in lanthanum zirconate, the amorphization proceeds through the accumulation of point defects. Finally the prospects of these studies are discussed. (author)

  3. Defects in oxide surfaces studied by atomic force and scanning tunneling microscopy

    Thomas König

    2011-01-01

    Full Text Available Surfaces of thin oxide films were investigated by means of a dual mode NC-AFM/STM. Apart from imaging the surface termination by NC-AFM with atomic resolution, point defects in magnesium oxide on Ag(001 and line defects in aluminum oxide on NiAl(110, respectively, were thoroughly studied. The contact potential was determined by Kelvin probe force microscopy (KPFM and the electronic structure by scanning tunneling spectroscopy (STS. On magnesium oxide, different color centers, i.e., F0, F+, F2+ and divacancies, have different effects on the contact potential. These differences enabled classification and unambiguous differentiation by KPFM. True atomic resolution shows the topography at line defects in aluminum oxide. At these domain boundaries, STS and KPFM verify F2+-like centers, which have been predicted by density functional theory calculations. Thus, by determining the contact potential and the electronic structure with a spatial resolution in the nanometer range, NC-AFM and STM can be successfully applied on thin oxide films beyond imaging the topography of the surface atoms.

  4. Genetics Home Reference: congenital bile acid synthesis defect type 1

    ... 88(4):1833-41. Citation on PubMed Clayton PT. Disorders of bile acid synthesis. J Inherit Metab ... 13. Review. Citation on PubMed Subramaniam P, Clayton PT, Portmann BC, Mieli-Vergani G, Hadzić N. Variable ...

  5. Investigating the Defect Structures in Transparent Conducting Oxides Using X-ray and Neutron Scattering Techniques

    Gabriela B. González

    2012-05-01

    Full Text Available Transparent conducting oxide (TCO materials are implemented into a wide variety of commercial devices because they possess a unique combination of high optical transparency and high electrical conductivity. Created during the processing of the TCOs, defects within the atomic-scale structure are responsible for their desirable optical and electrical properties. Therefore, studying the defect structure is essential to a better understanding of the behavior of transparent conductors. X-ray and neutron scattering techniques are powerful tools to investigate the atomic lattice structural defects in these materials. This review paper presents some of the current developments in the study of structural defects in n-type TCOs using x-ray diffraction (XRD, neutron diffraction, extended x-ray absorption fine structure (EXAFS, pair distribution functions (PDFs, and x-ray fluorescence (XRF.

  6. Photoluminescence emission of nanoporous anodic aluminum oxide films prepared in phosphoric acid

    Nourmohammadi, Abolghasem; Asadabadi, Saeid Jalali; Yousefi, Mohammad Hasan; Ghasemzadeh, Majid

    2012-12-01

    The photoluminescence emission of nanoporous anodic aluminum oxide films formed in phosphoric acid is studied in order to explore their defect-based subband electronic structure. Different excitation wavelengths are used to identify most of the details of the subband states. The films are produced under different anodizing conditions to optimize their emission in the visible range. Scanning electron microscopy investigations confirm pore formation in the produced layers. Gaussian analysis of the emission data indicates that subband states change with anodizing parameters, and various point defects can be formed both in the bulk and on the surface of these nanoporous layers during anodizing.

  7. d0 Ferromagnetism in Oxide Nanowires: Role of Intrinsic Defects

    Mandal Kalyan

    2013-01-01

    Full Text Available In this report, we have investigated the origin of defect-induced room-temperature d0 ferromagnetism in pure SnO2 and ZnO nanowires (NWs with average diameter ~ 50 nm, prepared by template assisted route. Photoluminescence (PL and electron paramagnetic resonance (EPR spectroscopic measurements show the singly ionized oxygen vacancy is inducing ferromagnetism in pure SnO2 NWs whereas cation (Zn vacancy is found to responsible for the ferromagnetic behaviour in pure ZnO NWs. Besides, it is found that the Zn vacancy-induced ferromagnetism in ZnO can be tuned by substituting few percentage of nonmagnetic alkali metal like potassium (K at Zn site. Saturation moment as well as Curie temperature has found to increase significantly with K-doping up to 4 at.% but a decrease of ferromagnetic response is observed for higher K-doping. X-ray photoelectron spectra show that K+1 ions substitute at Zn site and thus introduce hole through which a ferromagnetic interaction between Zn vacancies can be mediated. The direct correlation between the Zn vacancy concentration and the corresponding saturation moment indicates that Zn vacancyinduced ferromagnetism in ZnO can be successfully tuned by K-doping that can an exciting approach to prepare ZnO-based dilute magnetic semiconductors for modern spintronic technology.

  8. Mutation analysis in mitochondrial fatty acid oxidation defects

    Gregersen, N; Andresen, B S; Corydon, M J;

    2001-01-01

    systems may help to assess the balance between genetic and environmental factors in the clinical expression of a given mutation. The realization that the effect of the monogene, such as disease-causing mutations in the VLCAD, MCAD, and SCAD genes, may be modified by variations in other genes presages the...

  9. The nature of paramagnetic defects in tin (IV) oxide

    Highlights: • EPR signal at g = 1.8–1.9 (D) was studied in SnO2 prepared under different conditions. • Conditions appropriate for detection of D signal and parameters of them were defined. • Structure of paramagnetic center (PC) attributed to the D signal was proposed. • The PC is a complex of oxygen vacancies with entrapped electrons near SnO2 surface. - Abstract: The nature of paramagnetic centers which are responsible for the EPR signal at g = 1.8–1.9 in tin (IV) oxide was studied. Polycrystalline SnO2 samples were obtained by sol–gel method and by thermal treatment of the precursors containing tin atoms in different oxidation states. The parameters of the EPR spectra recorded after heat treatment of the samples in air, oxygen and hydrogen atmospheres, and in vacuum were analyzed. The observed parameters of the EPR spectra do not allow to assign the paramagnetic center with g = 1.8–1.9 to Sn3+ center. The structure of the paramagnetic center attributed to the EPR signal at g = 1.8–1.9 was proposed. The proposed structure of the paramagnetic center includes a complex of oxygen vacancies at (1 0 1) plane of rutile-type SnO2 lattice

  10. The nature of paramagnetic defects in tin (IV) oxide

    Ivanovskaya, M., E-mail: ivanovskaya@bsu.by [Research Institute for Physical Chemical Problems, Belarusian State University, Leningradskaya Str., 14, 220030 Minsk (Belarus); Ovodok, E., E-mail: ovodokea@gmail.com [Research Institute for Physical Chemical Problems, Belarusian State University, Leningradskaya Str., 14, 220030 Minsk (Belarus); Golovanov, V. [South-Ukrainian University, Staroportofrankovskaya Str., 26, 65008 Odessa (Ukraine)

    2015-08-18

    Highlights: • EPR signal at g = 1.8–1.9 (D) was studied in SnO{sub 2} prepared under different conditions. • Conditions appropriate for detection of D signal and parameters of them were defined. • Structure of paramagnetic center (PC) attributed to the D signal was proposed. • The PC is a complex of oxygen vacancies with entrapped electrons near SnO{sub 2} surface. - Abstract: The nature of paramagnetic centers which are responsible for the EPR signal at g = 1.8–1.9 in tin (IV) oxide was studied. Polycrystalline SnO{sub 2} samples were obtained by sol–gel method and by thermal treatment of the precursors containing tin atoms in different oxidation states. The parameters of the EPR spectra recorded after heat treatment of the samples in air, oxygen and hydrogen atmospheres, and in vacuum were analyzed. The observed parameters of the EPR spectra do not allow to assign the paramagnetic center with g = 1.8–1.9 to Sn{sup 3+} center. The structure of the paramagnetic center attributed to the EPR signal at g = 1.8–1.9 was proposed. The proposed structure of the paramagnetic center includes a complex of oxygen vacancies at (1 0 1) plane of rutile-type SnO{sub 2} lattice.

  11. The Iron-Catalyzed Oxidation of Hydrazine by Nitric Acid

    Karraker, D.G.

    2001-07-17

    To assess the importance of iron to hydrazine stability, the study of hydrazine oxidation by nitric acid has been extended to investigate the iron-catalyzed oxidation. This report describes those results.

  12. Advanced oxidation of acid and reactive dyes

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

    2008-01-01

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

  13. Nitrous oxides desorption from nitric acid (58–60 wt. %)

    Литвиненко, Олександр Олександрович; Печенко, Тамара Ивановна; Подустов, Михаил Алексеевич; Букатенко, Алексей Иванович

    2015-01-01

    The process of nitrous oxides desorption from nitric acid solutions (in domestic schemes) was considered. It is shown that in the process of desorption (or stripping), the nitrous oxides are not removed from solutions completely, so, the nitric acid does not satisfy the technical requirements in Ukraine.The research objective was to bring the quality of nitric acid to technological standards by removing (stripping) nitrous oxides from its solutions.To achieve the research objective, the balan...

  14. Interfacial strain and defects in asymmetric Fe-Mn oxide hybrid nanoparticles

    Mayence, Arnaud; Wéry, Madeleine; Tran, Dung Trung; Wetterskog, Erik; Svedlindh, Peter; Tai, Cheuk-Wai; Bergström, Lennart

    2016-07-01

    Asymmetric Fe-Mn oxide hybrid nanoparticles have been obtained by a seed-mediated thermal decomposition-based synthesis route. The use of benzyl ether as the solvent was found to promote the orientational growth of Mn1-xO onto the iron oxide nanocube seeds yielding mainly dimers and trimers whereas 1-octadecene yields large nanoparticles. HRTEM imaging and HAADF-STEM tomography performed on dimers show that the growth of Mn1-xO occurs preferentially along the edges of iron oxide nanocubes where both oxides share a common crystallographic orientation. Fourier filtering and geometric phase analysis of dimers reveal a lattice mismatch of 5% and a large interfacial strain together with a significant concentration of defects. The saturation magnetization is lower and the coercivity is higher for the Fe-Mn oxide hybrid nanoparticles compared to the iron oxide nanocube seeds.Asymmetric Fe-Mn oxide hybrid nanoparticles have been obtained by a seed-mediated thermal decomposition-based synthesis route. The use of benzyl ether as the solvent was found to promote the orientational growth of Mn1-xO onto the iron oxide nanocube seeds yielding mainly dimers and trimers whereas 1-octadecene yields large nanoparticles. HRTEM imaging and HAADF-STEM tomography performed on dimers show that the growth of Mn1-xO occurs preferentially along the edges of iron oxide nanocubes where both oxides share a common crystallographic orientation. Fourier filtering and geometric phase analysis of dimers reveal a lattice mismatch of 5% and a large interfacial strain together with a significant concentration of defects. The saturation magnetization is lower and the coercivity is higher for the Fe-Mn oxide hybrid nanoparticles compared to the iron oxide nanocube seeds. Electronic supplementary information (ESI) available: Materials characterization, powder X-ray diffraction, EFTEM images, EELS spectra, HAADF-STEM. See DOI: 10.1039/c6nr01373b

  15. Loss of adipose fatty acid oxidation does not potentiate obesity at thermoneutrality

    Jieun Lee; Joseph Choi; Susan Aja; Susanna Scafidi; Michael J. Wolfgang

    2016-01-01

    Ambient temperature affects energy intake and expenditure to maintain homeostasis in a continuously fluctuating environment. Here, mice with an adipose-specific defect in fatty acid oxidation (Cpt2A−/−) were subjected to varying temperatures to determine the role of adipose bioenergetics in environmental adaptation and body weight regulation. Microarray analysis of mice acclimatized to thermoneutrality revealed that Cpt2A−/− interscapular brown adipose tissue (BAT) failed to induce the expres...

  16. Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation.

    Zhang, Ning; Li, Xiyu; Ye, Huacheng; Chen, Shuangming; Ju, Huanxin; Liu, Daobin; Lin, Yue; Ye, Wei; Wang, Chengming; Xu, Qian; Zhu, Junfa; Song, Li; Jiang, Jun; Xiong, Yujie

    2016-07-20

    Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials. PMID:27351805

  17. Tailoring defect structure and optical absorption of porous anodic aluminum oxide membranes

    Defects influence the optical and electronic properties of nanostructured materials that may be relevant for applications. In self-organized anodic aluminum oxide (AAO) templates we have investigated the effect of annealing, doping and nanoscale metal deposition. Optical absorption spectroscopy has been used as a sensitive probe for the defect density in AAO templates. The electronic spectra are found to be dominated by bands which originate from oxygen-deficient color centers (F+, F and F2). In annealing studies, the integrated absorption of the bands changes non-monotonically with annealing temperature and annealing time. This demonstrates that the concentration of defects can be optimized to tailor the optical properties of the AAO. Metallic Au wires are deposited in the template to establish a plasmonic template or array. The investigations provide an interesting insight into the interplay of reactivity and diffusivity on nanoscales. - Highlights: ► Preparation of metal wire arrays in oxide templates with tailored plasmonic properties. ► Oxygen defects are characterized using optical absorption and fluorescence. ► Optical absorption spectra are assigned to energy levels of oxygen vacancies (color centers). ► Annealing and electrodeposition of Au wires minimize defects maintaining the morphology.

  18. Circumvention of defective neutral amino acid transport in Hartnup disease using tryptophan ethyl ester.

    Jonas, A J; Butler, I J

    1989-01-01

    Tryptophan ethyl ester, a lipid-soluble tryptophan derivative, was used to bypass defective gastrointestinal neutral amino acid transport in a child with Hartnup disease. The child's baseline tryptophan concentrations in serum (20 +/- 6 microM) and cerebrospinal fluid (1.0 +/- 0.2 microM) were persistently less than 50% of normal values. Cerebrospinal fluid 5-hydroxyindoleacetic acid (5-HIAA), a serotonin metabolite, was also less than 50% of normal (21 +/- 2 ng/ml). Serum tryptophan concentr...

  19. Acrylic acid obtaining from methanol and acetic acid in the presence of complex oxide catalysts

    Небесний, Роман Володимирович; Піх, Зорян Григорович; Шпирка, Ірина Іванівна; Івасів, Володимир Васильович; Небесна, Юлія Віталіївна; Фуч, Уляна Василівна

    2015-01-01

    The purpose of this work is to research process of single-stage acrylic acid obtaining from methanol and acetic acid, namely: to develop effective catalysts for the process of methanol oxidation to formaldehyde with its further aldol condensation with acetic acid to acrylic acid, and to determine optimum conditions for the process. Complex oxide catalysts consisting of oxides of boron, phosphorus, tungsten and vanadium supported on the silica gel have been investigated. The effect of vanadium...

  20. Fe-Catalyzed Oxidative Cleavage of Unsaturated Fatty Acids

    Spannring, P.

    2013-01-01

    The oxidative cleavage of unsaturated fatty acids into aldehydes or carboxylic acids gives access to valuable products. The products can be used as chemical building blocks, as emulsifiers or in the paint or polymer industry. Ozonolysis is applied industrially to cleave the fatty acid oleic acid into the aldehydes nonanal and 9-oxo-nonanoic acid or into pelargonic and azelaic acid. Considerable hazards, including explosion risks, are associated with the use of ozone, and alternative processes...

  1. Fe-Catalyzed Oxidative Cleavage of Unsaturated Fatty Acids

    Spannring, P.

    2013-01-01

    The oxidative cleavage of unsaturated fatty acids into aldehydes or carboxylic acids gives access to valuable products. The products can be used as chemical building blocks, as emulsifiers or in the paint or polymer industry. Ozonolysis is applied industrially to cleave the fatty acid oleic acid int

  2. Pyrrhotite oxidation in weakly acidic solutions

    Complete text of publication follows: The kinetics and mechanism of pyrrhotite (for simplicity noted FeS) oxidation by dissolved oxygen was investigated in weakly acidic solutions as a function of pH (2.75 to 3.45) and temperature (25 to 45 C). The changes in Eh, pH and total dissolved iron were monitored to quantify the reaction progress. Additionally, Fourier transform infrared spectroscopy (FTIR) was used to characterize the oxidation products of FeS. The experimental results demonstrate the importance of temperature and initial pH for the FeS oxidative dissolution. The amounts of dissolved iron (nFe) and removed H+ (nH) increase with temperature and initial [H+]. The activation energy of FeS oxidative dissolution is 41.6 ± 10.7 kJ mol-1 at initial pH=3.00 suggesting that the kinetic regime is controlled by a mix of diffusion and surface reaction (De Guidici et al., 2005). It was found that the reaction order of oxidative dissolution of FeS is 1.0 ± 0.02 (25 C) with respect to initial [H+]. FTIR spectroscopy indicated the presence of several sulfur species (S0, Sn2-, S2O32-, SO32- and SO42-) and ferric hydroxides or oxyhydroxide (Fe(OH)3 and goethite) on residual FeS surface. It is important to note that the experimental ratios of nH over nFe (nH:nFe) observed at 25 C decrease over a first period of time (0-4 h) of FeS oxidative dissolution from 7.97 down to 2.01. Afterwards, the nH:nFe ratio becomes lower than 2 and remains roughly constant (4-72 h). At higher temperatures (35 and 45 C) and pH 3.00, nH:nFe≤2 and is quasi-invariant over the reaction time. The experimental observations suggest a mechanism based on the protonation of FeS surface (Chirita and Descostes, 2006) followed by oxidation of FeS by dissolved oxygen to produce Fe2+, S0 and Sn2-. Fe2+ is unstable in oxidative conditions (Descostes et al., 2002) and transforms into Fe(OH)3(s) and goethite after approximately 30 h of reaction. References:1) De Guidici G., Rossi A., Fanfani L., Lattanzi P

  3. Pyrrhotite oxidation in weakly acidic solutions

    Chirita, P. [Univ Cariova, Craiova 200440 (Romania); Descostes, M. [CEA/DEN/DANS/DPC/SECR Lab Radionuclides Migrat Measurements and Modelling, F-91191 Gif Sur Yvette (France); Schlegel, M.L. [CEA/DEN/DANS/DPC/SCP Lab Reactiv Surfaces and Interfaces, F-91191 Gif Sur Yvette (France)

    2007-08-15

    Complete text of publication follows: The kinetics and mechanism of pyrrhotite (for simplicity noted FeS) oxidation by dissolved oxygen was investigated in weakly acidic solutions as a function of pH (2.75 to 3.45) and temperature (25 to 45 C). The changes in Eh, pH and total dissolved iron were monitored to quantify the reaction progress. Additionally, Fourier transform infrared spectroscopy (FTIR) was used to characterize the oxidation products of FeS. The experimental results demonstrate the importance of temperature and initial pH for the FeS oxidative dissolution. The amounts of dissolved iron (n{sub Fe}) and removed H{sup +} (n{sub H}) increase with temperature and initial [H{sup +}]. The activation energy of FeS oxidative dissolution is 41.6 {+-} 10.7 kJ mol{sup -1} at initial pH=3.00 suggesting that the kinetic regime is controlled by a mix of diffusion and surface reaction (De Guidici et al., 2005). It was found that the reaction order of oxidative dissolution of FeS is 1.0 {+-} 0.02 (25 C) with respect to initial [H{sup +}]. FTIR spectroscopy indicated the presence of several sulfur species (S{sup 0}, S{sub n}{sup 2-}, S{sub 2}O{sub 3}{sup 2-}, SO{sub 3}{sup 2-} and SO{sub 4}{sup 2-}) and ferric hydroxides or oxyhydroxide (Fe(OH){sub 3} and goethite) on residual FeS surface. It is important to note that the experimental ratios of n{sub H} over n{sub Fe} (n{sub H}:n{sub Fe}) observed at 25 C decrease over a first period of time (0-4 h) of FeS oxidative dissolution from 7.97 down to 2.01. Afterwards, the n{sub H}:n{sub Fe} ratio becomes lower than 2 and remains roughly constant (4-72 h). At higher temperatures (35 and 45 C) and pH 3.00, n{sub H}:n{sub Fe}{<=}2 and is quasi-invariant over the reaction time. The experimental observations suggest a mechanism based on the protonation of FeS surface (Chirita and Descostes, 2006) followed by oxidation of FeS by dissolved oxygen to produce Fe{sup 2+}, S{sup 0} and S{sub n}{sup 2-}. Fe{sup 2+} is unstable in

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

    B.Syama Sundar

    2014-06-01

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

  5. The Effect of Strontium on the Strength of Layers of Double Oxide Film Defects

    Bartar Esfahani, Hosein; Raiszadeh, Ramin; Doostmohammadi, Hamid

    2016-03-01

    The change in the strength of layers of oxide film (bifilm) defects when held in Al-0.05 and 0.1 wt pct melts was evaluated indirectly by comparing the porosity, average pore roundness, and pore number density results obtained from a reduced pressure test of the commercial purity and Sr-containing Al melts subjected to different holding and vibration regimes. Any changes in the composition of the pores were also studied using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results showed that the Al2O3 layers of a newly formed oxide film defect, when held in Al-0.05 or 0.1 wt pct Sr melt, transformed gradually into an Sr-containing oxide. This transformation caused the strength of the oxide layers to increase and the rate of the expansion of its atmosphere and removal of the defect from the melt to decrease. This might influence the increase in the porosity of Sr-modified Al castings.

  6. A method to study the history of a double oxide film defect in liquid aluminum alloys

    Raiszadeh, R.; Griffiths, W. D.

    2006-12-01

    Entrained double oxide films have been held responsible for reductions in mechanical properties in aluminum casting alloys. However, their behavior in the liquid metal, once formed, has not been studied directly. It has been proposed that the atmosphere entrapped in the double oxide film defect will continue to react with the liquid metal surrounding it, perhaps leading to its elimination as a significant defect. A silicon-nitride rod with a hole in one end was plunged into liquid aluminum to hold a known volume of air in contact with the liquid metal at a constant temperature. The change in the air volume with time was recorded by real-time X-ray radiography to determine the reaction rates of the trapped atmosphere with the liquid aluminum, creating a model for the behavior of an entrained double oxide film defect. The results from this experiment showed that first oxygen, and then nitrogen, was consumed by the aluminum alloy, to form aluminum oxide and aluminum nitride, respectively. The effect of adding different elements to the liquid aluminum and the effect of different hydrogen contents were also studied.

  7. Retinoic acid induction of genes associated with neural tube developmental defects

    Xinjun Li; Zhong Yang; Yi Zeng; Hong Xu; Hongli Li; Yangyun Han; Xiaodong Long; Chao You

    2010-01-01

    To date, little information has been available regarding genes involved in the regulation of embryonic cell development, which participate in retinoic acid-induced neural tube defects in mice.Previous studies have revealed seven differentially expressed genes involved in neural tube developmental defects. However, gene expression and regulation is a complex process. Therefore,gene expression differences between normal and defective neural tubes at 9.5 and 10.5 days were compared. A total of eight differentially expressed genes exhibited coincident alterations at embryonic 9.5 and 10.5 days. In mice with retinoic acid-induced neural tube defects, NeK7, IGFBP5,ZW10, Csf3r, PSMC6, Cdk5, and Rb1 expressions were downregulated, but Apoa-4 expression was upregulated. These results were confirmed by Northern blot hybridization. Results suggested that NeK7, IGFBP5, ZW10, Csf3r, PSMC6, Cdk5, Rb1, and Apoa-4 are important regulatory factors involved in neural tube defects.

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

    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 [14C]-palmitate oxidation (measured as [14C]O2 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

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

    Ndukwe Erlingsson, Uzochi Chimdinma [Division of Medical Genetics, Department of Pediatrics, University of Utah, 2C412 SOM, 50 North Mario Capecchi Drive, Salt Lake City, UT 84132 (United States); Iacobazzi, Francesco [Division of Medical Genetics, Department of Pediatrics, University of Utah, 2C412 SOM, 50 North Mario Capecchi Drive, Salt Lake City, UT 84132 (United States); Department of Basic Medical Sciences, University of Bari, Piazza Giulio Cesare 11, Policlinico, I-70124 Bari (Italy); Liu, Aiping [ARUP Institute for Clinical and Experimental Pathology, ARUP Laboratories, 500 Chipeta Way, Salt Lake City, UT 84108 (United States); Ardon, Orly; Pasquali, Marzia [Division of Medical Genetics, Department of Pediatrics, University of Utah, 2C412 SOM, 50 North Mario Capecchi Drive, Salt Lake City, UT 84132 (United States); ARUP Institute for Clinical and Experimental Pathology, ARUP Laboratories, 500 Chipeta Way, Salt Lake City, UT 84108 (United States); Department of Pathology, University of Utah, Salt Lake City, UT 84132 (United States); Longo, Nicola, E-mail: Nicola.Longo@hsc.utah.edu [Division of Medical Genetics, Department of Pediatrics, University of Utah, 2C412 SOM, 50 North Mario Capecchi Drive, Salt Lake City, UT 84132 (United States); ARUP Institute for Clinical and Experimental Pathology, ARUP Laboratories, 500 Chipeta Way, Salt Lake City, UT 84108 (United States); Department of Pathology, University of Utah, Salt Lake City, UT 84132 (United States)

    2013-08-09

    Highlights: •Valinomycin can cause mitochondrial stress and stimulate fatty acid oxidation. •Cells with VLCAD deficiency fail to increase fatty acid oxidation in response to valinomycin. •Response to valinomycin can help in the diagnosis of VLCAD deficiency. -- Abstract: Disorders of the carnitine cycle and of the beta oxidation spiral impair the ability to obtain energy from fats at time of fasting and stress. This can result in hypoketotic hypoglycemia, cardiomyopathy, cardiac arrhythmia and other chronic medical problems. The in vitro study of fibroblasts from patients with these conditions is impaired by their limited oxidative capacity. Here we evaluate the capacity of valinomycin, a potassium ionophore that increases mitochondrial respiration, to increase the oxidation of fatty acids in cells from patients with inherited fatty acid oxidation defects. The addition of valinomycin to fibroblasts decreased the accumulation of the lipophilic cation tetraphenylphosphonium (TPP{sup +}) at low concentrations due to the dissipation of the mitochondrial membrane potential. At higher doses, valinomycin increased TPP{sup +} accumulation due to the increased potassium permeability of the plasma membrane and subsequent cellular hyperpolarization. The incubation of normal fibroblasts with valinomycin increased [{sup 14}C]-palmitate oxidation (measured as [{sup 14}C]O{sub 2} release) in a dose-dependent manner. By contrast, valinomycin failed to increase palmitate oxidation in fibroblasts from patients with very long chain acyl CoA dehydrogenase (VLCAD) deficiency. This was not observed in fibroblasts from patients heterozygous for this condition. These results indicate that valinomycin can increase fatty acid oxidation in normal fibroblasts and could be useful to differentiate heterozygotes from patients affected with VLCAD deficiency.

  10. Hypothiocyanous acid oxidation of tubulin cysteines inhibits microtubule polymerization

    Clark, Hillary M; Hagedorn, Tara D.; Landino, Lisa M.

    2013-01-01

    Thiol oxidation is a probable outcome of cellular oxidative stress and is linked to degenerative disease progression. In addition, protein thiol redox reactions are increasingly identified as a mechanism to regulate protein structure and function. We assessed the effect of hypothiocyanous acid on the cytoskeletal protein tubulin. Total cysteine oxidation by hypothiocyanous and hypochlorous acids was monitored by labeling tubulin with 5-iodoacetamidofluorescein and by detecting higher molecula...

  11. Defects evolution and their impacts on conductivity of indium tin oxide thin films upon thermal treatment

    Indium tin oxide (ITO) thin films were deposited on silicon substrates by radio-frequency magnetron sputtering. The influence of annealing temperature on the crystallite, surface morphology, defects evolution, and electrical property of the thin films was studied. The conductivity of the ITO films was significantly enhanced by two orders of magnitude by increasing the annealing temperature up to 600 °C, which was interpreted in point view of defects evolution in ITO films as revealed by positron annihilation. It was interesting to find that positron diffusion length was amazingly comparable to crystallite size in ITO films annealed below 300 °C, indicating positrons were preferentially localized and annihilated in defects around crystallite boundaries. By further increasing the temperature, positron diffusion length was far beyond the grain size with little increment. This demonstrated that defects were effectively removed around grain boundaries. The results indicated defect structure around crystallite/grain boundaries played an important role on carrier transportation in nanocrystal ITO films

  12. Numerical study of metal oxide hetero-junction solar cells with defects and interface states

    Further to our previous work on ideal metal oxide (MO) hetero-junction solar cells, a systematic simulation has been carried out to investigate the effects of defects and interface states on the cells. Two structures of the window/absorber (WA) and window/absorber/voltage-enhancer (WAV) were modelled with defect concentration, defect energy level, interface state (ISt) density and ISt energy level as parameters. The simulation showed that the defects in the window layer and the voltage-enhancer layer have very limited effects on the performance of the cells, but those in the absorption layer have profound effects on the cell performance. The interface states at the W/A interface have a limited effect on the performance even for a density up to 1013 cm−2, while those at the A/V interface cause the solar cell to deteriorate severely even at a low density of lower than 1 × 1011 cm−2. It also showed that the back surface field (BSF) induced by band gap off-set in the WAV structure loses its function when defects with a modest concentration exist in the absorption layer and does not improve the open voltage at all. (paper)

  13. Final Technical Report for DE-SC0001878 [Theory and Simulation of Defects in Oxide Materials

    Chelikowsky, James R. [University of Texas at Austin

    2014-04-14

    We explored a wide variety of oxide materials and related problems, including materials at the nanoscale and generic problems associated with oxide materials such as the development of more efficient computational tools to examine these materials. We developed and implemented methods to understand the optical and structural properties of oxides. For ground state properties, our work is predominantly based on pseudopotentials and density functional theory (DFT), including new functionals and going beyond the local density approximation (LDA): LDA+U. To study excited state properties (quasiparticle and optical excitations), we use time dependent density functional theory, the GW approach, and GW plus Bethe-Salpeter equation (GW-BSE) methods based on a many-body Green function approaches. Our work focused on the structural, electronic, optical and magnetic properties of defects (such as oxygen vacancies) in hafnium oxide, titanium oxide (both bulk and clusters) and related materials. We calculated the quasiparticle defect states and charge transition levels of oxygen vacancies in monoclinic hafnia. we presented a milestone G0W0 study of two of the crystalline phases of dye-sensitized TiO{sub 2} clusters. We employed hybrid density functional theory to examine the electronic structure of sexithiophene/ZnO interfaces. To identify the possible effect of epitaxial strain on stabilization of the ferromagnetic state of LaCoO{sub 3} (LCO), we compare the total energy of the magnetic and nonmagnetic states of the strained theoretical bulk structure.

  14. Band alignment and defects of the diamond zinc oxide heterojunction; Bandstruktur und Defekte der Diamant-Zinkoxid-Heterostruktur

    Geithner, Peter

    2008-09-12

    Zinc oxide films were grown on diamond single crystals by rf sputtering of zinc oxide. The valence and conduction band offset was determined by photoelectron spectroscopy. A deep defect occurring in the zinc oxide films on diamond was characterized by cathodoluminescence spectroscopy. (orig.)

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

    Mohamed S. El-Deab

    2012-01-01

    The current study proposes a novel binary catalyst system (composed of metal/metal oxide nanoparticles) as a promising electrocatalyst in formic acid oxidation. The electro-catalytic oxidation of formic acid is carried out with binary catalysts of Pt nanoparticles (nano-Pt) and manganese oxide nanorods (nano-MnOx) electrodeposited onto glassy carbon (GC) electrodes. Cyclic voltammetric (CV) measurements showed that unmodified GC and nano-MnOx/GC electrodes have no catalytic activity. While tw...

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

    R S Yalgudre; G S Gokavi

    2012-07-01

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

  17. Non-destructive functionalisation for atomic layer deposition of metal oxides on carbon nanotubes: effect of linking agents and defects

    Kemnade, N.; Shearer, C. J.; Dieterle, D. J.; Cherevan, A. S.; Gebhardt, P.; Wilde, G.; Eder, D.

    2015-02-01

    The hybridisation of metal oxides and nanocarbons has created a promising new class of functional materials for environmental and sustainable energy applications. The performance of such hybrids can be further improved by rationally designing interfaces and morphologies. Atomic layer deposition (ALD) is among the most powerful techniques for the controlled deposition of inorganic compounds, due to its ability to form conformal coatings on porous substrates at low temperatures with high surface sensitivity and atomic control of film thickness. The hydrophobic nature of the nanocarbon surface has so far limited the applicability of ALD on CNTs. Herein we investigate the role of structural defects in CNTs, both intrinsic and induced by acid treatment, on coverage, uniformity and crystallinity of ZnO coatings. Furthermore, we demonstrate the potential of small aromatic molecules, including benzyl alcohol (BA), naphthalene carboxylic acid (NA) and pyrene carboxylic acid (PCA), as active nucleation sites and linking agents. Importantly, only PCA exhibits sufficiently strong interactions with the pristine CNT surface to withstand desorption under reaction conditions. Thus, PCA enables a versatile and non-destructive alternative route for the deposition of highly uniform metal oxide coatings onto pristine CNTs via ALD over a wide temperature range and without the typical surface corrosion induced by covalent functionalisation. Importantly, preliminary tests demonstrated that the improved morphology obtained with PCA has indeed considerably increased the hybrid's photocatalytic activity towards hydrogen evolution via sacrificial water splitting. The concept demonstrated in this work is transferable to a wide range of other inorganic compounds including metal oxides, metal (oxy)nitrides and metal chalcogenides on a variety of nanocarbons.The hybridisation of metal oxides and nanocarbons has created a promising new class of functional materials for environmental and

  18. Mechanisms of hydroxyl radical production from abiotic oxidation of pyrite under acidic conditions

    Zhang, Peng; Yuan, Songhu; Liao, Peng

    2016-01-01

    Hydroxyl radicals (radOH) produced from pyrite oxidation by O2 have been recognized, but mechanisms regarding the production under anoxic and oxic conditions are not well understood. In this study, the mechanisms of radOH production from pyrite oxidation under anoxic and oxic conditions were explored using benzoic acid (BA) as an radOH probe. Batch experiments were conducted at pH 2.6 to explore radOH production under anoxic and oxic conditions. The cumulative radOH concentrations produced under anoxic and oxic conditions increased linearly to 7.5 and 52.2 μM, respectively within 10 h at 10 g/L pyrite. Under anoxic conditions, radOH was produced from the oxidation of H2O on the sulfur-deficient sites on pyrite surface, showing an increased production with the increase of pyrite surface exposure due to oxidation. Under oxic conditions, the formation of radOH proceeds predominantly via the two-electron reduction of O2 on pyrite surface along with a minor contribution from the oxidation of H2O on surface sulfur-defects and the reactions of Fe2+/sulfur intermediates with O2. For both O2 reduction and H2O oxidation on the surface sulfur-defects, H2O2 was the predominant intermediate, which subsequently transformed to radOH through Fenton mechanism. The radOH produced had a significant impact on the transformation of contaminants in the environment. Anoxic pyrite suspensions oxidized 13.9% As(III) (C0 = 6.67 μM) and 17.6% sulfanilamide (C0 = 2.91 μM) within 10 h at pH 2.6 and 10 g/L pyrite, while oxic pyrite suspensions improved the oxidation percentages to 55.4% for As(III) and 51.9% for sulfanilamide. The ratios of anoxic to oxic oxidation are consistent with the relative contribution of surface sulfur-defects to radOH production. However, Fe2+ produced from pyrite oxidation competed with the contaminants for radOH, which is of particular significance with the increase of time in a static environment. We conclude that radOH can be produced from abiotic oxidation of

  19. Towards precise defect control in layered oxide structures by using oxide molecular beam epitaxy

    Federico Baiutti; Georg Christiani; Gennady Logvenov

    2014-01-01

    In this paper we present the atomic-layer-by-layer oxide molecular beam epitaxy (ALL-oxide MBE) which has been recently installed in the Max-Planck Institute for Solid State Research and we report on its present status, providing some examples that demonstrate its successful application in the synthesis of different layered oxides, with particular reference to superconducting La2CuO4 and insulator-to-metal La2−xSrxNiO4. We briefly review the ALL-oxide MBE technique and its unique capabilities...

  20. Investigation of products of molybdenite oxidation by nitric acid

    Physicochemical study of products of oxidation by nitric acid of molybdenum concentrate containing 98% MoS2 is carried out. It is shown that appearing molybdenum oxide forms block oxidizer access to the surface of sulfide phase and hinder its complete oxidation. When complexing reagents (H2SO4, H3PO4, HCl) are introduced in the solution the bulk of oxidized molybdenum transfers into solution in the form of a stable complex, at that. The effect of internal diffusion decreases and a considerable increase of MoS2 oxidation rate and completeness is achieved

  1. Modeling doped and defective oxides in catalysis with density functional theory methods: room for improvements.

    Pacchioni, Gianfranco

    2008-05-14

    Due to the well-known problem of the self-interaction, standard density functional theory (DFT) methods tend to produce delocalized holes and electrons in defective oxide materials even when there is ample experimental evidence of a strong localization. For late transition metal compounds or rare earth oxides, this results in the incorrect description of the electronic structure of the system (e.g., magnetic insulators are predicted to be metallic). Practical ways to correct this deficiency are based on the use of hybrid functionals or of the DFT+U approach. In this way, most of the limitations related to the self-interaction are removed, and the electronic structure is properly described. What is less clear is to what extent hybrid functionals, DFT+U approaches, or standard DFT functionals can properly describe the strength of the chemical bonds at the surface of an oxide. This is a crucial question if one is interested in the catalytic properties of oxide surfaces. Oxidation reactions often involve oxygen detachment from the surface and incorporation into an organic substrate. Oxides are doped with heteroatoms to create defects and facilitate oxygen removal from the surface, with formation of oxygen vacancies. Do standard DFT calculations provide a good binding energy of the missing oxygen despite the failure in giving the right electronic structure? Can hybrid functionals or the DFT+U approach provide a simple yet reliable way to get accurate reaction enthalpies and energy barriers? In this essay, we discuss these problems by analyzing some case histories and the relatively scarce data existing in the literature. The conclusion is that while modern electronic structure methods accurately reproduce and predict a wide range of electronic, optical, and magnetic properties of oxides, the description of the strength of chemical bonds still needs considerable improvements. PMID:18532790

  2. Field-Induced Point Defect Redistribution in Metal Oxides: Mesoscopic Length Scale Phenomena

    Moballegh, Ali

    The spatial redistribution of charged point defects under direct-current (DC) biasing can have significant implications for electroceramic device performance and lifetime. The transport behavior of point defects is regulated by the boundary conditions of the electrodes, which can block electronic charge and/or ion transfer across the interface to varying degrees. When the electrodes are impermeable to mass transport, there will be an accumulation of point defects in the near-electrode region that can lead to significant modifications in the local electronic carrier concentrations. Such defect redistribution is responsible for the long-term increases in leakage current in many capacitor devices via modification of the interface Schottky barrier at the reverse-biased cathode. While this leakage current enhancement is detrimental in capacitor devices, the phenomenon of lattice defect migration can be utilized to form novel functional behaviors, such as resistive switching in metal-oxides via modulation of the Schottky barrier or formation of nonstoichiometric filaments oriented along the applied field direction. The present work aims to understand the phenomenon of defect redistribution as a function of the initial defect chemistry state and electrode boundary conditions under the degradation process, using single-crystal rutile TiO 2 as a model material. Experiments are performed as a function of degradation voltage and crystallographic orientation since the self-diffusion coefficients of oxygen vacancies and titanium interstitials are known to be highly anisotropic in rutile. Rutile single crystals are equilibrated at specific oxygen partial pressures and temperatures to define the initial defect chemistry state. Platinum electrodes, which form Schottky contacts and are largely impermeable to oxygen transfer, are deposited on opposite faces of the crystal. The samples are then subjected to up to 200 V/cm electric field at 200¢ªC while the leakage current is

  3. Defects in fatty acid amide hydrolase 2 in a male with neurologic and psychiatric symptoms

    Sirrs, Sandra; van Karnebeek, Clara DM; Peng, Xiaoxue; Shyr, Casper; Tarailo-Graovac, Maja; Mandal, Rupasri; Testa, Daniel; Dubin, Devin; Carbonetti, Gregory; Glynn, Steven E.; Sayson, Bryan; Robinson, Wendy P.; Han, Beomsoo; Wishart, David; Ross, Colin J

    2015-01-01

    Background Fatty acid amide hydrolase 2 (FAAH2) is a hydrolase that mediates the degradation of endocannabinoids in man. Alterations in the endocannabinoid system are associated with a wide variety of neurologic and psychiatric conditions, but the phenotype and biochemical characterization of patients with genetic defects of FAAH2 activity have not previously been described. We report a male with autistic features with an onset before the age of 2 years who subsequently developed additional f...

  4. Nondestructive covalent functionalization of carbon nanotubes by selective oxidation of the original defects with K2FeO4

    Zhang, Zhao-yang; Xu, Xue-cheng

    2015-08-01

    Chemical oxidation is still the major approach to the covalent functionalization of carbon nanotubes (CNTs). Theoretically, the defects on CNTs are more reactive than skeletal hexagons and should be preferentially oxidized, but conventional oxidation methods, e.g., HNO3/H2SO4 treatment, have poor reaction selectivity and inevitably consume the Cdbnd C bonds in the hexagonal lattices, leading to structural damage, π-electrons loss and weight decrease. In this work, we realized the nondestructive covalent functionalization of CNTs by selective oxidation of the defects. In our method, potassium ferrate K2FeVIO4 was employed as an oxidant for CNTs in H2SO4 medium. The CNT samples, before and after K2FeO4/H2SO4 treatment, were characterized with colloid dispersibility, IR, Raman spectroscopy, FESEM and XPS. The results indicated that (i) CNTs could be effectively oxidized by Fe (VI) under mild condition (60 °C, 3 h), and hydrophilic CNTs with abundant surface sbnd COOH groups were produced; and (ii) Fe (VI) oxidation of CNTs followed a defect-specific oxidation process, that is, only the sp3-hybridized carbon atoms on CNT surface were oxidized while the Cdbnd C bonds remained unaffected. This selective/nondestructive oxidation afforded oxidized CNTs in yields of above 100 wt%. This paper shows that K2FeO4/H2SO4 is an effective, nondestructive and green oxidation system for oxidative functionalization of CNTs and probably other carbon materials as well.

  5. Folic acid supplement use in the prevention of neural tube defects.

    Delany, C

    2011-01-01

    In 2008, planned folic acid fortification for the prevention of Neural Tube Defects (NTD) was postponed. Concurrently, the economic recession may have affected dietary folic acid intake, placing increased emphasis on supplement use. This study examined folic acid supplement use in 2009. A cross-sectional survey of 300 ante-natal women was undertaken to assess folic acid knowledge and use. Associations between demographic, obstetric variables and folic acid knowledge and use were examined. A majority, 284\\/297 (96%), had heard of folic acid, and 178\\/297 (60%) knew that it could prevent NTD. Most, 270\\/297 (91%) had taken it during their pregnancy, but only 107\\/297 (36%) had used it periconceptionally. Being older, married, planned pregnancy and better socioeconomic status were associated with periconceptional use. Periconceptional folic acid use in 2009 was very low, little changed from economic status were associated with periconceptional use. Periconceptional folic acid use in 2009 was very low, little changed from earlier years. Continuous promotion efforts are necessary. Close monitoring of folic acid intake and NTD rates is essential, particularly in the absence of fortification.

  6. Anodic luminescence, structural, photoluminescent, and photocatalytic properties of anodic oxide films grown on niobium in phosphoric acid

    Stojadinović, Stevan; Tadić, Nenad; Radić, Nenad; Stefanov, Plamen; Grbić, Boško; Vasilić, Rastko

    2015-11-01

    This article reports on properties of oxide films obtained by anodization of niobium in phosphoric acid before and after the dielectric breakdown. Weak anodic luminescence of barrier oxide films formed during the anodization of niobium is correlated to the existence of morphological defects in the oxide layer. Small sized sparks generated by dielectric breakdown of formed oxide film cause rapid increase of luminescence intensity. The luminescence spectrum of obtained films on niobium under spark discharging is composed of continuum radiation and spectral lines caused by electronic spark discharging transitions in oxygen and hydrogen atoms. Oxide films formed before the breakdown are amorphous, while after the breakdown oxide films are partly crystalline and mainly composed of Nb2O5 hexagonal phase. The photocatalytic activity of obtained oxide films after the breakdown was investigated by monitoring the degradation of methyl orange. Increase of the photocatalytic activity with time is related to an increase of oxygen vacancy defects in oxide films formed during the process. Also, higher concentration of oxygen vacancy defects in oxide films results in higher photoluminescence intensity.

  7. Circumvention of defective neutral amino acid transport in Hartnup disease using tryptophan ethyl ester.

    Jonas, A J; Butler, I J

    1989-07-01

    Tryptophan ethyl ester, a lipid-soluble tryptophan derivative, was used to bypass defective gastrointestinal neutral amino acid transport in a child with Hartnup disease. The child's baseline tryptophan concentrations in serum (20 +/- 6 microM) and cerebrospinal fluid (1.0 +/- 0.2 microM) were persistently less than 50% of normal values. Cerebrospinal fluid 5-hydroxyindoleacetic acid (5-HIAA), a serotonin metabolite, was also less than 50% of normal (21 +/- 2 ng/ml). Serum tryptophan concentrations increased only modestly and briefly after an oral challenge with 200 mg/kg of oral L-tryptophan, reflecting the absorptive defect. An oral challenge with 200 mg/kg of tryptophan ethyl ester resulted in a prompt increase in serum tryptophan to a peak of 555 microM. Sustained treatment with 20 mg/kg q6h resulted in normalization of serum (66 +/- 15 microM) and cerebrospinal fluid tryptophan concentrations (mean = 2.3 microM). Cerebrospinal fluid 5-HIAA increased to more normal concentrations (mean = 33 ng/ml). No toxicity was observed over an 8-mo period of treatment, chronic diarrhea resolved, and body weight, which had remained unchanged for 7 mo before ester therapy, increased by approximately 26%. We concluded that tryptophan ethyl ester is effective at circumventing defective gastrointestinal neutral amino acid transport and may be useful in the treatment of Hartnup disease. PMID:2472426

  8. Formic Acid Oxidation at Platinum-Bismuth Clusters

    Lovic, J. D.; Stevanovic, S. I.; Tripkovic, D. V.; Tripkovic, Vladimir; Stevanovic, R. M.; Popovic, K. Dj.; Jovanovic, V. M.

    2014-01-01

    Formic acid oxidation was studied on platinum-bismuth deposits on glassy carbon (GC) substrate. The catalysts of equimolar ratio were prepared by potentiostatic deposition using chronocoulometry. Bimetallic structures obtained by two-step process, comprising deposition of Bi followed by deposition...... dissolution, deposits were subjected to electrochemical oxidation, in the relevant potential range and supporting electrolyte, prior to use as catalysts for HCOOH oxidation. Anodic striping charges indicated that along oxidation procedure most of deposited Bi was oxidized. ICP mass spectroscopy analysis of...... latter. 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...

  9. Intrinsic point defects in zinc oxide. Modeling of structural, electronic, thermodynamic and kinetic properties

    Erhart, P.

    2006-07-01

    The present dissertation deals with the modeling of zinc oxide on the atomic scale employing both quantum mechanical as well as atomistic methods. The first part describes quantum mechanical calculations based on density functional theory of intrinsic point defects in ZnO. To begin with, the geometric and electronic structure of vacancies and oxygen interstitials is explored. In equilibrium oxygen interstitials are found to adopt dumbbell and split interstitial configurations in positive and negative charge states, respectively. Semi-empirical self-interaction corrections allow to improve the agreement between the experimental and the calculated band structure significantly; errors due to the limited size of the supercells can be corrected by employing finite-size scaling. The effect of both band structure corrections and finite-size scaling on defect formation enthalpies and transition levels is explored. Finally, transition paths and barriers for the migration of zinc as well as oxygen vacancies and interstitials are determined. The results allow to interpret diffusion experiments and provide a consistent basis for developing models for device simulation. In the second part an interatomic potential for zinc oxide is derived. To this end, the Pontifix computer code is developed which allows to fit analytic bond-order potentials. The code is subsequently employed to obtain interatomic potentials for Zn-O, Zn-Zn, and O-O interactions. To demonstrate the applicability of the potentials, simulations on defect production by ion irradiation are carried out. (orig.)

  10. Tuning the reactivity of Ru nanoparticles by defect engineering of the reduced graphene oxide support

    Liu, Xin

    2014-01-01

    We systematically investigated the electronic structure of Ru nanoparticles supported on various local structures on reduced graphene oxide (rGO) by first-principles-based calculations. We showed that Ru nanoparticles prefer to nucleate at these localized defect structures on rGO, which act as strong trapping sites for Ru nanoparticles and inhibit their aggregation. The binding of Ru nanoparticles to rGO, which is dependent on these local defect structures and correlates with the interfacial charge transfer, determines the electronic structure of the composites. Further study reveals that the performance of these composites against oxygen adsorption changes proportionally with the shift of the d-band center of the nanoparticles. The correlation between the defect structures on rGO and the reactivity of the composites suggests that controlled modification of the graphenic support by defect engineering would be an efficient way to fabricate new transition metal/rGO composites with high stability and desired reactivity. This journal is © the Partner Organisations 2014.

  11. Chemical oxidation of phenolic acids by soil iron and manganese oxides

    The oxidation of six phenolic acids by soil Fe and Mn oxides was demonstrated by changes in phenolic acid extractability from soil with time, by production of Fe(II) and soluble Mn from the oxidation reaction, by quantitative recoveries of added phenolic acids from soil pretreated with dithionite-citrate to remove Fe and Mn oxides, and by the reactivity of phenolic acids in the presence of pure Mn and Fe oxides. The reactivities of phenolic acids were associated with the structures of the chemicals. Increasing methoxy substitution on the aromatic ring increased reactivity, and cinnamic acid derivatives were more reactive than benzoic acid derivatives. Oxidation products of 14C labeled ferulic acid were sorbed to MnO2 within minutes and were unextractable by organic solvents unless the mineral was pretreated with 6 M HCl or 0.5 M NaOH. The oxidation rate of ferulic acid by MnO2 approached zero after four days even with a surplus of reactants

  12. Zinc self-diffusion, electrical properties, and defect structure of undoped, single crystal zinc oxide

    Zinc self-diffusion was measured in single crystal zinc oxide using nonradioactive 70Zn as the tracer isotope and secondary ion mass spectrometry for data collection. Crystal mass was closely monitored to measure ZnO evaporation. Diffusion coefficients were isotropic with an activation energy of 372 kJ/mol. Zinc self-diffusion is most likely controlled by a vacancy mechanism. Electrical property measurements exhibit a plateau in conductivity at intermediate pO2 with an increase in reducing atmospheres. An analysis of the defect structure is presented that indicates that oxygen vacancies are probably the intrinsic ionic defects responsible for n-type conductivity in reducing atmospheres. (c) 2000 American Institute of Physics

  13. Defect engineered d0 ferromagnetism in tin-doped indium oxide nanostructures and nanocrystalline thin-films

    Origin of unexpected defect engineered room-temperature ferromagnetism observed in tin-doped indium oxide (ITO) nanostructures (Nanowires, Nano-combs) and nanocrystalline thin films fabricated by pulsed laser deposition has been investigated. It is found that the ITO nanostructures prepared under argon environment exhibit strongest ferromagnetic signature as compared to that nanocrystalline thin films grown at oxygen. The evidence of singly ionized oxygen vacancy (V0+) defects, obtained from various spectroscopic measurements, suggests that such V0+ defects are mainly responsible for the intrinsic ferromagnetic ordering. The exchange interaction of the defects provides extensive opportunity to tune the room-temperature d0 ferromagnetism and optical properties of ITOs

  14. Ferrous iron oxidation by Thiobacillus ferrooxidans: inhibition with benzoic acid, sorbic acid and sodium lauryl sulfate

    Onysko, S.J.

    1984-07-01

    Acid mine drainage is formed by the weathering or oxidation of pyritic material exposed during coal mining. The rate of pyritic material oxidation can be greatly accelerated by certain acidophilic bacteria such as Thiobacillus ferrooxidans which catalyse the oxidation of ferrous to ferric iron. A number of organic compounds, under laboratory conditions, can apparently inhibit both the oxidation of ferrous to ferric iron by T. ferrooxidans and the weathering of pyritic material by mixed cultures of acid mine drainage micro-organisms. Sodium lauryl sulphate (SLS), an anionic surfactant has proved effective in this respect. Benzoic acid, sorbic acid and SLS at low concentrations, each effectively inhibited bacterial oxidation of ferrous iron in batch cultures of T. ferrooxidans. The rate of chemical oxidation of ferrous iron in low pH, sterile, batch reactors was not substantially affected at the tested concentrations of any of the compounds.

  15. Ferrous iron oxidation by Thiobacillus ferrooxidans: inhibition with benzoic acid, sorbic acid, and sodium lauryl sulfate

    Onysko, S.J.; Kleinmann, R.L.P.; Erickson, P.M.

    1984-07-01

    Thiobacillus ferrooxidans promote indirect oxidation of pyrite through the catalysis of the oxidation of ferrous iron to ferric iron, which is an effective oxidant of pyrite. These bacteria also may catalyze direct oxidation of pyrite by oxygen. A number of organic compounds, under laboratory conditions, can apparently inhibit both the oxidation of ferrous iron to ferric iron by T. ferrooxidans and the weathering of pyritic material by mixed cultures of acid mine drainage microorganisms. In this study, 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.

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

    Elle, Ida Coordt; Rødkær, Steven Vestergaard; Fredens, Julius; Færgeman, Nils Joakim

    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 by scintillation counting. Treating animals with sodium azide, an inhibitor of the electron transport chain, reduced (3)H2O production to approximately 15%, while boiling of animals prior to assay completely blocked the production of labeled water. We demonstrate that worms fed different bacterial strains exhibit different fatty acid oxidation rates. We show that starvation results in increased fatty acid oxidation, which is independent of the transcription factor NHR-49. On the contrary, fatty acid oxidation is reduced to approximately 70% in animals lacking the worm homolog of the insulin receptor, DAF-2. Hence, the present methodology can be used to delineate the role of specific genes and pathways in the regulation of β-oxidation in C. elegans. PMID:24058820

  17. Mutagenesis and carcinogenesis caused by the oxidation of nucleic acids.

    Nakabeppu, Yusaku; Sakumi, Kunihiko; Sakamoto, Katsumi; Tsuchimoto, Daisuke; Tsuzuki, Teruhisa; Nakatsu, Yoshimichi

    2006-01-01

    KEYWORDS CLASSIFICATION: adverse effects;Animals;chemistry;deficiency;DNA Damage;DNA Glycosylases;DNA Repair;DNA Repair Enzymes;Enzymes;genetics;Genomics;Guanine;Hydrolases;Intestinal Neoplasms;Japan;Liver Neoplasms;metabolism;mechanisms of carcinogenesis;Mice;Mutagenesis;Mutation;Neoplasms;Nucleic Acids;Oxidation-Reduction;Oxidative Stress;Phosphoric Monoester Hydrolases;Skin Neoplasms;Ultraviolet Rays.

  18. Precipitation of plutonium from acidic solutions using magnesium oxide

    Magnesium oxide will be used as a neutralizing agent for acidic plutonium-containing solutions. It is expected that as the magnesium oxide dissolves, the pH of the solution will rise, and plutonium will precipitate. The resulting solid will be tested for suitability to storage. The liquid is expected to contain plutonium levels that meet disposal limit requirements

  19. Ghrelin reduces hepatic mitochondrial fatty acid beta oxidation.

    Rigault, C; Le Borgne, F; Georges, B; Demarquoy, J

    2007-04-01

    Ghrelin is a 28-amino-acid peptide secreted during starvation by gastric cells. Ghrelin physiologically induces food intake and seems to alter lipid and glucid metabolism in several tissues such as adipose tissue and liver. Liver has a key position in lipid metabolism as it allows the metabolic orientation of fatty acids between oxidation and esterification. We investigated the effects of peripheral ghrelin administration on 2 crucial parameters of fatty acid oxidation: the levocarnitine (L-carnitine)-dependent entry of the fatty acids in the mitochondria and the mitochondrial fatty acid oxidation. Ghrelin was either given to rats prior to the hepatocyte preparation and culture or used to treat hepatocytes prepared from control animals. Direct incubation of ghrelin to raw hepatocytes did not induce any change in the studied parameters. In hepatocytes prepared from 3 nmol ghrelin-treated rats, a 44% reduction of the mitochondrial fatty acid oxidation while no alteration of the L-carnitine-related parameters were observed. These results suggested (a) that ghrelin has no direct effect on liver, and (b) that when administrated to a whole organism, ghrelin may alter the lipid metabolism and the energy balance through a marked decrease in liver fatty acid oxidation. PMID:17556859

  20. Investigation of the radiation defect in aluminum oxide by the spectrum of diffuse reflection

    Full text : The results of investigation of radiation defects in the γ irradiated disperse aluminum oxide by the spectrum of diffuse reflection were given in this work. It was shown that, γ irradiation Al2O3 guides absorption in and around tied assistance generation of electron (F+) and hole (V) centers. Multicomponent structure was observed in V centers under hv=2,5-3,2 with maximum under γ=375,390 and 410 nm, appropriated hole centers of V, V= and VOH types. The study of kinetic regularity of capital of the V centers depending on absorbed dose. General concentration of the hole centers was calculated

  1. Defects and characteristics of the structure and properties of aluminum oxides

    Kopylov, V. B.; Aleksandrov, K. A.; Sergeev, E. V.

    2008-07-01

    Based on IR spectroscopy data, it was established that nonstoichiometry defects in the structure of aluminum oxides were components of the Wannier-Mott exciton states and included the Al-O, Al-Al, O2, O{2/+}, O{2/-}, O{2/2-}, O3, and O2 n isolated oscillators in the ground and electronically excited states. It was shown that their presence manifested itself by thermoemission of molecular oxygen singlet forms, excess heat capacity, and anomalous diamagnetism at elevated temperatures.

  2. Identification and Characterization of Arabidopsis Indole-3-Butyric Acid Response Mutants Defective in Novel Peroxisomal Enzymes

    Zolman, Bethany K.; Martinez, Naxhiely; Millius, Arthur; Adham, A. Raquel; Bartel, Bonnie

    2008-01-01

    Genetic evidence suggests that indole-3-butyric acid (IBA) is converted to the active auxin indole-3-acetic acid (IAA) by removal of two side-chain methylene units in a process similar to fatty acid β-oxidation. Previous studies implicate peroxisomes as the site of IBA metabolism, although the enzymes that act in this process are still being identified. Here, we describe two IBA-response mutants, ibr1 and ibr10. Like the previously described ibr3 mutant, which disrupts a putative peroxisomal ...

  3. Hafnium oxide gate dielectrics grown from an alkoxide precursor: structure and defects

    We present an infrared spectroscopy and X-ray diffraction study of hafnium oxide gate dielectric films deposited from hafnium tetra-tert-butoxide, Hf(OC(CH3)3)4. We characterize the crystal phase as a function of thickness and detect the chemical state of impurities in this high-permittivity (high-κ) material. The HfO2 films are composed of monoclinic crystallites in an amorphous matrix. The crystalline fraction increases with increasing film thickness. Infrared spectroscopy is used to obtain information about impurities, which may help to uncover the nature of electrical defects. We detect and quantify for instance the presence of incorporated hydroxyl groups or water that may be responsible for the deviation from ideal HfO2 stoichiometry. The concentration of residual C-H bonds is low. However, carbon is incorporated in an oxidized form, possibly as carbonate

  4. Modulating fatty acid oxidation in heart failure

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

    2011-01-01

    In the advanced stages of heart failure, many key enzymes involved in myocardial energy substrate metabolism display various degrees of down-regulation. The net effect of the altered metabolic phenotype consists of reduced cardiac fatty oxidation, increased glycolysis and glucose oxidation, and rigidity of the metabolic response to changes in workload. Is this metabolic shift an adaptive mechanism that protects the heart or a maladaptive process that accelerates structural and functional dera...

  5. Charged defects during alpha-irradiation of actinide oxides as revealed by Raman and luminescence spectroscopy

    Mohun, R.; Desgranges, L.; Léchelle, J.; Simon, P.; Guimbretière, G.; Canizarès, A.; Duval, F.; Jegou, C.; Magnin, M.; Clavier, N.; Dacheux, N.; Valot, C.; Vauchy, R.

    2016-05-01

    We have recently evidenced an original Raman signature of alpha irradiation-induced defects in UO2. In this study, we aim to determine whether the same signature also exists in different actinide oxides, namely ThO2 and PuO2. Sintered UO2 and ThO2 were initially irradiated with 21 MeV He2+ ions using a cyclotron device and were subjected to an in situ luminescence experiment followed by Raman analysis. In addition, a PuO2 sample which had accumulated self-irradiation damage due to alpha particles was investigated only by Raman measurement. Results obtained for the initially white ThO2 showed that a blue color appeared in the irradiated areas as well as luminescence signals during irradiation. However, Raman spectroscopic analysis showed the absence of Raman signature in ThO2. In contrast, the irradiated UO2 and PuO2 confirmed the presence of the Raman signature but no luminescence peaks were observed. The proposed mechanism involves electronic defects in ThO2, while a coupling between electronic defects and phonons is required to explain the Raman spectra for UO2 and PuO2.

  6. Reactive oxygen species in sarcopenia: Should we focus on excess oxidative damage or defective redox signalling?

    Jackson, Malcolm J

    2016-08-01

    Physical frailty in the elderly is driven by loss of muscle mass and function and hence preventing this is the key to reduction in age-related physical frailty. Our current understanding of the key areas in which ROS contribute to age-related deficits in muscle is through increased oxidative damage to cell constituents and/or through induction of defective redox signalling. Recent data have argued against a primary role for ROS as a regulator of longevity, but studies have persistently indicated that aspects of the aging phenotype and age-related disorders may be mediated by ROS. There is increasing interest in the effects of defective redox signalling in aging and some studies now indicate that this process may be important in reducing the integrity of the aging neuromuscular system. Understanding how redox-signalling pathways are altered by aging and the causes of the defective redox homeostasis seen in aging muscle provides opportunities to identify targeted interventions with the potential to slow or prevent age-related neuromuscular decline with a consequent improvement in quality of life for older people. PMID:27161871

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

    Elle, Ida Coordt; Rødkær, Steven Vestergaard; Fredens, Julius; Færgeman, Nils J.

    2012-01-01

    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 by...... scintillation counting. Treating animals with sodium azide, an inhibitor of the electron transport chain, reduced (3)H2O production to approximately 15%, while boiling of animals prior to assay completely blocked the production of labeled water. We demonstrate that worms fed different bacterial strains exhibit...

  8. Gene expression in retinoic acid-induced neural tube defects A cDNA mieroarray analysis

    Xiaodong Long; Zhong Yang; Yi Zeng; Hongli Li; Yangyun Han; Chao You

    2009-01-01

    BACKGROUND: Neural tube defects can be induced by abnormal factors in vivo or in vitro during development. However, the molecular mechanisms of neural tube defect induction, and the related gene expression and regulation are still unknown.OBJECTIVE: To compare the differences in gene expression between normal embryos and those with neural tube defects.DESIGN, TIME AND SETTING: A neural development study was performed at the Department of Neurobiology, Third Military Medical University of Chinese PLA between January 2006 and October 2007.MATERIALS: Among 120 adult Kunming mice, 60 pregnant mice were randomly and evenly divided into a retinoic acid group (n = 30) and a normal control group (n =30). The retinoic acid was produced by Sigma, USA, the gene microarray by the Amersham Pharmacia Company, Hong Kong, and the gene sequence was provided by the Incyte database, USA.METHODS: Retinoic acid was administered to prepare models of neural tube defects, and corn oil was similady administered to the normal control group. Total RNA was extracted from embryonic tissue of the two groups using a Trizol kit, and a cDNA microarray containing 1 100 known genes was used to compare differences in gene expression between the normal control group and the retinoic acid group on embryonic (E) clay 10.5 and 11.5. Several differentially expressed genes were randomly selected from the two groups for Northern blotting, to verify the results of the cDNA microarray.MAIN OUTCOME MEASURES: Morphological changes and differential gene expression between the normal control group and the retinoic acid group.RESULTS: Anatomical microscopy demonstrated that an intact closure of the brain was formed in the normal mouse embryos by days E10.5 and E11.5. The cerebral appearance was full and smooth, and the surface of the spine was intact. However, in the retinoic acid group on days E10.5 and E11.5, there were more dead embryos. Morphological malformations typically included non-closure at the top of

  9. Lack of periconceptional vitamins or supplements that contain folic acid and diabetes mellitus–associated birth defects

    Correa, Adolfo; Gilboa, Suzanne M.; Botto, Lorenzo D.; Moore, Cynthia A.; Hobbs, Charlotte A.; Cleves, Mario A.; Riehle-Colarusso, Tiffany J.; Waller, D. Kim; Reece, E. Albert

    2016-01-01

    OBJECTIVE The purpose of this study was to examine the risk of birth defects in relation to diabetes mellitus and the lack of use of periconceptional vitamins or supplements that contain folic acid. STUDY DESIGN The National Birth Defects Prevention Study (1997-2004) is a multicenter, population-based case-control study of birth defects (14,721 cases and 5437 control infants). Cases were categorized into 18 types of heart defects and 26 noncardiac birth defects. We estimated odds ratios for independent and joint effects of preexisting diabetes mellitus and a lack of periconceptional use of vitamins or supplements that contain folic acid. RESULTS The pattern of odds ratios suggested an increased risk of defects that are associated with diabetes mellitus in the absence vs the presence of the periconceptional use of vitamins or supplements that contain folic acid. CONCLUSION The lack of periconceptional use of vitamins or supplements that contain folic acid may be associated with an excess risk for birth defects due to diabetes mellitus. PMID:22284962

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

    Mohamed S. El-Deab

    2012-01-01

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

  11. The Biochemistry and Physiology of Mitochondrial Fatty Acid β-Oxidation and Its Genetic Disorders.

    Houten, Sander M; Violante, Sara; Ventura, Fatima V; Wanders, Ronald J A

    2016-01-01

    Mitochondrial fatty acid β-oxidation (FAO) is the major pathway for the degradation of fatty acids and is essential for maintaining energy homeostasis in the human body. Fatty acids are a crucial energy source in the postabsorptive and fasted states when glucose supply is limiting. But even when glucose is abundantly available, FAO is a main energy source for the heart, skeletal muscle, and kidney. A series of enzymes, transporters, and other facilitating proteins are involved in FAO. Recessively inherited defects are known for most of the genes encoding these proteins. The clinical presentation of these disorders may include hypoketotic hypoglycemia, (cardio)myopathy, arrhythmia, and rhabdomyolysis and illustrates the importance of FAO during fasting and in hepatic and (cardio)muscular function. In this review, we present the current state of knowledge on the biochemistry and physiological functions of FAO and discuss the pathophysiological processes associated with FAO disorders. PMID:26474213

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

    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

  13. Oxidative stability of fatty acid alkyl esters: a review.

    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

  14. Folic acid supplements to prevent neural tube defects: trends in East of Ireland 1996-2002.

    Ward, M

    2004-10-01

    Promotion of folic acid to prevent neural Tube Defects (NTD) has been ongoing for ten years in Ireland, without a concomitant reduction in the total birth prevalence of NTD. The effectiveness of folic acid promotion as the sole means of primary prevention of NTD is therefore questionable. We examined trends in folic acid knowledge and peri-conceptional use from 1996-2002 with the aim of assessing the value of this approach. From 1996-2002, 300 women attending ante-natal clinics in Dublin hospitals annually were surveyed regarding their knowledge and use of folic acid. During the period the proportion who had heard of folic acid rose from 54% to 94% between 1996 and 2002 (c2 test for trend: p<0.001). Knowledge that folic acid can prevent NTD also rose from 21% to 66% (c2 test for trend: p<0.001). Although the proportion who took folic acid during pregnancy increased from 14% to 83% from 1996 to 2002 (c2 test for trend: p<0.001), peri-conceptional intake did not rise above 24% in any year. There is a high awareness of folic acid and its relation to NTD, which is not matched by peri-conceptional uptake. The main barrier to peri-conceptional uptake is the lack of pregnancy planning. To date promotional campaigns appear to have been ineffective in reducing the prevalence of NTD in Ireland. Consequently, fortification of staple foodstuffs is the only practical and reliable means of primary prevention of NTD.

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

    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......H promoted oxidation. It is proposed that iron bridges between the egg yolk proteins low-density lipoproteins, lipovitellin, and phosvitin at the oil-water interface are broken at low pH values, whereby iron ions become accessible as oxidation initiators. In the presence of ascorbic acid, oxidation is...... further enhanced due to the reduction of Fe3+ to Fe2+ that rapidly catalyzes lipid oxidation via lipid hydroperoxide decomposition at the oil-water interface in mayonnaise...

  16. Defect modelling

    Calculations, drawing principally on developments at AERE Harwell, of the relaxation about lattice defects are reviewed with emphasis on the techniques required for such calculations. The principles of defect modelling are outlined and various programs developed for defect simulations are discussed. Particular calculations for metals, ionic crystals and oxides, are considered. (UK)

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

    Lykkesfeldt, Jens

    2007-01-01

    Lack of post-sampling stability of ascorbate and dehydroascorbic acid and failure to block their in vivo equilibrium have lowered their value as biomarkers of oxidative stress and limited the ability to further investigate their possible role in disease prevention. In the present paper, the...... analytical reproducibility was tested by repeated analysis of plasma aliquots from one individual over four years. The plasma was subjected to acidic deproteinization with an equal volume of 10% meta-phosphoric acid containing 2 mM EDTA and analyzed for ascorbate and dehydroascorbic acid by high-performance...

  18. Nondestructive covalent functionalization of carbon nanotubes by selective oxidation of the original defects with K2FeO4

    Graphical abstract: - Highlights: • Nondestructive covalent CNT functionalization is realized by defect oxidation. • A green oxidant K2FeVIO4 is used for CNT oxidation for the first time. • Effective CNT oxidation can be achieved at 60 °C in 3 h. • Oxidized CNTs are obtained in yields of above 100 wt%. • FeO3, an unusual Fe (VI) specie, is produced when K2FeO4 is dissolved in H2SO4. - Abstract: Chemical oxidation is still the major approach to the covalent functionalization of carbon nanotubes (CNTs). Theoretically, the defects on CNTs are more reactive than skeletal hexagons and should be preferentially oxidized, but conventional oxidation methods, e.g., HNO3/H2SO4 treatment, have poor reaction selectivity and inevitably consume the C=C bonds in the hexagonal lattices, leading to structural damage, π-electrons loss and weight decrease. In this work, we realized the nondestructive covalent functionalization of CNTs by selective oxidation of the defects. In our method, potassium ferrate K2FeVIO4 was employed as an oxidant for CNTs in H2SO4 medium. The CNT samples, before and after K2FeO4/H2SO4 treatment, were characterized with colloid dispersibility, IR, Raman spectroscopy, FESEM and XPS. The results indicated that (i) CNTs could be effectively oxidized by Fe (VI) under mild condition (60 °C, 3 h), and hydrophilic CNTs with abundant surface −COOH groups were produced; and (ii) Fe (VI) oxidation of CNTs followed a defect-specific oxidation process, that is, only the sp3-hybridized carbon atoms on CNT surface were oxidized while the C=C bonds remained unaffected. This selective/nondestructive oxidation afforded oxidized CNTs in yields of above 100 wt%. This paper shows that K2FeO4/H2SO4 is an effective, nondestructive and green oxidation system for oxidative functionalization of CNTs and probably other carbon materials as well

  19. The role of nitric oxide in muscle fibers with oxidative phosphorylation defects

    NO has been pointed as an important player in the control of mitochondrial respiration, especially because of its inhibitory effect on cytochrome c oxidase (COX). However, all the events involved in this control are still not completely elucidated. We demonstrate compartmentalized abnormalities on nitric oxide synthase (NOS) activity on muscle biopsies of patients with mitochondrial diseases. NOS activity was reduced in the sarcoplasmic compartment in COX deficient fibers, whereas increased activity was found in the sarcolemma of fibers with mitochondrial proliferation. We observed increased expression of neuronal NOS (nNOS) in patients and a correlation between nNOS expression and mitochondrial content. Treatment of skeletal muscle culture with an NO donor induced an increase in mitochondrial content. Our results indicate specific roles of NO in compensatory mechanisms of muscle fibers with mitochondrial deficiency and suggest the participation of nNOS in the signaling process of mitochondrial proliferation in human skeletal muscle

  20. Translucent tissue defect in potato (Solanum tuberosum L.) tubers is associated with oxidative stress accompanying an accelerated aging phenotype.

    Zommick, Daniel H; Kumar, G N Mohan; Knowles, Lisa O; Knowles, N Richard

    2013-12-01

    Translucent tissue defect (TTD) is an undesirable postharvest disorder of potato tubers characterized by the development of random pockets of semi-transparent tissue containing high concentrations of reducing sugars. Translucent areas turn dark during frying due to the Maillard reaction. The newly released cultivar, Premier Russet, is highly resistant to low temperature sweetening, but susceptible to TTD. Symptoms appeared as early as 170 days after harvest and worsened with time in storage (4-9 °C, 95 % RH). In addition to higher concentrations of glucose, fructose and sucrose, TTD resulted in lower dry matter, higher specific activities of starch phosphorylase and glc-6-phosphate dehydrogenase, higher protease activity, loss of protein, and increased concentrations of free amino acids (esp. asparagine and glutamine). The mechanism of TTD is unknown; however, the disorder has similarities with the irreversible senescent sweetening that occurs in tubers during long-term storage, where much of the decline in quality is a consequence of progressive increases in oxidative stress with advancing age. The respiration rate of non-TTD 'Premier Russet' tubers was inherently higher (ca. 40 %) than that of 'Russet Burbank' tubers (a non-TTD cultivar). Moreover, translucent tissue from 'Premier Russet' tubers had a 1.9-fold higher respiration rate than the average of non-translucent tissue and tissue from non-TTD tubers. Peroxidation of membrane lipids during TTD development resulted in increased levels of malondialdehyde and likely contributed to a measurable increase in membrane permeability. Superoxide dismutase and catalase activities and the ratio of oxidized to total glutathione were substantially higher in translucent tissue. TTD tubers also contained twofold less ascorbate than non-TTD tubers. TTD appears to be a consequence of oxidative stress associated with accelerated aging of 'Premier Russet' tubers. PMID:24037414

  1. Engineering the defect state and reducibility of ceria based nanoparticles for improved anti-oxidation performance

    Wang, Yan-Jie; Dong, Hao; Lyu, Guang-Ming; Zhang, Huai-Yuan; Ke, Jun; Kang, Li-Qun; Teng, Jia-Li; Sun, Ling-Dong; Si, Rui; Zhang, Jing; Liu, Yan-Jun; Zhang, Ya-Wen; Huang, Yun-Hui; Yan, Chun-Hua

    2015-08-01

    Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation mechanism of CeO2 nanoparticles. Adsorbed peroxide species are detected during the anti-oxidation process, which are responsible for the red-shifted UV-vis absorption spectra of CeO2 nanoparticles. Furthermore, the coordination number of Ce in the first coordination shell slightly increased after the addition of H2O2. On the basis of these experimental results, the reactivity of coordination sites for peroxide species is considered to play a key role in the anti-oxidation performance of CeO2 nanoparticles. Furthermore, we present a robust method to engineer the anti-oxidation performance of CeO2 nanoparticles through the modification of the defect state and reducibility by doping with Gd3+. Improved anti-oxidation performance is also observed in cell culture, where the biocompatible CeO2-based nanoparticles can protect INS-1 cells from oxidative stress induced by H2O2, suggesting the potential application of CeO2 nanoparticles in the treatment of diabetes.Due to their excellent anti-oxidation performance, CeO2 nanoparticles receive wide attention in pharmacological application. Deep understanding of the anti-oxidation mechanism of CeO2 nanoparticles is extremely important to develop potent CeO2 nanomaterials for anti-oxidation application. Here, we report a detailed study on the anti-oxidation process of CeO2 nanoparticles. The valence state and coordination structure of Ce are characterized before and after the addition of H2O2 to understand the anti-oxidation

  2. Studies of oxide/ZnO near-interfacial defects by photoluminescence and deep level transient spectroscopy

    Ling, CC; Wang, RS; Gu, QL; Ong, HC

    2008-01-01

    The evolution of near-interfacial defects from Al2 O3 ZnO and MgOZnO upon thermal annealing has been studied by photoluminescence, deep level transient spectroscopy, and secondary ion mass spectroscopy. We find that all the results are strongly connected and that they point to the direction that Zn outdiffuses from ZnO to the oxide layer during annealing and creates deep level defects near the interfacial region. These defects reduce the band-edge emission and increase the deep level emission...

  3. Peroxisomal beta-oxidation defect with detectable peroxisomes: a case with neonatal onset and progressive course.

    Barth, P G; Wanders, R J; Schutgens, R B; Bleeker-Wagemakers, E M; van Heemstra, D

    1990-07-01

    A progressive demyelinating cerebral disorder is described in a normally-appearing female infant with neonatal seizures, progressive psychomotor deterioration, deafness, retinopathy, peripheral neuropathy and loss of myelin observed on magnetic resonance imaging (MRI) scanning. MRI also showed the absence of macroscopic neocortical dysplasia which is usually found in Zellweger syndrome (ZS). Adrenal cortical function was normal. The patient died at the age of 37 months. Extensive biochemical investigations of peroxisomal functions in the patient revealed an impairment of peroxisomal beta-oxidation resulting in elevated levels of very long (greater than C22) chain fatty acids in plasma and fibroblasts. Moreover, elevated plasma levels of intermediates of bile acid biosynthesis such as tri- and dihydroxycholestanoic acid were found. Other peroxisomal functions were normal. Immunoblotting of the peroxisomal beta-oxidation enzyme proteins in liver from the patient revealed normal responses with antisera against acyl-CoA oxidase, bifunctional protein and thiolase respectively. From these data we conclude that the patient had a deficiency of a single peroxisomal beta-oxidation enzyme at the level of either the bifunctional protein or peroxisomal thiolase with retained immunoreactivity against these enzymes. PMID:2209666

  4. Acid-catalyzed kinetics of indium tin oxide etching

    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

  5. Phase Relations and Defect Chemistry of Bismuth Strontium Calcium Copper Oxide Superconducting Oxides at Elevated Temperature

    Hong, Byungsun

    1992-01-01

    Subsolidus phase relations in the system (Bi-Sr -Ca-Cu)-O at 800^circC were investigated via powder X-ray diffraction and electron probe microanalysis of solid-state reaction products. The only truly quaternary compound detected is the superconducting phase of n = 2 in Bi_2(Sr _{rm x}Ca_ {rm 1-x})_{ rm n+1}Cu_{rm n}O_{rm y} . The n = 2 phase is compatible with eight different binary or ternary phases. Tie lines, tie triangles, and compatibility tetrahedra involving superconducting phases were determined. The cation solubility limits of the n = 2 and n = 3 superconducting phases were established along tie lines with compatible phases via EPMA on bi- (or poly -) phasic samples prepared at 860^circ C. In each case football-shaped volumes in composition space were established as the solubility limits which bordered on the nominal compositions 2212 or 2223 with the long axis parallel to the Sr-Ca side of the quaternary but also extending toward Bi and Cu. T_{rm c} variations could be correlated with variations in Sr or (Bi+Sr) content and the length of the c-axis parameter. Via in-situ high temperature (550-650 ^circC) electrical conductivity and Seebeck coefficient measurements in Bi_ {2.1}Sr_{1.9} (Ca_{rm 1-x}Y _{rm x})Cu _2O_{rm y} , a point defect model/diagram is presented which explains the variation of thermopower with composition in the system. The reference, insulating composition should be between Bi_{2.1}Sr _{1.9}Ca_ {0.2}Y_{0.8} Cu_2O_{8.45 } and Bi_{2.1}Sr _{1.9}Ca_ {0.3}Y_{0.7} Cu_2O_{8.4 }. Y-contents higher than x = 0.8 result in a second phase. A structural phase transition from pseudo -tetragonal to orthorhombic takes place at x = 0.5, and plays a major role in determining the physical properties. Oxygen transfer from the Bi-O block to the Cu-O based perovskite block is suggested at the phase boundary of x = 0.5. Jonker analysis and oxygen pressure dependence of carrier concentration confirm p-type behavior despite the change in sign of the thermopower

  6. Modelling of liquid metal flow and oxide film defects in filling of aluminium alloy castings

    Dai, X.; Jolly, M.; Yang, X.; Campbell, J.

    2012-07-01

    The liquid metal flow behaviours in different runner system designs have important effects on the mechanical strength of aluminium alloy castings. In this paper, a new model has been developed which is a two-dimensional program using a finite difference technique and the Marker and Cell (MAC) method to simulate the flow of liquid metal during filling a mould. In the program the Eulerian method has been used for the liquid metal flow, while the Oxide Film Entrainment Tracking Algorithm (OFET) method (a Lagrangian method) has been used to simulate the movement of the oxide film on the liquid metal surface or in the liquid metal flow. Several examples have been simulated and tested and the relevant results were obtained. These results were compared with measured bending strengths. It was found that the completed program was capable of simulating effectively the filling processes of different runner systems. The simulation results are consistent with the experiment. In addition, the program is capable of providing clearer images for predicting the distribution of the oxide film defects generated during filling a mould.

  7. Nitric-phosphoric acid oxidation of organic waste materials

    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 NOx 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

  8. Loss of Adipose Fatty Acid Oxidation Does Not Potentiate Obesity at Thermoneutrality

    Jieun Lee

    2016-02-01

    Full Text Available Ambient temperature affects energy intake and expenditure to maintain homeostasis in a continuously fluctuating environment. Here, mice with an adipose-specific defect in fatty acid oxidation (Cpt2A−/− were subjected to varying temperatures to determine the role of adipose bioenergetics in environmental adaptation and body weight regulation. Microarray analysis of mice acclimatized to thermoneutrality revealed that Cpt2A−/− interscapular brown adipose tissue (BAT failed to induce the expression of thermogenic genes such as Ucp1 and Pgc1α in response to adrenergic stimulation, and increasing ambient temperature exacerbated these defects. Furthermore, thermoneutral housing induced mtDNA stress in Cpt2A−/− BAT and ultimately resulted in a loss of interscapular BAT. Although the loss of adipose fatty acid oxidation resulted in clear molecular, cellular, and physiologic deficits in BAT, body weight gain and glucose tolerance were similar in control and Cpt2A−/− mice in response to a high-fat diet, even when mice were housed at thermoneutrality.

  9. Loss of Adipose Fatty Acid Oxidation Does Not Potentiate Obesity at Thermoneutrality.

    Lee, Jieun; Choi, Joseph; Aja, Susan; Scafidi, Susanna; Wolfgang, Michael J

    2016-02-16

    Ambient temperature affects energy intake and expenditure to maintain homeostasis in a continuously fluctuating environment. Here, mice with an adipose-specific defect in fatty acid oxidation (Cpt2(A-/-)) were subjected to varying temperatures to determine the role of adipose bioenergetics in environmental adaptation and body weight regulation. Microarray analysis of mice acclimatized to thermoneutrality revealed that Cpt2(A-/-) interscapular brown adipose tissue (BAT) failed to induce the expression of thermogenic genes such as Ucp1 and Pgc1α in response to adrenergic stimulation, and increasing ambient temperature exacerbated these defects. Furthermore, thermoneutral housing induced mtDNA stress in Cpt2(A-/-) BAT and ultimately resulted in a loss of interscapular BAT. Although the loss of adipose fatty acid oxidation resulted in clear molecular, cellular, and physiologic deficits in BAT, body weight gain and glucose tolerance were similar in control and Cpt2(A-/-) mice in response to a high-fat diet, even when mice were housed at thermoneutrality. PMID:26854223

  10. The comparison of gamma-radiation and electrical stress influences on oxide and interface defects in power VDMOSFET

    Đorić-Veljković Snežana M.

    2013-01-01

    Full Text Available The behaviour of oxide and interface defects in n-channel power vertical double-diffused metal-oxide-semiconductor field-effect transistors, firstly degraded by the gamma-irradiation and electric field and subsequently recovered and annealed, is presented. By analyzing the transfer characteristic shifts, the changes of threshold voltage and underlying changes of gate oxide and interface trap densities during the stress (recovery, annealing of investigated devices, it is shown that these two types of stress influence differently on the gate oxide and the SiO2-Si interface. [Projekat Ministarstva nauke Republike Srbije, br. OI171026

  11. Prevention of neural tube defects with folic acid: The Chinese experience.

    Ren, Ai-Guo

    2015-08-01

    Neural tube defects (NTDs) are a group of congenital malformations of the central nervous system that are caused by the closure failure of the embryonic neural tube by the 28(th) day of conception. Anencephaly and spina bifida are the two major subtypes. Fetuses with anencephaly are often stillborn or electively aborted due to prenatal diagnosis, or they die shortly after birth. Most infants with spina bifida are live-born and, with proper surgical treatment, can survive into adulthood. However, these children often have life-long physical disabilities. China has one of the highest prevalence of NTDs in the world. Inadequate dietary folate intake is believed to be the main cause of the cluster. Unlike many other countries that use staple fortification with folic acid as the public health strategy to prevent NTDs, the Chinese government provides all women who have a rural household registration and who plan to become pregnant with folic acid supplements, free of charge, through a nation-wide program started in 2009. Two to three years after the initiation of the program, the folic acid supplementation rate increased to 85% in the areas of the highest NTD prevalence. The mean plasma folate level of women during early and mid-pregnancy doubled the level before the program was introduced. However, most women began taking folic acid supplements when they knew that they were pregnant. This is too late for the protection of the embryonic neural tube. In a post-program survey of the women who reported folic acid supplementation, less than a quarter of the women began taking supplements prior to pregnancy, indicating that the remaining three quarters of the fetuses remained unprotected during the time of neural tube formation. Therefore, staple food fortification with folic acid should be considered as a priority in the prevention of NTDs. PMID:26261765

  12. The influence of interfacial defects on fast charge trapping in nanocrystalline oxide-semiconductor thin film transistors

    Kim, Taeho; Hur, Jihyun; Jeon, Sanghun

    2016-05-01

    Defects in oxide semiconductors not only influence the initial device performance but also affect device reliability. The front channel is the major carrier transport region during the transistor turn-on stage, therefore an understanding of defects located in the vicinity of the interface is very important. In this study, we investigated the dynamics of charge transport in a nanocrystalline hafnium-indium-zinc-oxide thin-film transistor (TFT) by short pulse I-V, transient current and 1/f noise measurement methods. We found that the fast charging behavior of the tested device stems from defects located in both the front channel and the interface, following a multi-trapping mechanism. We found that a silicon-nitride stacked hafnium-indium-zinc-oxide TFT is vulnerable to interfacial charge trapping compared with silicon-oxide counterpart, causing significant mobility degradation and threshold voltage instability. The 1/f noise measurement data indicate that the carrier transport in a silicon-nitride stacked TFT device is governed by trapping/de-trapping processes via defects in the interface, while the silicon-oxide device follows the mobility fluctuation model.

  13. Structure, Raman spectra and defect chemistry modelling of conductive pyrochlore oxides

    Poulsen, F.W.; Glerup, M.; Holtappels, P.

    2000-01-01

    Mixed ionic-electronic conducting pyrochlore structure oxides, with Pr and Gd on the A site and Zr, Mn, Ce, Sn, In, Mo, and Ti on the B site, were characterised by X-ray powder diffraction and Raman spectroscopy. Mn and In have a solubility around x = 0.1-0.2 in Pr2Zr2-xMnxO7 and Pr2Sn2-xInxO7......-O(x) and V-O on the O site, interstitial oxygens O-i", and delocalised electrons and electron holes. Four mass action law expressions govern such a model. The defect model can rationalise why home-valent doping, i.e. substitution of Zr(4+) by Ce(4+), can lead to an increase in ionic conductivity...

  14. Expression of the Ciona intestinalis alternative oxidase (AOX) in Drosophila complements defects in mitochondrial oxidative phosphorylation.

    Fernandez-Ayala, Daniel J M; Sanz, Alberto; Vartiainen, Suvi; Kemppainen, Kia K; Babusiak, Marek; Mustalahti, Eero; Costa, Rodolfo; Tuomela, Tea; Zeviani, Massimo; Chung, Jongkyeong; O'Dell, Kevin M C; Rustin, Pierre; Jacobs, Howard T

    2009-05-01

    Defects in mitochondrial OXPHOS are associated with diverse and mostly intractable human disorders. The single-subunit alternative oxidase (AOX) found in many eukaryotes, but not in arthropods or vertebrates, offers a potential bypass of the OXPHOS cytochrome chain under conditions of pathological OXPHOS inhibition. We have engineered Ciona intestinalis AOX for conditional expression in Drosophila melanogaster. Ubiquitous AOX expression produced no detrimental phenotype in wild-type flies. However, mitochondrial suspensions from AOX-expressing flies exhibited a significant cyanide-resistant substrate oxidation, and the flies were partially resistant to both cyanide and antimycin. AOX expression was able to complement the semilethality of partial knockdown of both cyclope (COXVIc) and the complex IV assembly factor Surf1. It also rescued the locomotor defect and excess mitochondrial ROS production of flies mutated in dj-1beta, a Drosophila homolog of the human Parkinson's disease gene DJ1. AOX appears to offer promise as a wide-spectrum therapeutic tool in OXPHOS disorders. PMID:19416715

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

    Elle, Ida Coordt; Rødkær, Steven Vestergaard; Fredens, Julius; Færgeman, Nils Joakim

    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 liv...

  16. Oxidized Fatty Acids as Inter-Kingdom Signaling Molecules

    Pohl, Carolina H.; Johan L. F. Kock

    2014-01-01

    Oxylipins or oxidized fatty acids are a group of molecules found to play a role in signaling in many different cell types. These fatty acid derivatives have ancient evolutionary origins as signaling molecules and are ideal candidates for inter-kingdom communication. This review discusses examples of the ability of organisms from different kingdoms to “listen” and respond to oxylipin signals during interactions. The interactions that will be looked at are signaling between animals and plants; ...

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

    Claude Daneault; Saïd Barazzouk

    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, th...

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

    Mechanism of selective action of oxide catalysts (on the base of V2O4, MoO3) 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)

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

    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.

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

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

    2004-01-01

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

  1. Regulation and limitations to fatty acid oxidation during exercise

    Jeppesen, Jacob; Kiens, Bente

    2012-01-01

    turn is trapped by carnitine. This will lead to less availability of free carnitine for fatty acid transport into mitochondria. This review summarizes our present view on how FA metabolism is regulated during exercise with a special focus on the limitations in FA oxidation in the transition from...

  2. Oxidation of coal-based raw materials by nitric acid

    Novák, J.; Novák, František; Madronová, L.; Machovič, V.; Kozler, J.

    New York : Nova Science Publisher, 2011 - (Madronová, L.), s. 105-123 ISBN 978-1-61668-965-0. - ( Chemistry Research and Applications ) Institutional research plan: CEZ:AV0Z60660521 Keywords : oxidation * coal-based raw materials * nitric acid Subject RIV: CB - Analytical Chemistry , Separation

  3. Role of biologically assisted pyrrhotite oxidation in acid mine drainage

    Water contaminated by acidic mine drainage (AMD) from base metal tailings and waste rock is a serious environmental problem. Previous studies have focused on pyrite as the principal acid producing mineral. In this work, the significance of pyrrhotite (Fe1-xS) oxidation, both chemical and biochemical, on the acid generation process is discussed. Chemical and biochemical kinetic studies of pyrrhotite oxidation were conducted in pneumatically mixed, internal split flow reactors. Controlling variables included the specific surface area, temperature, pH, partial pressure of oxygen, and co-oxidation with pyrite. Bacterial oxidations, using Thiobacillus ferrooxidans as inoculant. included the inherent metabolic rate and cell sorption equilibria on the ore surface. Mathematical models were derived to couple the kinetics with oxygen mass transfer. The mass transport model combined mechanisms based on the shrinking radius (fine particles) and the shrinking reactive front (massive sulfides) concepts. The objective of the research was the application of fundamental kinetic and physical data to field conditions for simulating both the rate of mineral oxidation and simulating pore water quality

  4. Administration with Bushenkangshuai Tang alleviates UV irradiation- and oxidative stress-induced lifespan defects in nematode Caenorhabditis elegans

    Qi RUI; Qin LU; Dayong WANG

    2009-01-01

    During normal metabolism, oxidative bypro-ducts will inevitably generate and damage molecules thereby impairing their biological functions, including the is a traditional Chinese medicine widely used for clini-cally treating premature ovarian failure. In the present study, BT administration at high concentrations signifi-cantly increased lifespan, slowed aging-related decline, and delayed accumulation of aging-related cellular damage in wild-type Caenorhabditis elegans. BT admin-istration could further largely alleviate the aging defects induced by UV and oxidative stresses, and BT administra-tion at different concentrations could largely rescue the aging defects in mev-1 mutant animals. The protective effects of BT administration on aging process were at least partially dependent on the Ins/IGF-like signaling pathway. Moreover, BT administration at different concentrations obviously altered the expression patterns of antioxidant genes and suppressed the severe stress responses induced by UV and oxidative stresses, suggesting that BT-induced tolerance to UV or oxidative stress might result from reactive oxygen species scavenging. BT administration during development was not necessarily a requirement for UV and oxidative stress resistance, and the concentrations of administrated BT examined were not toxic for nematodes. Therefore, BT administration could effectively retrieve the aging defects induced by UV irradiation and oxidative stress in Caenorhabditis elegans.

  5. Solid state electrochemical techniques for studies on nonstoichiometry and defect structure of metal oxides

    The equilibrium oxygen partial pressures of several nonstoichiometric oxides were determined as a function of composition and temperature. The defect structures of nonstoichiometric phases are discussed. Thermodynamic properties of UO2+x were determined by using a stacked pellet-type cell and the variation of Δ bar SO2 with x was explained on the basis of the 2:2:2 Willis model. The phase relations and nonstoichiometry in V2O5-x, LiVO3-x, BaBiO3-x, PrOx and Ba2HoCu3O7-y were studied by coulometric titration and the results are discussed on the basis of the mass-action law and statistical models. The electrical conductivity measurements were made under the condition of constant oxygen content or temperature in-situ using a modified coulometric titration technique. Coulometric titration has proved to be very useful to study the phase relations particularly in the oxides with small deviations from the stoichiometric composition

  6. Complexes of low oxidated /sup 99/Tc with salicylic acid

    While several complexes of technetium with hydroxycarboxylic acids in solution are well known, little has been done about complexes of technetium with phenolcarboxylic acids. M.A. Kayssi suggested the use of sulphosalicylic acid as a reagent for the quantitative determination of technetium. The resulting complex shows a spectrophotometric maximum at 460 nm; the author supposes that the complex could contain technetium in the (V) oxidation state. In this paper the reaction between technetium and salicylic acid at concentrations between 10/sup -4/ and 5 x 10/sup -2/ M, in a pH range of 2 to 4.5, has been studied. The pH does not seem to influence the reaction, while the salicylic acid concentration is particularly significant

  7. Defect engineered d{sup 0} ferromagnetism in tin-doped indium oxide nanostructures and nanocrystalline thin-films

    Khan, Gobinda Gopal, E-mail: gobinda.gk@gmail.com, E-mail: sghoshphysics@gmail.com; Sarkar, Ayan [Centre for Research in Nanoscience and Nanotechnology, University of Calcutta, Technology Campus, Block JD-2, Sector III, Salt Lake City, Kolkata 700 098 (India); Ghosh, Shyamsundar, E-mail: gobinda.gk@gmail.com, E-mail: sghoshphysics@gmail.com [Department of Physics, Bejoy Narayan Mahavidyalaya, P.O. Itachuna, Hooghly 712 147 (India); Mandal, Guruprasad; Mukherjee, Goutam Dev [Department of Physical Sciences, Indian Institute of Science Education and Research, Kolkata, Mohanpur Campus, BCKV Campus Main Office, Nadia 741 252 (India); Manju, Unnikrishnan [Materials Characterization Division, CSIR-Central Glass and Ceramic Research Institute, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700 032 (India); Banu, Nasrin; Dev, Bhupendra Nath [Department of Material Science, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata 700 032 (India)

    2015-08-21

    Origin of unexpected defect engineered room-temperature ferromagnetism observed in tin-doped indium oxide (ITO) nanostructures (Nanowires, Nano-combs) and nanocrystalline thin films fabricated by pulsed laser deposition has been investigated. It is found that the ITO nanostructures prepared under argon environment exhibit strongest ferromagnetic signature as compared to that nanocrystalline thin films grown at oxygen. The evidence of singly ionized oxygen vacancy (V{sub 0}{sup +}) defects, obtained from various spectroscopic measurements, suggests that such V{sub 0}{sup +} defects are mainly responsible for the intrinsic ferromagnetic ordering. The exchange interaction of the defects provides extensive opportunity to tune the room-temperature d{sup 0} ferromagnetism and optical properties of ITOs.

  8. Riboflavin-responsive oxidative phosphorylation complex I deficiency caused by defective ACAD9: new function for an old gene

    M. Gerards; B.J.C. van den Bosch; K. Danhauser; V. Serre; M. van Weeghel; R.J.A. Wanders; G.A.F. Nicolaes; W. Sluiter; K. Schoonderwoerd; H.R. Scholte; H. Prokisch; A. Rötig; I.F.M. de Coo; H.J.M. Smeets

    2011-01-01

    Mitochondrial complex I deficiency is the most common oxidative phosphorylation defect. Mutations have been detected in mitochondrial and nuclear genes, but the genetics of many patients remain unresolved and new genes are probably involved. In a consanguineous family, patients presented easy fatiga

  9. Application of the integral method to modelling the oxidation of defected fuel elements

    The starting point for this report is the discrepancy reported in previous work between the reaction-diffusion calculations and the CEX-1 experiment, which involves storage of defected fuel elements in air at 150 deg C. This discrepancy is considerably diminished here by a more critical choice of theoretical parameters, and by taking into account the fact that different CEX-1 fuel elements were oxidized at very different rates and that the fuel element used previously for comparison with theoretical calculations actually underwent two limited-oxygen-supply cycles. Much better agreement is obtained here between the theory and the third, unlimited-air, storage period of the CEX-1 experiment. The approximate integral method is used extensively for the solution of the one-dimensional diffusion moving-boundary problems that may describe various storage periods of the CEX-1 experiment. In some cases it is easy to extend this method to arbitrary precision by using higher moments of the diffusion equation. Using this method, the validity of quasi-steady-state approximation is verified. Diffusion-controlled oxidation is also studied. In this case, for the unlimited oxygen supply, the integral method leads to an exact analytical solution for linear geometry, and to a good analytical approximation of the solution for the spherically symmetric geometry. These solutions may have some application in the analysis of experiments on the oxidation of small UO2 fragments or powders when the individual UO2 grains may be considered to be approximately spherical. (author). 23 refs., 5 tabs., 11 figs

  10. Studies of Tc oxidation states in humic acid solutions

    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 LaCl3 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 99Tc was determined using liquid scintillation spectrometry. The humic acid will influence the radiocounting ratio of 99Tc apparently, however, the quenching effect can be restrained once keep the volume of the cocktail to about twenty times of the sample volume. The LaCl3 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 LaCl3 precipitation method, and the experimental results demonstrate that tetravalent technetium and pertechnetate concentration are well agreement with the LaCl3 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)

  11. Effect of sulfonylureas on hepatic fatty acid oxidation

    Patel, T.B.

    1986-08-01

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

  12. Effect of sulfonylureas on hepatic fatty acid oxidation

    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 14C 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

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

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

    2014-10-01

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

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

    Raghvendra Shukla; Pradeep K Sharma; Kalyan K Banerji

    2004-03-01

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

  15. Selection and properties of Escherichia coli mutants defective in the synthesis of cyclopropane fatty acids.

    Taylor, F; Cronan, J E

    1976-01-01

    Mutants of Escherichia coli K-12 defective in the synthesis of cyclopropane fatty acids (CFA) have been selected and isolated by a L-[methyl-3H]methionine suicide procedure. Two mutants were isolated. Stationary-phase cultures of both mutants contain less than 0.7% of the CFA content found in the parental strain. The CFA deficiency is attributed to a deficiency of CFA synthetase activity. Extracts of both mutants contain less than 10% of the CFA synthetase activity found in extracts of the parental strain. Experiments in which parental and mutant extracts were mixed indicate that the lack of activity in the mutant strains is not due to an inhibitor of CFA synthetase present in the mutant extracts. We have not yet detected a physiological phenotype for these mutants. These strains grow normally at various temperatures in a variety of media. We have tested survival (colony-forming ability) in response to (i) prolonged incubation in stationary phase, (ii) exposure to drying, and (iii) exposure to detergents, heavy metals, low pH, high salt concentration, and a variety of other environmental conditions. The survival of both mutants is identical to that of the parental strain under all conditions tested. The compositions (excepting the CFA deficiency) and metabolic turnover rates of the phospholipids of both mutant strains are indistinguishable from those of the wild-type strain. The transport of several amino acids also seems normal in these mutants. PMID:1107324

  16. Impacts of acid gases on mercury oxidation across SCR catalyst

    A series of bench-scale experiments were completed to evaluate acid gases of HCl, SO2, and SO3 on mercury oxidation across a commercial selective catalytic reduction (SCR) catalyst. The SCR catalyst was placed in a simulated flue gas stream containing O2, CO2, H2O, NO, NO2, and NH3, and N2. HCl, SO2, and SO3 were added to the gas stream either separately or in combination to investigate their interactions with mercury over the SCR catalyst. The compositions of the simulated flue gas represent a medium-sulfur and low- to medium-chlorine coal that could represent either bituminous or subbituminous. The experimental data indicated that 5-50 ppm HCl in flue gas enhanced mercury oxidation within the SCR catalyst, possibly because of the reactive chlorine species formed through catalytic reactions. An addition of 5 ppm HCl in the simulated flue gas resulted in mercury oxidation of 45% across the SCR compared to only 4% mercury oxidation when 1 ppm HCl is in the flue gas. As HCl concentration increased to 50 ppm, 63% of Hg oxidation was reached. SO2 and SO3 showed a mitigating effect on mercury chlorination to some degree, depending on the concentrations of SO2 and SO3, by competing against HCl for SCR adsorption sites. High levels of acid gases of HCl (50 ppm), SO2 (2000 ppm), and SO3 (50 ppm) in the flue gas deteriorate mercury adsorption on the SCR catalyst. (author)

  17. Radiolytical oxidation of ascorbic acid in aqueous solutions

    Complete text of publication follows. Ascorbic acid, AsA (vitamin c), has been widely studied as an antioxidant or as an initiator of some technological processes, for example polymerization or nanoparticles formation. AsA can be easily oxidized to ascorbyl radical, in the first stage, and to dehydroascorbic acid, DHA, in the second stage. It has been found that several different ascorbyl radicals are formed during AsA oxidation but the main radical exists as the anion with the unpaired electron delocalized on a highly conjugated tricarbonyl system. Absorption spectrum of ascorbyl radical shows two bands with maxima at 300 and 360 nm, however only that at 360 nm is proportional to the dose and thus this wavelength was chosen for observations. We studied the oxidation of AsA by the following oxidizing radicals generated by the pulse radiolysis method ·OH, (SCN)2-·, Cl2-·, N3· and NO2·. The observed dependence of the yield and the formation rate of the AsA radical on the reduction potential of the oxidizing radical is discussed. The results obtained in water are compared with those obtained with AsA enclosed in the water pools of reverse micelles formed by AOT in n-heptane or by Igepal CO-520 in c-hexane. Somewhat surprising observation of different ascorbyl radical in pulse irradiated reverse micelles containing DHA is also commented.

  18. Formic acid oxidation at platinum-bismuth catalysts

    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

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

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

    2008-01-01

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

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

    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.

  1. Adipose fatty acid oxidation is required for thermogenesis and potentiates oxidative stress induced inflammation

    Jieun Lee; Jessica M. Ellis; Michael J. Wolfgang

    2015-01-01

    To understand the contribution of adipose tissue fatty acid oxidation to whole-body metabolism, we generated mice with an adipose-specific knockout of carnitine palmitoyltransferase 2 (CPT2A−/−), an obligate step in mitochondrial long-chain fatty acid oxidation. CPT2A−/− mice became hypothermic after an acute cold challenge, and CPT2A−/− brown adipose tissue (BAT) failed to upregulate thermogenic genes in response to agonist-induced stimulation. The adipose-specific loss of CPT2 resulted in d...

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

    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

  3. Oxidation of aniline in the presence of phenolic acids

    Janošević Aleksandra M.

    2010-01-01

    Full Text Available Aniline was oxidized with ammonium peroxydisulfate (APS in aqueous solutions of various phenolic acids: 5-sulfosalicylic acid (SSA, 3,5-dinitrosalicylic acid (DNSA and gallic acid (GA. Polymerizations were performed at the constant molar ratios [acid]/[aniline]=0.5 and [APS]/[aniline]=1.25. The conductivity of synthesized polyaniline (PANI is affected by the dopant anion type and decreases in order: PANI-SSA > PANI-DNSA > PANI-GA, the last polymer being nonconducting. This decrease is in accordance with the increase of initial pH value of the reaction mixture. The differences in molecular structure of synthesized PANI have been revealed by FTIR spectroscopy. FTIR spectra of PANI-SSA and PANI-DNSA show typical features of PANI conductive emeraldine salt segments. On the contrary, FTIR spectrum of PANI-GA shows absence of bands typical for conducting PANI polaronic lattice, and indicates the higher oxidation state of this polymer than that of emeraldine, the presence of substituted phenazines as constitutional units, as well as significant content of monosubstituted benzene rings which reflects low polymerization degree and/or pronounced chain branching. The strong hydrogen bonding between GA and PANI can obstruct propagation of oligoanilines and formation of longer conducting PANI chains.

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

    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-reactive ......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...

  5. Enhanced formic acid oxidation on Cu-Pd nanoparticles

    Dai, Lin; Zou, Shouzhong

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

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

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH...

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

    Mur, Luis A. J.; Prats, Elena; Pierre, Sandra; Hall, Michael A.; Hebelstrup, Kim H

    2013-01-01

    Plant defense against pests and pathogens is known to be conferred by either salicylic acid (SA) or jasmonic acid (JA)/ethylene (ET) pathways, depending on infection or herbivore-grazing strategy. It is well attested that SA and JA/ET pathways are mutually antagonistic allowing defense responses to be tailored to particular biotic stresses. Nitric oxide (NO) has emerged as a major signal influencing resistance mediated by both signaling pathways but no attempt has been made to integrate NO in...

  8. Bezafibrate in skeletal muscle fatty acid oxidation disorders

    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......-blind, crossover study of bezafibrate in patients with CPT II (n = 5) and VLCAD (n = 5) deficiencies. Primary outcome measures were changes in FAO, measured with stable-isotope methodology and indirect calorimetry, and changes in HR during exercise. RESULTS: Bezafibrate lowered low-density lipoprotein......, 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...

  9. Band-like transport in highly crystalline graphene films from defective graphene oxides

    Negishi, R.; Akabori, M.; Ito, T.; Watanabe, Y.; Kobayashi, Y.

    2016-01-01

    The electrical transport property of the reduced graphene oxide (rGO) thin-films synthesized from defective GO through thermal treatment in a reactive ethanol environment at high temperature above 1000 °C shows a band-like transport with small thermal activation energy (Ea~10 meV) that occurs during high carrier mobility (~210 cm2/Vs). Electrical and structural analysis using X-ray absorption fine structure, the valence band photo-electron, Raman spectra and transmission electron microscopy indicate that a high temperature process above 1000 °C in the ethanol environment leads to an extraordinary expansion of the conjugated π-electron system in rGO due to the efficient restoration of the graphitic structure. We reveal that Ea decreases with the increasing density of states near the Fermi level due to the expansion of the conjugated π-electron system in the rGO. This means that Ea corresponds to the energy gap between the top of the valence band and the bottom of the conduction band. The origin of the band-like transport can be explained by the carriers, which are more easily excited into the conduction band due to the decreasing energy gap with the expansion of the conjugated π-electron system in the rGO. PMID:27364116

  10. Band-like transport in highly crystalline graphene films from defective graphene oxides

    Negishi, R.; Akabori, M.; Ito, T.; Watanabe, Y.; Kobayashi, Y.

    2016-07-01

    The electrical transport property of the reduced graphene oxide (rGO) thin-films synthesized from defective GO through thermal treatment in a reactive ethanol environment at high temperature above 1000 °C shows a band-like transport with small thermal activation energy (Ea~10 meV) that occurs during high carrier mobility (~210 cm2/Vs). Electrical and structural analysis using X-ray absorption fine structure, the valence band photo-electron, Raman spectra and transmission electron microscopy indicate that a high temperature process above 1000 °C in the ethanol environment leads to an extraordinary expansion of the conjugated π-electron system in rGO due to the efficient restoration of the graphitic structure. We reveal that Ea decreases with the increasing density of states near the Fermi level due to the expansion of the conjugated π-electron system in the rGO. This means that Ea corresponds to the energy gap between the top of the valence band and the bottom of the conduction band. The origin of the band-like transport can be explained by the carriers, which are more easily excited into the conduction band due to the decreasing energy gap with the expansion of the conjugated π-electron system in the rGO.

  11. Chemical Bonding, Interfaces and Defects in Hafnium Oxide/Germanium Oxynitride Gate Stacks on Ge (100)

    Oshima, Yasuhiro; /Stanford U., Materials Sci. Dept.; Sun, Yun; /SLAC, SSRL; Kuzum, Duygu; /Stanford U.; Sugawara, Takuya; Saraswat, Krishna C.; Pianetta, Piero; /SLAC, SSRL; McIntyre, Paul C.; /Stanford U., Materials Sci. Dept.

    2008-10-31

    Correlations among interface properties and chemical bonding characteristics in HfO{sub 2}/GeO{sub x}N{sub y}/Ge MIS stacks were investigated using in-situ remote nitridation of the Ge (100) surface prior to HfO{sub 2} atomic layer deposition (ALD). Ultra thin ({approx}1.1 nm), thermally stable and aqueous etch-resistant GeO{sub x}N{sub y} interfaces layers that exhibited Ge core level photoelectron spectra (PES) similar to stoichiometric Ge{sub 3}N{sub 4} were synthesized. To evaluate GeO{sub x}N{sub y}/Ge interface defects, the density of interface states (D{sub it}) was extracted by the conductance method across the band gap. Forming gas annealed (FGA) samples exhibited substantially lower D{sub it} ({approx} 1 x 10{sup 12} cm{sup -2} eV{sup -1}) than did high vacuum annealed (HVA) and inert gas anneal (IGA) samples ({approx} 1x 10{sup 13} cm{sup -2} eV{sup -1}). Germanium core level photoelectron spectra from similar FGA-treated samples detected out-diffusion of germanium oxide to the HfO{sub 2} film surface and apparent modification of chemical bonding at the GeO{sub x}N{sub y}/Ge interface, which is related to the reduced D{sub it}.

  12. SHI induced defects in chemically synthesized graphene oxide for hydrogen storage applications

    Sharma, Preetam K.; Sharma, Vinay; Rajaura, Rajveer Singh; Srivastava, Subodh; Sharma, S. S.; Singh, M.; Vijay, Y. K.

    2016-05-01

    Graphene, due to its unique properties arising from the single carbon layer, is a potential candidate for applications in a variety of fields including sensors, photovoltaics and energy storage. The atomic structure and morphology of the carbon nanomaterials especially graphene can be tailored by energetic ionic irradiation. As graphene sheet is very stable, the surface have less reactivity as compared to the edges of the sheets. By surface modification with energetic ion-beams additional dangling bonds can be formed to enhance the surface activity of the graphene film which could be exploited in a variety of applications. In the present work, graphene oxide was synthesized by improved Hummers' Method. The irradiation was done with Ag+ ions carrying energy 100 MeV with the fluence of 3×1013. Raman spectrum of graphene irradiated by Ag+ beam shows additional disordered peaks of &Dacute; and D+G bands. There is also a decrease in the intensity of D band. AFM images depict the increase in the surface roughness of the films. This can be attributed to the increase in the defects in the flakes and intermixing of adjacent layers by irradiation.

  13. Oxide for valve-regulated lead-acid batteries

    Lam, L. T.; Lim, O. V.; Haigh, N. P.; Rand, D. A. J.; Manders, J. E.; Rice, D. M.

    In order to meet the increasing demand for valve-regulated lead-acid (VRLA) batteries, a new soft lead has been produced by Pasminco Metals. In this material, bismuth is increased to a level that produces a significant improvement in battery cycle life. By contrast, other common impurities, such as arsenic, cobalt, chromium, nickel, antimony and tellurium, that are known to be harmful to VRLA batteries are controlled to very low levels. A bismuth (Bi)-bearing oxide has been manufactured (Barton-pot method) from this soft lead and is characterized in terms of phase composition, particle size distribution, BET surface area, and reactivity. An investigation is also made of the rates of oxygen and hydrogen evolution on pasted electrodes prepared from the Bi-bearing oxide. For comparison, the characteristics and performance of a Bi-free (Barton-pot) oxide, which is manufactured in the USA, are also examined. Increasing the level of bismuth and lowering those of the other impurities in soft lead produces no unusual changes in either the physical or the chemical properties of the resulting Bi-bearing oxide compared with Bi-free oxide. This is very important because there is no need for battery manufacturers to change their paste formulae and paste-mixing procedures on switching to the new Bi-bearing oxide. There is little difference in the rates of oxygen and hydrogen evolution on pasted electrodes prepared from Bi-bearing or Bi-free oxides. On the other hand, these rates increase on the former electrodes when the levels of all the other impurities are made to exceed (by deliberately adding the impurities as oxide powders) the corresponding, specified values for the Bi-bearing oxide. The latter behaviour is particularly noticeable for hydrogen evolution, which is enhanced even further when a negative electrode prepared from Bi-bearing oxide is contaminated through the deposition of impurities added to the sulfuric acid solution. The effects of impurities in the positive

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

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

    2007-01-01

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

  15. Oxidation of amino acids and proteins by peroxynitrite

    Recent studies suggested that proteins exposed to free radicals and other strong oxidants generated by living organisms may be the source of damage to tissues even at sites distant from the original point of generation of the reactive species. In examining the ability of biologically significant oxidizing agents to generate protein peroxides, the authors have studied protein peroxidation by peroxynitrite (ONOO-), known to be a potential source of tissue damage. Treatment of bovine serum albumin, Iysozyme, apotransferrin, insulin or human serum albumin with peroxynitrous acid (POXNA) led to formation of hydroperoxide groups on the proteins, detected by their reaction with iodide. Under optimum conditions, up to one peroxide group formed on each molecule of protein. Hydroxyl radical scavengers, antioxidants, or metal chelators, were unable to affect the quantities of peroxides generated by POXNA. These findings suggest that the oxidation was not mediated by the hydroxyl free radicals. The iodide assay cannot be applied to the measurement of peroxides in presence of nitrite, which is a contaminant of most solutions of POXNA. Nitrite can be easily removed from proteins by molecular filtration, but this method cannot be applied to amino acids. Therefore an amino acid peroxide test based on chemiluminescence was used, which shows promise for general peroxide detection

  16. Influence of oxidation on fulvic acids composition and biodegradability.

    Kozyatnyk, Ivan; Świetlik, Joanna; Raczyk-Stanisławiak, Ursula; Dąbrowska, Agata; Klymenko, Nataliya; Nawrocki, Jacek

    2013-08-01

    Oxidation is well-known process of transforming natural organic matter during the treatment of drinking water. Chlorine, ozone, and chlorine dioxide are common oxidants used in water treatment technologies for this purpose. We studied the influence of different doses of these oxidants on by-products formation and changes in biodegradable dissolved organic carbon (BDOC) and molecular weight distribution (MWD) of fulvic acids (FA) with different BDOC content. Chlorination did not significantly change the MWD of FA and disinfection by-products formation. However, higher molecular weight compounds, than those in the initial FA, were formed. It could be a result of chlorine substitution into the FA structure. Chlorine dioxide oxidized FA stronger than chlorine. During ozonation of FA, we found the highest increase of BDOD due to the formation of a high amount of organic acids and aldehydes. FA molecules were transformed into a more biodegradable form. Ozonation is the most preferable process among those observed for pre-treatment of FA before biofiltration. PMID:23746389

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

    Mohamed S. El-Deab

    2010-01-01

    The electro-oxidation of formic acid (an essential reaction in direct formic acid fuel cells) is a challenging process because of the deactivation of anodes by the adsorption of the poisoning intermediate carbon monoxide (CO). Pt electrodes in two geometries (planar and nanohole-array) were modified by the electrodeposition of manganese oxide nanorods (nano-MnOx). The modified Pt electrodes were then tested for their electrocatalytic activity through the electro-oxidation of formic acid in a ...

  18. Adipose Fatty Acid Oxidation Is Required for Thermogenesis and Potentiates Oxidative Stress-Induced Inflammation

    Jieun Lee

    2015-01-01

    Full Text Available To understand the contribution of adipose tissue fatty acid oxidation to whole-body metabolism, we generated mice with an adipose-specific knockout of carnitine palmitoyltransferase 2 (CPT2A−/−, an obligate step in mitochondrial long-chain fatty acid oxidation. CPT2A−/− mice became hypothermic after an acute cold challenge, and CPT2A−/− brown adipose tissue (BAT failed to upregulate thermogenic genes in response to agonist-induced stimulation. The adipose-specific loss of CPT2 resulted in diet-dependent changes in adiposity but did not result in changes in body weight on low- or high-fat diets. Additionally, CPT2A−/− mice had suppressed high-fat diet-induced oxidative stress and inflammation in visceral white adipose tissue (WAT; however, high-fat diet-induced glucose intolerance was not improved. These data show that fatty acid oxidation is required for cold-induced thermogenesis in BAT and high-fat diet-induced oxidative stress and inflammation in WAT.

  19. Updated estimates of neural tube defects prevented by mandatory folic Acid fortification - United States, 1995-2011.

    Williams, Jennifer; Mai, Cara T; Mulinare, Joe; Isenburg, Jennifer; Flood, Timothy J; Ethen, Mary; Frohnert, Barbara; Kirby, Russell S

    2015-01-16

    In 1992, the U.S. Public Health Service recommended that all women capable of becoming pregnant consume 400 µg of folic acid daily to prevent neural tube defects (NTDs). NTDs are major birth defects of the brain and spine that occur early in pregnancy as a result of improper closure of the embryonic neural tube, which can lead to death or varying degrees of disability. The two most common NTDs are anencephaly and spina bifida. Beginning in 1998, the United States mandated fortification of enriched cereal grain products with 140 µg of folic acid per 100 g. Immediately after mandatory fortification, the birth prevalence of NTD cases declined. Fortification was estimated to avert approximately 1,000 NTD-affected pregnancies annually. To provide updated estimates of the birth prevalence of NTDs in the period after introduction of mandatory folic acid fortification (i.e., the post-fortification period), data from 19 population-based birth defects surveillance programs in the United States, covering the years 1999-2011, were examined. After the initial decrease, NTD birth prevalence during the post-fortification period has remained relatively stable. The number of births occurring annually without NTDs that would otherwise have been affected is approximately 1,326 (95% confidence interval = 1,122-1,531). Mandatory folic acid fortification remains an effective public health intervention. There remain opportunities for prevention among women with lower folic acid intakes, especially among Hispanic women, to further reduce the prevalence of NTDs in the United States. PMID:25590678

  20. DLTS study of annihilation of oxidation induced deep-level defects in Ni/SiO2/-Si MOS structures

    N Shashank; Sanjeev K Gupta; K V Madhu; J Akhtar; R Damle

    2011-12-01

    This paper describes the fabrication of MOS capacitor and DLTS study of annihilation of deeplevel defects upon thermal annealing. Ni/SiO2/-Si MOS structures fabricated on -type Si wafers were investigated for process-induced deep-level defects. The deep-level traps in Si substrates induced during the processing of Ni/SiO2/-Si have been investigated using deep-level transient spectroscopy (DLTS). A characteristic deep-level defect at C = 0.49 eV which was introduced during high-temperature thermal oxidation process was detected. The trap position was found to shift to different energy levels (C = 0.43, 0.46 and 0.34 eV) during thermal annealing process. The deep-level trap completely anneals at 350°C. Significant reduction in trap density with an increase in recombination life time and substrate doping concentration as a function of isochronal annealing were observed.

  1. Nitrate enhances skeletal muscle fatty acid oxidation via a nitric oxide-cGMP-PPAR-mediated mechanism

    Ashmore, Tom; Roberts, Lee D.; Morash, Andrea J.; Kotwica, Aleksandra O; Finnerty, John; James A. West; Murfitt, Steven A.; Fernandez, Bernadette O.; Branco, Cristina, 1960-; Cowburn, Andrew S.; Clarke, Kieran; Johnson, Randall S.; Feelisch, Martin; Griffin, Julian L; Murray, Andrew J.

    2015-01-01

    Background Insulin sensitivity in skeletal muscle is associated with metabolic flexibility, including a high capacity to increase fatty acid (FA) oxidation in response to increased lipid supply. Lipid overload, however, can result in incomplete FA oxidation and accumulation of potentially harmful intermediates where mitochondrial tricarboxylic acid cycle capacity cannot keep pace with rates of β-oxidation. Enhancement of muscle FA oxidation in combination with mitochondrial biogenesis is ther...

  2. Effects of a chitosan membrane coated with polylactic and polyglycolic acid on bone regeneration in a rat calvarial defect

    The purpose of this study was to evaluate the effects of a chitosan membrane coated with polylactic and polyglycolic acid (PLGA) on bone regeneration in a rat calvarial defect. Surgical implantation of chitosan membranes resulted in enhanced local bone formation at both 2 and 8 weeks. In conclusion, the chitosan membrane coated with PLGA had a significant potential to induce bone formation in the rat calvarial defect model. Within the selected PLGA dose range and observation intervals, there appeared to be no meaningful differences in bone formation

  3. Effects of a chitosan membrane coated with polylactic and polyglycolic acid on bone regeneration in a rat calvarial defect

    Jung, Ui-Won [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Song, Kun-Young [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Kim, Chang-Sung [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Lee, Yong-Keun [Department and Research Institute of Dental Biomaterials and Bioengineering, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-750 (Korea, Republic of); Cho, Kyoo-Sung [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Kim, Chong-Kwan [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Choi, Seong-Ho [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of)

    2007-09-15

    The purpose of this study was to evaluate the effects of a chitosan membrane coated with polylactic and polyglycolic acid (PLGA) on bone regeneration in a rat calvarial defect. Surgical implantation of chitosan membranes resulted in enhanced local bone formation at both 2 and 8 weeks. In conclusion, the chitosan membrane coated with PLGA had a significant potential to induce bone formation in the rat calvarial defect model. Within the selected PLGA dose range and observation intervals, there appeared to be no meaningful differences in bone formation.

  4. Riboflavin-responsive oxidative phosphorylation complex I deficiency caused by defective ACAD9: new function for an old gene.

    Gerards, Mike; van den Bosch, Bianca J C; Danhauser, Katharina; Serre, Valérie; van Weeghel, Michel; Wanders, Ronald J A; Nicolaes, Gerry A F; Sluiter, Wim; Schoonderwoerd, Kees; Scholte, Hans R; Prokisch, Holger; Rötig, Agnès; de Coo, Irenaeus F M; Smeets, Hubert J M

    2011-01-01

    Mitochondrial complex I deficiency is the most common oxidative phosphorylation defect. Mutations have been detected in mitochondrial and nuclear genes, but the genetics of many patients remain unresolved and new genes are probably involved. In a consanguineous family, patients presented easy fatigability, exercise intolerance and lactic acidosis in blood from early childhood. In muscle, subsarcolemmal mitochondrial proliferation and a severe complex I deficiency were observed. Exercise intolerance and complex I activity was improved by a supplement of riboflavin at high dosage. Homozygosity mapping revealed a candidate region on chromosome three containing six mitochondria-related genes. Four genes were screened for mutations and a homozygous substitution was identified in ACAD9 (c.1594 C>T), changing the highly conserved arginine-532 into tryptophan. This mutation was absent in 188 ethnically matched controls. Protein modelling suggested a functional effect due to the loss of a stabilizing hydrogen bond in an α-helix and a local flexibility change. To test whether the ACAD9 mutation caused the complex I deficiency, we transduced fibroblasts of patients with wild-type and mutant ACAD9. Wild-type, but not mutant, ACAD9 restored complex I activity. An unrelated patient with the same phenotype was compound heterozygous for c.380 G>A and c.1405 C>T, changing arginine-127 into glutamine and arginine-469 into tryptophan, respectively. These amino acids were highly conserved and the substitutions were not present in controls, making them very probably pathogenic. Our data support a new function for ACAD9 in complex I function, making this gene an important new candidate for patients with complex I deficiency, which could be improved by riboflavin treatment. PMID:20929961

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

    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.

  6. Oxidation in Acidic Medium of Lignins from Agricultural Residues

    Labat, Gisele Aparecida Amaral; Gonçalves, Adilson Roberto

    Agricultural residues as sugarcane straw and bagasse are burned in boilers for generation of energy in sugar and alcohol industries. However, excess of those by-products could be used to obtain products with higher value. Pulping process generates cellulosic pulps and lignin. The lignin could be oxidized and applied in effluent treatments for heavy metal removal. Oxidized lignin presents very strong chelating properties. Lignins from sugarcane straw and bagasse were obtained by ethanol-water pulping. Oxidation of lignins was carried out using acetic acid and Co/Mn/Br catalytical system at 50, 80, and 115 °C for 5 h. Kinetics of the reaction was accomplished by measuring the UV-visible region. Activation energy was calculated for lignins from sugarcane straw and bagasse (34.2 and 23.4 kJ mol-1, respectively). The first value indicates higher cross-linked formation. Fourier-transformed infrared spectroscopy data of samples collected during oxidation are very similar. Principal component analysis applied to spectra shows only slight structure modifications in lignins after oxidation reaction.

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

    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. PMID:27474618

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

    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.

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

    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

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

    Dimple Garg; Seema Kothari

    2004-11-01

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

  11. Refractory Oxide Coatings on Titanium for Nitric Acid Applications

    Ravi Shankar, A.; Kamachi Mudali, U.

    2014-07-01

    Tantalum and Niobium have good corrosion resistance in nitric acid as well as in molten chloride salt medium encountered in spent fuel nuclear reprocessing plants. Commercially, pure Ti (Cp-Ti) exhibits good corrosion resistance in nitric acid medium; however, in vapor condensates of nitric acid, significant corrosion was observed. In the present study, a thermochemical diffusion method was pursued to coat Ta2O5, Nb2O5, and Ta2O5 + Nb2O5 on Ti to improve the corrosion resistance and enhance the life of critical components in reprocessing plants. The coated samples were characterized by XRD, SEM, EDX, profilometry, micro-scratch test, and ASTM A262 Practice-C test in 65 pct boiling nitric acid. The SEM micrograph of the coated samples showed that uniform dense coating containing Ta2O5 and/or Nb2O5 was formed. XRD patterns indicated the formation of TiO2, Ta2O5/Nb2O5, and mixed oxide/solid solution phase on coated Ti samples. ASTM A262 Practice-C test revealed reproducible outstanding corrosion resistance of Ta2O5-coated sample in comparison to Nb2O5- and Ta2O5 + Nb2O5-coated sample. The hardness of the Ta2O5-coated Cp-Ti sample was found to be twice that of uncoated Cp-Ti. The SEM and XRD results confirmed the presence of protective oxide layer (Ta2O5, rutile TiO2, and mixed phase) on coated sample which improved the corrosion resistance remarkably in boiling liquid phase of nitric acid compared to uncoated Cp-Ti and Ti-5Ta-1.8Nb alloy. Three phase corrosion test conducted on Ta2O5-coated samples in boiling 11.5 M nitric acid showed poor corrosion resistance in vapor and condensate phases of nitric acid due to poor adhesion of the coating. The adhesive strength of the coated samples needs to be optimized in order to improve the corrosion resistance in vapor and condensate phases of nitric acid.

  12. Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides.

    Paniagua, Sergio A; Giordano, Anthony J; Smith, O'Neil L; Barlow, Stephen; Li, Hong; Armstrong, Neal R; Pemberton, Jeanne E; Brédas, Jean-Luc; Ginger, David; Marder, Seth R

    2016-06-22

    Transparent conducting oxides (TCOs), such as indium tin oxide and zinc oxide, play an important role as electrode materials in organic-semiconductor devices. The properties of the inorganic-organic interface-the offset between the TCO Fermi level and the relevant transport level, the extent to which the organic semiconductor can wet the oxide surface, and the influence of the surface on semiconductor morphology-significantly affect device performance. This review surveys the literature on TCO modification with phosphonic acids (PAs), which has increasingly been used to engineer these interfacial properties. The first part outlines the relevance of TCO surface modification to organic electronics, surveys methods for the synthesis of PAs, discusses the modes by which they can bind to TCO surfaces, and compares PAs to alternative organic surface modifiers. The next section discusses methods of PA monolayer deposition, the kinetics of monolayer formation, and structural evidence regarding molecular orientation on TCOs. The next sections discuss TCO work-function modification using PAs, tuning of TCO surface energy using PAs, and initiation of polymerizations from TCO-tethered PAs. Finally, studies that examine the use of PA-modified TCOs in organic light-emitting diodes and organic photovoltaics are compared. PMID:27227316

  13. Small-polaron hopping via defect centres: anomalous temperature and voltage dependence of current through fatty-acid monolayers

    We study electron hopping in thin metal-insulator-metal structures which involves two defect centres with a strong electron-phonon coupling. We calculate the dependences of the current, J, on voltage, V, and temperature, T, and show that they are consistent with those observed in molecular monolayers of fatty acids. We analyse in detail an unusual, near-exponential temperature dependence of the current: J(T) ∝ exp (T/T0) T ≥ 50 K in eicosanoic acid (C20) organic monolayers sandwiched between Pt electrodes, where the parameter T0 increases with the bias voltage. We show that at relatively high voltages the two-defect small-polaron hopping results in N-shape current-voltage characteristics which were observed in some organic molecular monolayers

  14. When folic acid fails: Insights from 20 years of neural tube defect surveillance in South Carolina.

    Bupp, Caleb P; Sarasua, Sara M; Dean, Jane H; Stevenson, Roger E

    2015-10-01

    Neural tube defects (NTDs) are the most common of the severe malformations of the brain and spinal cord. Increased maternal intake of folic acid (FA) during the periconceptional period is known to reduce NTD risk. Data from 1046 NTD cases in South Carolina were gathered over 20 years of surveillance. It was possible to determine maternal periconceptional FA use in 615 NTD-affected pregnancies. In 163 occurrent (26.9%) and two recurrent (22%) NTD cases, the mothers reported periconceptional FA use. These women were older and more likely to be white. Maternal periconceptional FA usage was reported in 40.4% of cases of spina bifida with other anomalies but in only 25.2% of isolated spina bifida cases (P = 0.02). This enrichment for associated anomalies was not noted among cases of anencephaly or of encephalocele. Among the 563 subsequent pregnancies to mothers with previous NTD-affected pregnancies, those taking FA had a 0.4% NTD recurrence rate, but the recurrence without FA was 8.5%. NTDs with other associated findings were less likely to be prevented by FA, suggesting there is a background NTD rate that cannot be further reduced by FA. Nonetheless, the majority (73.9%) of NTDs in pregnancies in which the mothers reported periconceptional FA use were isolated NTDs of usual types. Cases in which FA failed in prevention of NTDs provide potential areas for further study into the causation of NTDs. The measures and techniques implemented in South Carolina can serve as an effective and successful model for prevention of NTD occurrence and recurrence. PMID:26108864

  15. Lewis Acid Catalysis in the Oxidative Cycloaddition of Thiophenes

    Li, Yuanqiang; Thiemann, Thies; Sawada, Tsuyoshi; Mataka, Shuntaro; Tashiro, Masashi

    1997-01-01

    Thiophenes 1 were treated with m-chloroperbenzoic acid (m-CPBA) under BF3·Et2O catalysis to afford thiophene S-monoxides. These could be reacted in situ as intermediary species with a number of dienophiles to provide arenes (with alkynes as dienophiles) or 7-thiabicyclo[2.2.1]hept-2-ene 7-oxides (with alkenes as dienophiles). It was also possible to isolate thiophene S-monoxides in solution and to cycloadd them in a second step. In either way it could be shown that the use of BF3·Et2O enhance...

  16. In situ electrocatalytic oxidation of acid violet 12 dye effluent.

    Mohan, N; Balasubramanian, N

    2006-08-21

    Electrochemical treatment of organic pollutants is a promising treatment technique for substances which are recalcitrant to biodegradation. Experiments were carried out to treat acid violet 12 dye house effluent using electrochemical technique for removal color and COD reduction covering wide range in operating conditions. Ruthenium/lead/tin oxide coated titanium and stainless steel were used as anode and cathode, respectively. The influence of effluent initial concentration, pH, supporting electrolyte and the electrode material on rate of degradation has been critically examined. The results indicate that the electrochemical method can be used to treat dye house effluents. PMID:16730894

  17. Degradation of 2-hydroxybenzoic acid by advanced oxidation processes

    C. L. P. S. Zanta; Martínez-Huitle, C. A.

    2009-01-01

    In this study, advanced oxidation processes (AOPs) such as the UV/H2O2 and Fenton processes were investigated for the degradation of 2-hydroxybenzoic acid (2-HBA) in lab-scale experiments. Different [H2O2]/[2-HBA] molar ratios and pH values were used in order to establish the most favorable experimental conditions for the Fenton process. For comparison purposes, degradation of 2-HBA was carried out by the UV/H2O2 process under Fenton experimental conditions. The study showed that the Fenton p...

  18. Nitrogen isotope exchange in between nitric oxide and nitric acid

    The exchange rate law experimentally observed for 15 N/14 N exchange in NO - HNO3 system at low nitric acid concentration, both at atmospheric pressure and at low pressure of NO: R k[H+][NO3-][HNO2], is identical with the rate law for the reaction between NO and HNO3, when HNO2 is formed.The rate of nitrogen isotope exchange between NO and HNO3 has been measured as a function of nitric acid concentration of 1.5 4 M.l-1. The exchange rate law is shown to be R k[HNO3]2[N2O3] and the measured activation energy is E = 67.78 kJ.M-1. It is concluded that N2O3 participates in 15 N/14 N exchange between NO and HNO3 at nitric acid concentration higher than 1.5 M.l-1. The rate of the same isotope exchange in NO - HNO3 system has been also measured as a function of nitric oxide pressure 0.1 0.4 M.Pa for 1 and 2 M.l-1 HNO3. It is demonstrated that 15 N/14 N exchange in this system has a linear dependence on NO pressure as indicated by rate measurements at different NO partial pressures and constant overall pressure, by adding helium in reactor. Using the rate law presented above the nitrogen isotope exchange rate for nitric acid concentration 1.5 10 M.l-1 were calculated. Nitrogen isotope exchange between nitric oxide and concentrated nitric acid with a single stage separation factor = 1.055, for 10 M.l-1 nitric acid, at 25 deg. C, provides the bases for 15 N separation process that is most widely used at the present time, i.e. the method of Spindel and Taylor. In order to know what happens in 15N separation at higher pressure, when the isotopic transport is improved, a stainless steel laboratory experimental plant with a 1000 mm long and 18 mm i.d. column, packed with triangular wire springs of 1.8 x 1.8 x 0.2 mm, was utilised. At 1.5 atm (absolute) and 2.36 ml.cm-2.min-1 flow rate, HETP was 7% smaller than at atmospheric pressure and 1.5 times smaller flow rate. The operation of 15 N separation plant at 1.8 atm (absolute), instead atmospheric pressure, will permit doubling

  19. Oxidized Fatty Acids as Inter-Kingdom Signaling Molecules

    Carolina H. Pohl

    2014-01-01

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

  20. Formation of Nanoporous Tin Oxide Layers on Different Substrates during Anodic Oxidation in Oxalic Acid Electrolyte

    Leszek Zaraska

    2015-01-01

    Full Text Available Nanoporous tin oxide layers were obtained on various Sn substrates including high- and low-purity foils and wire by one-step anodic oxidation carried out in a 0.3 M oxalic acid electrolyte at various anodizing potentials. In general, amorphous oxide layers with the atomic ratio of Sn : O (1 : 1 were grown during anodization, and a typical structure of the as-obtained film consists of the “outer” layer with less regular, interconnetted pores and the “inner” layer with much more uniform and regular channels formed as a result of vigorous gas evolution. It was found that the use of electrochemical cell with the sample placed horizontally on the metallic support and stabilized by the Teflon cover, instead of the typical two-electrode system with vertically arranged electrodes, can affect the morphology of as-obtained layers and allows fabrication of nanoporous oxides even at anodizing potentials up to 11 V. An average pore diameter in the “outer” oxide layer increases with increasing anodizing potential, and no significant effect of substrate purity on the structure of anodic film was proved, except better uniformity of the oxides grown on high-purity Sn. A strong linear relationship between the average steady-state current density and anodizing potential was also observed.

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

    Herein reported is an atomic layer deposition (ALD) process of platinum (Pt) from (methylcyclopentadienyl) trimethylplatinum (MeCpPtMe3) and oxygen (O2) for synthesizing the Pt electrocatalysts toward methanol and formic acid oxidation. The as-synthesized Pt catalysts are thermally reduced in 5 vol% H2 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 PtO2. 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–Oads 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

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

    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.

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

    A. van Tol (Arie)

    1971-01-01

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

  4. A point defect model for the general and pitting corrosion on iron-oxide-electrolyte interface deduced from current oscillations

    Pagitsas, M; Sazou, D

    2003-01-01

    Analysis of the passive-active oscillatory region of the Fe-0.75 M H sub 2 SO sub 4 system, perturbed by adding small amounts of halide species, allow the distinction between pitting and general corrosion. Complex periodic and aperiodic current oscillations characterize pitting corrosion whereas monoperiodic oscillations of a relaxation type indicate general corrosion. A point defect model (PDM) is considered for the microscopic description of the growth and breakdown of the iron oxide film. The physicochemical processes leading to different types of corrosion can be clarified in terms of the PDM. Occupation of an anion vacancy by a halide ion results in the localized attack of the passive oxide and pitting corrosion. On the other hand, the formation of surface soluble iron complexes is related to the uniform dissolution of the passive oxide and general corrosion.

  5. The role of oxygen vacancies and defects on Lithium intercalation capacity of composite vanadium-titanium oxide thin films

    Sahana, M. B.; Sudakar, C.; Thapa, C.; Lawes, G.; Padmanabhan, K. R.; Naik, R.; Auner, G.; Naik, V. M.

    2008-03-01

    Composite films of vanadium-titanium oxides have been recognized as promising cathode materials for lithium ion batteries. While there is a consensus agreement that the cycling stability of the mixed V/Ti-oxide system is improved compared to V2O5 thin films, there are different findings on the Li+ intercalation capacity of V2O5 with the addition of TiO2. To understand the difference we have carried out a systematic semi quantitative investigations on the defect and oxygen vacancy concentration as determined using Raman and UV-visible spectroscopy and transmission electron microscopy of V2O5 and 5%Ti doped V2O5 films prepared by spin coating using two precursors: a metalorganic and a organic sol gel precursor. We observe that a critical concentration of defects and oxygen vacancies is important to have high capacity. With 5% Ti doping the capacity in films prepared using solgel precursor increases, but the capacity decreases in films prepared with the metalorganic precursor. We attribute this to the different concentrations of oxygen vacancy defects in the two samples.

  6. Arabidopsis thaliana cdd1 mutant uncouples the constitutive activation of salicylic acid signalling from growth defects

    Swain, S.; Roy, S.; Shah, J.; Wees, S.C.M. van; Pieterse, C.M.J.; Nandi, A.K.

    2011-01-01

    Arabidopsis genotypes with a hyperactive salicylic acidmediated signalling pathway exhibit enhanced disease resistance, which is often coupled with growth and developmental defects, such as dwarfing and spontaneous necrotic lesions on the leaves, resulting in reduced biomass yield. In this article,

  7. Defect-induced magnetism in undoped wide band gap oxides: Zinc vacancies in ZnO as an example

    G. Z. Xing

    2011-06-01

    Full Text Available To shed light on the mechanism responsible for the weak ferromagnetism in undoped wide band gap oxides, we carry out a comparative study on ZnO thin films prepared using both sol-gel and molecular beam epitaxy (MBE methods. Compared with the MBE samples, the sol-gel derived samples show much stronger room temperature ferromagnetism with a magnetic signal persisting up to ∼740 K, and this ferromagnetic order coexists with a high density of defects in the form of zinc vacancies. The donor-acceptor pairs associated with the zinc vacancies also cause a characteristic orange-red photoluminescence in the sol-gel films. Furthermore, the strong correlation between the ferromagnetism and the zinc vacancies is confirmed by our first-principles density functional theory calculations, and electronic band alteration as a result of defect engineering is proposed to play the critical role in stabilizing the long-range ferromagnetism.

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

    Sathler M.N.B.; Eon J.G.

    1998-01-01

    Gamma-alumina-supported niobium oxide was used as a support for vanadium oxides. The influence of the addition of niobium oxide was studied by looking for changes in the structure and acid-base character of superficial species. Vanadium oxide was deposited using the continuous adsorption method; niobium oxide was impregnated using the incipient wetness method. The catalysts were characterized by XPS, UV-visible and IR spectroscopy. Catalytic tests were performed using propane oxidation reacti...

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

    Puttaswamy; Nirmala Vaz

    2001-08-01

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

  10. Evolution of insoluble eutectic Si particles in anodic oxidation films during adipic-sulfuric acid anodizing processes of ZL114A aluminum alloys

    Hua, Lei; Liu, Jian-hua; Li, Song-mei; Yu, Mei; Wang, Lei; Cui, Yong-xin

    2015-03-01

    The effects of insoluble eutectic Si particles on the growth of anodic oxide films on ZL114A aluminum alloy substrates were investigated by optical microscopy (OM) and scanning electron microscopy (SEM). The anodic oxidation was performed at 25°C and a constant voltage of 15 V in a solution containing 50 g/L sulfuric acid and 10 g/L adipic acid. The thickness of the formed anodic oxidation film was approximately 7.13 μm. The interpore distance and the diameters of the major pores in the porous layer of the film were within the approximate ranges of 10-20 nm and 5-10 nm, respectively. Insoluble eutectic Si particles strongly influenced the morphology of the anodic oxidation films. The anodic oxidation films exhibited minimal defects and a uniform thickness on the ZL114A substrates; in contrast, when the front of the oxide oxidation films encountered eutectic Si particles, defects such as pits and non-uniform thickness were observed, and pits were observed in the films.

  11. Contribution to the study of the oxidation reaction of Np(V) by nitric acid catalyzed par nitrous acid

    The oxidation reaction kinetics of Np(V) to Np(VI) by nitric acid catalyzed by nitrous acid was studied. In a first part, a detailed bibliographical survey was made of the oxidation-reduction reactions of U, Np, Pu, Am with nitrous and nitric acids (51 references). It is shown that only when both the organic and aqueous phases are mixed up, the extraction of a reaction product (NpVI) induces an equilibrium displacement. TBP was used as solvent. It is shown that the extraction of nitrous acid from the solvent enables the nitrous acid concentration to be kept constant and in the same order of magnitude than that of Np. This enables to show that Np(V) and nitrous acid have no simple orders. The temperature and nitric acid concentration dependence was studied. It is shown that tetravalent nitrogen must play a major part in the Np(V) oxidation

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

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

    2015-04-01

    Among the phytotechnologies used for the reclamation of degraded mining sites, phytoextraction aims to diminish the concentration of polluting elements in contaminated soils. However, the biomass resulting from the phytoextraction processes (highly enriched in polluting elements) is too often considered as a problematic waste. The manganese-enriched biomass derived from native Mn-hyperaccumulating plants of New Caledonia was presented here as a valuable source of metallic elements of high interest in chemical catalysis. The preparation of the catalyst Eco-Mn1 and reagent Eco-Mn2 derived from Grevillea exul exul and Grevillea exul rubiginosa was investigated. Their unusual polymetallic compositions allowed to explore new reactivity of low oxidative state of manganese-Mn(II) for Eco-Mn1 and Mn(IV) for Eco-Mn2. Eco-Mn1 was used as a Lewis acid to catalyze the acetalization/elimination of aldehydes into enol ethers with high yields; a new green and stereoselective synthesis of (-)-isopulegol via the carbonyl-ene cyclization of (+)-citronellal was also performed with Eco-Mn1. Eco-Mn2 was used as a mild oxidative reagent and controlled the oxidation of aliphatic alcohols into aldehydes with quantitative yields. Oxidative cleavage was interestingly noticed when Eco-Mn2 was used in the presence of a polyol. Eco-Mn2 allowed direct oxidative iodination of ketones without using iodine, which is strongly discouraged by new environmental legislations. Finally, the combination of the properties in the Eco-Mn catalysts and reagents gave them an unprecedented potential to perform sequential tandem oxidation processes through new green syntheses of p-cymene from (-)-isopulegol and (+)-citronellal; and a new green synthesis of functionalized pyridines by in situ oxidation of 1,4-dihydropyridines. PMID:25263417

  13. Engineering the Saccharomyces cerevisiae β-oxidation pathway to increase medium chain fatty acid production as potential biofuel.

    Liwei Chen

    Full Text Available Fatty acid-derived biofuels and biochemicals can be produced in microbes using β-oxidation pathway engineering. In this study, the β-oxidation pathway of Saccharomyces cerevisiae was engineered to accumulate a higher ratio of medium chain fatty acids (MCFAs when cells were grown on fatty acid-rich feedstock. For this purpose, the haploid deletion strain Δpox1 was obtained, in which the sole acyl-CoA oxidase encoded by POX1 was deleted. Next, the POX2 gene from Yarrowia lipolytica, which encodes an acyl-CoA oxidase with a preference for long chain acyl-CoAs, was expressed in the Δpox1 strain. The resulting Δpox1 [pox2+] strain exhibited a growth defect because the β-oxidation pathway was blocked in peroxisomes. To unblock the β-oxidation pathway, the gene CROT, which encodes carnitine O-octanoyltransferase, was expressed in the Δpox1 [pox2+] strain to transport the accumulated medium chain acyl-coAs out of the peroxisomes. The obtained Δpox1 [pox2+, crot+] strain grew at a normal rate. The effect of these genetic modifications on fatty acid accumulation and profile was investigated when the strains were grown on oleic acids-containing medium. It was determined that the engineered strains Δpox1 [pox2+] and Δpox1 [pox2+, crot+] had increased fatty acid accumulation and an increased ratio of MCFAs. Compared to the wild-type (WT strain, the total fatty acid production of the strains Δpox1 [pox2+] and Δpox1 [pox2+, crot+] were increased 29.5% and 15.6%, respectively. The intracellular level of MCFAs in Δpox1 [pox2+] and Δpox1 [pox2+, crot+] increased 2.26- and 1.87-fold compared to the WT strain, respectively. In addition, MCFAs in the culture medium increased 3.29-fold and 3.34-fold compared to the WT strain. These results suggested that fatty acids with an increased MCFAs ratio accumulate in the engineered strains with a modified β-oxidation pathway. Our approach exhibits great potential for transforming low value fatty acid

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

    2007-01-01

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

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

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

    2007-01-01

    increased expression of proteins favoring fat oxidation (peroxisome proliferator-activated receptor gamma coactivator-1alpha, uncoupling protein 2, fasting-induced adipose factor, enzymes of mitochondrial fatty acid oxidation). These changes paralleled inactivation of the retinoblastoma protein and were...

  16. Mechanisms of oxide dissolution by acid chelating agents

    In this paper, the different possible rate controlling processes in the dissolution of metallic oxides are examined. In particular, the following situations are assessed: mass-transfer control; coupling of mass-transfer and reactions at the interface; interface equilibration with the solution; various interface disruption and reconstruction phenomena. For each of the above mentioned cases, the influence of variables such as reagent concentration, temperature, pH, fluid hydrodynamics and general and specific catalysts is discussed. Depending upon the particular situation it is found that a more rational basis for the development of reagent is given by these considerations. The influence of chelating agents on both the thermodynamics and kinetics of the process is discussed, and the results of experimental studies in batch on magnetite and various ferrites are presented and discussed. For this purpose, several reagents were studied, including some very effective ones like thioglycolic acid, and others commonly used in actual decontamination, like ethylenediaminetetraacetic acid and oxalic acid. The relation to other (reductive) chemical decontamination procedures is discussed. The relevance of these studies to decontamination of metallic surfaces is discussed

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

    Mohamed S. El-Deab

    2010-01-01

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

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

    Poonam Gupta; Seema Kothari

    2001-04-01

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

  19. Phytoagents for Cancer Management: Regulation of Nucleic Acid Oxidation, ROS, and Related Mechanisms

    Wai-Leng Lee; Jing-Ying Huang; Lie-Fen Shyur

    2013-01-01

    Accumulation of oxidized nucleic acids causes genomic instability leading to senescence, apoptosis, and tumorigenesis. Phytoagents are known to reduce the risk of cancer development; whether such effects are through regulating the extent of nucleic acid oxidation remains unclear. Here, we outlined the role of reactive oxygen species in nucleic acid oxidation as a driving force in cancer progression. The consequential relationship between genome instability and cancer progression highlights th...

  20. Electronic Structure of the Perylene / Zinc Oxide Interface: A Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects

    Li, Jingrui

    2015-07-29

    The electronic properties of dye-sensitized semiconductor surfaces consisting of pery- lene chromophores chemisorbed on zinc oxide via different spacer-anchor groups, have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.

  1. Linking diffusion kinetics to defect electronic structure in metal oxides: Charge-dependent vacancy diffusion in alumina

    We study the diffusion of charged vacancies in α-Al2O3 crystal using the first-principles calculation method. We predict that the migration energy for vacancy diffusion strongly depends on the charge state of the vacancy involved. Importantly, we reveal that this charge-dependent vacancy diffusion is directly related to the electron occupancy and energy level change of the defect states of the charged vacancy in alumina. Hence, our study establishes a direct link between the diffusion kinetics and electronic structure of metal oxides

  2. The endothelial nitric oxide synthase/nitric oxide system is involved in the defective quality of bovine oocytes from low mid-antral follicle count ovaries.

    Tessaro, I; Luciano, A M; Franciosi, F; Lodde, V; Corbani, D; Modina, S C

    2011-08-01

    In a previous survey concerning cows of reproductive age, we demonstrated that oocytes isolated from ovaries with ovaries; Lo) show less developmental competence than oocytes collected from ovaries with >10 medium antral follicles (high ovaries; Hi). The aim of the present study was to evaluate whether a defective endothelial nitric oxide synthase/nitric oxide (eNOS/NO) system and vasculature in healthy medium antral follicles is likely to reduce oocyte competence from Lo ovaries. Thus, experiments were conducted to 1) immunolocalize eNOS protein during folliculogenesis; 2) quantify eNOS protein/vasculature in the follicle wall; and 3) verify if NO donor, S-nitroso acetyl penicillamine (SNAP) administration during in vitro maturation affects developmental competence of oocytes isolated from Lo ovaries. Endothelial nitric oxide synthase protein was detected in granulosa and theca cells, as well as in blood vessels from primordial to antral follicles. Quantitative analysis indicated that in medium antral follicles from Lo ovaries, eNOS protein expression and vasculature were reduced (P ovaries, promoting a percentage similar to oocytes from Hi ovaries, and reduced the percentage of apoptotic nuclei in in vitro-produced blastocysts (P bovine ovaries with small mid antral follicle number, a defective eNOS/NO system is related to a reduced follicle vasculature and may affect oocyte quality, thus inducing a premature decline of fertility. PMID:21421835

  3. Effects of a tetracycline blended polylactic and polyglycolic acid membrane on the healing of one-wall intrabony defects in beagle dogs

    The purpose of this study was to evaluate the regenerative effects of a tetracycline blended polylactic and polyglycolic acid (TC-PLGA) and non-blended polylactic and polyglycolic acid (PLGA) barrier membrane on one-wall intrabony defects in beagle dogs. It can be concluded that when used for guided tissue regeneration TC-PLGA membranes show a beneficial effect on one-wall intrabony defects in beagle dogs

  4. Effects of a tetracycline blended polylactic and polyglycolic acid membrane on the healing of one-wall intrabony defects in beagle dogs

    Kim, Il-Young [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Jung, Ui-Won [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Kim, Chang-Sung [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Lee, Yong-Keun [Department and Research Institute of Dental Biomaterials and Bioengineering, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-750 (Korea, Republic of); Cho, Kyoo-Sung [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Chai, Jung-Kiu [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Kim, Chong-Kwan [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of); Choi, Seong-Ho [Department of Periodontology, Research Institute for Periodontal Regeneration, College of Dentistry, Yonsei University, 134 Shinchon-Dong, Seodaemun-gu, Seoul 120-752l (Korea, Republic of)

    2007-09-15

    The purpose of this study was to evaluate the regenerative effects of a tetracycline blended polylactic and polyglycolic acid (TC-PLGA) and non-blended polylactic and polyglycolic acid (PLGA) barrier membrane on one-wall intrabony defects in beagle dogs. It can be concluded that when used for guided tissue regeneration TC-PLGA membranes show a beneficial effect on one-wall intrabony defects in beagle dogs.

  5. Use of radiation for studying mechanically induced defects in polycrystalline samples of magnesium oxide

    The paper deals with study of structural defects, appearing in MgO polycrystalline samples under the mechanical treatment in the vibrating mill (type of effect - pressure and shift). At this effect the defects appear first of all in the near-surface grain layer, distortion of symmetry of close cation environment in the lattice, as well as increase of sample specific surface are observed. ν-radiation with a succeeding analysis of the formed paramagnetic centres by the EPR method has been used for identification of cation and anion vacancies in mechanically treated MgO samples. Under ν-radiaiton of MgO the radiation centres are formed only at the expense of filling ''biographical'' vacancies by electrons and holes. The investigation of nature and kinetics of radiation defect accumulation reveals a possibility of using ν-radiation as a radiation sonde for identification of mechanically induced anion and cation vacancies

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

    Sathler M.N.B.

    1998-01-01

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

  7. The Study of Nitric Oxide Effects in Control of Mouse Preimplantation Embryonic Defects in High Glucosis Media

    I. Amiri

    2003-10-01

    Full Text Available Pregnancy in diabetic females causes delay in early stages of embryonic growth and development and higher incidence of congenital malformations and spontaneous miscarriage compared with those of non- diabetic conditions. High glucosis tratogenicity seems to be related to reduction of Nitric Oxide production (NO in hyperglycemic condition. The goal of present work was study of nitric oxid role in control of mouse preimplantation embryonic defects in high glucosis media. In order to test above hypothesis, 2-cell stage embryos of normal mice were cultured with high concentration of glucose (30mM and different concentrations of L-arginine (5,10,20 mM or L-NAME (An antagonist of L- arginine. After 96h culture, the morphology of embryos was assessed by an inverted microscope then blastocysts were stained by TUNEL. After TUNEL the total cell number and apoptotic cells were counted by use a Fluorescence microscope. Finally the amount of nitrite in the media was assayed by Greiss method. The results indicated that high glucose decreases the blastocyst formation and Nitric Oxide production and increases their apoptotic index, but 10-20mM L-arginine significantly increases the developmental potential and nitric oxide production and significantly decreases apoptosis. On the contrary L-NAME significantly inhibits the development of pre-implantation embryos . It seems that during pregnancy supplementation of high glucose media with L-arginine increases Nitric Oxide production and prevents high glucosis embryotoxicity.

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

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

    2008-01-01

    Objective: Increased availability of fatty acids is important for accumulation of intracellular lipids and development of insulin resistance in human myotubes. It is unknown whether different types of fatty acids like eicosapentaenoic acid (EPA) or tetradecylthioacetic acid (TTA) influence these...... processes. Research Design and Methods: We examined fatty acid and glucose metabolism, and gene expression in cultured human skeletal muscle cells from control and T2D individuals after four days preincubation with EPA or TTA. Results: T2D myotubes exhibited reduced formation of CO(2) from palmitic acid (PA......), whereas release of beta-oxidation products was unchanged at baseline, but significantly increased with respect to control myotubes after preincubation with TTA and EPA. Preincubation with TTA enhanced both complete (CO(2)) and beta-oxidation of PA, whereas EPA increased only beta-oxidation significantly...

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

    The fate of [1(-14C] linoleic acid and [1(14C] 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 14C-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

  10. Nucleic acid-based approaches to investigate microbial-related cheese quality defects

    Daniel eO Sullivan

    2013-01-01

    Full Text Available AbstractThe microbial profile of cheese is a primary determinant of cheese quality. Microorganisms can contribute to aroma and taste defects, form biogenic amines, cause gas and secondary fermentation defects, and can contribute to cheese pinking and mineral deposition issues. These defects may be as a result of seasonality and the variability in the composition of the milk supplied, variations in cheese processing parameters, as well as the nature and number of the non-starter microorganisms which come from the milk or other environmental sources. Such defects can be responsible for production and product recall costs and thus represent a significant economic burden for the dairy industry worldwide. Traditional non-molecular approaches are often considered biased and have inherently slow turnaround times. Molecular techniques can provide early and rapid detection of defects that result from the presence of specific spoilage microbes and, ultimately, assist in enhancing cheese quality and reducing costs. Here we review the DNA-based methods that are available to detect/quantify spoilage bacteria, and relevant metabolic pathways, in cheeses and, in the process, highlight how these strategies can be employed to improve cheese quality and reduce the associated economic burden on cheese processors.

  11. [The influence of panthotenic acid mitochondrial oxidation and oxidative phosphorylation in liver of rats with alimentary obesity].

    Naruta, E E; Egorov, A I; Omel'ianchik, C N; Buko, V U

    2004-01-01

    Alimentary obesity induced by the long-term feeding of rats by high-fat diet results the reducing of rate and efficiency of oxidative phosphorylation in liver mitochondria when NAD-dependent substrates are used. The treatment of the obese rats with panthotenic acid derivatives (phosphopantotenate, panthetin, panthenol) enhanced oxidative phosphorylation of pyruvate and fatty acid carnitine esters. Among investigated compounds panthenol activated respiratory control and phosphorylation rate more effectively. Moreover, panthenol, but not phosphopanthotenate nor panthetine, increased the activity of carnitine palmitoyltransferase 1 that confirms the preferable usage of fatty acids for mitochondrial oxidation under the influence of this compound. PMID:15460980

  12. Oxygen reduction reaction over nitrogen-doped graphene oxide cathodes in acid and alkaline fuel cells at intermediate temperatures

    Highlights: • ORR for nitrogen-doped graphene in acid and alkaline fuel cells at intermediate temperatures. • Nitrogen-doped graphene had higher activity for the ORR than graphene. • The ORR activity was enhanced by an increase in the operating temperature. • The ORR activity was kept for long time in both acid and alkaline fuel cells. - Abstract: Graphene oxides with various nitrogen contents were prepared by annealing them in an NH3 flow between 350 and 850 °C, and their electrocatalytic properties toward the oxygen reduction reaction (ORR) in acid and alkaline fuel cells at intermediate temperatures were investigated. In both acid and alkaline fuel cells, graphene oxide treated with NH3 at 700 °C for 1 h was the most active cathode at operating temperatures between 75 and 200 °C, where the ORR activity was enhanced by an increase in the operating temperature. This cathode also exhibited high chemical and thermal stability toward the ORR. X-ray photoelectron and Raman spectroscopic measurements of the nitrogen-doped graphene oxides indicated that the pyridinic nitrogen introduced disordered edge planes into the graphene structure. BET analysis also revealed that the surface area of graphene oxide was increased by the exposure of such edge planes. These observations lead to the assumption that the defects introduced by pyridinic nitrogen act as active sites for the ORR. Considering the similarity in ORR activity between the acid and alkaline fuel cells, dissociative adsorption of O2 at the active site is a rate-determining step

  13. Catalytic oxidation of N-methyldiphenylamine-4-sulfonic acid in weakly acid solutions: a study by radiospectroscopic methods

    The mechanism of the catalytic oxidation of N-methyldiphenylamine-4-sulfonic acid (MDPASA) in weakly acid (10-3 M H2SO4) solutions is studied by EPR and 1H NMR spectroscopy. It is shown that the oxidation of the reagent with potassium periodate in the presence of ruthenium(4) proceeds through the radical mechanism that includes alternate steps of the oxidation and reduction of the catalyst. The suggested mechanism of the catalytic oxidation of MDPASA gave theoretical grounds to the conditions for the determination of ruthenium by kinetic methods that were selected previously in the basis of experimental data

  14. Electronic properties of hafnium oxide: A contribution from defects and traps

    Gritsenko, Vladimir A.; Perevalov, Timofey V.; Islamov, Damir R.

    2016-02-01

    In the present article, we give a review of modern data and latest achievements pertaining to the study of electronic properties of oxygen vacancies in hafnium oxide. Hafnium oxide is a key dielectric for use in many advanced silicon devices. Oxygen vacancies in hafnium oxide largely determine the electronic properties of the material. We show that the electronic transitions between the states due to oxygen vacancies largely determine the optical absorption and luminescent properties of hafnium oxide. We discuss the role of oxygen vacancies as traps that facilitate charge transport in hafnium oxide films. Also, we demonstrate the fact that the electrical conductivity in hafnium oxide is controlled by the phonon-assisted tunnelling of charge carriers between traps that were identified as oxygen vacancies.

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

    X-ray photoelectron spectroscopy is used to investigate the oxidation states of molybdenum in thin films formed potentiostatically, over a range of potentials, in either 1 mol dm−3 H2SO4 or 10 mol dm−3 NaOH at 20 °C. Mo 3d spectra suggested that MoO2 and Mo(OH)2 were the main components of the films, with smaller amounts of MoO3 and possibly Mo2O5. O 1s spectra indicated the presence of oxygen as oxide and hydroxide species and as bound water. Ion beam analysis revealed the formation of thin films at all potentials, with significant losses of oxidized molybdenum to the electrolyte. - Highlights: ► Oxides are formed on molybdenum in sulphuric acid and sodium hydroxide solutions. ► Molybdenum IV and VI are identified by XPS, with MoO2 species dominating. ► Thicknesses of films are determined by ion beam analysis for a range of potentials. ► Films form at low efficiency due to loss of molybdenum species to electrolyte.

  16. Defect structure of semiconducting and insulating epitaxial oxides. Progress report, May 1, 1993--April 30, 1994

    Wessels, B.W.

    1994-03-01

    The investigation has focused on epitaxial growth of BaSrTiO{sub 3} over the entire solid solution range, point defects in epitaxial BaTiO{sub 3} using temperature-dependent conductivity and deep-level optical spectroscopy, and their nonlinear optical properties.

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

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

    2014-01-01

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

  18. Investigation of the oxidation of hydrochloric acid in scrubbing solutions containing hydrogen peroxide

    Oxidation and absorption of nitrogen oxides by a solution containing sulphuric, nitric acids and hydrogen peroxide have been investigated. The oxidation of nitric oxide is dependent among others on hydrogen peroxide concentration total acidity and temperature. The absorption of N O2 by the scrubbing solution (H2 S O4,H N O3 and H2 O2) in all cases studied is not less than 98%. The oxidation of chloride into chlorine gas increases as the concentration of each of hydrochloric acid, nitric oxide and nitric acid increases. On the other hand as the concentration of hydrogen peroxide increases the amount of chlorine gas decreases. The results show that the oxidation of chloride into chlorine gas is mainly due to nitrogen dioxide. 7 fig., 2 tab

  19. Precipitation of plutonium from acidic solutions using magnesium oxide

    Plutonium (IV) is only marginally soluble in alkaline solution. Precipitation of plutonium using sodium or potassium hydroxide to neutralize acidic solutions produces a gelatinous solid that is difficult to filter and an endpoint that is difficult to control. If the pH of the solution is too high, additional species precipitate producing an increased volume of solids separated. The use of magnesium oxide as a reagent has advantages. It is added as a solid (volume of liquid waste produced is minimized), the pH is self-limiting (pH does not exceed about 8.5), and the solids precipitated are more granular (larger particle size) than those produced using KOH or NaOH. Following precipitation, the raffinate is expected to meet criteria for disposal to tank farms. The solid will be heated in a furnace to dry it and convert any hydroxide salts to the oxide form. The material will be cooled in a desiccator. The material is expected to meet vault storage criteria

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

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

    1988-01-01

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

  1. Extraction of rare earths and hydrochloric acid by trialkylphosphine oxide

    Extraction of rare earth chlorides and hydrochloric acid by trialkylphosphine oxide with different radicals (POR) (RR'2PO-POR, where RR'=alkyl of a normal structure, containing 7 to 9 carbon atoms, R=isoamyl) has been studied. Distribution of lanthanum-, neodymium-, lutetium- and yttrium chlorides during extraction with 1.28 mol/l POR solution in white spirit is investigated in the salt concentration range in the equilibrium aqueous phase from 0 to 2.8 mol/l. Lanthanide distribution coefficients increase with an increase in the order number of elements, with the separation coefficients of two extreme members of the series (Lu and La) for chlorides and nitrates constituting 100 and 80, respectively microquantities of Ln against the background of macroquantities of La is 2.6 mol/l. According to the results of measurements of viscosity, electric conductivity and water content in the extracts a conclusion is made on the state of salt in the organic phase. In the systems POR-LnCl3-HCl-H2O the hydrochloric acid extraction increases with an increase in the rare earth chloride concentration and order number of the element

  2. Synthesis and characterization of magnesium oxide nanocrystallites and probing the vacancy-type defects through positron annihilation studies

    Das, Anjan; Mandal, Atis Chandra; Roy, Soma; Prashanth, Pendem; Ahamed, Sk Izaz; Kar, Subhrasmita; Prasad, Mithun S.; Nambissan, P. M. G.

    2016-09-01

    Magnesium oxide nanocrystallites exhibit certain abnormal characteristics when compared to those of other wide band gap oxide semiconductors in the sense they are most prone to water absorption and formation of a hydroxide layer on the surface. The problem can be rectified by heating and pure nanocrystallites can be synthesized with controllable sizes. Inevitably the defect properties are distinctly divided between two stages, the one with the hydroxide layer (region I) and the other after the removal of the layer by annealing (region II). The lattice parameters, the optical band gap and even the positron annihilation characteristics are conspicuous by their distinct behavior in the two stages of the surface configurations of nanoparticles. While region I was specific with the formation of positronium-hydrogen complexes that drastically altered the defect-specific positron lifetimes, pick-off annihilation of orthopositronium atoms marked region II. The vacancy clusters within the nanocrystallites also trapped positrons. They agglomerated due to the effect of the higher temperatures and resulted in the growth of the nanocrystallites. The coincidence Doppler broadening spectroscopic measurements supported these findings and all the more indicated the trapping of positrons additionally into the neutral divacancies and negatively charged trivacancies. This is apart from the Mg2+ monovacancies which acted as the dominant trapping centers for positrons.

  3. Graphene oxide induces plasma membrane damage, reactive oxygen species accumulation and fatty acid profiles change in Pichia pastoris.

    Zhang, Meng; Yu, Qilin; Liang, Chen; Liu, Zhe; Zhang, Biao; Li, Mingchun

    2016-10-01

    During the past couple of years, graphene nanomaterials were extremely popular among the scientists due to the promising properties in many aspects. Before the materials being well applied, we should first focus on their biosafety and toxicity. In this study, we investigated the toxicity of synthesized graphene oxide (GO) against the model industrial organism Pichia pastoris. We found that the synthesized GO showed dose-dependent toxicity to P. pastoris, through cell membrane damage and intracellular reactive oxygen species (ROS) accumulation. In response to these cell stresses, cells had normal unsaturated fatty acid (UFA) levels but increased contents of polyunsaturated fatty acid (PUFA) with up-regulation of UFA synthesis-related genes on the transcriptional level, which made it overcome the stress under GO attack. Two UFA defective strains (spt23Δ and fad12Δ) were used to demonstrate the results above. Hence, this study suggested a close connection between PUFAs and cell survival against GO. PMID:27376352

  4. Bifunctional Nb/Ti-MCM-41 catalyst in oxidative acidic reaction of cyclohexene to diol

    Bifunctional oxidative and acidic catalyst was prepared by incorporating titanium ion (Ti4+) and niobic acid in meso porous molecular sieves MCM-41 structure. The catalyst is active both in oxidation, and acid-catalyzed reaction of olefin to diol. Nb/ Ti-MCM-41 catalyst was prepared by first synthesizing Ti-MCM-41 by hydrothermal method, followed by subsequent impregnation of niobic acid (Nb) into Ti-MCM-41 at various % wt Nb loading. The framework structure of Ti-MCM-41 collapsed after incorporation of Nb but the tetrahedral form of Ti4+ still maintained with octahedral Nb species. Both Bronsted and Lewis acid sites are present in all Nb/ Ti-MCM-41 samples. The formation of cyclohexanediol in the epoxidation of cyclohexene proved the bifunctional oxidative and acidic catalyst through the formation of cyclohexane oxide. The yield increased with the increase amount of the Bronsted acid sites provided by niobium species. (author)

  5. Electron spin resonance of paramagnetic defects and related charge carrier traps in complex oxide scintillators

    Laguta, Valentyn; Nikl, Martin

    2013-01-01

    Roč. 250, č. 2 (2013), s. 254-260. ISSN 0370-1972 R&D Projects: GA MŠk(CZ) LM2011029; GA ČR GAP204/12/0805; GA AV ČR IAA100100810 Grant ostatní: SAFMAT(XE) CZ.2.16/3.1.00/22132 Institutional support: RVO:68378271 Keywords : scintillators * point defects * electron spin resonance * polarons Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.605, year: 2013

  6. Structural and optical investigations of oxygen defects in zinc oxide nanoparticles

    ZnO nanoparticles (NPs) were prepared implementing chemical precipitation method. Structural and optical characterizations of synthesized ZnO NPs were thoroughly probed applying X-ray diffraction (XRD), transmission electron microscope (TEM), energy dispersive X-ray (EDX) analysis, X-ray photoelectron spectroscopy (XPS), UV- Visible absorption and fluorescence (FL) spectroscopy. The XRD and TEM analyses revealed hexagonal wurtzite phase with 25-30 nm size. EDX analysis indicated oxygen (O) rich composition of nanoparticles. In accordance with EDX, XPS analysis verifies Oi rich stoichiometry of prepared NPs. Furthermore, concurrence of lattice oxygen (OL), interstitial oxygen (Oi) and oxygen vacancy (VO) in ZnO NPs was demonstrated through XPS analysis. Size quantization of nanoparticles is evident by blue shift of UV-Visible absorption energy. The FL spectroscopic investigations ascertain the existence of several discrete and defect states and radiative transitions occurring therein. Display of visible emission from oxygen defect states and most importantly, excess of Oi defects in prepared ZnO nanoparticles, was well established through FL study

  7. Oxidation of carcinogenic polycylic hydrocarbons in the oleic acid under the effect of ionizing radiation

    The destruction of cancerogenic polycyclic hydrocarbons in oleic acid as a function of its oxidation degree was studied. Ionizing radiation was used as a factor initiating autooxidation. The effect of antioxidants on the cancerogens destruction was investigated. A correlation between the cancerogen destruction value and the oxidation rate of oleic acid was obtained. A mechanism of antioxidants action was discussed

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

    2001-01-01

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

  9. The Baeyer-Villiger Oxidation with Trifluoroacetic Acid and Household Sodium Percarbonate

    Kjonaas, Richard A.; Clemons, Anthony E.

    2008-01-01

    A method for carrying out the Baeyer-Villiger oxidation of cyclopentanone to [delta]-valerolactone in a large-section introductory organic chemistry laboratory course is reported. The oxidizing agent is trifluoroperoxyacetic acid generated in situ from trifluoroacetic acid and household sodium percarbonate such as OxiClean, Oxi Magic, or…

  10. Screening of anti-oxidative effects in Camellia sinensis L. leaves treated with boric acid

    İsmailoğlu, Işıl; COŞKUN, Zeynep Mine; Ersöz, Melike; Murat Ali TURAN

    2014-01-01

    Camellia sinensis L. (tea) is one of the most widely consumed drink in the World. The anti-oxidant role of boric acid has been reported. The present study was aimed to evaluate the alteration of anti-oxidative effects of C. sinensis L. leaves extract treated with boric acid.

  11. Raman spectroscopy characterization of actinide oxides (U 1-yPu y)O 2: Resistance to oxidation by the laser beam and examination of defects

    Jégou, C.; Caraballo, R.; Peuget, S.; Roudil, D.; Desgranges, L.; Magnin, M.

    2010-10-01

    Structural changes in four (U 1-yPu y)O 2 materials with very different plutonium concentrations (0 ⩽ y ⩽ 1) and damage levels (up to 110 dpa) were studied by Raman spectroscopy. The novel experimental approach developed for this purpose consisted in using a laser beam as a heat source to assess the reactivity and structural changes of these materials according to the power supplied locally by the laser. The experiments were carried out in air and in water with or without hydrogen peroxide. As expected, the material response to oxidation in air depends on the plutonium content of the test oxide. At the highest power levels U 3O 8 generally forms with UO 2 whereas no significant change in the spectra indicating oxidation is observed for samples with high plutonium content ( 239PuO 2). Samples containing 25 wt.% plutonium exhibit intermediate behavior, typified mainly by a higher-intensity 632 cm -1 peak and the disappearance of the 1LO peak at 575 cm -1. This can be attributed to the presence of anion sublattice defects without any formation of higher oxides. The range of materials examined also allowed us to distinguish partly the chemical effects of alpha self-irradiation. The results obtained with water and hydrogen peroxide (a water radiolysis product) on a severely damaged 238PuO 2 specimen highlight a specific behavior, observed for the first time.

  12. Peripheral insulin resistance in obese girls with hyperandrogenism is related to oxidative phosphorylation and elevated serum free fatty acids.

    Cree-Green, Melanie; Newcomer, Bradley R; Coe, Gregory; Newnes, Lindsey; Baumgartner, Amy; Brown, Mark S; Pyle, Laura; Reusch, Jane E; Nadeau, Kristen J

    2015-05-01

    Hyperandrogenic syndrome (HAS) is associated with insulin resistance (IR) and type 2 diabetes. Muscle IR in type 2 diabetes is linked with defects in mitochondrial oxidative capacity. In vivo muscle mitochondrial function has not been studied in HAS, especially in youth, who are early in the disease process. Our goal was to measure muscle mitochondrial oxidative function and peripheral IR in obese youth with HAS. Obese girls without HAS [n = 22, age 15(13,17) yr, BMI Z-score 2.05 ± 0.37] and with HAS [n = 35, age 15(14,16) yr, BMI Z-score 2.18 ± 0.30] were enrolled. Mitochondrial function was assessed with (31)phosphorus MR spectroscopy before, during, and after near-maximal isometric calf exercise, and peripheral IR was assessed with an 80 mU·m(-2)·min(-1) hyperinsulinemic euglycemic clamp. Girls with HAS had higher androgens [free androgen index 7.9(6.6,15.5) vs. 3.5(3.0,4.0), P lean(-1)·min(-1), P < 0.01]. HAS girls also had increased markers of inflammation including CRP, platelets, and white blood cell count and higher serum free fatty acids during hyperinsulinemia. Mitochondrial oxidative phosphorylation was lower in HAS [0.11(0.06,0.19) vs. 0.18(0.12,0.23) mmol/s, P < 0.05], although other spectroscopy markers of mitochondrial function were similar between groups. In multivariate analysis of the entire cohort, IR related to androgens, oxidative phosphorylation, and free fatty acid concentrations during hyperinsulinemia. These relationships were present in just the HAS cohort as well. Obese girls with HAS have significant peripheral IR, which is related to elevated androgens and free fatty acids and decreased mitochondrial oxidative phosphorylation. These may provide future options as targets for therapeutic intervention. PMID:25714677

  13. Defects in Mitochondrial and Peroxisomal β-Oxidation Influence Virulence in the Maize Pathogen Ustilago maydis

    Kretschmer, Matthias; Klose, Jana; Kronstad, James W.

    2012-01-01

    An understanding of metabolic adaptation during the colonization of plants by phytopathogenic fungi is critical for developing strategies to protect crops. Lipids are abundant in plant tissues, and fungal phytopathogens in the phylum basidiomycota possess both peroxisomal and mitochondrial β-oxidation pathways to utilize this potential carbon source. Previously, we demonstrated a role for the peroxisomal β-oxidation enzyme Mfe2 in the filamentous growth, virulence, and sporulation of the maiz...

  14. Application of layered poly (L-lactic acid cell free scaffold in a rabbit rotator cuff defect model

    Inui Atsuyuki

    2011-12-01

    Full Text Available Abstract Background This study evaluated the application of a layered cell free poly (L-lactic acid (PLLA scaffold to regenerate an infraspinatus tendon defect in a rabbit model. We hypothesized that PLLA scaffold without cultivated cells would lead to regeneration of tissue with mechanical properties similar to reattached infraspinatus without tendon defects. Methods Layered PLLA fabric with a smooth surface on one side and a pile-finished surface on the other side was used. Novel form of layered PLLA scaffold was created by superimposing 2 PLLA fabrics. Defects of the infraspinatus tendon were created in 32 rabbits and the PLLA scaffolds were transplanted, four rabbits were used as normal control. Contralateral infraspinatus tendons were reattached to humeral head without scaffold implantation. Histological and mechanical evaluations were performed at 4, 8, and 16 weeks after operation. Results At 4 weeks postoperatively, cell migration was observed in the interstice of the PLLA fibers. Regenerated tissue was directly connected to the bone composed mainly of type III collagen, at 16 weeks postoperatively. The ultimate failure load increased in a time-dependent manner and no statistical difference was seen between normal infraspinatus tendon and scaffold group at 8 and 16 weeks postoperatively. There were no differences between scaffold group and reattach group at each time of point. The stiffness did not improve significantly in both groups. Conclusions A novel form of layered PLLA scaffold has the potential to induce cell migration into the scaffold and to bridge the tendon defect with mechanical properties similar to reattached infraspinatus tendon model.

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

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

    2005-01-01

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

  16. Nondestructive covalent functionalization of carbon nanotubes by selective oxidation of the original defects with K{sub 2}FeO{sub 4}

    Zhang, Zhao-yang; Xu, Xue-cheng, E-mail: xcxu@phy.ecnu.edu.cn

    2015-08-15

    Graphical abstract: - Highlights: • Nondestructive covalent CNT functionalization is realized by defect oxidation. • A green oxidant K{sub 2}Fe{sup VI}O{sub 4} is used for CNT oxidation for the first time. • Effective CNT oxidation can be achieved at 60 °C in 3 h. • Oxidized CNTs are obtained in yields of above 100 wt%. • FeO{sub 3}, an unusual Fe (VI) specie, is produced when K{sub 2}FeO{sub 4} is dissolved in H{sub 2}SO{sub 4}. - Abstract: Chemical oxidation is still the major approach to the covalent functionalization of carbon nanotubes (CNTs). Theoretically, the defects on CNTs are more reactive than skeletal hexagons and should be preferentially oxidized, but conventional oxidation methods, e.g., HNO{sub 3}/H{sub 2}SO{sub 4} treatment, have poor reaction selectivity and inevitably consume the C=C bonds in the hexagonal lattices, leading to structural damage, π-electrons loss and weight decrease. In this work, we realized the nondestructive covalent functionalization of CNTs by selective oxidation of the defects. In our method, potassium ferrate K{sub 2}Fe{sup VI}O{sub 4} was employed as an oxidant for CNTs in H{sub 2}SO{sub 4} medium. The CNT samples, before and after K{sub 2}FeO{sub 4}/H{sub 2}SO{sub 4} treatment, were characterized with colloid dispersibility, IR, Raman spectroscopy, FESEM and XPS. The results indicated that (i) CNTs could be effectively oxidized by Fe (VI) under mild condition (60 °C, 3 h), and hydrophilic CNTs with abundant surface −COOH groups were produced; and (ii) Fe (VI) oxidation of CNTs followed a defect-specific oxidation process, that is, only the sp{sup 3}-hybridized carbon atoms on CNT surface were oxidized while the C=C bonds remained unaffected. This selective/nondestructive oxidation afforded oxidized CNTs in yields of above 100 wt%. This paper shows that K{sub 2}FeO{sub 4}/H{sub 2}SO{sub 4} is an effective, nondestructive and green oxidation system for oxidative functionalization of CNTs and probably other

  17. Interference by morpholine ethanesulfonic acid (MES) and related buffers in phenolic oxidation by peroxidase

    While characterizing the kinetic parameters of apoplastic phenolic oxidation by peroxidase, we found anomalies caused by the 4-morpholine ethanesulfonic acid (MES) buffer being used. In the presence of MES, certain phenolics appeared not to be oxidized by peroxidase, yet the oxidant, H2O2, was uti...

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

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

    2010-01-01

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

  19. Identification of vacancy defect complexes in transparent semiconducting oxides ZnO, In2O3 and SnO2.

    Makkonen, Ilja; Korhonen, Esa; Prozheeva, Vera; Tuomisto, Filip

    2016-06-01

    Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In2O3 and SnO2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies. PMID:26952670

  20. Identification of vacancy defect complexes in transparent semiconducting oxides ZnO, In2O3 and SnO2

    Positron annihilation spectroscopy, when combined with supporting high-quality modeling of positron states and annihilation in matter, is a powerful tool for detailed defect identification of vacancy-type defects in semiconductors and oxides. Here we demonstrate that the Doppler broadening of the positron annihilation radiation is a very sensitive means for observing the oxygen environment around cation vacancies, the main open-volume defects trapping positrons in measurements made for transparent semiconducting oxides. Changes in the positron annihilation signal due to external manipulation such as irradiation and annealing can be correlated with the associated changes in the sizes of the detected vacancy clusters. Our examples for ZnO, In2O3 and SnO2 demonstrate that oxygen vacancies in oxides can be detected directly using positron annihilation spectroscopy when they are complexed with cation vacancies. (paper)

  1. Folic acid supplementation reduces oxidative stress and hepatic toxicity in rats treated chronically with ethanol

    Lee, Soo-Jung; Kang, Myung-Hee; Min, Hyesun

    2011-01-01

    Folate deficiency and hyperhomocysteinemia are found in most patients with alcoholic liver disease. Oxidative stress is one of the most important mechanisms contributing to homocysteine (Hcy)-induced tissue injury. However it has not been examined whether exogenous administration of folic acid attenuates oxidative stress and hepatic toxicity. The aim of this study was to investigate the in vivo effect of folic acid supplementation on oxidative stress and hepatic toxicity induced by chronic et...

  2. Metabolic induction of experimental ulcerative colitis by inhibition of fatty acid oxidation.

    Roediger, W E; Nance, S.

    1986-01-01

    There is some evidence that failure of fatty acid or beta-oxidation in the epithelium of the colonic mucosa is associated with the development of ulcerative colitis. We tested the hypothesis that inhibition of fatty acid oxidation in the colonic mucosa of the rat reproduces the histological, clinical and biochemical lesions of acute ulcerative colitis of man. A specific inhibitor of beta-oxidation, sodium 2-bromo-octanoate, was instilled rectally for 5 days or exposed to isolated colonic epit...

  3. Kinetically Controlling Surface Structure to Construct Defect-Rich Intermetallic Nanocrystals: Effective and Stable Catalysts.

    Rong, Hongpan; Mao, Junjie; Xin, Pingyu; He, Dongsheng; Chen, Yuanjun; Wang, Dingsheng; Niu, Zhiqiang; Wu, Yuen; Li, Yadong

    2016-04-01

    Kinetic control of surface defects is achieved, and cubic, concave cubic, and defect-rich cubic intermetallic Pt3 Sn nanocrystals are prepared for the electro-oxidation of formic acid. The generality of this kinetic approach is demonstrated by the fabrication of Pt-Mn nanocrystals with different surface defects. The defect-rich nanocrystals exhibit high catalytic activity and stability concurrently, indicating their potential application in fuel cells. PMID:26836038

  4. Bile acids increase intracellular Ca2+ concentration and nitric oxide production in vascular endothelial cells

    Nakajima, Toshiaki; Okuda, Yukichi; Chisaki, Keigo; Shin, Wee-Soo; Iwasawa, Kuniaki; Morita, Toshihiro; Matsumoto, Akihiro; Suzuki, Jun-ichi; Suzuki, Seizi; Yamada, Nobuhiro; Toyo-Oka, Teruhiko; Nagai, Ryozo; Omata, Masao

    2000-01-01

    The effects of bile acids on intracellular Ca2+ concentration [Ca2+]i and nitric oxide production were investigated in vascular endothelial cells.Whole-cell patch clamp techniques and fluorescence measurements of [Ca2+]i were applied in vascular endothelial cells obtained from human umbilical and calf aortic endothelial cells. Nitric oxide released was determined by measuring the concentration of NO2−.Deoxycholic acid, chenodeoxycholic acid and the taurine conjugates increased [Ca2+]i concent...

  5. Elevated oxidative stress and sensorimotor deficits but normal cognition in mice that cannot synthesize ascorbic acid

    Harrison, Fiona E.; Yu, S Sarah; Van Den Bossche, Kristen L; Li, Liying; May, James M.; McDonald, Michael P.

    2008-01-01

    Oxidative stress is implicated in the cognitive deterioration associated with normal aging as well as neurodegenerative disorders such as Alzheimer’s and Parkinson's diseases. We investigated the effect of ascorbic acid (vitamin C) on oxidative stress, cognition and motor abilities in mice null for gulono-γ-lactone oxidase (Gulo). Gulo−/− mice are unable to synthesize ascorbic acid and depend on dietary ascorbic acid for survival. Gulo−/− mice were given supplements that provided them either ...

  6. Evaluation of effectiveness of hyaluronic acid in combination with bioresorbable membrane (poly lactic acid-poly glycolic acid for the treatment of infrabony defects in humans: A clinical and radiographic study

    Bhumika Sehdev

    2016-01-01

    Full Text Available Background: The combination of biomaterials, bone graft substitutes along with guided tissue regeneration (GTR has been shown to be an effective modality of periodontal regenerative therapy for infrabony defects. Therefore, the present randomized controlled clinical study was undertaken to evaluate the effectiveness of hyaluronic acid (HA in combination with bioresorbable membrane for the treatment of human infrabony defects. Materials and Methods: Twenty four infrabony defects in 20 systemically healthy patients were randomly assigned to test (HA in combination with bioresorbable membrane and control (bioresorbable membrane alone treatment groups. Probing pocket depth (PPD, relative attachment level, and relative gingival margin level were measured with a computerized Florida disc probe at baseline and at 6 months follow-up. Radiographic measurements were also evaluated at baseline and at 6 months of postsurgery. Results: At 6 months, the mean reduction in PPD in test group and control group was 4.52 mm and 2.97 mm, respectively. Significantly higher clinical attachment level with a gain of 2.20 mm was found in the test group as compared to control group. In addition, statistically significant greater reduction of radiographic defect depth was observed in the test group. Conclusion: Regenerative approach using hyaloss in combination with GTR for the treatment of human infrabony defects resulted in a significant added benefit in terms of CAL gains, PPD reductions and radiographic defect fill, as well as LBG, compared to the GTR alone.

  7. Evaluation of effectiveness of hyaluronic acid in combination with bioresorbable membrane (poly lactic acid-poly glycolic acid) for the treatment of infrabony defects in humans: A clinical and radiographic study

    Sehdev, Bhumika; Bhongade, Manohar Laxmanrao; Ganji, Kiran Kumar

    2016-01-01

    Background: The combination of biomaterials, bone graft substitutes along with guided tissue regeneration (GTR) has been shown to be an effective modality of periodontal regenerative therapy for infrabony defects. Therefore, the present randomized controlled clinical study was undertaken to evaluate the effectiveness of hyaluronic acid (HA) in combination with bioresorbable membrane for the treatment of human infrabony defects. Materials and Methods: Twenty four infrabony defects in 20 systemically healthy patients were randomly assigned to test (HA in combination with bioresorbable membrane) and control (bioresorbable membrane alone) treatment groups. Probing pocket depth (PPD), relative attachment level, and relative gingival margin level were measured with a computerized Florida disc probe at baseline and at 6 months follow-up. Radiographic measurements were also evaluated at baseline and at 6 months of postsurgery. Results: At 6 months, the mean reduction in PPD in test group and control group was 4.52 mm and 2.97 mm, respectively. Significantly higher clinical attachment level with a gain of 2.20 mm was found in the test group as compared to control group. In addition, statistically significant greater reduction of radiographic defect depth was observed in the test group. Conclusion: Regenerative approach using hyaloss in combination with GTR for the treatment of human infrabony defects resulted in a significant added benefit in terms of CAL gains, PPD reductions and radiographic defect fill, as well as LBG, compared to the GTR alone. PMID:27041838

  8. Neutron diffraction study on the defect structure of indium--tin--oxide

    Gonzalez, Gabriela B.; Cohen, Jerome B.; Hwang, Jin-Ha; Mason, Thomas O.; Hodges, Jason P.; Jorgensen, James D.

    2001-03-01

    The defect structure of undoped and Sn-doped In{sub 2}O{sub 3} (ITO) materials was studied by preparing powders under different processing environments and performing neutron powder diffraction. The effect of tin doping and oxygen partial pressure was determined. Structural information was obtained by analyzing neutron powder diffraction data using the Rietveld method. The results include positions of the atoms, their thermal displacements, the fractional occupancy of the interstitial oxygen site, and the fractional occupancies of Sn on each of the two nonequivalent cation sites. The tin cations show a strong preference for the b site versus the d site. The measured electrical properties are correlated with the interstitial oxygen populations, which agree with the proposed models for reducible (2Sn{sub In}{sup .}O{sub i}''){sup x} and nonreducible (2Sn{sub In}{sup .}3O{sub O}O{sub i}''){sup x} defect clusters.

  9. Comparison of defects in crystalline oxide semiconductor materials by electron spin resonance

    Matsuda, Tokiyoshi, E-mail: toki@rins.ryukoku.ac.jp; Kimura, Mutsumi [Department of Electronics and Informatics, Faculty of Science and Technology, Ryukoku University, 1-438, 1-5 Yokotani, Seta Oe-Cho, Otsu, Shiga 520-2194, Japan and Joint Research Center for Science and Technology, Ryukoku University, 1-5 Yokotani, Seta Oe-Cho, Otsu, Shiga 520-2194 (Japan)

    2015-03-15

    Defects in crystalline InGaZnO{sub 4} (IGZO) induced by plasma were investigated using electron spin resonance (ESR). Thermal stabilities and g factors of two ESR signals (A and B observed at g = 1.939 and 2.003, respectively) in IGZO were different from those of the ESR signals observed in component materials such as Ga{sub 2}O{sub 3} (signal observed at g = 1.969), In{sub 2}O{sub 3} (no signal), and ZnO (signal observed at g = 1.957). Signal A in IGZO increased upon annealing at 300 °C for 1 h, but decreased when annealing was continued for more than 2 h. On the other hand, signal B decreased upon annealing at 300 °C for 1 h. The ESR signal in ZnO decayed in accordance with a second-order decay model with a rate constant of 2.1 × 10{sup −4} s{sup −1}; however, this phenomenon was not observed in other materials. This difference might have been due to randomly formed IGZO lattices such as asymmetrical (Ga, Zn)O and In-O layers. Defects in signals A and B in IGZO were formed in trap states (at the deep level) and tail states, respectively.

  10. Hydrogen oxidation on gold electrode in perchloric acid solution

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

    2010-06-15

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

  11. Oxidative Decarboxylation of Levulinic Acid by Silver(I/Persulfate

    Yan Gong

    2011-03-01

    Full Text Available The oxidative decarboxylation of levulinic acid (LA by silver(I/persulfate [Ag(I/S2O82−] has been investigated in this paper. The effects of buffer solution, initial pH value, time and temperature and dosages of Ag(I/S2O82− on the decarboxylation of LA were examined in batch experiments and a reaction scheme was proposed on basis of the reaction process. The experimental results showed that a solution of NaOH-KH2PO4 was comparatively suitable for the LA decarboxylation reaction by silver(I/persulfate. Under optimum conditions (temperature 160 °C, pH 5.0, and time 0.5 h, the rate of LA conversion in NaOH-KH2PO4 solutions with an initial concentration of 0.01 mol LA reached 70.2%, 2-butanone (methyl ethyl ketone was the single product in the gas phase and the resulted molar yield reached 44.2%.

  12. Identification of defective illegitimate recombinational repair of oxidatively-induced DNA double-strand breaks in ataxia-telangiectasia cells

    Dar, M. E.; Winters, T. A.; Jorgensen, T. J.

    1997-01-01

    Ataxia-telangiectasia (A-T) is an autosomal-recessive lethal human disease. Homozygotes suffer from a number of neurological disorders, as well as very high cancer incidence. Heterozygotes may also have a higher than normal risk of cancer, particularly for the breast. The gene responsible for the disease (ATM) has been cloned, but its role in mechanisms of the disease remain unknown. Cellular A-T phenotypes, such as radiosensitivity and genomic instability, suggest that a deficiency in the repair of DNA double-strand breaks (DSBs) may be the primary defect; however, overall levels of DSB rejoining appear normal. We used the shuttle vector, pZ189, containing an oxidatively-induced DSB, to compare the integrity of DSB rejoining in one normal and two A-T fibroblast cells lines. Mutation frequencies were two-fold higher in A-T cells, and the mutational spectrum was different. The majority of the mutations found in all three cell lines were deletions (44-63%). The DNA sequence analysis indicated that 17 of the 17 plasmids with deletion mutations in normal cells occurred between short direct-repeat sequences (removing one of the repeats plus the intervening sequences), implicating illegitimate recombination in DSB rejoining. The combined data from both A-T cell lines showed that 21 of 24 deletions did not involve direct-repeats sequences, implicating a defect in the illegitimate recombination pathway. These findings suggest that the A-T gene product may either directly participate in illegitimate recombination or modulate the pathway. Regardless, this defect is likely to be important to a mechanistic understanding of this lethal disease.

  13. A novel system combining biocatalytic dephosphorylation of L-ascorbic acid 2-phosphate and electrochemical oxidation of resulting ascorbic acid.

    Kuwahara, Takashi; Homma, Toshimasa; Kondo, Mizuki; Shimomura, Masato

    2011-03-15

    An enzyme electrode was prepared with acid phosphatase (ACP) for development of a new electric power generation system using ascorbic acid 2-phosphate (AA2P) as a fuel. The properties of the electrode were investigated with respect to biocatalytic dephosphorylation of AA2P and electrochemical oxidation of resulting ascorbic acid (AA). The enzyme electrode was fabricated by immobilization of ACP through amide linkage onto a self-assembled monolayer of 3-mercaptopropionic acid on a gold electrode. AA2P was not oxidized on a bare gold electrode in the potential sweep range from -0.1 to +0.5 V vs. Ag/AgCl. However, the enzyme electrode gave an oxidation current in citric buffer solution of pH 5 containing 10 mM of AA2P. The oxidation current began to increase at +0.2V, and reached to 5.0 μA cm(-2) at +0.5 V. The potential +0.2 V corresponded to the onset of oxidation of ascorbic acid (AA). These results suggest that the oxidation current observed with the enzyme electrode is due to AA resulting from dephosphorylation of AA2P. The oxidation current increased with increasing concentration of AA2P and almost leveled off at around the concentration of 5mM. Thus the enzyme electrode brought about biocatalytic conversion of AA2P to AA, followed by electrochemical oxidation of the AA. The oxidation current is likely to be controlled by the biocatalytic reaction. PMID:21247749

  14. The role of surface and deep-level defects on the emission of tin oxide quantum dots

    This paper reports on the role of surface and deep-level defects on the blue emission of tin oxide quantum dots (SnO2 QDs) synthesized by the solution-combustion method at different combustion temperatures. X-ray diffraction studies showed the formation of a single rutile SnO2 phase with a tetragonal lattice structure. High resolution transmission electron microscopy studies revealed an increase in the average dot size from 2.2 to 3.6 nm with an increase of the combustion temperature from 350 to 550 °C. A decrease in the band gap value from 3.37 to 2.76 eV was observed with the increase in dot size due to the quantum confinement effect. The photoluminescence emission was measured for excitation at 325 nm and it showed a broad blue emission band for all the combustion temperatures studied. This was due to the creation of various oxygen and tin vacancies/defects as confirmed by x-ray photoelectron spectroscopy data. The origin of the blue emission in the SnO2 QDs is discussed with the help of an energy band diagram. (paper)

  15. Generation of organic acids and monosaccharides by hydrolytic and oxidative transformation of food processing residues.

    Fischer, Klaus; Bipp, Hans-Peter

    2005-05-01

    Carbohydrate-rich biomass residues, i.e. sugar beet molasses, whey powder, wine yeast, potato peel sludge, spent hops, malt dust and apple marc, were tested as starting materials for the generation of marketable chemicals, e.g. aliphatic acids, sugar acids and mono-/disaccharides. Residues were oxidized or hydrolyzed under acidic or alkaline conditions applying conventional laboratory digestion methods and microwave assisted techniques. Yields and compositions of the oxidation products differed according to the oxidizing agent used. Main products of oxidation by 30% HNO(3) were acetic, glucaric, oxalic and glycolic acids. Applying H(2)O(2)/CuO in alkaline solution, the organic acid yields were remarkably lower with formic, acetic and threonic acids as main products. Gluconic acid was formed instead of glucaric acid throughout. Reaction of a 10% H(2)O(2) solution with sugar beet molasses generated formic and lactic acids mainly. Na(2)S(2)O(8) solutions were very inefficient at oxidizing the residues. Glucose, arabinose and galactose were formed during acidic hydrolysis of malt dust and apple marc. The glucose content reached 0.35 g per gram of residue. Important advantages of the microwave application were lower reaction times and reduced reagent demands. PMID:15607197

  16. Ab initio Defect Energetics in LaBO3 Perovskite Solid Oxide Fuel Cell Materials

    Lee, Yueh-Lin; Morgan, Dane; Kleis, Jesper;

    2009-01-01

    Perovskite materials of the form ABO3 are a promising family of compounds for use in solid oxide fuel cell (SOFC) cathodes. Study of the physics of these compounds under SOFC conditions with ab initio methods is particularly challenging due to high temperatures, exchange of oxygen with O2 gas, and...

  17. The effects of L-carnitine and alpha-tocopherol on acid excretion defect during the acute ureteral obstruction in anaesthetized rats

    Ashtiyani SC

    2010-01-01

    Full Text Available "n Normal 0 false false false EN-US X-NONE AR-SA MicrosoftInternetExplorer4 /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal"; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-priority:99; mso-style-qformat:yes; mso-style-parent:""; mso-padding-alt:0in 5.4pt 0in 5.4pt; mso-para-margin:0in; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:11.0pt; font-family:"Calibri","sans-serif"; mso-ascii-font-family:Calibri; mso-ascii-theme-font:minor-latin; mso-fareast-font-family:"Times New Roman"; mso-fareast-theme-font:minor-fareast; mso-hansi-font-family:Calibri; mso-hansi-theme-font:minor-latin; mso-bidi-font-family:Arial; mso-bidi-theme-font:minor-bidi;} Background: Ureteral obstruction has been shown to induce renal oxidative stress, suppressed energy metabolism and defected acid excretion. This study was aimed to examine the improving effects of L-carnitine, a facilitating cofactor for mitochondrial oxidation of fatty-acids as well as a scavenger of free-radicals, and a-tocopherol as the most potent antioxidant on these renal disorders at early hours following release of unilateral ureteral obstruction. "n"nMethods: The left ureter was ligated in 60 anaesthetised rats, L-carnitine, a-tocopherol, or their vehicles (normal saline and olive oil, respectively were injected (i.p. in four groups. Each rat was re-anesthetized and cannulated, and ureteral legation was released at exactly 24h after UUO-induction. A 30-min clearance period performed to separately collect urine from both kidneys. The collected urine and arterial blood samples were given to pH-gas analyzer and autoanalyzer, and malondialdehyde (MDA, ATP and ADP levels were assessed in preserved kidneys. There were also sham and control groups (n=8-10 in each."n"nResults: In the post-obstructed kidney of vehicle-treated groups with respect to the equivalent kidney of sham group, there were increases in MDA (p<0

  18. Modeling of Semiconductors and Correlated Oxides with Point Defects by First Principles Methods

    Wang, Hao

    2014-06-15

    Point defects in silicon, vanadium dioxide, and doped ceria are investigated by density functional theory. Defects involving vacancies and interstitial oxygen and carbon in silicon are after formed in outer space and significantly affect device performances. The screened hybrid functional by Heyd-Scuseria-Ernzerhof is used to calculate formation energies, binding energies, and electronic structures of the defective systems because standard density functional theory underestimates the bang gap of silicon. The results indicate for the A-center a −2 charge state. Tin is proposed to be an effective dopant to suppress the formation of A-centers. For the total energy difference between the A- and B-type carbon related G-centers we find close agreement with the experiment. The results indicate that the C-type G-center is more stable than both the A- and B-types. The electronic structures of the monoclinic and rutile phases of vanadium dioxide are also studied using the Heyd-Scuseria-Ernzerhof functional. The ground states of the pure phases obtained by calculations including spin polarization disagree with the experimental observations that the monoclinic phase should not be magnetic, the rutile phase should be metallic, and the monoclinic phase should have a lower total energy than the rutile phase. By tuning the Hartree-Fock fraction α to 10% the agreement with experiments is improved in terms of band gaps and relative energies of the phases. A calculation scheme is proposed to simulate the relationship between the transition temperature of the metal-insulator transition and the dopant concentration in tungsten doped vanadium dioxide. We achieve good agreement with the experimental situation. 18.75% and 25% yttrium, lanthanum, praseodymium, samarium, and gadolinium doped ceria supercells generated by the special quasirandom structure approach are employed to investigate the impact of doping on the O diffusion. The experimental behavior of the conductivity for the

  19. Comparative Evaluation of Diagnostic Tools for Oxidative Deterioration of Polyunsaturated Fatty Acid-Enriched Infant Formulas during Storage

    Caroline Siefarth

    2013-12-01

    Full Text Available The challenge in the development of infant formulas enriched with polyunsaturated fatty acids (PUFAs is to meet the consumers’ expectations with regard to high nutritional and sensory value. In particular, PUFAs may be prone to fatty acid oxidation that can generate potential rancid, metallic and/or fishy off-flavors. Although such off-flavors pose no health risk, they can nevertheless lead to rejection of products by consumers. Thus, monitoring autoxidation at its early stages is of great importance and finding a suitable analytical tool to perform these evaluations is therefore of high interest in quality monitoring. Two formulations of infant formulas were varied systematically in their mineral composition and their presence of antioxidants to produce 18 model formulas. All models were aged under controlled conditions and their oxidative deterioration was monitored. A quantitative study was performed on seven characteristic odor-active secondary oxidation products in the formulations via two-dimensional high resolution gas chromatography-mass spectrometry/olfactometry (2D-HRGC-MS/O. The sensitivity of the multi-dimensional GC-MS/O analysis was supported by two additional analytical tools for monitoring autoxidation, namely the analysis of lipid hydroperoxides and conjugated dienes. Furthermore, an aroma profile analysis (APA was performed to reveal the presence and intensities of typical odor qualities generated in the course of fatty acid oxidation. The photometrical analyses of lipid hydroperoxides and conjugated dienes were found to be too insensitive for early indication of the development of sensory defects. By comparison, the 2D-HRGC-MS/O was capable of monitoring peroxidation of PUFAs at low ppb-level in its early stages. Thereby, it was possible to screen oxidative variances on the basis of such volatile markers already within eight weeks after production of the products, which is an earlier indication of oxidative deterioration

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

    Shin-Hae Lee

    2012-01-01

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

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

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

    2017-01-01

    The objective of this study was to evaluate the effects of acid and oxidation modifications on sorghum starch, as well as the effect of dual modification of starch on the physical, morphological, mechanical, and barrier properties of biodegradable films. The acid modification was performed with 3% lactic acid and the oxidation was performed with 1.5% active chlorine. For dual modification, the acid modification was performed first, followed by oxidation under the same conditions as above. Both films of the oxidized starches, single and dual, had increased stiffness, providing a higher tensile strength and lower elongation when compared to films based on native and single acid modified starches. However, the dual modification increased the water vapor permeability of the films without changing their solubility. The increase in sorghum starch concentration in the filmogenic solution increased the thickness, water vapor permeability, and elongation of the films. PMID:27507447

  2. Oxidation-Resistant Coating For Bipolar Lead/Acid Battery

    Bolstad, James J.

    1993-01-01

    Cathode side of bipolar substrate coated with nonoxidizable conductive layer. Coating prepared as water slurry of aqueous dispersion of polyethylene copolymer plus such conductive fillers as tin oxide, titanium, tantalum, or tungsten oxide. Applied easily to substrate of polyethylene carbon plastic. As slurry dries, conductive, oxidation-resistant coating forms on positive side of substrate.

  3. Oxidation and degradation of short-chain aliphatic compounds by hyperazeotropic nitric acid

    To determine the ultimate fate of organic material present in nuclear fuel reprocessing solutions and the chemical nature of the last surviving residues, organic products of the hydrolysis/nitrolysis of tributyl phosphate were subjected to further degradation with boiling 20 M HNO3 (Iodox Process) and carbon balances were run. Except for methyl nitrate, nitrate esters were oxidized in refluxing 20 M HNO3, primarily to a mixture of carbon dioxide and the corresponding and shorter chain aliphatic acids. Typically, 40% or more of the carbon from the nitrate esters was converted to CO2. Except for formic acid, the straight-chain monobasic acids oxidized slowly. Compounds identified among those resulting from oxidation of butyric acid (e.g., from the oxidation of butyl nitrate) included succinic and oxalic acids, 3- and 4-hydroxy-butyric acids, nitrate esters of 3- and 4-hydroxybutyric acid, butyrolactone, and 3-nitrobutyric acid. The mechanisms for formation of these products are briefly discussed. Oxalic acid and the hydroxyaliphatic acids have some potential for complexing ceertain metallic fission products. These results show that traces of organic materials will always be present in actual fuel processing solutions unless special measures are taken to ensure their removal. This conclusion was reinforced by analysis of recycle acid from the Savannah River Plant. The possible implications to a reprocessing plant using 100% recycle are briefly discussed

  4. Dissolution of thorium/uranium mixed oxide in nitric acid-hydrofluoric acid solution

    The dissolution process of thorium oxide and mixed uranium-thorium oxide is studied, as a step of the head-end of the fuel reprocessing. An extensive bibliography was analysed, concerning the main aspects of the system, specially the most important process variables. Proposed mechanisms and models for the thorium oxide dissolution are presented. The laboratory tests were performed in two phases: at first, powdered thoria was used as the material to be dissolved. The objective was to know how changes in he concentrations of the dissolvent solution components HNO3, HF and Al(NO3)3 affect the dissolution rate. The tests were planned according to the fractional factorial method. Thes results showed that it is advantageous to work with powdered material, since the reaction occurs rapidly. And, if the Thorex solution (HNO3 13M, HF 0.05M and Al(NO3)3 0.10M) is a suitable dissolvent, it was verified that it is possible to reduce the concentration of either nitric or fluoridric acid, without reducing the reaction rate to an undesirable value. It was also observed significant interaction between the components of the dissolvent solution. In the second phase of the tests, (Th, 5%U)O2 sintered pellets were used. The main goals were to know the pellets dissolution behaviour and to compare the results for different pellets among themselves. It was observed that the metallurgical history of the material strongly influences its dissolution, specially the density and the microstructure. It was also studied how the (Th,U)O2 mass/Thorex solution volume ratio affects the time needed to obtain an 1 M Th/liter solution. The activation energy for the reaction was obtained. (Author)

  5. The role of lattice defects in the catalytic oxidation of methanol over graphite catalysts

    Sanchez-Cortezon, E.

    2002-01-01

    In der vorliegenden Arbeit wurde die mechanische Aktivierung von Kohlenstoffmaterialien untersucht und ihr Einfluss auf die katalytischen Eigenschaften von gemahlenen Graphit aufgezeigt. Es wurde eine Korrelation zwischen der Struktur des gemahlen Graphits und der katalytischen Aktivität in der partiellen Oxidationsreaktion von Methanol zum Formaldehyd aufgestellt. Es wurde festgestellt, dass die Basalflächen des Graphits für die aktiven Zentren bei der Oxidation von Methanol verantwortlich s...

  6. Point defects and irradiation in oxides: simulations at the atomic scale; Defauts ponctuels et irradiation dans les oxydes: simulation a l'echelle atomique

    Crocombette, J.P

    2005-12-15

    The studies done by Jean-Paul Crocombette between 1996 and 2005 in the Service de Recherches de Metallurgie Physique of the Direction de l'Energie Nucleaire in Saclay are presented in this Habilitation thesis. These works were part of the material science researches on the ageing, especially under irradiation, of oxides of interest for the nuclear industry. In this context simulation studies at the atomic scale were performed on two elementary components of ageing under irradiation : point defects and displacement cascades ; using two complementary simulation techniques : ab initio electronic structure calculations and empirical potential molecular dynamics. The first part deals with point defects : self defects (vacancies or interstitials) or hetero-atomic dopants. One first recalls the energetics of such defects in oxides, the specific features of defects calculations and the expected accuracy of these calculations. Then one presents the results obtained on uranium dioxide, oxygen in silver and amorphous silica. The second part tackles the modelling of disintegration recoil nuclei in various?displacement cascades created by crystalline matrices for actinide waste disposal. Cascade calculations give access to the amorphization mechanisms under irradiation of these materials. One thus predicts that the amorphization in zircon takes place directly in the tracks whereas in lanthanum zirconate, the amorphization proceeds through the accumulation of point defects. Finally the prospects of these studies are discussed. (author)

  7. Effectiveness of Folic Acid Fortified Flour for Prevention of Neural Tube Defects in a High Risk Region.

    Wang, Haochen; De Steur, Hans; Chen, Gong; Zhang, Xiaotian; Pei, Lijun; Gellynck, Xavier; Zheng, Xiaoying

    2016-01-01

    Despite efforts to tackle folate deficiency and Neural Tube Defects (NTDs) through folic acid fortification, its implementation is still lacking where it is needed most, highlighting the need for studies that evaluate the effectiveness of folic acid fortified wheat flour in a poor, rural, high-risk, NTD region of China. One of the most affected regions, Shanxi Province, was selected as a case study. A community intervention was carried out in which 16,648 women of child-bearing age received fortified flour (eight villages) and a control group received ordinary flour (three villages). NTD birth prevalence and biological indicators were measured two years after program initiation at endline only. The effect on the NTD burden was calculated using the disability-adjusted life years (DALYs) method. In the intervention group, serum folate level was higher than in the control group. NTDs in the intervention group were 68.2% lower than in the control group (OR = 0.313, 95% CI = 0.207-0473, p Flour fortification was associated with lower birth prevalence and burden of NTDs in economically developing regions with a high risk of NTDs. The positive findings confirm the potential of fortification when selecting an appropriate food vehicle and target region. As such, this study provides support for decision makers aiming for the implementation of (mandatory) folic acid fortification in China. PMID:27005659

  8. Effectiveness of Folic Acid Fortified Flour for Prevention of Neural Tube Defects in a High Risk Region

    Haochen Wang

    2016-03-01

    Full Text Available Despite efforts to tackle folate deficiency and Neural Tube Defects (NTDs through folic acid fortification, its implementation is still lacking where it is needed most, highlighting the need for studies that evaluate the effectiveness of folic acid fortified wheat flour in a poor, rural, high-risk, NTD region of China. One of the most affected regions, Shanxi Province, was selected as a case study. A community intervention was carried out in which 16,648 women of child-bearing age received fortified flour (eight villages and a control group received ordinary flour (three villages. NTD birth prevalence and biological indicators were measured two years after program initiation at endline only. The effect on the NTD burden was calculated using the disability-adjusted life years (DALYs method. In the intervention group, serum folate level was higher than in the control group. NTDs in the intervention group were 68.2% lower than in the control group (OR = 0.313, 95% CI = 0.207–0473, p < 0.001. In terms of DALYs, burden in intervention group was approximately 58.5% lower than in the control group. Flour fortification was associated with lower birth prevalence and burden of NTDs in economically developing regions with a high risk of NTDs. The positive findings confirm the potential of fortification when selecting an appropriate food vehicle and target region. As such, this study provides support for decision makers aiming for the implementation of (mandatory folic acid fortification in China.

  9. Oxidation of uranium dioxide by hydrogen peroxide in sulfuric acid medium

    The oxidation of uranium dioxide by hydrogen peroxide in sulfuric acid medium was studied. It was found that in the UO2-H2O2-Fe/sup (II,III)/-H2SO4 system, the value of the oxidation potential (OP) is determined by the amount of Fe/sup (III)/ ions formed as the result of the oxidation of ferrous oxide by hydrogen peroxide. At normal temperature, H2O2 displays its oxidizing activity with respect to uranium dioxide at OP values of 500-550 mV, and at elevated temperature (40-600C) and in the presence of iron ions, at 400-450 mV. In a wide range of pH values, hydrogen peroxide as oxidizing agent considerably surpasses oxidizing agents such as nitrous acid, manganese dioxide, manganates, and permanganates. The process proceeds vigorously not only with the participation of iron ions, but also in their absence

  10. A comprehensive evaluation of food fortification with folic acid for the primary prevention of neural tube defects

    Lam Angeline

    2004-09-01

    Full Text Available Abstract Background Periconceptional use of vitamin supplements containing folic acid reduces the risk of a neural tube defect (NTD. In November 1998, food fortification with folic acid was mandated in Canada, as a public health strategy to increase the folic acid intake of all women of childbearing age. We undertook a comprehensive population based study in Newfoundland to assess the benefits and possible adverse effects of this intervention. Methods This study was carried out in women aged 19–44 years and in seniors from November 1997 to March 1998, and from November 2000 to March 2001. The evaluation was comprised of four components: I Determination of rates of NTDs; II Dietary assessment; III Blood analysis; IV Assessment of knowledge and use of folic acid supplements. Results The annual rates of NTDs in Newfoundland varied greatly between 1976 and 1997, with a mean rate of 3.40 per 1,000 births. There was no significant change in the average rates between 1991–93 and 1994–97 (relative risk [RR] 1.01, 95% confidence interval [CI] 0.76–1.34. The rates of NTDs fell by 78% (95% CI 65%–86% after the implementation of folic acid fortification, from an average of 4.36 per 1,000 births during 1991–1997 to 0.96 per 1,000 births during 1998–2001 (RR 0.22, 95% CI 0.14–0.35. The average dietary intake of folic acid due to fortification was 70 μg/day in women aged 19–44 years and 74 μg/day in seniors. There were significant increases in serum and RBC folate levels for women and seniors after mandatory fortification. Among seniors, there were no significant changes in indices typical of vitamin B12 deficiencies, and no evidence of improved folate status masking haematological manifestations of vitamin B12 deficiency. The proportion of women aged 19–44 years taking a vitamin supplement containing folic acid increased from 17% to 28%. Conclusions Based on these findings, mandatory food fortification in Canada should continue at the

  11. Activated Persulfate Oxidation of Perfluorooctanoic Acid (PFOA in Groundwater under Acidic Conditions

    Penghua Yin

    2016-06-01

    Full Text Available Perfluorooctanoic acid (PFOA is an emerging contaminant of concern due to its toxicity for human health and ecosystems. However, successful degradation of PFOA in aqueous solutions with a cost-effective method remains a challenge, especially for groundwater. In this study, the degradation of PFOA using activated persulfate under mild conditions was investigated. The impact of different factors on persulfate activity, including pH, temperature (25 °C–50 °C, persulfate dosage and reaction time, was evaluated under different experimental conditions. Contrary to the traditional alkaline-activated persulfate oxidation, it was found that PFOA can be effectively degraded using activated persulfate under acidic conditions, with the degradation kinetics following the pseudo-first-order decay model. Higher temperature, higher persulfate dosage and increased reaction time generally result in higher PFOA degradation efficiency. Experimental results show that a PFOA degradation efficiency of 89.9% can be achieved by activated persulfate at pH of 2.0, with the reaction temperature of 50 °C, molar ratio of PFOA to persulfate as 1:100, and a reaction time of 100 h. The corresponding defluorination ratio under these conditions was 23.9%, indicating that not all PFOA decomposed via fluorine removal. The electron paramagnetic resonance spectrometer analysis results indicate that both SO4−• and •OH contribute to the decomposition of PFOA. It is proposed that PFOA degradation occurs via a decarboxylation reaction triggered by SO4−•, followed by a HF elimination process aided by •OH, which produces one-CF2-unit-shortened perfluoroalkyl carboxylic acids (PFCAs, Cn−1F2n−1COOH. The decarboxylation and HF elimination processes would repeat and eventually lead to the complete mineralization all PFCAs.

  12. Activated Persulfate Oxidation of Perfluorooctanoic Acid (PFOA) in Groundwater under Acidic Conditions.

    Yin, Penghua; Hu, Zhihao; Song, Xin; Liu, Jianguo; Lin, Na

    2016-01-01

    Perfluorooctanoic acid (PFOA) is an emerging contaminant of concern due to its toxicity for human health and ecosystems. However, successful degradation of PFOA in aqueous solutions with a cost-effective method remains a challenge, especially for groundwater. In this study, the degradation of PFOA using activated persulfate under mild conditions was investigated. The impact of different factors on persulfate activity, including pH, temperature (25 °C-50 °C), persulfate dosage and reaction time, was evaluated under different experimental conditions. Contrary to the traditional alkaline-activated persulfate oxidation, it was found that PFOA can be effectively degraded using activated persulfate under acidic conditions, with the degradation kinetics following the pseudo-first-order decay model. Higher temperature, higher persulfate dosage and increased reaction time generally result in higher PFOA degradation efficiency. Experimental results show that a PFOA degradation efficiency of 89.9% can be achieved by activated persulfate at pH of 2.0, with the reaction temperature of 50 °C, molar ratio of PFOA to persulfate as 1:100, and a reaction time of 100 h. The corresponding defluorination ratio under these conditions was 23.9%, indicating that not all PFOA decomposed via fluorine removal. The electron paramagnetic resonance spectrometer analysis results indicate that both SO₄(-)• and •OH contribute to the decomposition of PFOA. It is proposed that PFOA degradation occurs via a decarboxylation reaction triggered by SO₄(-)•, followed by a HF elimination process aided by •OH, which produces one-CF₂-unit-shortened perfluoroalkyl carboxylic acids (PFCAs, Cn-1F2n-1COOH). The decarboxylation and HF elimination processes would repeat and eventually lead to the complete mineralization all PFCAs. PMID:27322298

  13. Activated Persulfate Oxidation of Perfluorooctanoic Acid (PFOA) in Groundwater under Acidic Conditions

    Yin, Penghua; Hu, Zhihao; Song, Xin; Liu, Jianguo; Lin, Na

    2016-01-01

    Perfluorooctanoic acid (PFOA) is an emerging contaminant of concern due to its toxicity for human health and ecosystems. However, successful degradation of PFOA in aqueous solutions with a cost-effective method remains a challenge, especially for groundwater. In this study, the degradation of PFOA using activated persulfate under mild conditions was investigated. The impact of different factors on persulfate activity, including pH, temperature (25 °C–50 °C), persulfate dosage and reaction time, was evaluated under different experimental conditions. Contrary to the traditional alkaline-activated persulfate oxidation, it was found that PFOA can be effectively degraded using activated persulfate under acidic conditions, with the degradation kinetics following the pseudo-first-order decay model. Higher temperature, higher persulfate dosage and increased reaction time generally result in higher PFOA degradation efficiency. Experimental results show that a PFOA degradation efficiency of 89.9% can be achieved by activated persulfate at pH of 2.0, with the reaction temperature of 50 °C, molar ratio of PFOA to persulfate as 1:100, and a reaction time of 100 h. The corresponding defluorination ratio under these conditions was 23.9%, indicating that not all PFOA decomposed via fluorine removal. The electron paramagnetic resonance spectrometer analysis results indicate that both SO4−• and •OH contribute to the decomposition of PFOA. It is proposed that PFOA degradation occurs via a decarboxylation reaction triggered by SO4−•, followed by a HF elimination process aided by •OH, which produces one-CF2-unit-shortened perfluoroalkyl carboxylic acids (PFCAs, Cn−1F2n−1COOH). The decarboxylation and HF elimination processes would repeat and eventually lead to the complete mineralization all PFCAs. PMID:27322298

  14. Formic-acid-induced depolymerization of oxidized lignin to aromatics

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.; Stahl, Shannon S.

    2014-11-01

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  15. Progress report on nitric-phosphoric acid oxidation

    The purpose of this program has been to demonstrate a nitric-phosphoric acid destruction technology which can treat a heterogeneous waste stream. This technology is being developed to convert hazardous liquid and solid organics to inorganic gases and salts while simultaneously performing a surface decontamination of the noncombustible items. Pu-238 waste is an issue because it must be shipped to WIPP. However, the presence of organics and Pu-238 waste is an issue because it must be shipped to WIPP. However, the presence of organics and Pu-238 exceeds packaging requirements because of concerns of hydrogen generation. If the TRU can be separated from the organics, the allowable heat load of a container increases a factor of 25. More importantly, since the current shipping package is limited by volume and not heat loading, destroying the organic compounds and decontaminating noncombustible can potentially create a three-order magnitude decrease in the number of shipments that must be made to WIPP. The process envisioned will be configured to handle 1 million pounds (as of 12/91) of a wide range of solid TRU-contaminated waste of which 600,000 pounds is combustible. The process will oxidize the combustibles (a mixture of 14% cellulose, 3% rubber, 64% plastics, 9% absorbed oil, 4% resins and sludges, and 6% miscellaneous organics) without requiring separation from the 400,000 pounds of noncombustibles. The system is being developed to operate below 200 C at moderate pressures (0--15 psig). This report primarily discusses results obtained over the past 3 1/2 months and their impact on the feasibility of a pilot-scale system

  16. Omega-3 fatty acids differentially modulate enzymatic anti-oxidant systems in skeletal muscle cells

    E. P. da Silva; Nachbar, R. T.; Levada-Pires, A. C.; Hirabara, S. M.; Lambertucci, R. H.

    2015-01-01

    During physical activity, increased reactive oxygen species production occurs, which can lead to cell damage and in a decline of individual’s performance and health. The use of omega-3 polyunsaturated fatty acids as a supplement to protect the immune system has been increasing; however, their possible benefit to the anti-oxidant system is not well described. Thus, the aim of this study was to evaluate whether the omega-3 fatty acids (docosahexaenoic acid and eicosapentaenoic acid) can be bene...

  17. Chronic exposure to perfluorooctane sulfonate induces behavior defects and neurotoxicity through oxidative damages, in vivo and in vitro.

    Na Chen

    Full Text Available Perfluorooctane sulfonate (PFOS is an emerging persistent pollutant which shows multiple adverse health effects. However, the neurotoxicity of PFOS and its mechanisms have not been fully elucidated. Using a combination of in vivo and in vitro methods, the present study provides a detailed description of PFOS-induced neurotoxicity. Results showed that the median lethal concentration of PFOS was 2.03 mM in Caenorhabditis elegans for 48 h exposure. 20 µM PFOS caused decrease of locomotor behaviors including forward movement, body bend and head thrash. Additionally, PFOS exposure reduced chemotaxis index of C. elegans, which indicates the decline of chemotaxis learning ability. Using green fluorescent protein (GFP labelled transgenic strains, we found that PFOS caused down-regulated expression of a chemoreceptor gene, gcy-5, in ASE chemosensory neurons, but did not affect cholinergic neurons and dopaminergic neurons. In SH-SY5Y cells, 48 h exposure to 25 µM and 50 µM PFOS induced cell damage, apoptosis and the reactive oxygen species (ROS generation. PFOS caused significant increases of lipid peroxidation and superoxide dismutase activity, but an actual decrease of glutathione peroxidase activity. Furthermore, antioxidant N-acetylcysteine rescued cells from PFOS-induced apoptosis via blocking ROS. Our results demonstrate that chronic exposure to PFOS can cause obvious neurotoxicity and behavior defects. Oxidative damage and anti-oxidative deficit are crucial mechanisms in neurotoxicity of PFOS.

  18. A Semi-empirical Mathematical Model to Estimate the Duration of the Atmosphere within a Double Oxide Film Defect in Pure Aluminum Alloy

    Raiszadeh, R.; Griffiths, W. D.

    2008-04-01

    It has been shown that the oxygen and nitrogen within the atmosphere of a double oxide film defect can be consumed by the surrounding Al melt. Experimentally determined reaction rates were used to construct a semi-empirical model to predict the change in volume with time of a bubble of air trapped in an Al melt, with the model including the diffusion of H from the metal into the bubble. Comparison with experimental results showed that the model predicted the change in volume well. The model was then used to estimate the duration of the internal atmosphere within double oxide film defects, which suggested that these would be consumed in a time of up to 3 minutes, depending upon assumptions made about the initial defect size.

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

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

    2001-01-01

    attributed to its ability to chelate free metal ions and iron from egg yolk located at the oil-water interface. Gallic acid reduced the levels of both free radicals and lipid hydroperoxides but promoted slightly the oxidative flavor deterioration in mayonnaise and influenced the profile of volatiles. Gallic......The antioxidative effects of gallic acid, EDTA, and extra emulsifier Panodan DATEM TR in mayonnaise enriched with 16% fish oil were investigated. EDTA reduced the formation of free radicals, lipid hydroperoxides, volatiles, and fishy and rancid off-flavors. The antioxidative effect of EDTA was...... 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...

  20. Nature of radiation hole defects on oxide surfaces and their role in adsorption and catalysis

    By spectral methods such as ESR and ultra-violet spectrometry studied are the properties of 0- surface hydrogen ''holes'', formed in silica gels, containing alloyed ions Co2+, Ni2+, Al5H+, B3+, Mo6+, W6+ in ultra-violet radiation field and stabilized near alloys after preliminary γ-radiation. It is shown that surface ''holes'' posess free radical properties. Discussed is the initiation mechanism of free radicals on the oxide surfaces and that of excessive catalytic activity in the deuterium-hydrogen exchange reaction and in radiation-catalytic transformations of various molecules after preliminary γ-radiation

  1. Generation of highly N-type, defect passivated transition metal oxides using plasma fluorine insertion

    Baker, L. Robert; Seo, Hyungtak; Hervier, Antoine; Somorjai, Gabor A.

    2016-04-12

    A new composition of matter is disclosed wherein oxygen vacancies in a semiconducting transition metal oxide such as titanium dioxide are filled with a halogen such as Fluorine, whereby the conductivity of the composition is greatly enhanced, while at the same time the chemical stability of the composition is greatly improved. Stoichiometric titanium dioxide having less than 3 % oxygen vacancies is subject to fluorine insertion such that oxygen vacancies are filled, limited amounts of fluorine replace additional oxygen atoms and fluorine interstitially inserts into the body of the TiO.sub.2 composition.

  2. Fiber optic hydrogen gas sensor utilizing surface plasmon resonance and native defects of zinc oxide by palladium

    We present an experimental study on a surface plasmon resonance (SPR) based fiber optic hydrogen gas sensor employing a palladium doped zinc oxide nanocomposite (ZnO(1−x)Pdx, 0 ≤ x ≤ 0.85) layer over the silver coated unclad core of the fiber. Palladium doped zinc oxide nanocomposites (ZnO(1−x)Pdx)  are prepared by a chemical route for different composition ratios and their structural, morphological and hydrogen sensing properties are investigated experimentally. The sensing principle involves the absorption of hydrogen gas by ZnO(1−x)Pdx, altering its dielectric function. The change in the dielectric constant is analyzed in terms of the red shift of the resonance wavelength in the visible region of the electromagnetic spectrum. To check the sensing capability of sensing probes fabricated with varying composition ratio (x) of nanocomposite, the SPR curves are recorded typically for 0% H2 and 4% H2 in N2 atmosphere for each fabricated probe. On changing the concentration of hydrogen gas from 0% to 4%, the red shift in the SPR spectrum confirms the change in dielectric constant of ZnO(1−x)Pdx on exposure to hydrogen gas. It is noted that the shift in the SPR spectrum increases monotonically up to a certain fraction of Pd in zinc oxide, beyond which it starts decreasing. SEM images and the photoluminescence (PL) spectra reveal that Pd dopant atoms substitutionally incorporated into the ZnO lattice profoundly affect its defect levels; this is responsible for the optimal composition of ZnO(1−x)Pdx to sense the hydrogen gas. The sensor is highly selective to hydrogen gas and possesses high sensitivity. Since optical fiber sensing technology is employed along with the SPR technique, the present sensor is capable of remote sensing and online monitoring of hydrogen gas. (paper)

  3. Fiber optic hydrogen gas sensor utilizing surface plasmon resonance and native defects of zinc oxide by palladium

    Tabassum, Rana; Gupta, Banshi D.

    2016-01-01

    We present an experimental study on a surface plasmon resonance (SPR) based fiber optic hydrogen gas sensor employing a palladium doped zinc oxide nanocomposite (ZnO(1-x)Pd x , 0 ≤ x ≤ 0.85) layer over the silver coated unclad core of the fiber. Palladium doped zinc oxide nanocomposites (ZnO(1-x)Pd x ) are prepared by a chemical route for different composition ratios and their structural, morphological and hydrogen sensing properties are investigated experimentally. The sensing principle involves the absorption of hydrogen gas by ZnO(1-x)Pd x , altering its dielectric function. The change in the dielectric constant is analyzed in terms of the red shift of the resonance wavelength in the visible region of the electromagnetic spectrum. To check the sensing capability of sensing probes fabricated with varying composition ratio (x) of nanocomposite, the SPR curves are recorded typically for 0% H2 and 4% H2 in N2 atmosphere for each fabricated probe. On changing the concentration of hydrogen gas from 0% to 4%, the red shift in the SPR spectrum confirms the change in dielectric constant of ZnO(1-x)Pd x on exposure to hydrogen gas. It is noted that the shift in the SPR spectrum increases monotonically up to a certain fraction of Pd in zinc oxide, beyond which it starts decreasing. SEM images and the photoluminescence (PL) spectra reveal that Pd dopant atoms substitutionally incorporated into the ZnO lattice profoundly affect its defect levels; this is responsible for the optimal composition of ZnO(1-x)Pd x to sense the hydrogen gas. The sensor is highly selective to hydrogen gas and possesses high sensitivity. Since optical fiber sensing technology is employed along with the SPR technique, the present sensor is capable of remote sensing and online monitoring of hydrogen gas.

  4. Changes in lipid composition, fatty acid profile and lipid oxidative stability during Cantonese sausage processing.

    Qiu, Chaoying; Zhao, Mouming; Sun, Weizheng; Zhou, Feibai; Cui, Chun

    2013-03-01

    Lipid composition, fatty acid profile and lipid oxidative stability were evaluated during Cantonese sausage processing. Free fatty acids increased with concomitant decrease of phospholipids. Total content of free fatty acids at 72 h in muscle and adipose tissue was 7.341 mg/g and 3.067 mg/g, respectively. Total amount of saturated, monounsaturated and polyunsaturated fatty acids (SFA, MUFA, and PUFA) in neutral lipid exhibited a little change during processing, while the proportion of PUFA significantly decreased in the PL fraction. The main triacylglycerols were POO+SLO+OOO, PSO (P = palmitic acid, O = oleic acid, L = linoleic acid, S = stearic acid), and a preferential hydrolysis of palmitic, oleic and linoleic acid was observed. Phosphatidylcholines (PC) and phosphatidylethanolamines (PE) were the main components of phospholipids and PE exhibited the most significant degradation during processing. Thiobarbituric acid values (TBARS) increased while peroxide values and hexanal contents varied during processing. PMID:23273460

  5. Neurodegeneration in Friedreich’s Ataxia: From Defective Frataxin to Oxidative Stress

    Cláudio M. Gomes

    2013-01-01

    Full Text Available Friedreich’s ataxia is the most common inherited autosomal recessive ataxia and is characterized by progressive degeneration of the peripheral and central nervous systems and cardiomyopathy. This disease is caused by the silencing of the FXN gene and reduced levels of the encoded protein, frataxin. Frataxin is a mitochondrial protein that functions primarily in iron-sulfur cluster synthesis. This small protein with an α/β sandwich fold undergoes complex processing and imports into the mitochondria, generating isoforms with distinct N-terminal lengths which may underlie different functionalities, also in respect to oligomerization. Missense mutations in the FXN coding region, which compromise protein folding, stability, and function, are found in 4% of FRDA heterozygous patients and are useful to understand how loss of functional frataxin impacts on FRDA physiopathology. In cells, frataxin deficiency leads to pleiotropic phenotypes, including deregulation of iron homeostasis and increased oxidative stress. Increasing amount of data suggest that oxidative stress contributes to neurodegeneration in Friedreich’s ataxia.

  6. Fatty acids and oxidative stress in psychiatric disorders

    Tonello Lucio; Cocchi Massimo; Tsaluchidu Sofia; Puri Basant K

    2008-01-01

    Abstract Background The aim of this study was to determine whether there is published evidence for increased oxidative stress in neuropsychiatric disorders. Methods A PubMed search was carried out using the MeSH search term 'oxidative stress' in conjunction with each of the DSM-IV-TR diagnostic categories of the American Psychiatric Association in order to identify potential studies. Results There was published evidence of increased oxidative stress in the following DSM-IV-TR diagnostic categ...

  7. Intra-articular injection of synovium-derived mesenchymal stem cells and hyaluronic acid promote regeneration of massive cartilage defects in rabbits

    Vyacheslav Ogay

    2014-01-01

    Full Text Available Introduction: The purpose of this study was to investigate whether intra-articular injection of synovium-derived mesenchymal stem cells (SD MSCs with low molecular weight hyaluronic acid (HA could promote regeneration of massive cartilage in rabbits. Material and methods: The SD MSCs were harvested from the knees of 10 Flemish giant rabbits, expanded in culture, and characterized. A reproducible 4-mm cylindrical defect was created in the intercondylar groove area using a kit for the mosaic chondroplasty of femoral condyle COR (De Puy, Mitek. The defect was made within the cartilage layer without destruction of subchondral bone. Two weeks after the cartilage defect, SD MSCs (2 × 106 cell/0.15 ml were suspended in 0.5% low molecular weight HA (0.15 ml and injected into the left knee, and HA solution (0.30 ml alone was placed into the right knee. Cartilage regeneration in the experimental and control groups were evaluated by macroscopically and histologically at 10, 30, and 60 days. Results: On day 10, after intra-articular injection of SD MSCs, we observed an early process of cartilage regeneration in the defect area. Histological studies revealed that cartilage defect was covered by a thin layer of spindle-shaped undifferentiated cells and proliferated chodroblasts. In contrast, an injection of HA did not induce reparation of cartilage in the defect area. At 30 days, macroscopic observation showed that the size of cartilage defect after SD MSC injection was significantly smaller than after HA injection. Histological score was also better in the MSC- treated intercondylar defect. At 60 days after MSC treatment, cartilage defect was nearly nonexistent and looked similar to an intact cartilage. Conclusion: Thus, intra-articular injection of SD MSCs can adhere to the defect in the intercondylar area, and promote cartilage regeneration in rabbits.

  8. Synthesis of pteroylglutamic acid-3',5'-2H2 by trifluoroacetic acid catalyzed exchange with deuterium oxide

    Pteroylglutamic acid (PGA) was deuterated by trifluoroacetic acid catalyzed exchange with deuterium oxide. The product, pteroylglutamic acid-3',5'-2H2, was specifically deuterated in the aromatic protons of the p-aminobenzoyl (PABA) moiety; the protons on C7 and C9 and in the glutamic acid residue were not exchanged. Deuterium incorporation was measured by chemical ionization mass spectrometry (CI-MS). Pteroylglutamates were cleaved by a base-catalyzed, oxidative hydrolysis to PABA, which was converted to the methyl ester, N-trifluoroacetate for analysis by gas chromatography-chemical ionization-mass spectrometry. Products from the exchange typically contained 1 percent 2H1 and 90 percent 2H2 species. The procedure may be used to label specifically various analogs of PGA with deuterium in the PABA portion of the molecule

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

    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 O2, 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 14C-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

  10. Novel amino acids: synthesis of furoxan and sydnonimine containing amino acids and peptides as potential nitric oxide releasing motifs.

    Nortcliffe, Andrew; Botting, Nigel P; O'Hagan, David

    2013-07-28

    The incorporation of furoxan and sydnonimine ring systems into amino acid side chains is demonstrated with the preparation of four novel amino acids which carry these nitric oxide-releasing motifs. N-((4-Nitrophenoxy)carbonyl)-3-phenylsydnonimine 9 and bis(phenylsulfonyl)furoxan 10 are the key intermediates for introducing the heterocycle side chains onto appropriate amine and alcohol functionalities respectively. Furoxan 5 and 7 both displayed NO release based on determination of nitrite production. Orthogonal amino acid protecting group strategies were deployed to demonstrate that the amino acids could be incorporated into peptide frameworks. By way of demonstration the amino acids were placed centrally into several tripeptide motifs. Griess test assays showed that these amino acids released NO in the presence of γ-glutathione (GST). PMID:23753002

  11. Omega-3 fatty acids differentially modulate enzymatic anti-oxidant systems in skeletal muscle cells.

    da Silva, E P; Nachbar, R T; Levada-Pires, A C; Hirabara, S M; Lambertucci, R H

    2016-01-01

    During physical activity, increased reactive oxygen species production occurs, which can lead to cell damage and in a decline of individual's performance and health. The use of omega-3 polyunsaturated fatty acids as a supplement to protect the immune system has been increasing; however, their possible benefit to the anti-oxidant system is not well described. Thus, the aim of this study was to evaluate whether the omega-3 fatty acids (docosahexaenoic acid and eicosapentaenoic acid) can be beneficial to the anti-oxidant system in cultured skeletal muscle cells. C2C12 myocytes were differentiated and treated with either eicosapentaenoic acid or docosahexaenoic acid for 24 h. Superoxide content was quantified using the dihydroethidine oxidation method and superoxide dismutase, catalase, and glutathione peroxidase activity, and expression was quantified. We observed that the docosahexaenoic fatty acids caused an increase in superoxide production. Eicosapentaenoic acid induced catalase activity, while docosahexaenoic acid suppressed superoxide dismutase activity. In addition, we found an increased protein expression of the total manganese superoxide dismutase and catalase enzymes when cells were treated with eicosapentaenoic acid. Taken together, these data indicate that the use of eicosapentaenoic acid may present both acute and chronic benefits; however, the treatment with DHA may not be beneficial to muscle cells. PMID:26386577

  12. A novel application of horseradish peroxidase: Oxidation of alcohol ethoxylate to alkylether carboxylic acid

    2008-01-01

    A novel application of horseradish peroxidase (HRP) in the oxidation of alcohol ethoxylate to alkylether carboxylie acid in the present of H2O2 was reported in this paper. We propose the mechanism for the catalytic oxidation reaction is that the hydrogen transfers from the substrate to the ferryl oxygen to form the a-hydroxy carbon radical intermediate. The reaction offers a new approach for further research structure and catalytic mechanism of HRP and production of alkylether carboxylic acid.

  13. Low ascorbic acid and increased oxidative stress in gulo−/− mice during development

    Harrison, Fiona E.; Meredith, M. Elizabeth; Dawes, Sean M.; Saskowski, Jeanette L.; May, James M.

    2010-01-01

    Vitamin C (ascorbic acid, AA) depletion during pre-natal and post-natal development can lead to oxidative stress in the developing brains and other organs. Such damage may lead to irreversible effects on later brain function. We studied the relationship between AA deficiency and oxidative stress during development in gulonolactone oxidase (gulo) knockout mice that are unable to synthesize their own ascorbic acid. Heterozygous gulo(+/−) mice can synthesize AA and typically have similar tissue ...

  14. Fundamental Studies of Irradiation-Induced Defect Formation and Fission Product Dynamics in Oxide Fuels

    Stubbins, James

    2012-12-19

    The objective of this research program is to address major nuclear fuels performance issues for the design and use of oxide-type fuels in the current and advanced nuclear reactor applications. Fuel performance is a major issue for extending fuel burn-up which has the added advantage of reducing the used fuel waste stream. It will also be a significant issue with respect to developing advanced fuel cycle processes where it may be possible to incorporate minor actinides in various fuel forms so that they can be 'burned' rather than join the used fuel waste stream. The potential to fission or transmute minor actinides and certain long-lived fission product isotopes would transform the high level waste storage strategy by removing the need to consider fuel storage on the millennium time scale.

  15. Fundamental Studies of Irradiation-Induced Defect Formation and Fission Product Dynamics in Oxide Fuels

    The objective of this research program is to address major nuclear fuels performance issues for the design and use of oxide-type fuels in the current and advanced nuclear reactor applications. Fuel performance is a major issue for extending fuel burn-up which has the added advantage of reducing the used fuel waste stream. It will also be a significant issue with respect to developing advanced fuel cycle processes where it may be possible to incorporate minor actinides in various fuel forms so that they can be 'burned' rather than join the used fuel waste stream. The potential to fission or transmute minor actinides and certain long-lived fission product isotopes would transform the high level waste storage strategy by removing the need to consider fuel storage on the millennium time scale

  16. Biological implications of oxidation and unidirectional chiral inversion of D-amino acids.

    Wang, Yong-Xiang; Gong, Nian; Xin, Yan-Fei; Hao, Bin; Zhou, Xiang-Jun; Pang, Catherine C Y

    2012-03-01

    Recent progress in chiral separation of D- and L-amino acids by chromatography ascertained the presence of several free Damino acids in a variety of mammals including humans. Unidirectional chiral inversion of many D-amino acid analogs such as exogenous NG-nitro-D-arginine (D-NNA), endogenous D-leucine, D-phenylanine and D-methionine have been shown to take place with inversion rates of 4-90%, probably dependent on various species D-amino acid oxidase (DAAO) enzymatic activities. DAAO is known to catalyze the oxidative deamination of neutral and basic D-amino acids to their corresponding α-keto acids, hydrogen peroxide and ammonia, and is responsible for the chiral inversion. This review provides an overview of recent research in this area: 1) oxidation and chiral inversion of several D-amino acid analogs in the body; 2) the indispensable but insufficient role of DAAO particularly in the kidneys and brain for the oxidation and chiral inversion of D-amino acids analogs; and 3) unidentified transaminase(s) responsible for the second step of chiral inversion. The review also discusses the physiological significance of oxidation and chiral inversion of D-amino acids, which is still a subject of dispute. PMID:22304623

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

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

    1986-01-01

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

  18. Insulin binding and stimulation of hexose and amino acid transport by normal and receptor-defective human fibroblasts

    The authors analyzed insulin receptors in cells cultured from a sibship of related parents who had two offspring with severe insulin resistance (Leprechaunism). 124I-Insulin (1 ng/ml) binding to skin fibroblasts from the proband, mother, and father was 9, 60 and 62% of control cells, respectively, at equilibrium, Non-linear regression analysis, utilizing a two receptors model, of curvilinear Scatchard plots indicated a reduced number of high-affinity binding sites in both parents. Influx of L-Proline (System A), L-Serine (ASC) and L-Leucine (L) was similar in control and mutant cells. Similarly, during the depletion of intracellular amino acid pools, there was a release from transinhibition for System A and a decrease of transstimulation of Systems ASC and L in both cell lines. Surprisingly, insulin augmented, normally, A system influx with an ED50 = 70 ng/ml at 240C and 7 ng/ml at 370C. By contrast insulin failed to simulated 3-0-methyl-D-glucose influx into the proband's cells, while normal cells were stimulated 30% with an ED50 of 6 ng/ml. These results indicate that defective high-affinity insulin binding is inherited as an autosomal recessive trait; that general membrane functions are intact; that insulin regulates A system amino acid and hexose transport by two different mechanisms; and, that the latter mechanism is impaired by this family's receptor mutation

  19. Acidity-induced watercourse defects and their prevention on the River Sanginjoki; Happamuuden aiheuttamat vesistoehaitat ja niiden torjuntakeinot Sanginjoella

    Tertsunen, J.; Martinmaeki, K.; Heikkinen, K. [and others

    2012-11-15

    As the first tributary of the River Oulujoki, the River Sanginjoki is one of the most important recreational areas in the Oulu region. It is also the closest potential reproduction area for salmon and trout using the Merikoski fishway. During flood peaks, occasional low pH values reduce the recreational and ecological value of the River Sanginjoki. The origin of low pH values was located as part of the 'City and Water - Improving the recreational value and ecological restoration of River Sanginjoki -project', during the years 2008-2011. This project involved largescale monitoring of the River Sanginjoki area for pH changes, while methods for preventing and reducing low pH values were tested. Based on the project's results, guidelines were drawn up for controlling problems associated with low pH values. The report also contains general information on the River Sanginjoki and its watershed, the river's ecological state and the development of its water quality. The results demonstrated a connection between low pH values and high discharges, but the lowest pH values were measured during summer and autumn rain floods in particular. A water sample analysis with other information showed that low pH values mainly originate in soil, land use and vegetation. The origin of acid runoff mainly lies in organic acids from peatlands and moss, but local factors such as acid sulphate soils and black shales may also contribute. Due to acidic peatlands, the water of the River Sanginjoki has naturally been slightly acidic, but ditch drainage of peat- and forestland has probably increased this effect. The effect of the restoration and water protection methods used in the project varied. Some methods proved effective and can be suggested for practical use at the Sanginjoki watershed, as well as other watersheds suffering from the same problems. Development of these methods should be continued, to improve their effectiveness and durability. Although defects due to

  20. Measurement of the oxidation-extraction of uranium from wet-process phosphoric acid

    The present invention relates to processes for the recovery of uranium from wet-process phosphoric acid and more particularly to the oxidation-extraction steps in the DEPA-TOPO process for such recovery. A more efficient use of oxidant is obtained by monitoring the redox potential during the extraction step

  1. Oxidation of L-tyrosine by vanadium (V) in presence of sulphuric acid

    Oxidation of L-tyrosine with vanadium (V) in sulphuric acid mediumn at constant ionic strength is first order in oxidant and H+. The order in tyrosine varies from 1 to 0. A mechanism consistent with the kinetic results is proposed in which the rate determining step is the decompostition of the complex formed in the prior equilibrium. (Author)

  2. Compromised mitochondrial fatty acid synthesis in transgenic mice results in defective protein lipoylation and energy disequilibrium.

    Stuart Smith

    Full Text Available A mouse model with compromised mitochondrial fatty acid synthesis has been engineered in order to assess the role of this pathway in mitochondrial function and overall health. Reduction in the expression of mitochondrial malonyl CoA-acyl carrier protein transacylase, a key enzyme in the pathway encoded by the nuclear Mcat gene, was achieved to varying extents in all examined tissues employing tamoxifen-inducible Cre-lox technology. Although affected mice consumed more food than control animals, they failed to gain weight, were less physically active, suffered from loss of white adipose tissue, reduced muscle strength, kyphosis, alopecia, hypothermia and shortened lifespan. The Mcat-deficient phenotype is attributed primarily to reduced synthesis, in several tissues, of the octanoyl precursors required for the posttranslational lipoylation of pyruvate and α-ketoglutarate dehydrogenase complexes, resulting in diminished capacity of the citric acid cycle and disruption of energy metabolism. The presence of an alternative lipoylation pathway that utilizes exogenous free lipoate appears restricted to liver and alone is insufficient for preservation of normal energy metabolism. Thus, de novo synthesis of precursors for the protein lipoylation pathway plays a vital role in maintenance of mitochondrial function and overall vigor.

  3. Tritium suicide selection of mammalian cell mutants defective in the transport of neutral amino acids

    Mouse lymphocytic cells of the established line GF-14 were allowed to accumulate intracellular 3H-labeled aminoisobutyric acid (AIB), frozen and stored over liquid N2. After internal radiation had reduced survival to 1 in 104, survivors were plated and tested for their ability to transport AIB. Out of 200 clones tested, two (designated GF-17 and GF-18) were found to have reductions to 13 to 35% of the parent in the rate of transport of AIB, L-alanine, L-proline, and L-serine; GF-18 also showed significant reductions in the rate of transport of L-glutamate and DL-cysteine. Little or no change was observed for 10 other amino acids or for thymidine. Kinetic analyses revealed that the mutants were not altered in K/sub m/ for AIB uptake, but had V/sub max/ values approximately 20% the value of the parent strain, GF-14, suggesting that either the number of AIB transport sites or the turnover rate of the sites has been reduced in the two mutants

  4. Stereoselective and nonstereoselective effects of ibuprofen enantiomers on mitochondrial beta-oxidation of fatty acids

    The effects of the R-(-) and S-(+)ibuprofen enantiomers were first studied in vitro with mouse liver mitochondria incubated in the presence of various concentrations of exogenous coenzyme A. In the presence of a low concentration of coenzyme A (2.5 microM), the R-(-)enantiomer (which forms an acylcoenzyme A) inhibited stereoselectively the beta oxidation of [1-14C]palmitic acid but not that of [1-14C]palmitoyl-L-carnitine (which can directly enter the mitochondria). In the presence, however, of a concentration of coenzyme A (50 microM) reproducing that present in liver cell cytosol, both enantiomers (2 mM) slightly inhibited the beta oxidation of [1-14C]palmitic acid and markedly inhibited the beta oxidation of [1-14C]octanoic acid and [1-14C]butyric acid. In vivo, both enantiomers (1 mmol.kg-1) similarly inhibited the formation of [14C]CO2 from [1-14C]fatty acids. Both enantiomers similarly decreased plasma ketone bodies. Both similarly increased hepatic triglycerides, and both produced mild microvesicular steatosis of the liver. We conclude that both ibuprofen enantiomers inhibit beta oxidation of fatty acids in vitro and in vivo. In addition, the R-(-)enantiomer may stereoselectively sequester coenzyme A; at low concentrations of coenzyme A in vitro, this may stereoselectively inhibit the mitochondrial uptake and beta oxidation of long chain fatty acids

  5. Stereoselective and nonstereoselective effects of ibuprofen enantiomers on mitochondrial beta-oxidation of fatty acids

    Freneaux, E.; Fromenty, B.; Berson, A.; Labbe, G.; Degott, C.; Letteron, P.; Larrey, D.; Pessayre, D. (Unite de Recherches de Physiolopathologie Hepatique (INSERM U-24), Hopital Beaujon, Clichy (France))

    1990-11-01

    The effects of the R-(-) and S-(+)ibuprofen enantiomers were first studied in vitro with mouse liver mitochondria incubated in the presence of various concentrations of exogenous coenzyme A. In the presence of a low concentration of coenzyme A (2.5 microM), the R-(-)enantiomer (which forms an acylcoenzyme A) inhibited stereoselectively the beta oxidation of (1-{sup 14}C)palmitic acid but not that of (1-{sup 14}C)palmitoyl-L-carnitine (which can directly enter the mitochondria). In the presence, however, of a concentration of coenzyme A (50 microM) reproducing that present in liver cell cytosol, both enantiomers (2 mM) slightly inhibited the beta oxidation of (1-{sup 14}C)palmitic acid and markedly inhibited the beta oxidation of (1-{sup 14}C)octanoic acid and (1-{sup 14}C)butyric acid. In vivo, both enantiomers (1 mmol.kg-1) similarly inhibited the formation of ({sup 14}C)CO{sub 2} from (1-{sup 14}C)fatty acids. Both enantiomers similarly decreased plasma ketone bodies. Both similarly increased hepatic triglycerides, and both produced mild microvesicular steatosis of the liver. We conclude that both ibuprofen enantiomers inhibit beta oxidation of fatty acids in vitro and in vivo. In addition, the R-(-)enantiomer may stereoselectively sequester coenzyme A; at low concentrations of coenzyme A in vitro, this may stereoselectively inhibit the mitochondrial uptake and beta oxidation of long chain fatty acids.

  6. Efficient Catalytic Ozonation over Reduced Graphene Oxide for p-Hydroxylbenzoic Acid (PHBA) Destruction: Active Site and Mechanism.

    Wang, Yuxian; Xie, Yongbing; Sun, Hongqi; Xiao, Jiadong; Cao, Hongbin; Wang, Shaobin

    2016-04-20

    Nanocarbons have been demonstrated as promising environmentally benign catalysts for advanced oxidation processes (AOPs) upgrading metal-based materials. In this study, reduced graphene oxide (rGO) with a low level of structural defects was synthesized via a scalable method for catalytic ozonation of p-hydroxylbenzoic acid (PHBA). Metal-free rGO materials were found to exhibit a superior activity in activating ozone for catalytic oxidation of organic phenolics. The electron-rich carbonyl groups were identified as the active sites for the catalytic reaction. Electron spin resonance (ESR) and radical competition tests revealed that superoxide radical ((•)O2(-)) and singlet oxygen ((1)O2) were the reactive oxygen species (ROS) for PHBA degradation. The intermediates and the degradation pathways were illustrated from mass spectroscopy. It was interesting to observe that addition of NaCl could enhance both ozonation and catalytic ozonation efficiencies and make ·O2(-) as the dominant ROS. Stability of the catalysts was also evaluated by the successive tests. Loss of specific surface area and changes in the surface chemistry were suggested to be responsible for catalyst deactivation. PMID:27007603

  7. Interplay of dopant, defects and electronic structure in driving ferromagnetism in Co-doped oxides: TiO2, CeO2 and ZnO

    A comprehensive study of the defects and impurity (Co)-driven ferromagnetism is undertaken in the oxide semiconductors: TiO2, ZnO and CeO2. The effect of magnetic (Co2+) and non-magnetic (Cu2+) impurities in conjunction with defects, such as oxygen vacancies (Vo), have been thoroughly investigated. Analyses of the x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) data reveal the incorporation of cobalt in the lattice, with no signature of cobalt segregation. It is shown that oxygen vacancies are necessary for the ferromagnetic coupling in the Co-doped oxides mentioned above. The possible exchange mechanisms responsible for the ferromagnetism are discussed in light of the energy levels of dopants in the host oxides. In addition, Co and Cu co-doped TiO2 samples are studied in order to understand the role of point defects in establishing room temperature ferromagnetism. The parameters calculated from the bound magnetic polaron (BMP) and Jorgensen's optical electronegativity models offer a satisfactory explanation of the defect-driven ferromagnetism in the doped/co-doped samples.

  8. Oxidation-reduction reactions of simple hydroxamic acids and plutonium(IV) ions in nitric acid

    Carrott, M. J.; Fox, O. D.; LeGurun, G.; Jones, C J; Mason, C; Taylor, Robin; Andrieux, Fabrice; Boxall, Colin

    2008-01-01

    Simple hydroxamic acids such as formo- and aceto-hydroxamic acids have been proposed as suitable reagents for the separation of either Pu and/or Np from U in modified or single cycle Purex based solvent extraction processes designed to meet the emerging requirements of advanced fuel cycles. The stability of these hydroxamic acids is dominated by their decomposition through acid hydrolysis. Kinetic studies of the acid hydrolysis of formo- and acetohydroxamic acids are reported in the absence a...

  9. Electronic structure of defects in oxides. Final report, December 1, 1980-November 30, 1981

    Details of the electronic structure of F-type centers and charge trapping in the series of oxides SrO, CaO, MgO, α-Al2O3 and MgAl2O4 have been determined using photoconductivity, luminescence, and fluorescence lifetimes. Measurements were made over the spectral range 1.5 to 6.5 eV and over the temperature range 4 to 350 K. The centers were introduced into SrO by electron, proton or neutron bombardment, into CaO, MgO, and α-Al2O3 by electron or neutron bombardment, or thermochemical reduction, and into MgAl2O4 by particle bombardment. In some cases, notably CaO, MgO, and α-Al2O3 exhibit phosphorescence near room temperature, with the emission occurring at the wavelength corresponding to the F center. Our work suggests that the electron trap involved is H- ions, but this has only so far been confirmed for MgO

  10. Hydroxyapatite formation on graphene oxide modified with amino acids: arginine versus glutamic acid.

    Tavafoghi, M; Brodusch, N; Gauvin, R; Cerruti, M

    2016-01-01

    Hydroxyapatite (HA, Ca5(PO4)3OH) is the main inorganic component of hard tissues, such as bone and dentine. HA nucleation involves a set of negatively charged phosphorylated proteins known as non-collagenous proteins (NCPs). These proteins attract Ca(2+) and PO4(3-) ions and increase the local supersaturation to a level required for HA precipitation. Polar and charged amino acids (AAs) are highly expressed in NCPs, and seem to be responsible for the mineralizing effect of NCPs; however, the individual effect of these AAs on HA mineralization is still unclear. In this work, we investigate the effect of a negatively charged (Glu) and positively charged (Arg) AA bound to carboxylated graphene oxide (CGO) on HA mineralization in simulated body fluids (SBF). Our results show that Arg induces HA precipitation faster and in larger amounts than Glu. We attribute this to the higher stability of the complexes formed between Arg and Ca(2+) and PO4(3-) ions, and also to the fact that Arg exposes both carboxyl and amino groups on the surface. These can electrostatically attract both Ca(2+) and PO4(3-) ions, thus increasing local supersaturation more than Glu, which exposes carboxyl groups only. PMID:26791001

  11. Identification of genes required for secretion of the Francisella oxidative burst-inhibiting acid phosphatase AcpA

    John S Gunn

    2016-04-01

    Full Text Available Francisella tularensis is a Tier 1 bioterror threat and the intracellular pathogen responsible for tularemia in humans and animals. Upon entry into the host, Francisella uses multiple mechanisms to evade killing. Our previous studies have shown that after entering its primary cellular host, the macrophage, Francisella immediately suppresses the oxidative burst by secreting a series of acid phosphatases including AcpA-B-C and HapA, thereby evading the innate immune response of the macrophage and enhancing survival and further infection. However, the mechanism of acid phosphatase secretion by Francisella is still unknown. In this study, we screened for genes required for AcpA secretion in Francisella. We initially demonstrated that the known secretion systems, the putative Francisella-pathogenicity island (FPI-encoded Type VI secretion system and the Type IV pili, do not secrete AcpA. Using random transposon mutagenesis in conjunction with ELISA, Western blotting and acid phosphatase enzymatic assays, a transposon library of 5450 mutants was screened for strains with a minimum 1.5-fold decrease in secreted (culture supernatant AcpA, but no defect in cytosolic AcpA. Three mutants with decreased supernatant AcpA were identified. The transposon insertion sites of these mutants were revealed by direct genomic sequencing or inverse-PCR and sequencing. One of these mutants has a severe defect in AcpA secretion (at least 85% decrease and is a predicted hypothetical inner membrane protein. Interestingly, this mutant also affected the secretion of the FPI-encoded protein, VgrG. Thus, this screen identified novel protein secretion factors involved in the subversion of host defenses.

  12. Identification of Genes Required for Secretion of the Francisella Oxidative Burst-Inhibiting Acid Phosphatase AcpA.

    Hoang, Ky Van; Chen, Carolyn G; Koopman, Jacob; Moshiri, Jasmine; Adcox, Haley E; Gunn, John S

    2016-01-01

    Francisella tularensis is a Tier 1 bioterror threat and the intracellular pathogen responsible for tularemia in humans and animals. Upon entry into the host, Francisella uses multiple mechanisms to evade killing. Our previous studies have shown that after entering its primary cellular host, the macrophage, Francisella immediately suppresses the oxidative burst by secreting a series of acid phosphatases including AcpA-B-C and HapA, thereby evading the innate immune response of the macrophage and enhancing survival and further infection. However, the mechanism of acid phosphatase secretion by Francisella is still unknown. In this study, we screened for genes required for AcpA secretion in Francisella. We initially demonstrated that the known secretion systems, the putative Francisella-pathogenicity island (FPI)-encoded Type VI secretion system and the Type IV pili, do not secrete AcpA. Using random transposon mutagenesis in conjunction with ELISA, Western blotting and acid phosphatase enzymatic assays, a transposon library of 5450 mutants was screened for strains with a minimum 1.5-fold decrease in secreted (culture supernatant) AcpA, but no defect in cytosolic AcpA. Three mutants with decreased supernatant AcpA were identified. The transposon insertion sites of these mutants were revealed by direct genomic sequencing or inverse-PCR and sequencing. One of these mutants has a severe defect in AcpA secretion (at least 85% decrease) and is a predicted hypothetical inner membrane protein. Interestingly, this mutant also affected the secretion of the FPI-encoded protein, VgrG. Thus, this screen identified novel protein secretion factors involved in the subversion of host defenses. PMID:27199935

  13. Biologically relevant oxidants and terminology, classification and nomenclature of oxidatively generated damage to nucleobases and 2-deoxyribose in nucleic acids

    Cadet, Jean; Loft, Steffen; Olinski, Ryszard;

    2012-01-01

    A broad scientific community is involved in investigations aimed at delineating the mechanisms of formation and cellular processing of oxidatively generated damage to nucleic acids. Perhaps as a consequence of this breadth of research expertise, there are nomenclature problems for several of the...

  14. Natural and pyrogenic humic acids at goethite and natural oxide surfaces interacting with phosphate

    Hiemstra, T.; Mia, S.; Duhaut, P.B.; Molleman, B.

    2013-01-01

    Fulvic and humic acids have a large variability in binding to metal (hydr) oxide surfaces and interact differently with oxyanions, as examined here experimentally. Pyrogenic humic acid has been included in our study since it will be released to the environment in the case of large-scale application

  15. Selective Oxidative Decarboxylation of Amino Acids to Produce Industrially Relevant Nitriles by Vanadium Chloroperoxidase

    But, A.; Notre, le J.E.L.; Scott, E.L.; Wever, R.; Sanders, J.P.M.

    2012-01-01

    Industrial nitriles from biomass: Vanadium-chloroperoxidase is successfully used to transform selectively glutamic acid into 3-cyanopropanoic acid, a key intermediate for the synthesis of bio-succinonitrile and bio-acrylonitrile, by using a catalytic amount of a halide salt. This clean oxidative dec

  16. Oxidative stability of structured lipids produced from sunflower oil and caprylic acid

    Timm Heinrich, Maike; Xu, Xuebing; Nielsen, Nina Skall;

    2003-01-01

    commercial antioxidant blend Grindox 117 (propyl gallate/citric acid/ascorbyl palmitate) or gallic acid to the SL was investigated. The lipid type affected the oxidative stability: SL was less stable than SO and RL. The reduced stability was most likely caused by both the structure of the lipid and...

  17. Effect of insulin-like growth factor-1 and hyaluronic acid in experimentally produced osteochondral defects in rats

    Celil Alemdar

    2016-01-01

    Full Text Available Background: The common purpose of almost all methods used to treat the osteochondral injuries is to produce a normal cartilage matrix. However current methods are not sufficient to provide a normal cartilage matrix. For that reason, researchers have studied to increase the effectiveness of this methods using chondrogenic and chondroprotective molecules in recent experimental studies. Insulin-like growth factor-1 (IGF-1 and hyaluronic acid (HA are two important agents used in this field. This study compared the effects of IGF-1 and HA in an experimental osteochondral defect in rat femora. Materials and Methods: The rats were divided into three groups ( n = 15 per group as follows: The IGF-1 group, HA group, and control group. An osteochondral defect of a diameter of 1.5 mm and a depth of 2 mm was created on the patellar joint side of femoral condyles. The IGF-1 group received an absorbable gelatin sponge soaked with 15 μg/15 μl of IGF-1, and the HA group received an absorbable gelatin sponge soaked with 80 μg HA. The control group received only an absorbable gelatin sponge. Rats were sacrificed at the 6 th week, and the femur condyles were evaluated histologically. Results: According to the total Mankin scale, there was a statistically significant difference between IGF-1 and HA groups and between IGF-1 and control groups. There was also a significant statistical difference between HA and control groups. Conclusion: It was shown histopathologically that IGF-1 is an effective molecule for osteochondral lesions. Although it is weaker than IGF-1, HA also strengthened the repair tissue.

  18. Oxidative stability of milk drinks containing structured lipids produced from sunflower oil and caprylic acid

    Timm Heinrich, Maike; Xu, Xuebing; Nielsen, Nina Skall; Jacobsen, Charlotte

    2003-01-01

    adding potential antioxidants EDTA or gallic acid to the milk drink based on SL was investigated. The lipid type significantly affected the oxidative stability of the milk drinks: Milk drink based on SL oxidized faster than milk drink based on RL or SO. The reduced oxidative stability in the SL milk...... drink could not be ascribed was most likely influenced by the structure of the lipid and to a single factor, differences in the process applied to produce and purify the lipids. EDTA was a strong antioxidant, while gallic acid did not exert a distinct antioxidative effect in the milk drink based on SL....

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

    Fukushima, Arata; Lopaschuk, Gary D

    2016-10-01

    Obesity and diabetes are major public health problems, and are linked to the development of heart failure. Emerging data highlight the importance of alterations in cardiac energy metabolism as a major contributor to cardiac dysfunction related to obesity and diabetes. Increased rates of fatty acid oxidation and decreased rates of glucose utilization are two prominent changes in cardiac energy metabolism that occur in obesity and diabetes. This metabolic profile is probably both a cause and consequence of a prominent cardiac insulin resistance, which is accompanied by a decrease in both cardiac function and efficiency, and by the accumulation of potentially toxic lipid metabolites in the heart that can further exaggerate insulin resistance and cardiac dysfunction. The high cardiac fatty acid oxidation rates seen in obesity and diabetes are attributable to several factors, including: 1) increased fatty acid supply and uptake into the cardiomyocyte, 2) increased transcription of fatty acid metabolic enzymes, 3) decreased allosteric control of mitochondrial fatty acid uptake and fatty acid oxidation, and 4) increased post-translational acetylation control of various fatty acid oxidative enzymes. Emerging evidence suggests that therapeutic approaches aimed at switching the balance of cardiac energy substrate preference from fatty acid oxidation to glucose use can prevent cardiac dysfunction associated with obesity and diabetes. Modulating acetylation control of fatty acid oxidative enzymes is also a potentially attractive strategy, although presently this is limited to precursors of nicotinamide adenine or nonspecific activators of deacetylation such as resveratrol. This review will focus on the metabolic alterations in the heart that occur in obesity and diabetes, as well as on the molecular mechanisms controlling these metabolic changes. This article is part of a Special Issue entitled: Heart Lipid Metabolism edited by G.D. Lopaschuk. PMID:26996746

  20. Ferrous iron oxidation by molecular oxygen under acidic conditions: The effect of citrate, EDTA and fulvic acid

    Jones, Adele M.; Griffin, Philippa J.; Waite, T. David

    2015-07-01

    In this study, the rates of Fe(II) oxidation by molecular oxygen in the presence of citrate, ethylenediaminetetraacetic acid (EDTA) and Suwannee River fulvic acid (SRFA) were determined over the pH range 4.0-5.5 and, for all of the ligands investigated, found to be substantially faster than oxidation rates in the absence of any ligand. EDTA was found to be particularly effective in enhancing the rate of Fe(II) oxidation when sufficient EDTA was available to complex all Fe(II) present in solution, with a kinetic model of the process found to adequately describe all results obtained. When Fe(II) was only partially complexed by EDTA, reactions with reactive oxygen species (ROS) and heterogeneous Fe(II) oxidation were found to contribute significantly to the removal rate of iron from solution at different stages of oxidation. This was possible due to the rapid rate at which EDTA enhanced Fe(II) oxidation and formed ROS and Fe(III). The rapid rate of Fe(III) generation facilitated the formation of free ferric ion activities in excess of those required for ferric oxyhydroxide precipitation following Fe(III)-EDTA dissociation. In comparison, the rate of Fe(II) oxidation was slower in the presence of citrate, and therefore the concentrations of free Fe(III) able to form in the initial stages of Fe(II) oxidation were much lower than those formed in the presence of EDTA, despite the resultant Fe(III)-citrate complex being less stable than that of Fe(III)-EDTA. The slower rate of citrate enhanced oxidation also resulted in slower rates of ROS generation, and, as such, oxidation of the remaining inorganic Fe(II) species by ROS was negligible. Overall, this study demonstrates that organic ligands may substantially enhance the rate of Fe(II) oxidation. Even under circumstances where the ligand is not present at sufficient concentrations to complex all of the Fe(II) in solution, ensuing oxidative processes may sustain an enhanced rate of Fe(II) oxidation relative to that of

  1. COMPLEX OXIDE CATALYSTS OF ACRYLIC ACID OBTAINING BY ALDOL CONDENSATION METHOD

    Nebesnyi, R.

    2015-01-01

    The present work is dedicated to solving the problem of diversification of the raw materials base for acrylate monomers obtaining,  first of all acrylic acid. Acrylic acid and its derivatives are bulk products of organic synthesis with a wide range of applications. The main industrial method of acrylic acid production is  propylene oxidation. But this method has instable economic indicators as propylene is petroleum origin raw material.It is possible to expand the resource base of acrylic aci...

  2. Kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium

    The kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium has been carried out. The reaction is first order with respect to vanadium(V) and the substrate and is acid catalysed. Hammett acidity function (H0) and Bunnett hypothesis have been applied. The formation of free radicals during the course of the reaction has been indicated. A probable reaction mechansim is proposed. (Author)

  3. Oxidized Fatty Acid Analysis by Charge Switch Derivatization, Selected Reaction Monitoring and Accurate Mass Quantification

    Liu, Xinping; Moon, Sung Ho; Mancuso, David J.; Jenkins, Christopher M.; Guan, Shaoping; Sims, Harold F.; Gross, Richard W.

    2013-01-01

    A highly sensitive, specific and robust method for the analysis of oxidized metabolites of linoleic, acid (LA), arachidonic acid (AA) and docosahexaenoic acid (DHA) was developed using charge-switch derivatization, LC-ESI MS/MS with selected reaction monitoring (SRM) and quantitation by high mass accuracy analysis of product ions thereby minimizing interferences from contaminating ions. Charge-switch derivatization of LA, AA and DHA metabolites with N-(4-aminomethylphenyl)-pyridinium resulted...

  4. Electrochemical Oxidation of Methanol and Formic Acid in Fuel Cell Processes

    Seland, Frode

    2005-01-01

    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 ...

  5. Epididymis response partly compensates for spermatozoa oxidative defects in snGPx4 and GPx5 double mutant mice.

    Anaïs Noblanc

    Full Text Available We report here that spermatozoa of mice lacking both the sperm nucleus glutathione peroxidase 4 (snGPx4 and the epididymal glutathione peroxidase 5 (GPx5 activities display sperm nucleus structural abnormalities including delayed and defective nuclear compaction, nuclear instability and DNA damage. We show that to counteract the GPx activity losses, the epididymis of the double KO animals mounted an antioxydant response resulting in a strong increase in the global H(2O(2-scavenger activity especially in the cauda epididymis. Quantitative RT-PCR data show that together with the up-regulation of epididymal scavengers (of the thioredoxin/peroxiredoxin system as well as glutathione-S-transferases the epididymis of double mutant animals increased the expression of several disulfide isomerases in an attempt to recover normal disulfide-bridging activity. Despite these compensatory mechanisms cauda-stored spermatozoa of double mutant animals show high levels of DNA oxidation, increased fragmentation and greater susceptibility to nuclear decondensation. Nevertheless, the enzymatic epididymal salvage response is sufficient to maintain full fertility of double KO males whatever their age, crossed with young WT female mice.

  6. Effect of Oxygen Defects on the Catalytic Performance of VOx/CeO2 Catalysts for Oxidative Dehydrogenation of Methanol

    Li, Yan; Wei, Zhehao; Gao, Feng; Kovarik, Libor; Baylon, Rebecca A.; Peden, Charles HF; Wang, Yong

    2015-05-01

    In this work, CeO2 nanocubes with controlled particle size and dominating (100) facets are synthesized as supports for VOx catalysts. Combined TEM, SEM, XRD, and Raman study reveals that the oxygen vacancy density of CeO2 supports can be tuned by tailoring the particle sizes without altering the dominating facets, where smaller particle sizes result in larger oxygen vacancy densities. At the same vanadium coverage, the VOx catalysts supported on small-sized CeO2 supports with higher oxygen defect densities exhibit promoted redox property and lower activation energy for methoxyl group decomposition, as evidenced by H2-TPR and methanol TPD study. These results further confirm that the presence of oxygen vacancies plays an important role in promoting the activity of VOx species in methanol oxidation. We gratefully acknowledge financial support from the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Part of this work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle.

  7. The role of neutral and ionized oxygen defects in the emission of tin oxide nanocrystals for near white light application

    Kumar, Vinod; Swart, H. C.; Gohain, Mukut; Bezuidenhoudt, Barend C. B.; Janse van Vuuren, A.; Lee, M.; Ntwaeaborwa, O. M.

    2015-07-01

    Tin oxide (SnO2) nanocrystals (NCs) based phosphor was synthesized by a green chemistry microwave-assisted hydrothermal method at different reactor pressures. The x-ray diffraction analysis showed that a single rutile SnO2 phase with a tetragonal lattice structure was formed. The photoluminescence emission was measured for He-Cd laser excitation at 325 nm and it showed a broad band emission from 400 to 800 nm for all the synthesized reactor pressures. The broad emission spectra were due to the creation of various oxygen and tin defects as confirmed by x-ray photoelectron spectroscopy data. The origin of the emission in the SnO2 NCs is discussed with the help of an energy band diagram. Analysis suggests that the visible emission of SnO2 NCs is due to a transition of an electron from a level close to the conduction band edge to a deeply trapped hole in the SnO2 NCs. The NCs were found to be suitable for warm near white light emission device applications.

  8. Oxidation of saturated hydrocarbons with peroxyacetic acid catalyzed by vanadium complexes

    Gonzalez Cuervo, Laura; Kozlov, Yuriy N.; Süss-Fink, Georg; Shul’pin, Georgiy B.

    2009-01-01

    Peroxyacetic acid (PAA) oxidizes alkanes in acetonitrile or acetic acid at 60 °C if a soluble vanadium(V) salt, n-Bu4NVO3 (1), is used as a catalyst. Corresponding ketones, alcohols and alkyl hydroperoxides are the main products. Methane, ethane, propane, cyclohexane, and other higher alkanes were substrates in the oxidations. The proposed mechanism involves the formation of a complex between (1) and PAA with equilibrium constants 3.3 and 6.8 dm3 mol−1 for acetonitrile and acetic acid as solv...

  9. Oxidation of aromatic alcohols on zeolite-encapsulated copper amino acid complexes

    Ernst, S.; Teixeira Florencio, J.M. [Kaiserslautern Univ. (Germany). Dept. of Chemistry, Chemical Technology

    1998-12-31

    Copper complexes of the amino acids histidine, arginine and lysine have been introduced into the supercages of zeolite Y and, for the first time, into the large intracrystalline cavities of zeolites EMT and MCM-22. The resulting host/guest compounds are characterized by X-ray powder diffraction, UV/VIS-spectroscopy in the diffuse reflectance mode and by catalytic tests in the liquid-phase oxidation of aromatic alcohols (viz. benzyl alcohol, 2- and 3-methylbenzyl alcohol and 2,5-dimethylbenzyl alcohol) with tertiary-butylhydroperoxide as oxidant. It was observed that intracrystalline copper-amino acid complexes possess remarkable catalytic activity, yielding the corresponding aromatic aldehydes and acids. (orig.)

  10. Novel Approach: Tungsten Oxide Nanoparticle as a Catalyst for Malonic Acid Ester Synthesis via Ozonolysis

    Bilal A. Wasmi

    2014-01-01

    Full Text Available Malonic acid ester was synthesized via the one-step ozonolysis of palm olein. Malonic acid ester was spectroscopically characterized using gas chromatography mass spectroscopy (GC-MS. Tungsten oxide nanoparticles were used as the catalyst, which was characterized via X-ray powder diffraction (XRD and field emission scanning electron microscopy (FE-SEM. Tungsten oxide provided several advantages as a catalyst for the esterification malonic acid such as simple operation for a precise ozonation method, an excellent yield of approximately 10%, short reaction times of 2 h, and reusability due to its recyclability.

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

    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

  12. Oxidation of microquantities of transplutonium elements to tetravalent state in mineral acid solutions and their stability

    Kinetics of americium(3) microquantity oxidation and stability of forming americium(4), as well as possibility of curium and californium oxidation to tetravalent state in solutions of sulfuric and nitric acids depending on the concentration of mineral acid, potassium tungstophosphate and ammonium persulfate are studied by the extraction method. It is shown that curium(3) and californium(3) in solutions of 0.05-2.5 mol/l H2SO4 and HNO3 containing 10-3 mol/l potassium tungstophosphate is not practically oxidized by the mixture of silver nitrate and ammonium persulfate. Americium(3) is oxidized to the utmost to Am(4) for 2-3 min at room temperature, but stability of Am(4) depends on the concentration of sulfuric acid and potassium tungstophosphate

  13. Electro-oxidation of ascorbic acid catalyzed on cobalt hydroxide-modified glassy carbon electrode

    GHASEM KARIM-NEZHAD

    2009-05-01

    Full Text Available The electrochemical behavior of ascorbic acid on a cobalt hydroxide modified glassy carbon (CHM–GC electrode in alkaline solution was investigated. The process of the involved oxidation and its kinetics were established using the cyclic voltammetry, chronoamperometry techniques, as well as by steady state polarization measurements. The results revealed that cobalt hydroxide promotes the rate of oxidation by increasing the peak current; hence ascorbic acid is oxidized at lower potentials, which is thermodynamically more favorable. The cyclic voltammograms and chronoamperometry indicate a catalytic EC mechanism is operative with the electrogeneration of Co(IV as the electrochemical process. Also, the process is diffusion-controlled and the current–time responses follow Cottrellian behavior. This result was confirmed by steady state measurements. The rate constants of the catalytic oxidation of ascorbic acid and the electron-transfer coefficient are reported.

  14. Deranged Bioenergetics and Defective Redox Capacity in T Lymphocytes and Neutrophils Are Related to Cellular Dysfunction and Increased Oxidative Stress in Patients with Active Systemic Lupus Erythematosus

    Ko-Jen Li

    2012-01-01

    Full Text Available Urinary excretion of N-benzoyl-glycyl-Nε-(hexanonyllysine, a biomarker of oxidative stress, was higher in 26 patients with active systemic lupus erythematosus (SLE than in 11 non-SLE patients with connective tissue diseases and in 14 healthy volunteers. We hypothesized that increased oxidative stress in active SLE might be attributable to deranged bioenergetics, defective reduction-oxidation (redox capacity, or other factors. We demonstrated that, compared to normal cells, T lymphocytes (T and polymorphonuclear neutrophils (PMN of active SLE showed defective expression of facilitative glucose transporters GLUT-3 and GLUT-6, which led to increased intracellular basal lactate and decreased ATP production. In addition, the redox capacity, including intracellular GSH levels and the enzyme activity of glutathione peroxidase (GSH-Px and γ-glutamyl-transpeptidase (GGT, was decreased in SLE-T. Compared to normal cells, SLE-PMN showed decreased intracellular GSH levels, and GGT enzyme activity was found in SLE-PMN and enhanced expression of CD53, a coprecipitating molecule for GGT. We conclude that deranged cellular bioenergetics and defective redox capacity in T and PMN are responsible for cellular immune dysfunction and are related to increased oxidative stress in active SLE patients.

  15. An environment-friendly preparation of reduced graphene oxide nanosheets via amino acid

    Chemically modified graphene has been studied in many applications due to its excellent electrical, mechanical, and thermal properties. Among the chemically modified graphenes, reduced graphene oxide is the most important for its structure and properties, which are similar to pristine graphene. Here, we introduce an environment-friendly approach for preparation of reduced graphene oxide nanosheets through the reduction of graphene oxide that employs L-cysteine as the reductant under mild reaction conditions. The conductivity of the reduced graphene oxide nanosheets produced in this way increases by about 106 times in comparison to that of graphene oxide. This is the first report about using amino acids as a reductant for the preparation of reduced graphene oxide nanosheets, and this procedure offers an alternative route to large-scale production of reduced graphene oxide nanosheets for applications that require such material.

  16. Graphitic carbon nitride nanosheets doped graphene oxide for electrochemical simultaneous determination of ascorbic acid, dopamine and uric acid

    Graphical abstract: Schematic drawing of electrochemical oxidize AA, DA and UA on graphitic carbon nitride nanosheets-graphene oxide composite modified electrode. - Highlights: • Synthesize g-C3N4, GO and CNNS-GO composite. • CNNS-GO composite was the first time for simultaneous determination of AA, DA and UA. • CNNS-GO/GCE displays fantastic selectivity and sensitivity for AA, DA and UA. • CNNS-GO/GCE was applied to detect real sample with satisfactory results. - Abstract: Graphitic carbon nitride nanosheets with a graphite-like structure have strong covalent bonds between carbon and nitride atoms, and nitrogen atoms in the carbon architecture can accelerate the electron transfer and enhance electrical properties effectually. The graphitic carbon nitride nanosheets-graphene oxide composite was synthesized. And the electrochemical performance of the composite was investigated by cyclic voltammetry and differential pulse voltammetry ulteriorly. Due to the synergistic effects of layer-by-layer structures by π-π stacking or charge-transfer interactions, graphitic carbon nitride nanosheets-graphene oxide composite can improved conductivity, electro-catalytic and selective oxidation performance. The proposed graphitic carbon nitride nanosheets-graphene oxide composite modified electrode was employed for simultaneous determination of ascorbic acid, dopamine and uric acid in their mixture solution, it exhibited distinguished sensitivity, wide linear range and low detection limit. Moreover, the modified electrode was applied to detect urine and dopamine injection sample, and then the samples were spiked with certain concentration of three substances with satisfactory recovery results

  17. 7-deoxyloganetic acid synthase catalyzes a key 3 step oxidation to form 7-deoxyloganetic acid in Catharanthus roseus iridoid biosynthesis.

    Salim, Vonny; Wiens, Brent; Masada-Atsumi, Sayaka; Yu, Fang; De Luca, Vincenzo

    2014-05-01

    Iridoids are key intermediates required for the biosynthesis of monoterpenoid indole alkaloids (MIAs), as well as quinoline alkaloids. Although most iridoid biosynthetic genes have been identified, one remaining three step oxidation required to form the carboxyl group of 7-deoxyloganetic acid has yet to be characterized. Here, it is reported that virus-induced gene silencing of 7-deoxyloganetic acid synthase (7DLS, CYP76A26) in Catharanthus roseus greatly decreased levels of secologanin and the major MIAs, catharanthine and vindoline in silenced leaves. Functional expression of this gene in Saccharomyces cerevisiae confirmed its function as an authentic 7DLS that catalyzes the 3 step oxidation of iridodial-nepetalactol to form 7-deoxyloganetic acid. The identification of CYP76A26 removes a key bottleneck for expression of iridoid and related MIA pathways in various biological backgrounds. PMID:24594312

  18. Growth behavior of anodic oxide formed by aluminum anodizing in glutaric and its derivative acid electrolytes

    Nakajima, Daiki; Kikuchi, Tatsuya; Natsui, Shungo; Suzuki, Ryosuke O.

    2014-12-01

    The growth behavior of anodic oxide films formed via anodizing in glutaric and its derivative acid solutions was investigated based on the acid dissociation constants of electrolytes. High-purity aluminum foils were anodized in glutaric, ketoglutaric, and acetonedicarboxylic acid solutions under various electrochemical conditions. A thin barrier anodic oxide film grew uniformly on the aluminum substrate by glutaric acid anodizing, and further anodizing caused the film to breakdown due to a high electric field. In contrast, an anodic porous alumina film with a submicrometer-scale cell diameter was successfully formed by ketoglutaric acid anodizing at 293 K. However, the increase and decrease in the temperature of the ketoglutaric acid resulted in non-uniform oxide growth and localized pitting corrosion of the aluminum substrate. An anodic porous alumina film could also be fabricated by acetonedicarboxylic acid anodizing due to the relatively low dissociation constants associated with the acid. Acid dissociation constants are an important factor for the fabrication of anodic porous alumina films.

  19. Dietary ellagic acid attenuates oxidized LDL uptake and stimulates cholesterol efflux in murine macrophages.

    Park, Sin-Hye; Kim, Jung-Lye; Lee, Eun-Sook; Han, Seon-Young; Gong, Ju-Hyun; Kang, Min-Kyung; Kang, Young-Hee

    2011-11-01

    Foam cell formation is the hallmark of early atherosclerosis. Lipid uptake by scavenger receptors (SR) in macrophages initiates chronic proinflammatory cascades linked to atherosclerosis. It has been reported that the upregulation of cholesterol efflux may be protective in the development of atherosclerosis. Ellagic acid, a polyphenolic compound mostly found in berries, walnuts, and pomegranates, possesses antioxidative, growth-inhibiting and apoptosis-promoting activities in cancer cells. However, the antiatherogenic actions of ellagic acid are not well defined. The current study elucidated oxidized LDL handling of ellagic acid in J774A1 murine macrophages. Noncytotoxic ellagic acid suppressed SR-B1 induction and foam cell formation within 6 h after the stimulation of macrophages with oxidized LDL, confirmed by Oil red O staining of macrophages. Ellagic acid at ≤5 μmol/L upregulated PPARγ and ATP binding cassette transporter-1 in lipid-laden macrophages, all responsible for cholesterol efflux. In addition, 5 μmol/L ellagic acid accelerated expression and transcription of the nuclear receptor of liver X receptor-α highly implicated in the PPAR signaling. Furthermore, ellagic acid promoted cholesterol efflux in oxidized LDL-induced foam cells. These results provide new information that ellagic acid downregulated macrophage lipid uptake to block foam cell formation of macrophages and boosted cholesterol efflux in lipid-laden foam cells. Therefore, dietary and pharmacological interventions with berries rich in ellagic acid may be promising treatment strategies to interrupt the development of atherosclerosis. PMID:21940512

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

    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.

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

    Highlights: ► Photocatalyst powder was prepared by acid leaching of TiO2/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 (TiO2)/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 TiO2/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 TiO2 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 TiO2 powder, Degussa P25. The highest rate was obtained in the TiO2/HAp composite treated with the dilute (0.25 mol/l) acid in spite of its low content of TiO2 photocatalyst. This enhanced photocatalytic activity was attributed to the result that the deactivation with repeated injections of ethanol gas was suppressed in the TiO2/HAp composites compared with the TiO2 powders

  2. Kinetics and mechanism of N-chlorosaccharin oxidation of malic acid

    Sanjay Kumar Singh

    2010-12-01

    Full Text Available Kinetic study of N-chlorosaccharin (NCSA oxidation of malic acid (MA in aqueous acetic acid medium in presence of perchloric acid has been investigated. The reactions exhibit first-order dependency in oxidant and HClO4 while order varies from one to zero in substrate. The reactions are acid catalyzed and retarded by the addition of saccharin, a byproduct of reaction. The rate of oxidation decreases with decrease in dielectric constant of the medium. The effect of temperature on the reaction has been investigated in the temperature range 313-333 K. The stochiometric studies revealed 1:1 mole ratio. Various thermodynamic parameters have been computed and a possible operative mechanism is proposed.

  3. Fatty Acid Oxidation and Cardiovascular Risk during Menopause: A Mitochondrial Connection?

    Paulo J. Oliveira

    2012-01-01

    Full Text Available Menopause is a consequence of the normal aging process in women. This fact implies that the physiological and biochemical alterations resulting from menopause often blur with those from the aging process. It is thought that menopause in women presents a higher risk for cardiovascular disease although the precise mechanism is still under discussion. The postmenopause lipid profile is clearly altered, which can present a risk factor for cardiovascular disease. Due to the role of mitochondria in fatty acid oxidation, alterations of the lipid profile in the menopausal women will also influence mitochondrial fatty acid oxidation fluxes in several organs. In this paper, we propose that alterations of mitochondrial bioenergetics in the heart, consequence from normal aging and/or from the menopausal process, result in decreased fatty acid oxidation and accumulation of fatty acid intermediates in the cardiomyocyte cytosol, resulting in lipotoxicity and increasing the cardiovascular risk in the menopausal women.

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

    Madhu Khurana; Pradeep K Sharma; Kalyan K Banerji

    2000-04-01

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

  5. Critical evaluation of pressurized microwave-assisted digestion efficiency using nitric acid oxidizing systems (M7)

    Full text: The possibilities of enhancement of a medium-pressure microwave-assisted digestion system for sample preparation in trace element analysis of biological material was investigated. Based on optimal digestion conditions for oxidizing systems with nitric acid, different digestion procedures were examined to minimize residual carbon. The substitution of nitric acid and the addition of hydrogen peroxide and ozone to nitric acid was evaluated. The residual carbon content of the digestate was determined coulometrically. Addition of hydrogen peroxide during organic oxidation reactions does not lower the resolved carbon in the solution. Ozone was tested as an additional, potentially non-contaminating, digestion/oxidation system to the nitric acid used in the sample preparation method. (author)

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

    Sun A

    2015-04-01

    Full Text Available 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 myopathy often resulting in rhabdomyolysis in adolescents and adults. Treatments for these long-chain fatty acid oxidation disorders have typically focused upon avoidance of fasting with dietary fat restriction and medium-chain triglyceride supplementation. These treatments have resulted in only a partial response with improvements in hypoglycemia, reduction in frequency of rhabdomyolysis, and improvement in cardiomyopathy with early therapy, but significant risk remains. Recent advances in therapies for long-chain fatty acid oxidation disorders are reviewed in this article. These include sodium D,L-3-hydroxybutyrate, triheptanoin, gene therapy, and bezafibrates. Sodium D,L-3-hydroxybutyrate has shown clinical effect, with improvements in muscle tone, neurological abnormalities, and some cases of cardiomyopathy and leukodystrophy. Triheptanoin has been used as an alternative medium-chain triglyceride in a number of fatty acid oxidation disorders and has shown promising findings in the treatment of cardiomyopathy and hypoglycemia. However, it does not significantly reduce episodes of rhabdomyolysis. Gene therapy has been shown to improve acylcarnitine levels in very-long-chain acyl-coenzyme A dehydrogenase deficiency mouse models, with preservation of glucose levels. Bezafibrates have shown improvements in acylcarnitine concentrations in fibroblast studies, but clinical observations have not demonstrated consistent effects. Together, these treatments have shown some

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

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

    2015-04-18

    Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent. PMID:25773363

  8. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    Schobesberger, Siegfried; Junninen, Heikki; 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 molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions. PMID:24101502

  9. Empirical Modeling of Iron Oxide Dissolution in Sulphuric and Hydrochloric Acid

    Hemmelmann, Jan C.; Xu, Hao; Krumm, Wolfgang

    2013-10-01

    A new approach is presented to an empirical modeling of chemical pickling processes, based on the activation energy of oxide dissolution in hydrochloric acid (HCl) and sulfuric acid (H2SO4). The model allows us to calculate pickling times as a function of definite parameters. The main oxide layers on hot-rolled materials are magnetite (Fe3O4), hematite (Fe2O3), and wustite (FeO). On the laboratory scale, the activation energy of each oxide has been determined. FeO is a metastable oxide and has been produced based on magnetite powder in a H2/H2O atmosphere. The oxide powders used for the experimental procedure have been analyzed by X-ray powder diffraction to insure the proper stoichiometry and composition. The model allows us to calculate the time of oxide dissolution based on the parameters temperature, acid concentration, and the composition of the oxide layer. Calculated values are verified by surface potential measurement on industrial oxide layers. The hot-rolled material used for verification is low carbon steel. A comparison between calculated pickling times and experimental data will be presented.

  10. Electrochemically oxidized carbon anode in direct L-ascorbic acid fuel cells

    The activity of electrochemically oxidized carbon electrode was investigated in the operation of a direct L-ascorbic acid fuel cell anode. The surface oxygen species placed on electrochemically oxidized carbon electrode were analyzed by X-ray photoelectron spectroscopy and cyclic voltammetry. The electrochemical oxidation process of carbon electrode can facilitate the pore-filling process (i.e., wetting) of the electrolyte into the microstructure of the carbon electrode by increasing the number of more polar functional groups on the electrode surface. The electrochemically oxidized carbon electrode exhibited significantly enhanced electro-catalytic oxidation activity of L-ascorbic acid compared to an unmodified carbon electrode. Moreover, the simplified electrode structure using carbon paper without an additional powder-based precious catalyst layer is very favorable in creating percolation network and generates power density of 18 mW/cm2 at 60 deg. C

  11. Solid-State 17O NMR Study of Benzoic Acid Adsorption On Metal Oxide Surfaces

    Solid-state 17O NMR spectra of 17O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry-mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the 17O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. 27Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

  12. Neuroprotective Effects of Alpha Lipoic Acid on Haloperidol-Induced Oxidative Stress in the Rat Brain

    Perera Joachim

    2011-03-01

    Full Text Available Abstract Haloperidol is an antipsychotic drug that exerts its' antipsychotic effects by inhibiting dopaminergic neurons. Although the exact pathophysiology of haloperidol extrapyramidal symptoms are not known, the role of reactive oxygen species in inducing oxidative stress has been proposed as one of the mechanisms of prolonged haloperidol-induced neurotoxicity. In the present study, we evaluate the protective effect of alpha lipoic acid against haloperidol-induced oxidative stress in the rat brain. Sprague Dawley rats were divided into control, alpha lipoic acid alone (100 mg/kg p.o for 21 days, haloperidol alone (2 mg/kg i.p for 21 days, and haloperidol with alpha lipoic acid groups (for 21 days. Haloperidol treatment significantly decreased levels of the brain antioxidant enzymes super oxide dismutase and glutathione peroxidase and concurrent treatment with alpha lipoic acid significantly reversed the oxidative effects of haloperidol. Histopathological changes revealed significant haloperidol-induced damage in the cerebral cortex, internal capsule, and substantia nigra. Alpha lipoic acid significantly reduced this damage and there were very little neuronal atrophy. Areas of angiogenesis were also seen in the alpha lipoic acid-treated group. In conclusion, the study proves that alpha lipoic acid treatment significantly reduces haloperidol-induced neuronal damage.

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

    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

  14. Nitric-phosphoric acid oxidation of solid and liquid organic materials

    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

  15. Uric acid correlates to oxidation and inflammation in opposite directions in women

    Wu, Sheng Hui; Shu, Xiao Ou; Milne, Ginger; Xiang, Yong-Bing; Zhang, Xianglan; Cai, Qiuyin; Fazio, Sergio; Linton, MacRae F; Chen, Honglei; Purdue, Mark; Rothman, Nathaniel; Gao, Yu-Tang; Zheng, Wei; Yang, Gong

    2016-01-01

    Objective To evaluate the association of uric acid (UA) levels with a panel of markers of oxidative stress and inflammation. Methods Plasma UA levels, along with a panel of oxidative stress and inflammatory markers, were measured in 755 Chinese women. Results Plasma UA levels were inversely associated with urinary levels of the oxidative stress marker F2-isoprostanes and positively correlated to levels of inflammatory markers such as C-reactive protein and some proinflammatory cytokines (tumor necrosis factor-α and interleukin-6) in blood as well as prostaglandin E2 metabolites in urine. Conclusions Plasma UA levels correlate to oxidation and inflammation biomarkers in opposite directions in women. PMID:26301880

  16. The graphene nanopowder for electro-catalytic oxidation of dopamine and uric acid in the presence of ascorbic acid

    Yuan; Bu; Wenle; Dai; Nan; Li; Xinran; Zhao; Xia; Zuo

    2013-01-01

    The graphene nanopowder for electro-catalytic oxidation of dopamine and uric acid in the presence of ascorbic acid has been investigated by cyclic voltammetry,linear polarization and chronoamperometry.The graphene nanopowder modified electrode was prepared using the drop coating method,which displayed excellent electrocatalytic activity towards the oxidation of dopamine and uric acid compared with the bare glassy carbon electrode in phosphate buffer solution at pH=7.0.Linear responses for dopamine and uric acid were obtained in the ranges of3.3μmol/L to 249.1μmol/L and 6.7μmol/L to 386.3μmol/L with detection limits of 1.5μmol/L and 2.7μmol/L(S/N=3),respectively.The response time was less than 2 s in case of dopamine and 3 s in case of uric acid,respectively.The results demonstrated that the graphene nanopowder had potential for detecting dopamine and uric acid.

  17. Possible role of mtDNA depletion and respiratory chain defects in aristolochic acid I-induced acute nephrotoxicity

    Jiang, Zhenzhou, E-mail: jiangcpu@yahoo.com.cn; Bao, Qingli, E-mail: bao_ql@126.com; Sun, Lixin, E-mail: slxcpu@126.com; Huang, Xin, E-mail: huangxinhx66@sohu.com; Wang, Tao, E-mail: wangtao1331@126.com; Zhang, Shuang, E-mail: cat921@sina.com; Li, Han, E-mail: hapo1101@163.com; Zhang, Luyong, E-mail: lyzhang@cpu.edu.cn

    2013-01-15

    This report describes an investigation of the pathological mechanism of acute renal failure caused by toxic tubular necrosis after treatment with aristolochic acid I (AAI) in Sprague–Dawley (SD) rats. The rats were gavaged with AAI at 0, 5, 20, or 80 mg/kg/day for 7 days. The pathologic examination of the kidneys showed severe acute tubular degenerative changes primarily affecting the proximal tubules. Supporting these results, we detected significantly increased concentrations of blood urea nitrogen (BUN) and creatinine (Cr) in the rats treated with AAI, indicating damage to the kidneys. Ultrastructural examination showed that proximal tubular mitochondria were extremely enlarged and dysmorphic with loss and disorientation of their cristae. Mitochondrial function analysis revealed that the two indicators for mitochondrial energy metabolism, the respiratory control ratio (RCR) and ATP content, were reduced in a dose-dependent manner after AAI treatment. The RCR in the presence of substrates for complex I was reduced more significantly than in the presence of substrates for complex II. In additional experiments, the activity of respiratory complex I, which is partly encoded by mitochondrial DNA (mtDNA), was more significantly impaired than that of respiratory complex II, which is completely encoded by nuclear DNA (nDNA). A real-time PCR assay revealed a marked reduction of mtDNA in the kidneys treated with AAI. Taken together, these results suggested that mtDNA depletion and respiratory chain defects play critical roles in the pathogenesis of kidney injury induced by AAI, and that the same processes might contribute to aristolochic acid-induced nephrotoxicity in humans. -- Highlights: ► AAI-induced acute renal failure in rats and the proximal tubule was the target. ► Tubular mitochondria were morphologically aberrant in ultrastructural examination. ► AAI impair mitochondrial bioenergetic function and mtDNA replication.

  18. Possible role of mtDNA depletion and respiratory chain defects in aristolochic acid I-induced acute nephrotoxicity

    This report describes an investigation of the pathological mechanism of acute renal failure caused by toxic tubular necrosis after treatment with aristolochic acid I (AAI) in Sprague–Dawley (SD) rats. The rats were gavaged with AAI at 0, 5, 20, or 80 mg/kg/day for 7 days. The pathologic examination of the kidneys showed severe acute tubular degenerative changes primarily affecting the proximal tubules. Supporting these results, we detected significantly increased concentrations of blood urea nitrogen (BUN) and creatinine (Cr) in the rats treated with AAI, indicating damage to the kidneys. Ultrastructural examination showed that proximal tubular mitochondria were extremely enlarged and dysmorphic with loss and disorientation of their cristae. Mitochondrial function analysis revealed that the two indicators for mitochondrial energy metabolism, the respiratory control ratio (RCR) and ATP content, were reduced in a dose-dependent manner after AAI treatment. The RCR in the presence of substrates for complex I was reduced more significantly than in the presence of substrates for complex II. In additional experiments, the activity of respiratory complex I, which is partly encoded by mitochondrial DNA (mtDNA), was more significantly impaired than that of respiratory complex II, which is completely encoded by nuclear DNA (nDNA). A real-time PCR assay revealed a marked reduction of mtDNA in the kidneys treated with AAI. Taken together, these results suggested that mtDNA depletion and respiratory chain defects play critical roles in the pathogenesis of kidney injury induced by AAI, and that the same processes might contribute to aristolochic acid-induced nephrotoxicity in humans. -- Highlights: ► AAI-induced acute renal failure in rats and the proximal tubule was the target. ► Tubular mitochondria were morphologically aberrant in ultrastructural examination. ► AAI impair mitochondrial bioenergetic function and mtDNA replication.

  19. Characteristics of Oxidative Storage Stability of Canola Fatty Acid Methyl Ester Stabilised with Antioxidants

    Tirto Prakoso

    2012-11-01

    Full Text Available The storage effects on the oxidation characteristics of fatty acid methyl ester of canola oil (CME were investigated in this study. CME stabilised with two antioxidants, i.e. 2,6-di-tert-bytyl-p-cresol (BHT and 6,6-di-tert-butyl-2, 2’-methylendi-p-cresol (BPH, was stored at 20, 40 and 60°C. The oxidation stability data were measured by the Rancimat test method and it was found that both BHT and BPH addition increased the oxidation resistance of the CME. The results showed that when BPH or BHT was added at a concentration of 100 ppm, the oxidation induction period of the neat CME samples increased from 5.53 h to 6.93 h and 6.14 h, respectively. Comparing both antioxidants, BPH proved to be more effective in increasing the oxidation resistance when both antioxidants were added at the same concentration. Furthermore, the oxidation induction time decreased linearly with the storage time. It was shown that the oxidation occurred rapidly in the first 8 weeks of storage. Later, a kinetic study was undertaken and first-order kinetics were applied to explain the oxidation characteristics of the CME added with antioxidants. This kinetic study focused on exploiting the activation energy values obtained from the Arrhenius equations. Also, the oxidation effects on other quality parameters, including acid value, peroxide value, kinematic viscosity, and water content, were examined.

  20. The Role of Chronic Exposure to Amoxicillin/Clavulanic Acid on the Developmental Enamel Defects in Mice.

    Mihalaş, Eugeniu; Matricala, Lavinia; Chelmuş, Alina; Gheţu, Nicolae; Petcu, Ana; Paşca, Sorin

    2016-01-01

    Amoxicillin used in early childhood may be associated with enamel hypomineralization. Our aim was to assess disturbances of amelogenesis in mice lower incisors induced by chronic administration of amoxicillin/clavulanic acid (AMC). Twenty-eight C57BL/6 male mice, of similar age, randomly divided into a control and 3 treatment groups (n = 7) received subcutaneous injection, once per day, for 60 days: 50, 100, and 150 mg/kg BW of AMC. Scanning electron microscopy/energy dispersive X-ray spectroscopy analysis in AMC treatment groups showed higher content in F and a decrease in P and Ca. Morphology changes ranged from scratched patterns, and small isolated pits-like enamel loss, to generalized demineralized enamel surface, giving a rough, foamy, scaly, or even cracked eggshell appearance to the affected areas. Histological analysis showed disturbances of maturation ameloblasts, which were less organized, with increased amounts of clear vacuoles in the cytoplasm and slightly more elongated and less condensed nucleus. Additionally, they were often detached from the enamel matrix. Transitional ameloblasts formed underlying the cysts of varied sizes. In conclusion, AMC dose-dependently affect ameloblast functions especially in the maturation phase, causing hypomineralized enamel formation with quantitative and/or qualitative defects. PMID:26534941

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

    Jacob P. Beam

    2016-02-01

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

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

    Beam, Jacob P; Bernstein, Hans C; Jay, Zackary J; Kozubal, Mark A; Jennings, Ryan deM; Tringe, Susannah G; Inskeep, William P

    2016-01-01

    Biomineralized ferric oxide microbial mats are ubiquitous features on Earth, are common in hot springs of Yellowstone National Park (YNP, WY, USA), and form due to direct interaction between microbial and physicochemical processes. The overall goal of this study was to determine the contribution of different community members to the assembly and succession of acidic high-temperature Fe(III)-oxide mat ecosystems. Spatial and temporal changes in Fe(III)-oxide accretion and the abundance of relevant community members were monitored over 70 days using sterile glass microscope slides incubated in the outflow channels of two acidic geothermal springs (pH = 3-3.5; temperature = 68-75°C) in YNP. Hydrogenobaculum spp. were the most abundant taxon identified during early successional stages (4-40 days), and have been shown to oxidize arsenite, sulfide, and hydrogen coupled to oxygen reduction. Iron-oxidizing populations of Metallosphaera yellowstonensis were detected within 4 days, and reached steady-state levels within 14-30 days, corresponding to visible Fe(III)-oxide accretion. Heterotrophic archaea colonized near 30 days, and emerged as the dominant functional guild after 70 days and in mature Fe(III)-oxide mats (1-2 cm thick). First-order rate constants of Fe(III)-oxide accretion ranged from 0.046 to 0.05 day(-1), and in situ microelectrode measurements showed that the oxidation of Fe(II) is limited by the diffusion of O2 into the Fe(III)-oxide mat. The formation of microterracettes also implicated O2 as a major variable controlling microbial growth and subsequent mat morphology. The assembly and succession of Fe(III)-oxide mat communities follows a repeatable pattern of colonization by lithoautotrophic organisms, and the subsequent growth of diverse organoheterotrophs. The unique geochemical signatures and micromorphology of extant biomineralized Fe(III)-oxide mats are also useful for understanding other Fe(II)-oxidizing systems. PMID:26913020

  3. Low interface defect density of atomic layer deposition BeO with self-cleaning reaction for InGaAs metal oxide semiconductor field effect transistors

    In this paper, we discuss atomic configuration of atomic layer deposition (ALD) beryllium oxide (BeO) using the quantum chemistry to understand the theoretical origin. BeO has shorter bond length, higher reaction enthalpy, and larger bandgap energy compared with those of ALD aluminum oxide. It is shown that the excellent material properties of ALD BeO can reduce interface defect density due to the self-cleaning reaction and this contributes to the improvement of device performance of InGaAs MOSFETs. The low interface defect density and low leakage current of InGaAs MOSFET were demonstrated using X-ray photoelectron spectroscopy and the corresponding electrical results

  4. Synthesis, structuring and characterization of rare earth oxide thin films: Modeling of the effects of stress and defects on the phase stability

    This work studies the effects of the deposition parameters on the microstructure and the related residual stress in a rare earth oxide thin film. This study is focused on the yttrium sesquioxide (Y2O3) thin films deposited on Si (100) substrates using the ion beam sputtering technique. This technique allows the control of the microstructure and the related residual stress in the thin films by monitoring the energy of the argon beam used in the deposition process. Measurements of the stresses within the oxide layer were performed by the X-ray diffraction-sin2Ψ method. The results show that the classic model of a pure biaxial in-plane model of stress, generally proposed in thin films, is not satisfying. A model that includes a hydrostatic stress due to the crystalline defects generated during the deposition process and a biaxial stress called a fixation stress, gives a good agreement with the experimental results. This modeling of the residual stress, based on nanometer-scale inclusions (point, extended defects) inducing a hydrostatic stress field, leads to a quantitative analysis of the nature and the concentration of the defects. This work shows results that establish a relationship between residual stress, defects and non-equilibrium phase stabilization during growth. - Highlights: • Microstructure of Y2O3 thin films • Measurements of residual stresses in the thin films • Modeling of a triaxial residual stress state • Stress-induced stabilization of non-equilibrium phase

  5. Peroxisomal fatty acid oxidation and inhibitors of the mitochondrial carnitine palmitoyltransferase I in isolated rat hepatocytes.

    Skorin, C; Necochea, C; Johow, V; Soto, U; Grau, A M; Bremer, J; Leighton, F

    1992-01-01

    Fatty acid oxidation was studied in the presence of inhibitors of carnitine palmitoyltransferase I (CPT I), in normal and in peroxisome-proliferated rat hepatocytes. The oxidation decreased in mitochondria, as expected, but in peroxisomes it increased. These two effects were seen, in variable proportions, with (+)-decanoylcarnitine, 2-tetradecylglycidic acid (TDGA) and etomoxir. The decrease in mitochondrial oxidation (ketogenesis) affected saturated fatty acids with 12 or more carbon atoms, whereas the increase in peroxisomal oxidation (H2O2 production) affected saturated fatty acids with 8 or more carbon atoms. The peroxisomal increase was sensitive to chlorpromazine, a peroxisomal inhibitor. To study possible mechanisms, palmitoyl-, octanoyl- and acetyl-carnitine acyltransferase activities were measured, in homogenates and in subcellular fractions from control and TDGA-treated cells. The palmitoylcarnitine acyltransferase was inhibited, as expected, but the octanoyltransferase activity also decreased. The CoA derivative of TDGA was synthesized and tentatively identified as being responsible for inhibition of the octanoylcarnitine acyltransferase. These results show that inhibitors of the mitochondrial CPT I may also inhibit the peroxisomal octanoyl transferase; they also support the hypothesis that the octanoyltransferase has the capacity to control or regulate peroxisomal fatty acid oxidation. PMID:1736904

  6. Hypochlorite-induced oxidation of amino acids, peptides and proteins

    Hawkins, C L; Pattison, D I; Davies, Michael Jonathan

    2003-01-01

    Activated phagocytes generate the potent oxidant hypochlorite (HOCl) via the release of the enzyme myeloperoxidase and hydrogen peroxide. HOCl is known to react with a number of biological targets including proteins, DNA, lipids and cholesterol. Proteins are likely to be major targets for reactio...

  7. Enhanced photoluminescence in transparent thin films of polyaniline–zinc oxide nanocomposite prepared from oleic acid modified zinc oxide nanoparticles

    Sajimol Augustine, M., E-mail: sajimollazar@gmail.com [Department of Physics, St. Teresa' s College, Kochi-11, Kerala (India); Jeeju, P.P.; Varma, S.J.; Francis Xavier, P.A. [Division for Research in Advanced Materials, Department of Physics, Cochin University of Science and Technology, Kochi-22, Kerala (India); Jayalekshmi, S., E-mail: lakshminathcusat@gmail.com [Division for Research in Advanced Materials, Department of Physics, Cochin University of Science and Technology, Kochi-22, Kerala (India)

    2014-07-01

    Oleic acid capped zinc oxide (ZnO) nanoparticles have been synthesized by a wet chemical route. The chemical oxidative method is employed to synthesize polyaniline (PANI) and PANI/ZnO nanocomposites doped with four different dopants such as orthophosphoric acid (H{sub 3}PO{sub 4}), hydrochloric acid (HCl), naphthalene-2-sulphonic acid and camphor sulphonic acid (CSA). The samples have been structurally characterized by X-ray diffraction (XRD), field emission scanning electron microscopy and Fourier transform infrared (FT-IR) spectroscopic techniques. A comparison of the photoluminescence (PL) emission intensity of PANI and PANI/ZnO nanocomposites is attempted. The enhanced PL intensity in PANI/ZnO nanocomposites is caused by the presence of nanostructured and highly fluorescent ZnO in the composites. It has been observed that, among the composites, the H{sub 3}PO{sub 4} doped PANI/ZnO nanocomposite is found to exhibit the highest PL intensity because of the higher extent of (pi) conjugation and the more orderly arrangement of the benzenoid and quinonoid units. In the present work, transparent thin films of PANI and PANI/ZnO nanocomposite for which PL intensity is found to be maximum, have been prepared after re-doping with CSA by the spin-coating technique. The XRD pattern of the PANI/ZnO film shows exceptionally good crystallanity compared to that of pure PANI, which suggests that the addition of ZnO nanocrystals helps in enhancing the crystallanity of the PANI/ZnO nanocomposite. There is a significant increase in the PL emission intensity of the PANI/ZnO nanocomposite film making it suitable for the fabrication of optoelectronic devices. - Highlights: • Oleic acid capped zinc oxide nanoparticles are synthesized by wet chemical method. • Polyaniline/zinc oxide nanocomposites are prepared by in-situ polymerization. • Polyaniline and polyaniline/zinc oxide thin films are deposited using spin-coating. • Enhanced photoluminescence is observed in polyaniline

  8. The role of peroxisomal fatty acyl-CoA beta-oxidation in bile acid biosynthesis

    Hayashi, H.; Miwa, A. (Josai Univ., Saitama (Japan))

    1989-11-01

    The physiological role of the peroxisomal fatty acyl-CoA beta-oxidizing system (FAOS) is not yet established. We speculated that there might be a relationship between peroxisomal degradation of long-chain fatty acids in the liver and the biosynthesis of bile acids. This was investigated using (1-{sup 14}C)butyric acid and (1-{sup 14}C)lignoceric acid as substrates of FAOS in mitochondria and peroxisomes, respectively. The incorporation of ({sup 14}C)lignoceric acid into primary bile acids was approximately four times higher than that of ({sup 14}C)butyric acid (in terms of C-2 units). The pools of these two fatty acids in the liver were exceedingly small. The incorporations of radioactivity into the primary bile acids were strongly inhibited by administration of aminotriazole, which is a specific inhibitor of peroxisomal FAOS in vivo. Aminotriazole inhibited preferentially the formation of cholate, the major primary bile acid, from both ({sup 14}C)lignoceric acid and ({sup 14}C)butyric acid, rather than the formation of chenodeoxycholate. The former inhibition was about 70% and the latter was approximately 40-50%. In view of reports that cholate is biosynthesized from endogenous cholesterol, the above results indicate that peroxisomal FAOS may have an anabolic function, supplying acetyl CoA for bile acid biosynthesis.

  9. On the Defect Chemistry, Electrical Properties and Electrochemical Performances As Solid Oxide Fuel Cell Cathode Materials of New La-(Sr/Vac)-Co-Ti-O Perovskites

    García-Alvarado, Flaviano; Gómez-Pérez, Alejandro; Pérez-Flores, Juan Carlos;

    2015-01-01

    Perovskite-type oxides are well known materials that have been proposed as electrodes and electrolytes for solid oxide fuel cells (SOFCs). The structure, which is referred to the ABO3 stoichiometry, can accommodate many different transition metal ions in the B-site; its electronic conductivity will...... materials with valuable properties for SOFCs. We have analysed the effect of La3+ by Sr2+ substitution and vacancies creation in several double perovskites, La2MTiO6 (M = Co, Ni, Cu). Defect chemistry and electrical behavior have been investigated in order to unveil the nature of charge carriers...

  10. Iron and hydroxyl radicals in lipid oxidation: Fenton reactions in lipid and nucleic acids co-oxidized with lipid

    Borg, D.C.; Schaich, K.M.

    1987-01-01

    Hydroxyl radicals can initiate lipid peroxidation in liquids, but their high reactivity affords reaction paths so short that they are unlikely to reach lipids in membrane bilayers when formed exteriorly. EPR studies of Fenton-like reactions inducing oxidation in bulk lipids indicate that iron-dependent initiation of lipid oxidation in organelles and vesicles may result from hydroxyl radicals formed within the hydrophobic membrane interiors, where they would be inaccessible to typical hydrophilic radical scavengers. The cytotoxic or cytogenetic results of lipid peroxidation, especially in nuclear membranes, may include radiominetic chemical damage to adjacent DNA or nucleoprotein. Preliminary product analyses of nucleic acid basis cooxidized with lipids in vitro support this view.

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

    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. PMID:25955644

  12. Ligand field splittings in core level transitions for transition metal (TM) oxides: Tanabe-Sugano diagrams and (TM) dangling bonds in vacated O-atom defects

    Defect states in the forbidden band-gap below the conduction band edge are active as electron traps in nano-grain high-) transition metal (TM) oxides with thickness >0.3 nm, e.g., ZrO2 and HfO2. These oxides have received considerable attention as gate-dielectrics in complementary metal oxide semiconductor (CMOS) devices, and more recently are emerging as candidates for charge storage and memory devices. To provide a theoretical basis for device functionality, ab-initio many-electron theory is combined with X-ray absorption spectroscopy (XAS) to study O K edge and TM core level transitions. These studies identify ligand field splittings (ΔLF) for defect state features,. When compared with those obtained from O-atom and TM-atom core spectroscopic transitions, this provides direct information about defect state sun-nm bonding arrangements. comparisons are made for (i) elemental TiO2 and Ti2O3 with different formal ionic charges, Ti4+ and Ti3+ and for (ii) Magneli Phase alloys, TinO2n-1, n is an integer 9≥n>3, and (TiO2)x(HfO2)1−x alloys. The alloys display multi-valent behavior from (i) different ionic-charge states, (ii) local bond-strain, and (iii) metallic hopping transport. The intrinsic bonding defects in TM oxides are identified as pairs of singly occupied dangling bonds. For 6-fold coordinated Ti-oxides defect excited states in 2nd derivative O K pre-edge spectra are essentially the same as single Ti-atom d2 transitions in Tanabe-Sugano (T-S) diagrams. O-vacated site defects in 8-fold coordinated ZrO2 and HfO2 are described by d8 T-S diagrams. T-S defect state ordering and splittings are functions of the coordination and symmetry of vacated site bordering TM atoms. ΔLF values from the analysis of T-S diagrams indicate medium range order (MRO) extending to 3rd and 4th nearest-neighbor (NN) TM-atoms. Values are different for 6-fold Ti, and 8-fold ZrO2 and HfO2, and scale inversely with differences in respective formal ionic radii. O-vacated site bonding

  13. RDH10 oxidation of Vitamin A is a critical control step in synthesis of retinoic acid during mouse embryogenesis.

    Lisa L Sandell

    Full Text Available Retinoic Acid (RA is a small lipophilic signaling molecule essential for embryonic development and adult tissue maintenance. Both an excess of RA and a deficiency of RA can cause pathogenic anomalies, hence it is critical to understand the mechanisms controlling the spatial and temporal distribution of RA. However, our current understanding of these processes remains incomplete. Vitamin A is metabolized to RA via two sequential enzymatic reactions. The first requires retinol dehydrogenase (RDH activity to oxidize Vitamin A (retinol to retinal, and the second requires retinaldehyde activity (RALDH to oxidize retinal into RA. The first reaction has previously been attributed to the alcohol dehydrogenase (ADH family, whose genes are ubiquitously or redundantly expressed. Consequently, the specificity of RA synthesis was thought to reside exclusively at the level of the second reaction. To better understand the metabolism of Vitamin A into RA during embryogenesis, we generated new mouse models that disrupt this process. Here we describe a new targeted knockout of Rdh10 in which RA synthesis is severely impaired, particularly at critical early embryonic stages. We also introduce a new mutant allele of Aldh1a2. Both mutations produce similar developmental defects resulting in lethality around embryonic day 10.5 (E10.5. The severity of the Rdh10 null phenotype demonstrates that embryonic oxidation of retinol is carried out primarily by RDH10 and that neither ADHs nor other enzymes contribute significantly to this reaction. We also show that reduced RA production results in upregulation of Rdh10. These data demonstrate that RDH10 plays a critical role in mediating the rate limiting RDH step of Vitamin A metabolism and functions as a nodal point in feedback regulation of RA synthesis. Moreover, RDH10-mediated oxidation of retinol plays as important a role in the control and regulation of RA production during embryogenesis as does the subsequent RALDH

  14. Graphene Oxide Reinforced Polylactic Acid/Polyurethane Antibacterial Composites

    Xiaoli An; Haibin Ma; Bin Liu; Jizeng Wang

    2013-01-01

    Nanocomposites from PLA/PU containing small concentrations of graphene oxide (GO) were prepared by simple liquid-phase mixing followed by casting. The as-prepared ternary PLA/PU/GO composite films exhibited good antibacterial activity against the gram-positive Staphylococcus aureus and the gram-negative Escherichia coli, due to the excellent antibacterial property of GO sheets with high specific surface area. The addition of GO inhibited the attachment and proliferation of microbes on the fil...

  15. The kinetics of the 15N/14N isotopic exchange between nitric oxide and nitric acid

    The rate of the 15N isotopic exchange between NO-NHO3 at high nitric acid concentration (2-10M) have been measured. The experimental data were obtained by contacting nitric oxide at atmospheric pressure with nitric acid solution labelled with 15N, in a glass contactor. The measurements were carried out in a glass vessel with magnetic stirrer maintaining always the same stirring rate (17 rot.s-1). The temperature was kept constant at 25 +-0.5 deg C. The reaction vessel was connected to a vacuum line and a purified nitric oxide source. The rate of the isotopic exchange and of the nitric oxide absorption in nitric acid were determined with a gas-burette in the simple apparatus described earlier. (T.G.)

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

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

    2007-01-01

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

  17. Fatty acid oxidation and carnitine palmitoyltransferase I: emerging therapeutic targets in cancer.

    Qu, Q; Zeng, F; Liu, X; Wang, Q J; Deng, F

    2016-01-01

    Tumor cells exhibit unique metabolic adaptations that are increasingly viewed as potential targets for novel and specific cancer therapies. Among these targets, the carnitine palmitoyltransferase system is responsible for delivering the long-chain fatty acid (FA) from cytoplasm into mitochondria for oxidation, where carnitine palmitoyltransferase I (CPTI) catalyzes the rate-limiting step of fatty acid oxidation (FAO). With increasing understanding of the crucial role had by fatty acid oxidation in cancer, CPTI has received renewed attention as a pivotal mediator in cancer metabolic mechanism. CPTI activates FAO and fuels cancer growth via ATP and NADPH production, constituting an essential part of cancer metabolism adaptation. Moreover, CPTI also functionally intertwines with other key pathways and factors to regulate gene expression and apoptosis of cancer cell. Here, we summarize recent findings and update the current understanding of FAO and CPTI in cancer and provide theoretical basis for this enzyme as an emerging potential molecular target in cancer therapeutic intervention. PMID:27195673

  18. Selective liquid phase oxidation of glycerol to glyceric acid over novel supported Pt catalysts

    Sproge Elina

    2013-01-01

    Full Text Available Several supported platinum catalysts were prepared by extractive-pyrolytic method for the selective glyceric acid production from glycerol. Al2O3, Y2O3, Lu2O3, ZrO2-Y2O3 TiO2, SG, Fe2O3, γ-AlO(OH and C were used as catalyst supports, glycerol oxidation was carried out in the alkaline solutions and oxygen was used as oxidant. The optimal catalyst preparation parameters and glycerol oxidation conditions to obtain glyceric acid were determined. The best result (selectivity to glyceric acid 57% with glycerol conversion 92% was achieved in the presence of 4.8%Pt/Al2O3 catalyst.

  19. Catalytic ozonation of sulfosalicylic acid over manganese oxide supported on mesoporous ceria.

    Xing, Shengtao; Lu, Xiaoyang; Liu, Jia; Zhu, Lin; Ma, Zichuan; Wu, Yinsu

    2016-02-01

    Manganese oxide supported on mesoporous ceria was prepared and used as catalyst for catalytic ozonation of sulfosalicylic acid (SA). Characterization results indicated that the manganese oxide was mostly incorporated into the pores of ceria. The synthesized catalyst exhibited high activity and stability for the mineralization of SA in aqueous solution by ozone, and more than 95% of total organic carbon was removed in 30 min under various conditions. Mechanism studies indicated that SA was mainly degraded by ozone molecules, and hydroxyl radical reaction played an important role for the degradation of its ozonation products (small molecular organic acids). The manganese oxide in the pores of CeO2 improved the adsorption of small molecular organic acids and the generation of hydroxyl radicals from ozone decomposition, resulting in high TOC removal efficiency. PMID:26344143

  20. Sublethal concentrations of salicylic acid decrease the formation of reactive oxygen species but maintain an increased nitric oxide production in the root apex of the ethylene-insensitive Never ripe tomato mutants

    Tari, Irma; Poór, Péter; Gémes, Katalin

    2011-01-01

    The pattern of salicylic acid (SA)-induced production of reactive oxygen species (ROS) and nitric oxide (NO) were different in the apex of adventitious roots in wild-type and in the ethylene-insensitive Never ripe (Nr) mutants of tomato (Solanum lycopersicum L. cv Ailsa Craig). ROS were upregulated, while NO remained at the control level in apical root tissues of wildtype plants exposed to sublethal concentrations of SA. In contrast, Nr plants expressing a defective ethylene receptor displaye...

  1. Effects of ascorbic acid and antioxidants on color, lipid oxidation and volatiles of irradiated ground beef

    Beef loins with 3 different aging times after slaughter were ground, added with none, 0.1% ascorbic acid, 0.01% sesamol+0.01% α-tocopherol, or 0.1% ascorbic acid+0.01% sesamol+0.01% tocopherol. The meats were packaged in oxygen-permeable bags, irradiated at 2.5 kGy, and color, oxidation-reduction potential (ORP), lipid oxidation and volatile profiles were determined. Irradiation decreased the redness of ground beef, and visible color of beef changed from a bright red to a green/brown depending on the age of meat. Addition of ascorbic acid prevented color changes in irradiated beef, and the effect of ascorbic acid became greater as the age of meat or storage time after irradiation increased. The ground beef added with ascorbic acid had lower ORP than control, and the low ORP of meat helped maintaining the heme pigments in reduced form. During aerobic storage, S-volatiles disappeared while volatile aldehydes significantly increased in irradiated beef. Addition of ascorbic acid at 0.1% or sesamol+α-tocopherol at each 0.01% level to ground beef prior to irradiation were effective in reducing lipid oxidation and S-volatiles. As storage time increased, however, the antioxidant effect of sesamol+tocopherol in irradiated ground beef was superior to that of ascorbic acid

  2. Erythrocyte Sialic Acid Content during Aging in Humans: Correlation with Markers of Oxidative Stress

    Mehdi, Mohammad Murtaza; Singh, Prabhakar; Rizvi, Syed Ibrahim

    2012-01-01

    Sialic acids are substituted neuraminic acid derivatives which are typically found at the outermost end of glycan chains on the membrane in all cell types. The role of erythrocyte membrane sialic acids during aging has been established however the relationship between sialic acid and oxidative stress is not fully understood. The present work was undertaken to analyze the relationship between erythrocyte membrane sialic acid with its plasma level, membrane and plasma lipid hydroperoxide levels and plasma total antioxidant capacity. Results show that sialic acid content decreases significantly (P < 0.001) in RBC membrane (r = −0.901) and increases in plasma (r = 0.860) as a function of age in humans. Lipid peroxidation measured in the form of hydroperoxides increases significantly (P < 0.001) in plasma (r = 0.830) and RBC membranes (r = 0.875) with age in humans. The Trolox Equivalent Total Antioxidant Capacity (TETAC) of plasma was found to be significantly decreased (P < 0.001, r = −0.844). We observe significant correlations between decrease of erythrocyte membrane sialic acid and plasma lipid hydroperoxide and TETAC. Based on the observed correlations, we hypothesize that increase in oxidative stress during aging may influence the sialic acid decomposition from membrane thereby altering the membrane configuration affecting many enzymatic and transporter activities. Considering the importance of plasma sialic acid as a diagnostic parameter, it is important to establish age-dependent reference. PMID:22377734

  3. Aqueous Phase Photo-Oxidation of Succinic Acid: Changes in Hygroscopic Properties and Reaction Products

    Hudson, P. K.; Ninokawa, A.; Hofstra, J.; de Lijser, P.

    2013-12-01

    Atmospheric aerosol particles have been identified as important factors in understanding climate change. The extent to which aerosols affect climate is determined, in part, by hygroscopic properties which can change as a result of atmospheric processing. Dicarboxylic acids, components of atmospheric aerosol, have a wide range of hygroscopic properties and can undergo oxidation and photolysis reactions in the atmosphere. In this study, the hygroscopic properties of succinic acid aerosol, a non-hygroscopic four carbon dicarboxylic acid, were measured with a humidified tandem differential mobility analyzer (HTDMA) and compared to reaction products resulting from the aqueous phase photo-oxidation reaction of hydrogen peroxide and succinic acid. Reaction products were determined and quantified using gas chromatography-flame ionization detection (GC-FID) and GC-mass spectrometry (GC-MS) as a function of hydrogen peroxide:succinic acid concentration ratio and photolysis time. Although reaction products include larger non-hygroscopic dicarboxylic acids (e.g. adipic acid) and smaller hygroscopic dicarboxylic acids (e.g. malonic and oxalic acids), comparison of hygroscopic growth curves to Zdanovskii-Stokes-Robinson (ZSR) predictions suggests that the hygroscopic properties of many of the product mixtures are largely independent of the hygroscopicity of the individual components. This study provides a framework for future investigations to fully understand and predict the role of chemical reactions in altering atmospheric conditions that affect climate.

  4. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    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...

  5. Electrochemical oxidation of 243Am(III) in nitric acid by a terpyridyl-derivatized electrode

    Dares, C. J.; Lapides, A. M.; Mincher, B. J.; Meyer, T. J.

    2015-11-05

    A high surface area, tin-doped indium oxide electrode surface-derivatized with a terpyridine ligand has been applied to the oxidation of trivalent americium to Am(V) and Am(VI) in nitric acid. Potentials as low as 1.8 V vs. the saturated calomel electrode are used, 0.7 V lower than the 2.6 V potential for one-electron oxidation of Am(III) to Am(IV) in 1 M acid. This simple electrochemical procedure provides, for the first time, a method for accessing the higher oxidation states of Am in non-complexing media for developing the coordination chemistries of Am(V) and Am(VI) and, more importantly, for separation of americium from nuclear waste streams.

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

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

    2011-01-01

    Increasing evidence demonstrated the involvement of ammonia-oxidizing archaea (AOA) in the global nitrogen cycle, but the relative contributions of AOA and ammonia-oxidizing bacteria (AOB) to ammonia oxidation are still in debate. Previous studies suggest that AOA would be more adapted to ammonia-limited oligotrophic conditions, which seems to be favored by protonation of ammonia, turning into ammonium in low-pH environments. Here, we investigated the autotrophic nitrification activity of AOA...

  7. A high linoleic acid diet increases oxidative stress in vivo and affects nitric oxide metabolism in humans.

    Turpeinen, A M; Basu, S; Mutanen, M

    1998-09-01

    Evidence from in vitro studies shows that increased intake of polyunsaturated fatty acids leads to increased oxidative stress, which may be associated with endothelial damage. We measured the urinary levels of 8-iso-PGF2alpha and nitric oxide metabolites as well as plasma sICAM-1 levels from healthy subjects after strictly controlled diets rich in either linoleic acid (LA, C18:2 n-6) or oleic acid (OA, C18:1 n-9). Thirty-eight volunteers (20 women and 18 men, mean age 27 years) consumed a baseline diet rich in saturated fatty acids (SFA) for 4 weeks and were then switched to either a high LA diet (11.5 en%) or a high OA diet (18.0 en%) also for 4 weeks. During the LA and OA diets, nearly all food was provided for the whole day. A control group of 13 subjects consumed their habitual diet throughout the study. Urinary excretion of 8-iso-PGF2alpha was significantly increased after the LA diet (170 vs 241 ng/mmol creatinine, P=0.04), whereas the urinary concentration of nitric oxide metabolites decreased (4.2 vs 2.6 mg/mmol creatinine, P=0.03). No significant changes were seen in the OA group. Significant differences between the LA and control group were found for both 8-oxo-PGF2alpha (P=0.03) and NO (P=0.02), whereas the OA and LA groups did not differ with respect to any parameter. Also plasma sICAM-1 remained unchanged in both groups throughout the study. In conclusion, the high-LA diet increased oxidative stress and affected endothelial function in a way which may in the long-term predispose to endothelial dysfunction. PMID:9844997

  8. Determining organic impurities in mother liquors from oxidative terephthalic acid synthesis by microemulsion electrokinetic chromatography.

    Huang, Hsi-Ya; Wei, Mercury; Lin, Yu-Ru; Lu, Pin-Hsuan

    2009-03-20

    In this study, a microemulsion electrokinetic chromatography (MEEKC) method was developed to analyze and detect several aromatic acids (benzoic acid (BA), isophthalic acid (IPA), terephthalic acid (TPA), p-toluic acid (p-TA), 4-carboxylbenzaldehyde (4-CBA), trimesic acid (TSA), trimellitic acid (TMA), o-phthalic acid (OPA), and hemimellitic acid (HMA)), which are common organic impurities produced by liquid-phase catalytic oxidation of p-xylene to TPA. The effects of microemulsion composition, column temperature, column length and applied voltage were examined in order to optimize the aromatic acid separations. This work demonstrated that variation in the concentration of surfactant (sodium dodecyl sulfate (SDS)) and oil phase (octane) had a pronounced effect on separation of the nine aromatic acids. It was also found that a decrease in column length had the greatest effect on shortening separation time and improving separation resolution for these aromatic acids when compared to that of an increase in column temperature or applied voltage. However, the nature and concentration of cosurfactants and organic modifiers were found to play only minor roles in the separation mechanism. Thus, a separation with baseline resolution was achieved within 14 min by using a microemulsion solution of pH 2.0 containing 3.7% SDS, 0.975% octane, and 5.0% cyclohexanol; and a 50-cm capillary column (effective length of 40-cm) at 26 degrees C. As a result, the developed MEEKC method successfully determined eight impurities of aromatic acids in the mother liquors produced from the oxidation synthesis of TPA. PMID:19167001

  9. Oxidation and Textural Characteristics of Butter and Ice Cream with Modified Fatty Acid Profiles

    Gonzalez, Sonia

    2001-01-01

    Milk fat composition determines specific rheological, sensory and physicochemical properties of dairy products such as texture, melting point, flavor, color, oxidation rates, and viscosity. Previous studies have shown that milkfats containing higher levels of long chain polyunsaturated fatty acids have lower melting points and decreased solid fat contents which leads to softer-textured products. An increased risk of higher oxidation rates can be a disadvantage of high levels of polyunsaturate...

  10. Therapeutic inhibition of fatty acid oxidation in right ventricular hypertrophy: exploiting Randle’s cycle

    Fang, Yong-Hu; Piao, Lin; Hong, Zhigang; Toth, Peter T.; Marsboom, Glenn; Bache-Wiig, Peter; Rehman, Jalees; Archer, Stephen L.

    2011-01-01

    Right ventricular hypertrophy (RVH) and RV failure are major determinants of prognosis in pulmonary hypertension and congenital heart disease. In RVH, there is a metabolic shift from glucose oxidation (GO) to glycolysis. Directly increasing GO improves RV function, demonstrating the susceptibility of RVH to metabolic intervention. However, the effects of RVH on fatty acid oxidation (FAO), the main energy source in adult myocardium, are unknown. We hypothesized that partial inhibitors of FAO (...

  11. Nitric oxide secretion in human conjunctival fibroblasts is inhibited by alpha linolenic acid

    Erdinest, Nir; Shohat, Noam; Moallem, Eli; Yahalom, Claudia; Mechoulam, Hadas; Anteby, Irene; Ovadia, Haim; Solomon, Abraham

    2015-01-01

    Purpose It is known that both human conjunctival fibroblasts (HCF) and corneal epithelial (HCE) cells contribute to the inflammatory process in the ocular surface by releasing inflammatory cytokines. In addition, nitric oxide (NO) has an important role in inflammatory responses in the ocular surface. In the present study, we aimed to characterize the capacity of these cells to release nitric oxide in response to cytokines and Lipopolysaccharide (LPS), and show that Alpha-linoleic acid (ALA) i...

  12. Neuroprotective Effects of Alpha Lipoic Acid on Haloperidol-Induced Oxidative Stress in the Rat Brain

    Perera Joachim; Tan Joon; Jeevathayaparan S; Chakravarthi Srikumar; Haleagrahara Nagaraja

    2011-01-01

    Abstract Haloperidol is an antipsychotic drug that exerts its' antipsychotic effects by inhibiting dopaminergic neurons. Although the exact pathophysiology of haloperidol extrapyramidal symptoms are not known, the role of reactive oxygen species in inducing oxidative stress has been proposed as one of the mechanisms of prolonged haloperidol-induced neurotoxicity. In the present study, we evaluate the protective effect of alpha lipoic acid against haloperidol-induced oxidative stress in the ra...

  13. Influence of concentration in phosphoric acid treatment of titanium oxide and their powder properties

    Hiroaki Onoda; Aki Matsukura

    2015-01-01

    Titanium oxide that has the photocatalytic activity is used as a white pigment for cosmetics. A certain degree of sebum on the skin is decomposed by the ultraviolet radiation in sunlight. In this work, titanium oxide was shaken with various concentrations of phosphoric acid to synthesize a novel white pigment for cosmetics. Their chemical composition, powder properties, photocatalytic activity, color phase, and smoothness were studied. The obtained materials indicated XRD peaks of titanium ox...

  14. Characterization of Bronze Surface Layer Formed by Microarc Oxidation Process in 12-Tungstophosphoric Acid

    Zoran Nedić; Stevan Stojadinović; Ubavka B. Mioč

    2009-01-01

    This paper is a brief review of our recent research into novel uses for heteropoly compounds as precursors for thin films that can be used as catalysts and materials with good optical, conductive and other characteristics. In view of this, we have chosen thin film obtained with 12-tungsphosphoric acid on aluminum substrates. In all cases, a relatively new, microarc oxidation technique has been used to prepare oxide coatings on substrate surfaces. Advanced physicochemical methods, AFM and SEM-...

  15. Studying post-etching silicon crystal defects on 300mm wafer by automatic defect review AFM

    Zandiatashbar, Ardavan; Taylor, Patrick A.; Kim, Byong; Yoo, Young-kook; Lee, Keibock; Jo, Ahjin; Lee, Ju Suk; Cho, Sang-Joon; Park, Sang-il

    2016-03-01

    Single crystal silicon wafers are the fundamental elements of semiconductor manufacturing industry. The wafers produced by Czochralski (CZ) process are very high quality single crystalline materials with known defects that are formed during the crystal growth or modified by further processing. While defects can be unfavorable for yield for some manufactured electrical devices, a group of defects like oxide precipitates can have both positive and negative impacts on the final device. The spatial distribution of these defects may be found by scattering techniques. However, due to limitations of scattering (i.e. light wavelength), many crystal defects are either poorly classified or not detected. Therefore a high throughput and accurate characterization of their shape and dimension is essential for reviewing the defects and proper classification. While scanning electron microscopy (SEM) can provide high resolution twodimensional images, atomic force microscopy (AFM) is essential for obtaining three-dimensional information of the defects of interest (DOI) as it is known to provide the highest vertical resolution among all techniques [1]. However AFM's low throughput, limited tip life, and laborious efforts for locating the DOI have been the limitations of this technique for defect review for 300 mm wafers. To address these limitations of AFM, automatic defect review AFM has been introduced recently [2], and is utilized in this work for studying DOI on 300 mm silicon wafer. In this work, we carefully etched a 300 mm silicon wafer with a gaseous acid in a reducing atmosphere at a temperature and for a sufficient duration to decorate and grow the crystal defects to a size capable of being detected as light scattering defects [3]. The etched defects form a shallow structure and their distribution and relative size are inspected by laser light scattering (LLS). However, several groups of defects couldn't be properly sized by the LLS due to the very shallow depth and low

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

    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 CO2 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 PPAR

  17. Influence of fatty acid oxidation rate on glycerol release from cardiac myocytes

    Quiescent cardiac myocytes are characterized by low rates of fatty acid oxidation due to the reduced energy demand compared with beating hearts. The accumulation of intracellular fatty acid metabolites may, therefore, result in feed-back inhibition of the cardiac lipase responsible for the mobilization of triacylglycerols (lipolysis). The objective of this study was to examine if interventions that increase fatty acid oxidation rates in myocytes have an effect on lipolysis. Addition of 100 μM dinitrophenol (DNP) to calcium-tolerant rat ventricular myocytes caused an increase in the rate of 14C-oleic acid oxidation from 1.11 +/- 0.06 to 2.38 +/- 0.17 nmol 14CO2/106 cells/min (115% stimulation; mean +/- S.D., n = 3). In parallel incubations, DNP increased the rate of lipolysis from 4.4 +/- 1.7 to 13.6 +/- 3.2 nmol glycerol/106 cells/30 min (215% stimulation). The addition of 1 mM barium to a modified Ringer's incubation medium produced an increase in the contractile activity of the myocytes, and increased the rates of oleic acid oxidation from 0.62 +/- 0.16 to 0.88 +/- 0.23 nmol/106 cells/min (42% stimulation; n = 6) and lipolysis from 13.1 +/- 6.5 to 22.2 +/- 6.4 nmol/106 cells/30 min (70% stimulation). These data show that stimulation of fatty acid oxidation in myocardial myocytes is accompanied by increased lipolytic rates, the latter probably due to release of feed-back inhibition of cardiac lipases by accumulated fatty acid metabolites

  18. Influence of fatty acid oxidation rate on glycerol release from cardiac myocytes

    Larsen, T.S.; Severson, D.L.

    1986-03-05

    Quiescent cardiac myocytes are characterized by low rates of fatty acid oxidation due to the reduced energy demand compared with beating hearts. The accumulation of intracellular fatty acid metabolites may, therefore, result in feed-back inhibition of the cardiac lipase responsible for the mobilization of triacylglycerols (lipolysis). The objective of this study was to examine if interventions that increase fatty acid oxidation rates in myocytes have an effect on lipolysis. Addition of 100 ..mu..M dinitrophenol (DNP) to calcium-tolerant rat ventricular myocytes caused an increase in the rate of /sup 14/C-oleic acid oxidation from 1.11 +/- 0.06 to 2.38 +/- 0.17 nmol /sup 14/CO/sub 2//10/sup 6/ cells/min (115% stimulation; mean +/- S.D., n = 3). In parallel incubations, DNP increased the rate of lipolysis from 4.4 +/- 1.7 to 13.6 +/- 3.2 nmol glycerol/10/sup 6/ cells/30 min (215% stimulation). The addition of 1 mM barium to a modified Ringer's incubation medium produced an increase in the contractile activity of the myocytes, and increased the rates of oleic acid oxidation from 0.62 +/- 0.16 to 0.88 +/- 0.23 nmol/10/sup 6/ cells/min (42% stimulation; n = 6) and lipolysis from 13.1 +/- 6.5 to 22.2 +/- 6.4 nmol/10/sup 6/ cells/30 min (70% stimulation). These data show that stimulation of fatty acid oxidation in myocardial myocytes is accompanied by increased lipolytic rates, the latter probably due to release of feed-back inhibition of cardiac lipases by accumulated fatty acid metabolites.

  19. Electrocatalytic Activity of Carbonized Nanostructured Polyanilines for Oxidation Reactions: Sensing of Nitrite Ions and Ascorbic Acid

    Highlights: • Carbonized PANIs prepared from various nanostructured PANI precursors • Electroanalytical performances of carbonized PANIs evaluated using voltammetry • Study of carbonized PANIs physico-chemical properties related to electroactivity • The lowest over-potential for NO2− oxidation at c-PANI (+0.87 V vs. SCE) • The lowest over-potential for ascorbic acid oxidation at both c-PANI and c-PANI-SSA - Abstract: A comparative study of the electrocatalytic activity of nitrogen-containing carbon nanomaterials, prepared by the carbonization of nanostructured polyaniline (PANI) salts, for the electrooxidation reactions is presented. Nanostructured PANI salts were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous solution in the presence of 5-sulfosalicylic acid (PANI-SSA), 3,5-dinitrosalicylic acid (PANI-DNSA) as well as without added acid (PANI), and subsequently carbonized to c-PANI-SSA, c-PANI-DNSA and c-PANI, respectively. Glassy carbon tip was modified with nanostructured c-PANIs and used for the investigation of sensing of nitrite and ascorbic acid in aqueous solutions as model analytes by linear sweep voltammetry. All three types of the investigated c-PANIs gave excellent response to the nitrite ions and ascorbic acid electrooxidation. The lowest peak potential for nitrite ion oxidation exhibited c-PANI (+0.87 V vs. SCE), and for ascorbic acid oxidation both c-PANI and c-PANI-SSA (ca. + 0.13 V vs. SCE). Electrochemical data were correlated with structural and textural data obtained by Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, elemental and nitrogen sorption analysis

  20. Kinetics and Mechanism of Oxidation of Methimazole by Chlorite in Slightly Acidic Media.

    Chipiso, Kudzanai; Simoyi, Reuben H

    2016-06-01

    The kinetics and mechanism of the oxidation of methimazole (1-methyl-3H-imidazole), MMI, by chlorite in mildly acidic environments were studied. It is a complex reaction that gives oligo-oscillations in chlorine dioxide concentrations in excess chlorite conditions. The stoichiometry is strictly 2:1, with the sulfur center being oxidized to sulfate and the organic moiety being hydrolyzed to several indeterminate species. In excess MMI conditions over chlorite, the sulfinic acid and sulfonic acid were observed as major intermediates. The sulfenic acid, which was observed in the electrochemical oxidation of MMI, was not observed with chlorite oxidations. Initial reduction of chlorite produced HOCl, an autocatalytic species in chlorite oxidations. HOCl rapidly reacts with chlorite to produce chlorine dioxide, which, in turn, reacts rapidly with MMI to produce more chlorite. The reaction of chlorine dioxide with MMI is competitive, in rate, with the chlorite-MMI and HOCl-ClO2(-) reactions. This explains the oligo-oscillations in ClO2 concentrations. PMID:27126471

  1. Electro-oxidation of perfluorooctanoic acid by carbon nanotube sponge anode and the mechanism.

    Xue, An; Yuan, Zi-Wen; Sun, Yan; Cao, An-Yuan; Zhao, Hua-Zhang

    2015-12-01

    As an emerging persistent organic pollutant (POPs), perfluorooctanoic acid (PFOA) exists widely in natural environment. It is of particular significance to develop efficient techniques to remove low-concentration PFOA from the contaminated waters. In this work, we adopted a new material, carbon nanotube (CNT) sponge, as electrode to enhance electro-oxidation and achieve high removal efficiency of low-concentration (100μgL(-1)) PFOA from water. CNT sponge was pretreated by mixed acids to improve the surface morphology, hydrophilicity and the content of carbonyl groups on the surface. The highest removal efficiencies for low-concentration PFOA electrolyzed by acid-treated CNT sponge anode proved higher than 90%. The electro-oxidation mechanism of PFOA on CNT sponge anode was also discussed. PFOA is adsorbed on the CNT sponge rapidly increasing the concentration of PFOA on anode surface. When the potential on the anode is adjusted to more than 3.5V, the adsorbed PFOA undergoes electrochemically oxidation and hydrolysis to produce shorter-chain perfluorocarboxylic acids with less CF2 unit. The efficient electro-oxidation of PFOA by CNT sponge anode is due to the combined effect of adsorption and electrochemical oxidation. These findings provide an efficient method to remove actual concentration PFOA from water. PMID:26172515

  2. Catalytic oxidative conversion of cellulosic biomass to formic acid and acetic acid with exceptionally high yields

    Zhang, Jizhe

    2014-09-01

    Direct conversion of raw biomass materials to fine chemicals is of great significance from both economic and ecological perspectives. In this paper, we report that a Keggin-type vanadium-substituted phosphomolybdic acid catalyst, namely H4PVMo11O40, is capable of converting various biomass-derived substrates to formic acid and acetic acid with high selectivity in a water medium and oxygen atmosphere. Under optimized reaction conditions, H4PVMo11O40 gave an exceptionally high yield of formic acid (67.8%) from cellulose, far exceeding the values achieved in previous catalytic systems. Our study demonstrates that heteropoly acids are generally effective catalysts for biomass conversion due to their strong acidities, whereas the composition of metal addenda atoms in the catalysts has crucial influence on the reaction pathway and the product selectivity. © 2013 Elsevier B.V.

  3. The active component of vanadium-molybdenum catalysts for the oxidation of acrolein to acrylic acid

    The catalytic properties of the vanadium-molybdenum oxide system were investigated in the oxidation of acrolein to acrylic acid. The active component of the catalyst is the compound VMo3O11, the maximum amount of which is observed at a content of 7-15 mole% V2O4. The compound VMo3O11 is formed in the thermodecomposition of silicomolybdovanadium heteropoly acids or isopoly compounds, reduced with respect to vanadium, and contains V4+ and Mo6+. The optimum treatment for the formation of this compound is treatment in the reaction mixture at 400 degrees C

  4. Kinetics and mechanism of oxidation of acetanilide by quinquevalent vanadium in acid medium

    The kinetics of the oxidation of acetanilide with vanadium(V) in sulphuric acid medium at constant ionic strength has been studied. The reaction is first order with oxidant. The order of reaction in acetanilide varies from one to zero. The reaction follows an acid catalyzed independent path, exhibiting square dependence in H+. A Bunnett plot indicates that the water acts as a nucleophile. The thermodynamic parameters have been computed. A probable reaction mechanism and rate law consistent with these data are given. (Author)

  5. Electrochemical oxidation of substituted benzylamines in aquo-acetic acid medium: substituent and solvent effects

    A Thirumoorthi; K P Elango

    2007-07-01

    Electrochemical oxidation of nine para- and meta-substituted benzylamines in varying mole fractions of acetic acid in water has been investigated in the presence of 0.1 M sulphuric acid as supporting electrolyte. The oxidation potentials correlate well with Hammett’s substituent constants affording negative reaction constants. The correlation of potential values with macroscopic solvent parameters is non-linear suggesting that the operation of both specific and non-specific solvent-solvent-solute interaction mechanisms. Multiple correlation analysis of the experimental data with Kamlet-Taft solvatochromic parameters is employed.

  6. Radiolytic chain oxidation of dithiothreitol in aerated acidic solutions

    In the radiolysis of dithiothreitol (DTT or HS-D-SH) in air saturated acidic and neutral solutions sulphur centered radicals are formed. In the presence of oxygen the final products are ox - DTT and H2O2 via certain complex reactions. G(ox - DTT) and G(H2O2) are dependent upon DTT and acid concentrations and dose rate. The chain is predominant only at low pH. The HO2 radical carries the chain by abstracting an H atom from DTT (k = 120 dm3mol-1s-1). The chain is continued when the DTT radicals react with oxygen to give an unstable peroxyl radical finally yielding ox - DTT and HO2. (author)

  7. Malic acid assisted precursor route to hierarchical structured nickel oxide

    Wang, Haizhen [Zhejiang California International Nanosystems Institute, Zhejiang University, Hangzhou, Zhejiang (China); Qian, Yitai [Hefei National Laboratory for Physical Science at Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui (China)

    2010-05-15

    A novel malic acid assisted precursor route to prepare NiO materials with novel hierarchical structures has been investigated in this work. The Ni-based precursors can be synthesized by a malic acid-assisted hydrothermal route, which have been characterized by powder X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TGA). NiO materials can be prepared via the thermal treatment of the precursor in ambient atmosphere. The XRD, SEM, Energy dispersive X-ray spectroscopy (EDS) and UV-Vis spectroscopy of the NiO materials were also examined. The effects of the reaction conditions, such as the reaction temperature, the quantity of the raw materials on the morphologies of the precursors were discussed, which indicates that it is an effective method to synthesize NiO materials with different hierarchical structures. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  8. Potential in vitro Protective Effect of Quercetin, Catechin, Caffeic Acid and Phytic Acid against Ethanol-Induced Oxidative Stress in SK-Hep-1 Cells

    Lee, Ki-Mo; Kang, Hyung-Sik; Yun, Chul-Ho; Kwak, Hahn-Shik

    2012-01-01

    Phytochemicals have been known to exhibit potent antioxidant activity. This study examined cytoprotective effects of phytochemicals including quercetin, catechin, caffeic acid, and phytic acid against oxidative damage in SK-Hep-1 cells induced by the oxidative and non-oxidative metabolism of ethanol. Exposure of the cells to excess ethanol resulted in a significant increase in cytotoxicity, reactive oxygen species (ROS) production, lipid hydroperoxide (LPO), and antioxidant enzyme activity. E...

  9. Synthesis and characterization of nanocrystalline nickel oxide using NaOH and oxalic acid as oxide sources

    Precursors of nickel oxide (NiO) nanoparticles were synthesized through a simple chemical precipitation method by changing the oxide source used for the synthesis. The synthesized precursors were subjected to thermo gravimetric analysis (TGA) to determine the temperature at which the precursors decompose into nickel oxide. The obtained results of TGA suggest that precursor NiO prepared using sodium hydroxide (NaOH) showed NiO formation at 600 °C, whereas, when oxalic acid was used as oxide source the formation of NiO took place at 400 °C. After calcinations of the precursors at respective temperatures, NiO nanocrystals have been harvested. The synthesized NiO powders were characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectroscopy, field emission scanning electron microscopy (FE-SEM), energy dispersive x-ray analysis (EDX), and vibrating sample magnetometer (VSM) analysis. An FE-TEM image of NiO prepared using oxalic acid showed spherical and elliptical particles with sizes in the range of 15 nm. The Williamson–Hall (W–H) plots were drawn for the annealed products to study their lattice strain and crystallite size. The sizes of NiO nanocrystals obtained from W–H analysis are well correlated with sizes estimated using Scherrer’s formula. The relatively low saturation magnetization of NiO confirms its super paramagnetic behavior. (papers)

  10. Vanadium oxides supported on hydrotalcite-type precursors: the effect of acid base properties on the oxidation of isopropanol

    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 deg 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. (author)

  11. Vanadium oxides supported on hydrotalcite-type precursors: the effect of acid-base properties on the oxidation of isopropanol

    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.

  12. Formic Acid Modified Co3O4-CeO2 Catalysts for CO Oxidation

    Ruishu Shang

    2016-03-01

    Full Text Available A formic acid modified catalyst, Co3O4-CeO2, was prepared via facile urea-hydrothermal method and applied in CO oxidation. The Co3O4-CeO2-0.5 catalyst, treated by formic acid at 0.5 mol/L, performed better in CO oxidation with T50 obtained at 69.5 °C and T100 obtained at 150 °C, respectively. The characterization results indicate that after treating with formic acid, there is a more porous structure within the Co3O4-CeO2 catalyst; meanwhile, despite of the slightly decreased content of Co, there are more adsorption sites exposed by acid treatment, as suggested by CO-TPD and H2-TPD, which explains the improvement of catalytic performance.

  13. Large discharge capacity from carbon electrodes in sulfuric acid with oxidant

    Inagaki, M.; Iwashita, N.

    The discharge performance of the graphite intercalation compounds in sulfuric acid containing nitric acid (H 2SO 4-GICs) was studied by focusing on the effects of oxidant and carbon nanotexture. A large discharge capacity from H 2SO 4-GICs synthesized by using an excess amount of HNO 3, more than 150 times of the theoretical value (93 mAh/g carbon), was obtained depending on the amount of oxidant added, the discharge current, and the nanotexture of carbon electrode. The experimental results are explained in terms of competition between the de-intercalation of sulfuric acid due to galvanostatic reduction and the re-intercalation due to chemical oxidation by HN03 during discharging. However, a subsidiary reaction decreases the effective amount of HNO 3 on the discharge by a small current and also on the cycle of chemical charging and electrochemical discharging. The oxidant KMnO 4 gave only a little larger capacity for discharge than the theoretical one, because it was reduced to the manganese oxide precipitates during the oxidation of the carbon electrode.

  14. Oxidation Effect on Tribological Pproperties of Rapeseed oil and Lard Mixtures Containing Monoglycerides and Fatty Acids

    Violeta Makareviciene

    2012-10-01

    Full Text Available Vegetable oils and animal fats are increasingly popular base material to produce environmentally friendly lubricants. This is a renewable and easily biodegradable in the natural environment material. The main disadvantage of vegetable oils and animal fats as raw materials and its lubricants is pour oxidation stability. There are already a wide range of environmentally friendly lubricants in the market, while the variety of greases offer is not so high. This research aims to explore the properties of prepared compositions of lubricating greases produced from rapeseed oil and lard, modifying them with monoglycerides, stearic and oleic acids. The plastic properties (penetration and oxidation influence on tribological and corrosive properties of these compositions were studied. It was found that modifying rapeseed oil and lard with monoglycerides, oleic and stearic acids a few lubricating compositions of NLGI grades can be achieved: soft or very soft rapeseed oil based greases and medium or nearly hard consistency lard based compositions. The oxidation studies showed that it decreases the tribological properties of base and monoglycerides modified lubricants. Oxidation has greater negative impact on lard and lard based compositions. Oleic and stearic acids reduces or completely eliminates the negative influence of oxidation. Corrosion studies have shown that both fresh and oxidized lubricant compositions have no significant affect on copper strip corrosion.DOI: http://dx.doi.org/10.5755/j01.erem.61.3.1763

  15. Oxidative degradation of salicylic acid by sprayed WO3 photocatalyst

    Highlights: • The photoactivity of sprayed WO3 thin film. • Photoelectrocatalytic degradation of salicylic acid. • Reaction kinetics and mineralization of pollutants by COD. - Abstract: The WO3 thin films were deposited using spray pyrolysis technique. The prepared WO3 thin films were characterized using photoelectrochemical (PEC), X-ray diffraction, atomic force microscopy (AFM), and UV–vis absorbance spectroscopy techniques. PEC measurements of WO3 films deposited at different deposition temperatures were carried out to study photoresponse. The maximum photocurrent (Iph = 261 μA/cm2) was observed for the film deposited at the 225 °C. The monoclinic crystal structure of WO3 has been confirmed from X-ray diffraction studies. AFM studies were used to calculate particle size and average roughness of the films. Optical absorbance was studied to estimate the bandgap energy of WO3 thin film which was about 2.65 eV. The photoelectrocatalytic activity of WO3 film was studied by degradation of salicylic acid with reducing concentrations as function of reaction time. The WO3 photocatalyst degraded salicylic acid to about 67.14% with significant reduction in chemical oxygen demand (COD) value

  16. The contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using diamond anodes.

    Bensalah, Nasr; Dbira, Sondos; Bedoui, Ahmed

    2016-07-01

    In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond (BDD) anodes was investigated in different electrolytes. A complete mineralization of cyanuric acid was obtained in NaCl; however lower degrees of mineralization of 70% and 40% were obtained in Na2SO4 and NaClO4, respectively. This can be explained by the nature of the oxidants electrogenerated in each electrolyte. It is clear that the contribution of active chlorine (Cl2, HClO, ClO(-)) electrogenerated from oxidation of chlorides on BDD is much more important in the electrolytic degradation of cyanuric acid than the persulfate and hydroxyl radicals produced by electro-oxidation of sulfate and water on BDD anodes. This could be explained by the high affinity of active chlorine towards nitrogen compounds. No organic intermediates were detected during the electrolytic degradation of cyanuric acid in any the electrolytes, which can be explained by their immediate depletion by hydroxyl radicals produced on the BDD surface. Nitrates and ammonium were the final products of electrolytic degradation of cyanuric acid on BDD anodes in all electrolytes. In addition, small amounts of chloramines were formed in the chloride medium. Low current density (≤10mA/cm(2)) and neutral medium (pH in the range 6-9) should be used for high efficiency electrolytic degradation and negligible formation of hazardous chlorate and perchlorate. PMID:27372125

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

    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.

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

    Weinberger Klaus M

    2009-01-01

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

  19. Reactivity of aminophosphonic acids. Oxidative dephosphonylation of 1-aminoalkylphosphonic acids by aqueous halogens.

    Drabowicz, Józef; Jordan, Frank; Kudzin, Marcin H; Kudzin, Zbigniew H; Stevens, Christian V; Urbaniak, Paweł

    2016-02-01

    The reactions of 1-aminoalkylphosphonic acids with bromine-water, chlorine-water and iodine-water were investigated. The formation of phosphoric(v) acid, as a result of a halogen-promoted cleavage of the Cα-P bond, accompanied by nitrogen release, was observed. The dephosphonylation of 1-aminoalkylphosphonic acids was found to occur quantitatively. In the reactions of 1-aminoalkylphosphonic acids with other halogen-water reagents investigated by (31)P NMR, scission of the Cα-P bond was also observed, the reaction rates being comparable for bromine and chlorine, but much slower for iodine. PMID:26631424

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

    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

  1. Performance of Caro's acid as an oxidant at the Nabarlek Mill

    Pyrolusite (manganese dioxide) was originally chosen as the oxidant at the Nabarlek Mill in northern Australia. Subsequent laboratory and plant trial investigations showed that if Caro's acid were to replace pyrolusite, acid consumption in the leaching circuit could be reduced by 15-20% for the same uranium extraction. Lime required to neutralize the tailings/raffinate slurry could also be similarly reduced. A Caro's acid generator was commissioned at Nabarlek in April 1983. Caro's acid is manufactured at the mill site by reaction of hydrogen peroxide with concentrated sulphuric acid. This installation is the first commercial utilization of Caro's acid in uranium processing. The system has operated successfully for three months and reagent savings have resulted in a reduction in operating costs of greater than $3.t-1 ore processed. (author)

  2. Mechanism of β-FeSi2 precipitates growth-and-dissolution and pyramidal defects' formation during oxidation of Fe-contaminated silicon wafers

    Fe-implanted Si-wafers have been oxidized at 900 °C and 1100 °C in order to investigate the behaviour of Fe atoms at the growing SiO2/Si interface and the impact on the integrity of microelectronic devices of an involuntary Fe contamination before or during the oxidation process. As-implanted and oxidized wafers have been characterized using secondary ion mass spectroscopy, atom probe tomography, and high-resolution transmission electron microscopy. Experimental results were compared to calculated implantation profiles and simulated images. Successive steps of iron disilicide precipitation and oxidation were evidenced during the silicon oxidation process. The formation of characteristic pyramidal-shaped defects, at the SiO2/Si interface, was notably found to correlate with the presence of β-FeSi2 precipitates. Taking into account the competitive oxidation of these precipitates and of the surrounding silicon matrix, dynamic mechanisms are proposed to model the observed microstructural evolution of the SiO2/Si interface, during the growth of the silicon oxide layer

  3. 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

    Klingelhoeffer Christoph; Kämmerer Ulrike; Koospal Monika; Mühling Bettina; Schneider Manuela; Kapp Michaela; Kübler Alexander; Germer Christoph-Thomas; Otto Christoph

    2012-01-01

    Abstract Background Ascorbic acid demonstrates a cytotoxic effect by generating hydrogen peroxide, a reactive oxygen species (ROS) involved in oxidative cell stress. A panel of eleven human cancer cell lines, glioblastoma and carcinoma, were exposed to serial dilutions of ascorbic acid (5-100 mmol/L). The purpose of this study was to analyse the impact of catalase, an important hydrogen peroxide-detoxifying enzyme, on the resistance of cancer cells to ascorbic acid mediated oxidative stress. ...

  4. ABA biosynthesis defective mutants reduce some free amino acids accumulation under drought stress in tomato leaves in comparison with Arabidopsis plants tissues

    Adnan Ali Al.Asbahi

    2012-05-01

    Full Text Available The ability of plants to tolerate drought conditions is crucial for plant survival and crop production worldwide. The present data confirm previous findings reported existence of a strong relation between abscisic acid (ABA content and amino acid accumulation as response water stress which is one of the most important defense mechanism activated during water stress in many plant species. Therefore, free amino acids were measured to determine any changes in the metabolite pool in relation to ABA content. The ABA defective mutants of Arabidopsis plants were subjected to leaf dehydration for Arabidopsis on Whatman 3 mm filter paper at room temperature while, tomato mutant plants were subjected to drought stresses for tomato plants by withholding water. To understand the signal transduction mechanisms underlying osmotic stress-regulating gene induction and activation of osmoprotectant free amino acid synthesizing genes, we carried out a genetic screen to isolate Arabidopsis mutants defective in ABA biosynthesis under drought stress conditions. The present results revealed an accumulation of specific free amino acid in water stressed tissues in which majority of free amino acids are increased especially those playing an osmoprotectant role such as proline and glycine. Drought stress related Amino acids contents are significantly reduced in the mutants under water stress condition while they are increased significantly in the wild types plants. The exhibited higher accumulation of other amino acids under stressed condition in the mutant plants suggest that, their expressions are regulated in an ABA independent pathways. In addition, free amino acids content changes during water stress condition suggest their contribution in drought toleration as common compatible osmolytes.

  5. Heat generates oxidized linoleic acid metabolites that activate TRPV1 and produce pain in rodents

    Patwardhan, Amol M.; Akopian, Armen N.; Ruparel, Nikita B.; Diogenes, Anibal; Weintraub, Susan T; Uhlson, Charis; Murphy, Robert C.; Hargreaves, Kenneth M.

    2010-01-01

    The transient receptor potential vanilloid 1 (TRPV1) channel is the principal detector of noxious heat in the peripheral nervous system. TRPV1 is expressed in many nociceptors and is involved in heat-induced hyperalgesia and thermoregulation. The precise mechanism or mechanisms mediating the thermal sensitivity of TRPV1 are unknown. Here, we have shown that the oxidized linoleic acid metabolites 9- and 13-hydroxyoctadecadienoic acid (9- and 13-HODE) are formed in mouse and rat skin biopsies b...

  6. Bile acid induced colonic irritation stimulates intracolonic nitric oxide release in humans.

    F. Casellas; Mourelle, M; Papo, M; Guarner, F; Antolin, M; Armengol, J R; J. R. Malagelada

    1996-01-01

    AIM--To measure the intracolonic release of nitric oxide end products (nitrates plus nitrites) and eicosanoids in response to intraluminal irritation with deoxycholic acid (DCA). PATIENTS--Seven patients with irritable bowel syndrome. METHODS--The left colon was perfused with a solution with or without 3 mM deoxycholic acid. Aspirates were assayed for eicosanoids by specific radioimmuno-assay, and for nitrates plus nitrites by the Griess reaction. To confirm that stimulated colonic mucosa can...

  7. Nanocarbons as catalyst for selective oxidation of acrolein to acrylic acid

    Frank, B.; Blume, R.; Rinaldi, A.; Trunschke, A.; Schloegl, R. [Fritz Haber Institute of the Max Planck Society, Berlin (Germany). Dept. of Inorganic Chemistry

    2011-07-01

    Selective oxidations are key steps of industrial oil and gas processing for the synthesis of high-value chemicals. Mixed metal oxides based on redox active V or Mo are frequently used for oxidative C-H bond activation. However, multiple processes require precious metals or suffer from low product selectivity demanding an ongoing search for cost-effective alternatives. Recently, the nanostructured carbon was reported to catalyze the metal-free selective alkane activation by oxidative dehydrogenation (ODH). Electron-rich surface carbonyls coordinate this reaction and mimic the active oxygen species in metal oxide catalysts. Here we show that the graphitic carbon, beyond ODH, has the potential to selectively mediate the insertion of an oxygen atom into an organic molecule, i.e., acrolein. Multi-step atom rearrangements considerably exceed the mechanistic complexity of hydrogen abstraction and were so far believed to be the exclusive domain of metal (oxide) catalysis. In the carbon catalyzed process, the nucleophilic oxygen atoms terminating the graphite (0001) surface abstract the formyl hydrogen and the activated aldehyde gets oxidized by epoxide-type mobile oxygen, thus the sp{sup 2} carbon acts as a bifunctional catalyst. Substantial similarities between the metal oxide- and carbon-catalyzed reactions could be identified. Our results shed light on a rarely known facet of applications of nanostructured carbon materials being decorated with diverse oxygen functionalities to coordinate complex catalytic processes. We could successfully transfer the results obtained from the graphite model to carbon nanotubes (CNTs) providing a higher surface area, defect density, and intrinsic activity, to substantially increase the reactivity per catalyst volume. Indeed, low dimensional nanostructured carbon is a highly flexible and robust material which can be modified in a multiple manner to optimize its properties with respect to the intended application. The exploration of

  8. Effect of acid oxidization of carbon nanotube electrode on the capacitances of double layer capacitors

    LI; Chensha; WANG; Dazhi; LIANG; Tongxiang; WANG; Xiaofen

    2004-01-01

    Polarizable electrode of electric double layer capacitor was made from carbon nanotubes. The effect of acid oxidation of electrode on the specific capacitance was studied. Oxidation removed the redundant carbon, expanded the pore size and introduced some kinds of functional groups on the surface of CNTs. The specific capacit ance of the electrodes with organic electrolyte was increased from 21.4 to 49.6 F/gafter being oxidized at a volume ratio of H2SO4 to HNO3 of 3:1.

  9. Highly dispersed Pd nanoparticles on chemically modified graphene with aminophenyl groups for formic acid oxidation

    Yang Su-Dong; Shen Cheng-Min; Tong Hao; He Wei; Zhang Xiao-Gang; Gao Hong-Jun

    2011-01-01

    A novel electrode material based on chemically modified graphene (CMG) with aminophenyl groups is covalently functionalized by a nucleophilic ring-opening reaction between the epoxy groups of graphene oxide and the aminophenyl groups of p-phenylenediamine.Palladium nanoparticles with an average diameter of 4.2 nm are deposited on the CMG by a liquid-phase borohydride reduction.The electrocatalytic activity and stability of the Pd/CMG composite towards formic acid oxidation are found to be higher than those of reduced graphene oxide and commercial carbon materials such as Vulcan XC-72 supported Pd electrocatalysts.

  10. Nitrification of archaeal ammonia oxidizers in acid soils is supported by hydrolysis of urea

    Lu, Lu; Han, Wenyan; Zhang, Jinbo; Wu, Yucheng; Wang, Baozhan; Lin, Xiangui; Zhu, Jianguo; Cai, Zucong; Jia, Zhongjun

    2012-01-01

    The hydrolysis of urea as a source of ammonia has been proposed as a mechanism for the nitrification of ammonia-oxidizing bacteria (AOB) in acidic soil. The growth of Nitrososphaera viennensis on urea suggests that the ureolysis of ammonia-oxidizing archaea (AOA) might occur in natural environments. In this study, 15N isotope tracing indicates that ammonia oxidation occurred upon the addition of urea at a concentration similar to the in situ ammonium content of tea orchard soil (pH 3.75) and ...

  11. Direct synthesis of graphene nanosheets support Pd nanodendrites for electrocatalytic formic acid oxidation

    Yang, Su-Dong; Chen, Lin

    2015-11-01

    We report a solvothermal method preparation of dendritic Pd nanoparticles (DPNs) and spherical Pd nanoparticles (SPNs) supported on reduced graphene oxide (RGO). Drastically different morphologies of Pd NPs with nanodendritic structures or spherical structures were observed on graphene by controlling the reduction degree of graphene oxide (GO) under mild conditions. In addition to being a commonplace substrate, GO plays a more important role that relies on its surface groups, which serves as a shape-directing agent to direct the dendritic growth. As a result, the obtained DPNs/RGO catalyst exhibits a significantly enhanced electro-catalytic behavior for the oxidation of formic acid compared to the SPNs/RGO catalyst.

  12. Highly dispersed Pd nanoparticles on chemically modified graphene with aminophenyl groups for formic acid oxidation

    A novel electrode material based on chemically modified graphene (CMG) with aminophenyl groups is covalently functionalized by a nucleophilic ring-opening reaction between the epoxy groups of graphene oxide and the aminophenyl groups of p-phenylenediamine. Palladium nanoparticles with an average diameter of 4.2 nm are deposited on the CMG by a liquid-phase borohydride reduction. The electrocatalytic activity and stability of the Pd/CMG composite towards formic acid oxidation are found to be higher than those of reduced graphene oxide and commercial carbon materials such as Vulcan XC-72 supported Pd electrocatalysts. (atomic and molecular physics)

  13. Oxidative acid treatment and characterization of new biocarbon from sustainable Miscanthus biomass.

    Anstey, Andrew; Vivekanandhan, Singaravelu; Rodriguez-Uribe, Arturo; Misra, Manjusri; Mohanty, Amar Kumar

    2016-04-15

    Oxidative acid treatments of biochar produced from Miscanthus were performed in this study using nitric acid, sulfuric acid, and a mixture of both. The structural and morphological changes of the acid-treated biochar were investigated using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Raman spectroscopy, organic elemental analysis and energy-dispersive X-ray spectroscopy (EDS). Improved surface functionality of the treated biochars was observed in their respective FT-IR spectra through the presence of nitro and carboxylic acid functional groups. SEM-EDS and elemental analysis revealed a large increase in the oxygen to carbon ratio in the biochar, which was evidence of chemical oxidation from the acid treatment. Further, TGA study showed the reduced thermal stability of acid-treated biochar over 200°C due to the increased oxygen content. Acid treatments also influenced the graphitic structure of the biochar, as observed in the Raman spectra. The results suggest that biochar can be successfully functionalized for composite applications and provide a sustainable alternative to petroleum-based carbon additives. PMID:26820927

  14. Dietary Berries and Ellagic Acid Prevent Oxidative DNA Damage and Modulate Expression of DNA Repair Genes

    Ramesh C. Gupta

    2008-03-01

    Full Text Available DNA damage is a pre-requisite for the initiation of cancer and agents that reduce this damage are useful in cancer prevention. In this study, we evaluated the ability of whole berries and berry phytochemical, ellagic acid to reduce endogenous oxidative DNA damage. Ellagic acid was selected based on > 95% inhibition of 8-oxodeoxyguosine (8-oxodG and other unidentified oxidative DNA adducts induced by 4-hydroxy-17B;-estradiol and CuCl2 in vitro. Inhibition of the latter occurred at lower concentrations (10 u(microM than that for 8-oxodG (100 u(microM. In the in vivo study, female CD-1 mice (n=6 were fed either a control diet or diet supplemented with ellagic acid (400 ppm and dehydrated berries (5% w/w with varying ellagic acid contents -- blueberry (low, strawberry (medium and red raspberry (high, for 3 weeks. Blueberry and strawberry diets showed moderate reductions in endogenous DNA adducts (25%. However, both red raspberry and ellagic acid diets showed a significant reduction of 59% (p < 0.001 and 48% (p < 0.01, respectively. Both diets also resulted in a 3-8 fold over-expression of genes involved in DNA repair such as xeroderma pigmentosum group A complementing protein (XPA, DNA excision repair protein (ERCC5 and DNA ligase III (DNL3. These results suggest that red raspberry and ellagic acid reduce endogenous oxidative DNA damage by mechanisms which may involve increase in DNA repair.

  15. Boronic acid functionalized superparamagnetic iron oxide nanoparticle as a novel tool for adsorption of sugar

    Synthesis of boronic acid functionalized superparamagnetic iron oxide nanoparticles has been reported. Magnetite nanoparticles were prepared by simple co-precipitation from Fe2+ and Fe3+ solution. m-Aminophenyl boronic acid was attached to iron oxide particles through 3,4-dihydroxy benzaldehyde through C=N bond. X-ray diffraction and selected area electron diffraction have shown the formation of inverse spinel phase magnetite of both as prepared and functionalized magnetite particles. FTIR shows attachment of boronic acid-imine onto iron oxide surface through enediol group. Transmission electron microscopy shows well dispersion of boronic acid functionalized particles of size 8 ± 2 nm. Vibration sample magnetometry shows both the particles are superparamagnetic at room temperature having saturation magnetization (Ms) 52 emu/g. In this work the affinity of these boronic acid functionalized particles towards sugar binding was studied taking dextrose sugar as a model. The influence of pH and sugar concentration has been extensively investigated. The results show that such boronic acid modified superparamagnetic particles are efficient support for sugar separation having maximum sugar loading capacity (60 μg/50 μl) at pH 8.

  16. Boronic acid functionalized superparamagnetic iron oxide nanoparticle as a novel tool for adsorption of sugar

    Mohapatra, S., E-mail: sasmita05@gmail.com [Department of Chemistry, National Institute of Technology, Rourkela-769008 (India); Panda, N. [Department of Chemistry, National Institute of Technology, Rourkela-769008 (India); Pramanik, P. [Department of Chemistry, Indian Institute of Technology, Kharagpur-721302 (India)

    2009-08-31

    Synthesis of boronic acid functionalized superparamagnetic iron oxide nanoparticles has been reported. Magnetite nanoparticles were prepared by simple co-precipitation from Fe{sup 2+} and Fe{sup 3+} solution. m-Aminophenyl boronic acid was attached to iron oxide particles through 3,4-dihydroxy benzaldehyde through C=N bond. X-ray diffraction and selected area electron diffraction have shown the formation of inverse spinel phase magnetite of both as prepared and functionalized magnetite particles. FTIR shows attachment of boronic acid-imine onto iron oxide surface through enediol group. Transmission electron microscopy shows well dispersion of boronic acid functionalized particles of size 8 {+-} 2 nm. Vibration sample magnetometry shows both the particles are superparamagnetic at room temperature having saturation magnetization (Ms) 52 emu/g. In this work the affinity of these boronic acid functionalized particles towards sugar binding was studied taking dextrose sugar as a model. The influence of pH and sugar concentration has been extensively investigated. The results show that such boronic acid modified superparamagnetic particles are efficient support for sugar separation having maximum sugar loading capacity (60 {mu}g/50 {mu}l) at pH 8.

  17. DEFECTS SIMULATION OF ROLLING STRIP

    Rudolf Mišičko; Tibor Kvačkaj; Martin Vlado; Lucia Gulová; Miloslav Lupták; Jana Bidulská

    2009-01-01

    The defects in the continuous casting slabs can be developed or kept down in principle by rolling technology, especially depend to sort, size and distribution of primary defects, as well as used of rolling parameters. Scope of the article is on observation behavior artificial surface and undersurface defects (scores) without filler (surface defects) and filling by oxides and casting powder (subsurface defects). First phase of hot rolling process have been done by software simulation DEFORM 3D...

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

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

    2013-01-01

    Plant defence against pests and pathogens is known to be conferred by either salicylic acid (SA) or jasmonic acid (JA)/ethylene (ET) pathways, depending on infection or herbivore-grazing strategy. It is well attested that SA and JA/ET pathways are mutually antagonistic allowing defence responses...

  19. Formation of Porous Anodic Oxide Film on Titanium in Phosphoric Acid Electrolyte

    Liu, Z.; Thompson, G. E.

    2015-01-01

    A sequential breakdown anodizing conditions on cp-Ti in phosphoric acid has been investigated in the present study. Anodic oxide films were formed at 100, 150, and 200 V, examined by scanning electron microscopy, Raman spectroscopy, glow discharge optical emission spectrometry, and electrochemical impedance spectroscopy. A porous oxide texture was formed at each voltage. The thickness of anodic porous oxide increased with the increase of anodic voltage. Nano-particulates were formed around and within the pores, and the size of pores increased with increased voltage due to the expansion of particulates. The amorphous-to-crystalline transition was initiated during the film growth. The degree of crystallinity in the anodic oxide film fabricated at 200 V is more abundant than 150 and 100 V. Increased content of the phosphorus species was incorporated into the porous film with the increase of anodic voltage, stabilizing for the nanocrystals developed within the oxide.

  20. Changes in oxidative properties of Kalanchoe blossfeldiana leaf mitochondria during development of Crassulacean acid metabolism.

    Rustin, P; Queiroz-Claret, C

    1985-06-01

    Kalanchoe blossfeldiana plants grown under long days (16 h light) exhibit a C3-type photosynthetic metabolism. Switching to short days (9 h light) leads to a gradual development of Crassulacean acid metabolism (CAM). Under the latter conditions, dark CO2 fixation produces large amounts of malate. During the first hours of the day, malate is rapidly decarboxylated into pyruvate through the action of a cytosolic NADP(+)-or a mitochondrial NAD(+)-dependent malic enzyme. Mitochondria were isolated from leaves of plants grown under long days or after treatment by an increasing number of short days. Tricarboxylic acid cycle intermediates as well as exogenous NADH and NADPH were readily oxidized by mitochondria isolated from the two types of plants. Glycine, known to be oxidized by C3-plant mitochondria, was still oxidized after CAM establishment. The experiments showed a marked parallelism in the increase of CAM level and the increase in substrate-oxidation capacity of the isolated mitochondria, particularly the capacity to oxidize malate in the presence of cyanide. These simultaneous variations in CAM level and in mitochondrial properties indicate that the mitochondrial NAD(+)-malic enzyme could account at least for a part of the oxidation of malate. The studies of whole-leaf respiration establish that mitochondria are implicated in malate degradation in vivo. Moreover, an increase in cyanide resistance of the leaf respiration has been observed during the first daylight hours, when malate was oxidized to pyruvate by cytosolic and mitochondrial malic enzymes. PMID:24249613