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Sample records for acid components kinetics

  1. Kinetic analysis of the reactions of hypobromous acid with protein components

    Pattison, David I; Davies, Michael Jonathan

    2004-01-01

    proteins isolated from patients with atherosclerosis, asthma, and cystic fibrosis, implicating the production of HOX in these diseases. The quantitative significance of these findings requires knowledge of the kinetics of reaction of HOX with protein targets, and such data have not been previously...... more, and Cys and Met much less, important targets for HOBr than HOCl. Kinetic models have been developed to predict the targets of HOX attack on proteins and free amino acids. Overall, these results shed light on the mechanisms of cell damage induced by HOX and indicate, for example, that the 3-chloro...

  2. Radiomimeticity of the system H2O2/Fe(II) on nucleic acid components. Kinetics study

    The kinetic study of the action of a redox system on DNA monomers allowed us to make criticisms on radiomimetic character of this system. Assuming that in both cases, gamma radiolysis of aerated aqueous solutions and action of H2O2 / Fe(II) system in the same conditions, the reactive species is the OH radical, we propose the kinetic expressions that are confirmed by our experimental results. Some of the accepted G-values are corrected in view of our results. Al so these results put in evidence mechanisms of molecular repair after radical attack. (Author) 79 refs

  3. Synergistic role of different soil components in slow sorption kinetics of polar organic contaminants

    We observed that the sorption kinetics of nitrobenzene and 2,4-dinitrotoluene (two model polar compounds) was significantly slower than that of 1,4-dichlorobenzene and phenanthrene (two model apolar compounds). The difference was attributable to the strong non-hydrophobic interactions between the polar molecules and soil. Interestingly, sorption kinetics of the polar sorbates to the soil organic matter-free soil, humic/fulvic acid-free soil, and extracted humic acids was very fast, indicating that different soil components played a synergetic role in the observed slow kinetics. We propose that slow sorption kinetics of highly polar sorbates stems mainly from the strong specific interactions (H-bonding, electron donor–acceptor interactions, etc.) with humic/fulvic acids; such specific interactions occur when sorbate molecules diffuse through humic/fulvic acids coiled, in relatively compressed confirmations, within the complex, tortuous, and porous soil matrices formed by mineral grains/particles and soil organic matter. -- Highlights: • Polar sorbates exhibit much slower sorption kinetics to soil than apolar sorbates. • Slow sorption is not from sorptive interaction with any single soil component. • Polar interactions with humic/fulvic acids coiled in soil matrices hinder sorption. • Humin/minerals contribute to slow sorption by forming tortuous, porous network. -- Slow sorption kinetics of polar organic contaminants is a result of synergistic contribution from different soil components

  4. On the kinetic theory of the one-component plasma

    In this thesis, kinetic theory is applied to transport phenomena of a one-component plasma. Existing kinetic equations, containing both dynamical screening effects and close binary collisions do not suffer from divergencies. Recently an approximation for the pair correlation function has been proposed that is valid for small values of the plasma collision parameter. Upon insertion of this expression into the general form of the collision integral, one obtains another convergent kinetic equation. This thesis shows that both kinetic equations yield the same coefficient of heat conductivity and viscosity; and that for a hot dilute plasma the arbitrary transport coefficient is rather insensitive to the pair correlation function. In the second part, the author studies the diffusion of a tagged particle in an external magnetic field. It is found that the longitudinal self-diffusion coefficient contra-varies monotonically with the magnetic field strength. (Auth.)

  5. Kinetic Modeling of Sunflower Grain Filling and Fatty Acid Biosynthesis.

    Durruty, Ignacio; Aguirrezábal, Luis A N; Echarte, María M

    2016-01-01

    Grain growth and oil biosynthesis are complex processes that involve various enzymes placed in different sub-cellular compartments of the grain. In order to understand the mechanisms controlling grain weight and composition, we need mathematical models capable of simulating the dynamic behavior of the main components of the grain during the grain filling stage. In this paper, we present a non-structured mechanistic kinetic model developed for sunflower grains. The model was first calibrated for sunflower hybrid ACA855. The calibrated model was able to predict the theoretical amount of carbohydrate equivalents allocated to the grain, grain growth and the dynamics of the oil and non-oil fraction, while considering maintenance requirements and leaf senescence. Incorporating into the model the serial-parallel nature of fatty acid biosynthesis permitted a good representation of the kinetics of palmitic, stearic, oleic, and linoleic acids production. A sensitivity analysis showed that the relative influence of input parameters changed along grain development. Grain growth was mostly affected by the specific growth parameter (μ') while fatty acid composition strongly depended on their own maximum specific rate parameters. The model was successfully applied to two additional hybrids (MG2 and DK3820). The proposed model can be the first building block toward the development of a more sophisticated model, capable of predicting the effects of environmental conditions on grain weight and composition, in a comprehensive and quantitative way. PMID:27242809

  6. Kinetic Modeling of Sunflower Grain Filling and Fatty Acid Biosynthesis

    Durruty, Ignacio; Aguirrezábal, Luis A. N.; Echarte, María M.

    2016-01-01

    Grain growth and oil biosynthesis are complex processes that involve various enzymes placed in different sub-cellular compartments of the grain. In order to understand the mechanisms controlling grain weight and composition, we need mathematical models capable of simulating the dynamic behavior of the main components of the grain during the grain filling stage. In this paper, we present a non-structured mechanistic kinetic model developed for sunflower grains. The model was first calibrated for sunflower hybrid ACA855. The calibrated model was able to predict the theoretical amount of carbohydrate equivalents allocated to the grain, grain growth and the dynamics of the oil and non-oil fraction, while considering maintenance requirements and leaf senescence. Incorporating into the model the serial-parallel nature of fatty acid biosynthesis permitted a good representation of the kinetics of palmitic, stearic, oleic, and linoleic acids production. A sensitivity analysis showed that the relative influence of input parameters changed along grain development. Grain growth was mostly affected by the specific growth parameter (μ′) while fatty acid composition strongly depended on their own maximum specific rate parameters. The model was successfully applied to two additional hybrids (MG2 and DK3820). The proposed model can be the first building block toward the development of a more sophisticated model, capable of predicting the effects of environmental conditions on grain weight and composition, in a comprehensive and quantitative way. PMID:27242809

  7. 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...

  8. Kinetics of Demineralization of Shrimp Shell Using Lactic Acid

    Alewo Opuada AMEH

    2014-02-01

    Full Text Available Shrimp exoskeleton was demineralized using lactic acid and the kinetics of the demineralisation was studied. The residual concentration of calcium after acid treatment was used as a measure of the degree of demineralisation. Kinetic data was obtained using five acid concentrations (0.2, 0.4, 0.6, 0.8 and 1M and the obtained kinetic data was fitted to the shrinking core model. For all concentrations, the best predictive model was determined to be ash layer diffusion controlled mechanism.

  9. Kinetics of molecular transformations in connective tissue hyaluronic acid

    When exposed to ionizing radiations or inflammatory disease, the glycosaminolycan component of connective tissue is preferentially degraded, probably by a free-radical mediate pathway. The resulting changes in molecular structure adversely change the properties of the matrix. Rooster comb hyaluronic acid of high molecular weight was used to investigate the mechanisms of these structural changes at macro and molecular level. Intrinsic viscosity and gel permeation chromatography measurements are suitable for demonstrating that random chain session occurs. Fast kinetic techniques are necessary to identify the mechanisms of single strand breaks. Pulse conductivity and low-angle laser light scattering pulse radiolysis can quantify the rate and yield of strand breaks. Competitive radical scavenging methods have also allowed the quantification of the rate of spontaneous and alkali-catalyzed hydrolysis of a-hydroxy radicals on polysaccharide chains, which control molecular structure changes

  10. Kinetic Modeling of Esterification of Ethylene Glycol with Acetic Acid

    The reaction kinetics of the esterification of ethylene glycol with acetic acid in the presence of cation exchange resin has been studied and kinetic models based on empirical and Langmuir approach has been developed. The Langmuir based model involving eight kinetic parameters fits experimental data much better compared to empirical model involving four kinetic parameters. The effect of temperature and catalyst loading on the reaction system has been analyzed. Further, the activation energy and frequency factor of the rate constants for Langmuir based model has been estimated.

  11. Single molecule DNA interaction kinetics of retroviral nucleic acid chaperone proteins

    Williams, Mark

    2010-03-01

    Retroviral nucleocapsid (NC) proteins are essential for several viral replication processes including specific genomic RNA packaging and reverse transcription. The nucleic acid chaperone activity of NC facilitates the latter process. In this study, we use single molecule biophysical methods to quantify the DNA interactions of wild type and mutant human immunodeficiency virus type 1 (HIV-1) NC and Gag and human T-cell leukemia virus type 1 (HTLV-1) NC. We find that the nucleic acid interaction properties of these proteins differ significantly, with HIV-1 NC showing rapid protein binding kinetics, significant duplex destabilization, and strong DNA aggregation, all properties that are critical components of nucleic acid chaperone activity. In contrast, HTLV-1 NC exhibits significant destabilization activity but extremely slow DNA interaction kinetics and poor aggregating capability, which explains why HTLV-1 NC is a poor nucleic acid chaperone. To understand these results, we developed a new single molecule method for quantifying protein dissociation kinetics, and applied this method to probe the DNA interactions of wild type and mutant HIV-1 and HTLV-1 NC. We find that mutations to aromatic and charged residues strongly alter the proteins' nucleic acid interaction kinetics. Finally, in contrast to HIV-1 NC, HIV-1 Gag, the nucleic acid packaging protein that contains NC as a domain, exhibits relatively slow binding kinetics, which may negatively impact its ability to act as a nucleic acid chaperone.

  12. 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

  13. Kinetic and Thermodynamic Parameters for Uncatalyzed Esterification of Carboxylic Acid

    Kehinde S. Bankole

    2014-06-01

    Full Text Available A fundamental study on uncatalyzed esterification of various biomass-derived aliphatic carboxylic acids with stoichiometric amount of ethanol has been investigated in an isothermal batch reactor, with the objective to convert carboxylic acids to corresponding ethyl esters and to determine both the kinetic and thermodynamic parameters. The effects of temperature on the conversion of carboxylic acid, kinetic and thermodynamic parameters have been investigated. Temperature was found to have significant effect on the rate of reaction and conversion of carboxylic acid. A simple second order reversible kinetic model was developed to determine the kinetic and thermodynamic parameters. The thermodynamic and kinetic parameters varied for uncatalyzed esterification reaction of both short-chain and long-chain carboxylic acids considered. The predicted data from the kinetic model were correlated with experimental data and the two sets of data agreed reasonably well for the uncatalyzed esterification systems. It was observed that the Van’t Hoff plot for uncatalyzed esterification of linoleic acid was non-linear curve, whereas for the Arrhenius and Eyring plots, they were linear. Additional experiments to assess the catalytic and corrosion effects of several metallic substances revealed Inconel 625 alloy, nickel wire and stainless steel materials were susceptible to corrosion problem with uncatalyzed esterification reaction at elevated reaction temperatures. However, tantalum and grade-5 titanium materials were corrosion resistance metals, suitable for similar reaction conditions and this can encourage the design of a flow reactor system. Although, uncatalyzed esterification of carboxylic acids at elevated reaction temperature is still at laboratory scale. It is our hope that the estimated kinetic and thermodynamic parameters would be the guiding tools for reactor scale-up, thus providing a new perspective into the conversion of biomass-derived carboxylic

  14. Kinetics of Hydrogen Evolution on Copper Electrode Involving Organic Acids as Proton Donors

    A. Survila; Kanapeckaitė, S.; Pileckienė, J.; Būdienė, J.

    2011-01-01

    Linear potential sweep (LPS) voltammetry was applied to study the kinetics of hydrogen evolution in solutions containing glycolic, malic, tartaric, and gluconic acids. The CE mechanism of hydrogen evolution was analyzed invoking the 2nd Fick's law equations supplemented by terms that account for chemical interactions between diffusing particles. Acids are considered as components that are capable of releasing hydrated protons taking part in the charge-transfer step. Current peaks observed on ...

  15. Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid

    Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.

    2007-01-01

    A variety of interesting bulk chemicals is accessible by the acid-catalyzed hydrolysis of cellulose. An interesting example is levulinic acid, a versatile precursor for fuel additives, polymers, and resins. A detailed kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid is r

  16. Thermodynamic and kinetic aspects of surface acidity. Progress report

    Dumesic, J.A.

    1992-04-01

    Our research in the general area of acid catalysis involves the characterization of solid acidity and the corresponding assessment of catalytic performance of acidic materials. Acid characterization studies are required to provide essential information about the type of acid site (i.e., Lewis versus Bronsted), the strength of the sites, and the mobility of molecules adsorbed on the acid sites. An accurate measure of acid strength is given by the heat of adsorption of a basic probe molecule on the acid site. A thermodynamic representation of the mobility of adsorbed species on these sites is given by the entropy of adsorption. Important techniques used in these acid site characterization studies include microcalorimetry, thermogravimetric measurements, temperature programmed desorption, infrared spectroscopy and solid state nuclear magnetic resonance. The combination of these acid site characterization studies with reaction kinetics measurements of selected catalytic processes allows the elucidation of possible relationships between surface thermodynamic and kinetic properties of acidic sites. Such relationships are important milestones in formulating effective strategies for the effective utilization of solid acid catalysts. Current work in this direction involves methylamine syntheses over various zeolites, and the basic probe molecules employed include ammonia, methanol, water and mono-, di- and tri-methylamines. 31 refs., 18 figs., 1 tab.

  17. 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...

  18. 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.

  19. Kinetics of esterification of methanol and acetic acid with mineral homogeneous acid catalyst

    Mallaiah Mekala; Venkat Reddy Goli

    2015-01-01

    In this work, esterification of acetic acid and methanol to synthesize methyl acetate in a batch stirred reactor is studied in the temperature range of 305.15–333.15 K. Sulfuric acid is used as the homogeneous catalyst with concentrations ranging from 0.0633 mol·L−1 to 0.3268 mol·L−1. The feed molar ratio of acetic acid to methanol is varied from 1:1 to 1:4. The influences of temperature, catalyst concentration and reactant concentration on the reaction rate are investigated. A second order kinetic rate equation is used to correlate the experimental data. The forward and backward reaction rate constants and activation energies are determined from the Arrhenius plot. The developed kinetic model is compared with the models in literature. The developed kinetic equation is useful for the simulation of reactive distillation column for the synthesis of methyl acetate.

  20. Sulfuric acid leaching kinetics of South African chromite

    Qing Zhao; Cheng-jun Liu; Pei-yang Shi; Bo Zhang; Mao-fa Jiang; Qing-song Zhang; Ron Zevenhoven; Henrik Saxn

    2015-01-01

    The sulfuric acid leaching kinetics of South African chromite was investigated. The negative influence of a solid product layer constituted of a silicon-rich phase and chromium-rich sulfate was eliminated by crushing the chromite and by selecting proper leaching con-ditions. The dimensionless change in specific surface area and the conversion rate of the chromite were observed to exhibit a proportional re-lationship. A modified shrinking particle model was developed to account for the change in reactive surface area, and the model was fitted to experimental data. The resulting model was observed to describe experimental findings very well. Kinetics analysis revealed that the leach-ing process is controlled by a chemical reaction under the employed experimental conditions and the activation energy of the reaction is 48 kJ·mol–1.

  1. 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

  2. Kinetics of xylose dehydration into furfural in acetic acid

    Zhou Chen; Weijiang Zhang; Jiao Xu; Pingli Li

    2015-01-01

    In this paper kinetics of xylose dehydration into furfural using acetic acid as catalyst was studied comprehensively and systematical y. The reaction order of both furfural and xylose dehydration was determined and the reaction activation energy was obtalned by nonlinear regression. The effect of acetic acid concentration was also investi-gated. Reaction rate constants were galned. Reaction rate constant of xylose dehydration is k1 ¼ 4:189 . 1010 ½A.0:1676 exp −108:6.1000RT . ., reaction rate constant of furfural degradation is k2 ¼ 1:271 . 104½A.0:1375 exp−63:413.1000RT . and reaction rate constant of condensation reaction is k3 ¼ 3:4051 . 1010½A.0:1676 exp−104:99.1000RT .. Based on this, the kinetics equation of xylose dehydration into furfural in acetic acid was set up according to theory of Dunlop and Furfural generating rate equation is dd½F.t ¼ k1½X.0e−k1t−k2½F.−k3½X.0e−k1t½F.. © 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. Al rights reserved.

  3. Lipid-Nucleic Acid Supramolecular Complexes: Lipoplex Structure and the Kinetics of Formation

    Nily Dan

    2015-06-01

    Full Text Available The need for synthetic gene therapy or gene silencing vehicles that can insert therapeutic nucleic acids (DNA or siRNA into cells (so-called transfection has focused interest on lipid-nucleic acid assemblies (lipoplexes. This paper reviews the kinetics pathways leading to lipoplex formation and structure. The process is qualitatively comparable to those of cluster nucleation and growth and to the adsorption of polyelectrolytes on colloidal particles: Initially is a rapid stage where the nucleic acid binds onto the surface of the cationic lipid aggregate (adsorption, or nucleation. This is followed by an intermediate step where the lipid/nucleic acid complexes flocculate to form larger structures (growth. The last and final step involves internal rearrangement, where the overall global structure remains constant while local adjustment of the nucleic acid/lipid organization takes place until the equilibrium lipoplex characteristics are obtained. This step can require unusually long time scales of order hours or longer. Understanding the kinetics of lipoplex formation is not only of fundamental interest as a multi-component, multi-length scale and multi-time scale process, but also has significant implications for the utilization of lipoplexes as carriers for gene delivery and gene silencing agents.

  4. Kinetic Optimization of Folic Acid Polymer Conjugates for Drug Targeting

    Jacob M. Ngoy

    2011-01-01

    Full Text Available Problem statement: Folic Acid (FA is an essential, bioavailable water soluble B-complex vitamin that helps in the replication of normal cells. It is obtained from natural sources and it deficiency can leads to oncogenic cells development. Within this frame work in mind, we designed and synthesized a new bioconjugate carrier that can enhance the effectiveness of FA. Approach: The polymeric carrier: Polysucscinimide (PSI was synthesized via the polycondensation of aspartic acid by attaching 3-(N,N-Dimethylamino Propylamine (DMP and 1,3-P-propylenediamine (PDA for solubility behavior and reactivity for FA site anchoring. Also the use of an ester 2-(1H-benzotrial-1- yl-1,1,3,3-tetramethylurium Hexafluorophosphate (HBTU as coupling agent to FA. The bioreversible binding of the water-soluble and biocompatible macromolecular were attested through kinetic studies. The kinetic reactions were investigated through the nuclear resonance (H1NMR spectra analysis. Results and Conclusion: The H1NMR optimization reaction times were found within the range of 120-130 min (80-85% as optimum coupling. The yield of the FA occurred within the same time range but with maximum incorporation between 90-100%. The growth of FA incorporation in terms of reaction time resulted to an increase inherent viscosity relative to the decrease of water solubility of the conjugate obtained.

  5. Acid base catalyzed transesterification kinetics of waste cooking oil

    Jain, Siddharth; Sharma, M.P.; Rajvanshi, Shalini [Alternate Hydro Energy Centre, Indian Institute of Technology, Roorkee (India)

    2011-01-15

    The present study reports the results of kinetics study of acid base catalyzed two step transesterification process of waste cooking oil, carried out at pre-determined optimum temperature of 65 C and 50 C for esterification and transesterification process respectively under the optimum condition of methanol to oil ratio of 3:7 (v/v), catalyst concentration 1%(w/w) for H{sub 2}SO{sub 4} and NaOH and 400 rpm of stirring. The optimum temperature was determined based on the yield of ME at different temperature. Simply, the optimum concentration of H{sub 2}SO{sub 4} and NaOH was determined with respect to ME Yield. The results indicated that both esterification and transesterification reaction are of first order rate reaction with reaction rate constant of 0.0031 min{sup -1} and 0.0078 min{sup -1} respectively showing that the former is a slower process than the later. The maximum yield of 21.50% of ME during esterification and 90.6% from transesterification of pretreated WCO has been obtained. This is the first study of its kind which deals with simplified kinetics of two step acid-base catalyzed transesterification process carried under the above optimum conditions and took about 6 h for complete conversion of TG to ME with least amount of activation energy. Also various parameters related to experiments are optimized with respect to ME yield. (author)

  6. Study of the kinetics and equilibria of the oligomerization reactions of 2-methylglyceric acid

    A. W. Birdsall

    2012-11-01

    Full Text Available The presence of a variety of chemical species related to the gaseous precursor isoprene in ambient secondary organic aerosol (SOA has stimulated investigations of the nature of SOA-phase chemical processing. Recent work has demonstrated that 2-methylglyceric acid (2-MG is an important isoprene-derived ambient SOA component and atmospheric chamber experiments have suggested that 2-MG may exist in oligomeric form (as oligoesters under conditions of low SOA water content. In order to better understand the thermodynamic and kinetic parameters of such oligomerization reactions, nuclear magnetic resonance techniques were used to study the bulk phase acid-catalyzed aqueous reactions (Fischer esterification of 2-MG. While the present results indicate that 2-MG oligoesters are formed in the bulk phase with similar water content equilibrium dependences as observed in atmospheric chamber SOA experiments, the acid-catalyzed rate of the Fischer esterification mechanism may be too slow to rationalize the 2-MG oligoester production timescales observed in the atmospheric chamber experiments. Furthermore, it appears that unrealistically high ambient SOA acidities would also be required for significant 2-MG oligoester content to arise via Fischer esterification. Therefore, the present results suggest that other, more kinetically facile, esterification mechanisms may be necessary to rationalize the existence of 2-MG oligomers in atmospheric chamber-generated and ambient SOA.

  7. Study of the kinetics and equilibria of the oligomerization reactions of 2-methylglyceric acid

    A. W. Birdsall

    2013-03-01

    Full Text Available The presence of a variety of chemical species related to the gaseous precursor isoprene in ambient secondary organic aerosol (SOA has stimulated investigations of the nature of SOA-phase chemical processing. Recent work has demonstrated that 2-methylglyceric acid (2-MG is an important isoprene-derived ambient SOA component and atmospheric chamber experiments have suggested that 2-MG may exist in oligomeric form (as oligoesters under conditions of low SOA water content. In order to better understand the thermodynamic and kinetic parameters of such oligomerization reactions, nuclear magnetic resonance techniques were used to study the bulk phase acid-catalyzed aqueous reactions (Fischer esterification of 2-MG. While the present results indicate that 2-MG oligoesters are formed in the bulk phase with similar water content equilibrium dependences as observed in atmospheric chamber SOA experiments, the acid-catalyzed rate of the Fischer esterification mechanism may be too slow to rationalize the 2-MG oligoester production timescales observed in the atmospheric chamber experiments. Furthermore, it appears that unrealistically high ambient SOA acidities would also be required for significant 2-MG oligoester content to arise via Fischer esterification. Therefore, the present results suggest that other, more kinetically facile, esterification mechanisms may be necessary to rationalize the existence of 2-MG oligomers in atmospheric chamber-generated and ambient SOA.

  8. Radiomimeticity of the system H{sub 2}O{sub 2}/Fe(II) on nucleic acid components. Kinetics study; Radiomimeticidad del sistema H{sub 2}O{sub 2}/Fe(II) sobre components de Acidos Nucleicos. Estudio Cinetico

    Cirauqui, R.; Mingot, F.; Davila, C. A.

    1974-07-01

    The kinetic study of the action of a redox system on DNA monomers allowed us to make criticisms on radiomimetic character of this system. Assuming that in both cases, gamma radiolysis of aerated aqueous solutions and action of H{sub 2}O{sub 2} / Fe(II) system in the same conditions, the reactive species is the OH radical, we propose the kinetic expressions that are confirmed by our experimental results. Some of the accepted G-values are corrected in view of our results. Al so these results put in evidence mechanisms of molecular repair after radical attack. (Author) 79 refs.

  9. [Leaching kinetics of josephinite tailings with sulfuric acid].

    Chen, An-An; Zhou, Shao-Qi; Huang, Peng-Fei

    2013-07-01

    Leaching is the most important step of josephinite tailing recycle technology. This step can separate the valuable metal Mg from Si and other impure metal. Effects of sulfuric acid on leaching Mg efficiency from josephinite tailings were investigated. To obtain the leaching behavior, a modified unreacted shrinking core model that based on the experimental data was used to determine the dissolution kinetic parameters. The model was significant and showed that the dissolution of Mg2+ in josephinite tailing was controlled by the produce layer diffusion, apparent activation reaction energy E = 34.04 kJ x mol(-1). The produce layers obstruct the forward reaction of the dissolution of Mg2+. PMID:24028005

  10. Intramolecular Lactonization of Poly(α-hydroxyacrylic acid: Kinetics and Reaction Mechanism

    Heli Virkki

    2015-01-01

    Full Text Available Poly(α-hydroxyacrylic acid, PHA, is one of the few polymers with biodegradable properties used in mechanical pulp bleaching to stabilize hydrogen peroxide. A new method for the in situ follow-up of the lactone ring formation of PHA has been developed. The results have further been applied to describe the reaction kinetics of the lactonization and hydrolysis reactions through parameter estimation. In addition, the reaction mechanism is elucidated by multivariate data analysis. Satisfactory identification and semiquantitative separation of the lactone ring as well as the acyclic (carboxyl and hydroxyl groups forms have been established by 1H NMR in the pH range of 1–9. The lactonization reaction approaching equilibrium can be described by pseudo-first-order kinetics in the pH range of 1–6. The rate constants of the pseudo-first-order kinetic model have been estimated by nonlinear regression. Due to the very low rates of lactonization as well as the weak pH dependency of the reaction, an addition-elimination mechanism is proposed. Additionally, the presence of a transient reaction intermediate during lactonization reaction could be identified by subjecting the measurement data to multivariate data analysis (PCA, principal component analysis. A good correlation was found between the kinetic and the PCA models in terms of model validity.

  11. Kinetics and mechanism of reduction of iron (III) kojic acid complex by ascorbic acid

    Kinetics of reduction of iron (III) kojic acid complex by ascorbic acid has been carried out using photodiode array spectrophotometer over the ranges: 4.0<=pH<=5.5 and 5.0<=T<=25.0 degree C at ionic strength 0.2 M under pseudo-first order conditions by stopped-flow technique. Rate of the reaction was found to be pH dependent. The redox reaction followed the saturation kinetics. The rate law is deduced as follows: Rate = (k/sub 3/k/sub eq(H/sup +/)(HAsc/sup -/)(Fe(KA)/sub 3/) / (HKA) + K/sub eq/(H/sup +/)(HAsc/sup -/) The activation parameters of this reaction were determined. A mechanism consistent with this rate law has been proposed. (author)

  12. 3.6. The kinetics of sulfuric acid decomposition of calcined concentrate of borosilicate ore

    Present article is devoted to kinetics of sulfuric acid decomposition of calcined concentrate of borosilicate ore. The experimental data of kinetics of extraction of boron oxide from danburite at sulfuric acid decomposition were obtained at 20-90 deg C temperature range and process duration 15-90 minutes. The flowsheet of obtaining of boric acid from borosilicate ores of Ak-Arkhar Deposit by sulfuric acid method was proposed.

  13. Cometary impact and amino acid survival - Chemical kinetics and thermochemistry

    Ross, D.S.

    2006-01-01

    The Arrhenius parameters for the initiating reactions in butane thermolysis and the formation of soot, reliable to at least 3000 K, have been applied to the question of the survival of amino acids in cometary impacts on early Earth. The pressure/temperature/time course employed here was that developed in hydrocode simulations for kilometer-sized comets (Pierazzo and Chyba, 1999), with attention to the track below 3000 K where it is shown that potential stabilizing effects of high pressure become unimportant kinetically. The question of survival can then be considered without the need for assignment of activation volumes and the related uncertainties in their application to extreme conditions. The exercise shows that the characteristic times for soot formation in the interval fall well below the cooling periods for impacts ranging from fully vertical down to about 9?? above horizontal. Decarboxylation, which emerges as more rapid than soot formation below 2000-3000 K, continues further down to extremely narrow impact angles, and accordingly cometa??ry delivery of amino acids to early Earth is highly unlikely. ?? 2006 American Chemical Society.

  14. Kinetics and effects of dichloroacetic acid in rainbow trout.

    Fitzsimmons, Patrick N; Hoffman, Alex D; Lien, Gregory J; Hammermeister, Dean E; Nichols, John W

    2009-09-14

    Halogenated acetic acids (HAAs) produced by chlorine disinfection of municipal drinking water represent a potentially important class of environmental contaminants. Little is known, however, about their potential to adversely impact fish and other aquatic life. In this study we examined the kinetics and effects of dichloroacetic acid (DCA) in rainbow trout. Branchial uptake was measured in fish confined to respirometer-metabolism chambers. Branchial uptake efficiency was passive diffusion through aqueous channels in the gill epithelium. DCA concentrations in tissues following prolonged (72, 168, or 336 h) waterborne exposures were expressed as tissue:plasma concentration ratios. Concentration ratios for the kidney and muscle at 168 and 336 h were consistent with the suggestion that DCA distributes primarily to tissue water. Reduced concentration ratios for the liver, particularly at 72 h, indicated that DCA was highly metabolized by this tissue. Routes and rates of elimination were characterized by injecting chambered animals with a high (5.0mg/kg) or low (50 microg/kg) bolus dose. DCA was rapidly cleared by naïve animals resulting in elimination half-lives (t(1/2)) of less than 4h. Waterborne pre-treatment of fish with DCA increased the persistence of a subsequently injected dose. In high dose animals, pre-treatment caused a 4-fold decrease in whole-body clearance (CL(B)) and corresponding increases in the area under the plasma concentration-time curve (extrapolated to infinity; AUC(0-->infinity)) and t(1/2). Qualitatively similar results were obtained in low dose fish, although the magnitude of the pre-treatment effect ( approximately 2.5-fold) was reduced. Renal and branchial clearance contributed little (combined, <3% of CL(B)) to the elimination of DCA. Biliary elimination of DCA was also negligible. The steady-state volume of distribution (V(SS)) did not vary among treatment groups and was consistent with results of the tissue distribution study. DCA had no

  15. 3.3. The kinetics of sulfuric acid decomposition of calcined borosilicate ore

    Present article is devoted to kinetics of sulfuric acid decomposition of calcined borosilicate ore. The experimental data of kinetics of extraction of boron oxide from calcined borosilicate ore at sulfuric acid decomposition were obtained at 30-95 deg C temperature ranges and process duration from 15 to 60 minutes.

  16. 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.

  17. Green chemicals : A Kinetic Study on the Conversion of Glucose to Levulinic Acid

    Girisuta, B.; Janssen, L.P.B.M.; Heeres, H.J.

    2006-01-01

    Levulinic acid has been identified as a promising green, biomass derived platform chemical. A kinetic study on one of the key steps in the conversion of biomass to levulinic acid, i.e., the acid catalysed decomposition of glucose to levulinic acid has been performed. The experiments were performed i

  18. Kinetics of reaction between acetic acid and Ag2+ in nitric acid medium

    The reaction kinetics between acetic acid and Ag2+ in nitric acid medium is studied by spectrophotometry. The effects of concentrations of acetic acid (HAc), H+, NO3- and temperature on the reaction are investigated. The rate equation has been determined to be -dc(Ag2+)/dt=kc(Ag2+)c(HAc)c-1(H+), where k = (610±15) (mol/L)-1·min-1 with an activation energy of about (48.8±3.5) kJ·mol-1 when the temperature is 25degC and the ionic strength is 4.0 mol/L. The reduction rate of Ag2+ increases with the increase of HAc concentration or temperature and the decrease of HNO3 concentration. However, the effect of NO3- concentrations on the reaction rate is negligible. (author)

  19. 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.

  20. Kinetic characterization of a novel acid ectophosphatase from Enterobacter asburiae.

    Sato, Vanessa Sayuri; Galdiano Júnior, Renato F; Rodrigues, Gisele Regina; Lemos, Eliana G M; Pizauro Junior, João Martins

    2016-02-01

    Expression of acid ectophosphatase by Enterobacter asburiae, isolated from Cattleya walkeriana (Orchidaceae) roots and identified by the 16S rRNA gene sequencing analysis, was strictly regulated by phosphorus ions, with its optimal activity being observed at an inorganic phosphate concentration of 7 mM. At the optimum pH 3.5, intact cells released p-nitrophenol at a rate of 350.76 ± 13.53 nmol of p-nitrophenolate (pNP)/min/10(8) cells. The membrane-bound enzyme was obtained by centrifugation at 100,000 × g for 1 h at 4 °C. p-Nitrophenylphosphate (pNPP) hydrolysis by the enzyme follows "Michaelis-Menten" kinetics with V = 61.2 U/mg and K0.5 = 60 μM, while ATP hydrolysis showed V = 19.7 U/mg, K0.5 = 110 μM, and nH = 1.6 and pyrophosphate hydrolysis showed V = 29.7 U/mg, K0.5 = 84 μM, and nH = 2.3. Arsenate and phosphate were competitive inhibitors with K i = 0.6 mM and K i = 1.8 mM, respectively. p-Nitrophenyl phosphatase (pNPPase) activity was inhibited by vanadate, while p-hydroxymercuribenzoate, EDTA, calcium, copper, and cobalt had no inhibitory effects. Magnesium ions were stimulatory (K0.5 = 2.2 mM and nH = 0.5). Production of an acid ectophosphatase can be a mechanism for the solubilization of mineral phosphates by microorganisms such as Enterobacter asburiae that are versatile in the solubilization of insoluble minerals, which, in turn, increases the availability of nutrients for plants, particularly in soils that are poor in phosphorus. PMID:26832666

  1. Surface components of chylomicrons from rats fed glyceryl or alkyl esters of fatty acids: minor components.

    Yang, L Y; Kuksis, A; Myher, J J; Pang, H

    1992-08-01

    The lipid class, fatty acid and molecular species composition of the minor polar surface components of rat lymph chylomicrons were determined during absorption of menhaden oil and corn oil or of the corresponding fatty acid ethyl esters. In addition to the previously reported minor polar lipids (sphingomyelin, phosphatidylserine, phosphatidylinositol, phosphatidic acid and lysophosphatidylcholine), we identified phosphatidylglycerol, dimethylphosphatidylethanolamine, ceramide and cholesteryl sulfate in the chylomicrons from both oil and ester feeding. The dietary fatty acids were found to be incorporated to a variable extent into the different phospholipid classes, the proportions of which remained the same during both types of feeding. No evidence was obtained for the presence of the minor glycerophospholipids characteristic of the lysosomal membranes (e.g., bis-phosphatidic, lysobisphosphatidic and semilysobis-phosphatidic acids), although special efforts were made to identify them. These results indicate that the chylomicrons arising from the monoacylglycerol and phosphatidic acid pathways of triacylglycerol biosynthesis become enveloped in closely similar monolayers of phospholipids. Hence, all triacylglycerols may be secreted from the villus cells via a common mechanism as suggested by the previously demonstrated convergence (at the 2-monoacylglycerol stage) of the monoacylglycerol and the phosphatidic acid pathways of mucosal triacylglycerol formation [Yang, Y.L., and Kuksis, A. (1991) J. Lipid Res. 32, 1173-1186]. PMID:1406072

  2. Kinetic isotope effect of carbon-13 in decarboxylation of phenylpropiolic acid in anhydrous formic acid

    Carbon-13 kinetic isotope effects in the decarboxylation of phenylpropiolic acid (carboxyl-13C) in formic acid medium and in the decarbonylation of liquid formic acid assisted with phenylpropiolic acid (PPA) and acetophenone (AP) have been studied in the 70-100oC temperature interval. The carboxyl-13C KIEs are in the range 1.0034 at 71.6oC and 1.0047 at 101.2oC respectively. The C-13C KIE, k-12/k-13, in the decarbonylation of liquid formic acid assisted with PPA were found to be of 1.0419 at 71.6oC and 1.0383 at 101.2oC. The C-13 KIE in the decarbonylation of pure formic acid are 1.0464 at 70.2oC and 1.0411 at 98oC respectively. The above experimental results have been discussed and interpreted as indicating that the formation of Cα-H bond preceded by the protonation of triple acetylenic bond of PPA is the rate determining step followed by carbon dioxide splitting. The 13-CO-KIE in the carbon monooxide generation assisted with PPA is much larger than the 13-CO-KIE generated in the presence of phenylacetylene. This shows that the decarboxylation of PPA and decarboxylation of FA are interrelated processes proceeding in the reaction cage. The formic acid involved in the formation of TS is decarbonylating directly avoiding probably largely the formic acid anhydride intermediate formation. (author)

  3. Components development for sulfuric acid processing in the IS process

    The Japan Atomic Energy Agency (JAEA) has been conducting research and development on a thermochemical iodine–sulfur (IS) process, one of most attractive water-splitting hydrogen production methods, that uses the nuclear heat of a high-temperature gas-cooled reactor (HTGR). An examination is planned to verify the integrity of the components in the sulfuric acid decomposition section. A bayonet-type sulfuric acid decomposer made of SiC ceramics, a key component in the section, was test-fabricated. In parallel, a direct-contact heat exchanger (DCHX) is contemplated for use in the sulfuric acid decomposition section to simplify the process. The application of the DCHX makes it possible to perform heat recovery and separate undecomposed sulfuric acid from the decomposed gaseous mixture in one reactor. Although the concept is very attractive, little is known about the heat and mass transfer behavior in the DCHX. Therefore, a test apparatus was constructed to measure the gas-phase mass transfer coefficients required for the optimal design of the DCHX. These coefficients of water were acquired and compared with an empirical correlation. The experimental data were in good agreement with those obtained from empirical correlation, and thus, the apparatus was confirmed to be reasonable

  4. PCB congener sorption to carbonaceous sediment components: Macroscopic comparison and characterization of sorption kinetics and mechanism

    Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparative results on 2-chlorobiphenyl sorption to carbonaceous components in sediments (activated carbon, carbon black, coal, soot, graphite, flyash, wood) were macroscopically correlated with the structural, morphological, crystallographic, and compositional properties of the carbonaceous components. Since the Freundlich sorption constant, KF (L kg-1) spanned several orders of magnitude, ranging from log KF of 6.13-5.27 for activated carbon, 5.04 for carbon black, 3.83 for coal to 3.08 for wood, organic carbon partitioning approach should be more specifically categorized, considering the various forms, nature and origins of organic carbon in sediment. Sorption rate constants and fraction parameters, which were numerically defined from empirical kinetic model with fast and slow sorption fractions, were closely related to the physicochemical properties of the carbonaceous components. Sorption interpretation approaches with a specific property and viewpoint, such as organic carbon partitioning, soot carbon distribution, or surface area correlation, did not properly explain the overall results on sorption capacity, fast and slow sorption kinetics, and partitioning coefficient. It is also important to emphasize the heterogeneous nature of sediment and the difficulties of encompassing the partitioning among its carbonaceous components.

  5. Kinetic modelling of the demineralization of shrimp exoskeleton using citric acid

    Alewo Opuada AMEH; Muhammed Tijani ISA; David ABUTU; Alibaba DANLAMI

    2014-01-01

    Citric acid was used in the demineralization of shrimp exoskeleton and the kinetics of the demineralization process was studied. Kinetic data was obtained by demineralisation using five acid concentrations (0.1, 0.2, 0.3, 0.4 and 0.5M). The obtained kinetic data were fitted to the shrinking core model for fluid particle reactions. The concentration of calcium was found to decrease with time. For all acid concentrations considered, the best predictive mechanism for the demineralization process...

  6. Kinetics of Formic Acid-autocatalyzed Preparation of Performic Acid in Aqueous Phase

    孙晓英; 赵雪冰; 杜伟; 刘德华

    2011-01-01

    Performic acid (PFA) is an oxidant used in chemical processing, synthesis and bleaching. The macro kinetic models of synthesis, hydrolysis and decomposition of PFA were investigated via formic acid-autocatalyzed reaction. It was found that the intrinsic activation energies of PFA synthesis and hydrolysis were 75.2 kJ·mol^-1 and 40.4 kJ·mol^-1 respectively. The observed activation energy of PFA decomposition was 95.4 kJ·mol^-1. The experi-mental results indicated that the decomposition of PFA was liable to occur even at the ambient temperature. Both the spontaneous decomposition and the radical-introduced decomposition contributed to the decomposition of PFA.

  7. Kinetics of Acid Reactions: Making Sense of Associated Concepts

    Tan, Kim Chwee Daniel; Treagust, David F.; Chandrasegaran, A. L.; Mocerino, Mauro

    2010-01-01

    In chemical kinetics, in addition to the concepts related to kinetics, stoichiometry, chemical equilibrium and the characteristics of the reactants are often involved when comparing the rates of different reactions, making such comparisons very challenging for students at all levels, as well as for pre-service science teachers. Consequently, four…

  8. Kinetic Study of the Reaction between Tert-butyl Hydrazine and Nitrous Acid

    2001-01-01

    The kinetic study of the reaction between tert-butyl hydrazine(TBH)and nitrous acid in nitric acid system is performed by spectrophotometry. The effect of some factors such as the concentration of TBH, the concentration of nitric acid, ionic strength, temperature and the

  9. Esterification of Oleic Acid for Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation

    Marcio J. da Silva

    2008-09-01

    Full Text Available The production of biodiesel from low-cost raw materials which generally contain high amounts of free fatty acids (FFAs is a valuable alternative that would make their production costs more competitive than petroleum-derived fuel. Currently, the production of biodiesel from this kind of raw materials comprises a two-stage process, which requires an initial acid-catalyzed esterification of the FFA, followed by a basecatalyzed transesterification of the triglycerides. Commonly, the acid H2SO4 is the catalyst on the first step of this process. It must be said, however, that major drawbacks such as substantial reactor corrosion and the great generation of wastes, including the salts formed due to neutralization of the mineral acid, are negative and virtually unsurmountable aspects of this protocol. In this paper, tin(II chloride dihydrate (SnCl2·2H2O, an inexpensive Lewis acid, was evaluated as catalyst on the ethanolysis of oleic acid, which is the major component of several fat and vegetable oils feedstocks. Tin chloride efficiently promoted the conversion of oleic acid into ethyl oleate in ethanol solution and in soybean oil samples, under mild reaction conditions. The SnCl2 catalyst was shown to be as active as the mineral acid H2SO4. Its use has relevant advantages in comparison to mineral acids catalysts, such as less corrosion of the reactors and as well as avoiding the unnecessary neutralization of products. Herein, the effect of the principal parameters of reaction on the yield and rate of ethyl oleate production has been investigated. Kinetic measurements revealed that the esterification of oleic acid catalyzed by SnCl2·2H2O is first-order in relation to both FFAs and catalyst concentration. Experimentally, it was verified that the energy of activation of the esterification reaction of oleic acid catalyzed by SnCl2 was very close those reported for H2SO4.

  10. Conversion of hemicellulose sugars catalyzed by formic acid: kinetics of the dehydration of D-xylose, L-arabinose, and D-glucose.

    Dussan, Karla; Girisuta, Buana; Lopes, Marystela; Leahy, James J; Hayes, Michael H B

    2015-04-24

    The pre-treatment of lignocellulosic biomass produces a liquid stream of hemicellulose-based sugars, which can be further converted to high-value chemicals. Formosolv pulping and the Milox process use formic acid as the fractionating agent, which can be used as the catalyst for the valorisation of hemicellulose sugars to platform chemicals. The objective of this study was to investigate the reaction kinetics of major components in the hemicelluloses fraction of biomass, that is, D-xylose, L-arabinose and D-glucose. The kinetics experiments for each sugar were performed at temperatures between 130 and 170 °C in various formic acid concentrations (10-64 wt %). The implications of these kinetic models on the selectivity of each sugar to the desired products are discussed. The models were used to predict the reaction kinetics of solutions that resemble the liquid stream obtained from the fractionation process of biomass using formic acid. PMID:25821128

  11. Kinetics of the esterification of active pharmaceutical ingredients containing carboxylic Acid functionality in polyethylene glycol

    Schou-Pedersen, Anne Marie V; Hansen, Steen Honoré; Moesgaard, Birthe;

    2014-01-01

    reactions. In this study, kinetics of two active pharmaceutical ingredients, cetirizine and indomethacin possessing carboxylic acid functionality, has been studied in PEG 400 and PEG 1000 at 50°C, 60°C, 70°C, and 80°C. HPLC-UV was applied for the determination of concentrations in the kinetic studies...

  12. Kinetic study of CO2 with various amino acid salts in aqueous solution

    Holst, van J.; Versteeg, G.F.; Brilman, D.W.F.; Hogendoorn, J.A.

    2009-01-01

    A study towards the kinetics of CO2 with several aqueous salts of amino acids was performed at a temperature of 298 K. Absorption rate experiments were carried out in the pseudo-first-order regime, enabling the determination of the kinetic rate constant from the flux. In a preliminary screening at a

  13. Kinetic study of CO2 with various amino acid salts in aqueous solution

    van Hoist, J.; Versteeg, G. F.; Brilman, D. W. F.; Hogendoorn, J. A.; Holst, J. v

    2009-01-01

    A study towards the kinetics Of CO2 with several aqueous salts of amino acids was performed at a temperature of 298 K. Absorption rate experiments were carried out in the pseudo-first-order regime, enabling the determination of the kinetic rate constant from the flux. In a preliminary screening at a

  14. 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

  15. Kinetics of fatty acid binding ability of glycated human serum albumin

    Eiji Yamazaki; Minoru Inagaki; Osamu Kurita; Tetsuji Inoue

    2005-09-01

    Kinetics of fatty acid binding ability of glycated human serum albumin (HSA) were investigated by fluorescent displacement technique with 1-anilino-8-naphtharene sulphonic acid (ANS method), and photometric detection of nonesterified-fatty-acid (NEFA method). Changing of binding affinities of glycated HSA toward oleic acid, linoleic acid, lauric acid, and caproic acid, were not observed by the ANS method. However, decreases of binding capacities after 55 days glycation were confirmed by the NEFA method in comparison to control HSA. The decrease in binding affinities was: oleic acid (84%), linoleic acid (84%), lauric acid (87%), and caproic acid (90%), respectively. The decreases were consistent with decrease of the intact lysine residues in glycated HSA. The present observation indicates that HSA promptly loses its binding ability to fatty acid as soon as the lysine residues at fatty acid binding sites are glycated.

  16. KINETIC OF ESTERIFICATION OF ETHYL ALCOHOL BY ACETIC ACID ON A CATALYTIC RESIN

    Erol İNCE

    2002-01-01

    Full Text Available The conversion kinetics of diluted acetic acid to ethyl acetate by ethanol esterification in a batch reactor in liquid phase with an acidic polymer catalyst (lewatit series was studied. The intrinsic rate constants have been correlated with the reaction temperature, concentration of catalyst, initial ratios of reactants and initial water concentrations. The kinetic analysis was restricted to the system at hand in which a liquid and vapor phase are at equilibrium.

  17. KINETIC OF ESTERIFICATION OF ETHYL ALCOHOL BY ACETIC ACID ON A CATALYTIC RESIN

    Erol İNCE

    2002-01-01

    The conversion kinetics of diluted acetic acid to ethyl acetate by ethanol esterification in a batch reactor in liquid phase with an acidic polymer catalyst (lewatit series) was studied. The intrinsic rate constants have been correlated with the reaction temperature, concentration of catalyst, initial ratios of reactants and initial water concentrations. The kinetic analysis was restricted to the system at hand in which a liquid and vapor phase are at equilibrium.

  18. Development of acid-resistant HEPA filter components

    Laboratory and in-service tests of various HEPA filter media and separators were conducted to establish their relative resistances to HNO3-HF vapors. Filter medium of glass fiber with Nomex additive and aluminum separators with an epoxy-vinyl coating have performed quite well in the acid environment in the laboratory, and in prototype-filters placed in service in a plenum at Rocky Flats. Proprietary filters with new design and/or components were also tested in service with generally good results

  19. Study on the Hydrolysis Kinetics of Xylan on Different Acid Catalysts

    In this study, we investigated kinetic model for the acid-catalyzed xylan hydrolysis at temperature 120-150 .deg. C. Also, we analyzed the kinetic parameters for xylose production and furfural decomposition. The hydrolysis of xylan and the degradation of xylose were promoted by high reaction temperature and acid concentration. The optimal hydrolysis condition for the highest reaction rate constants (k1) was different depending on the acid catalysts. Among sulfuric, oxalic and maleic acid, the xylan reaction rate constants (k1) to xylose had the highest value of 0.0241 min-1 when 100 mM sulfuric acid was used at 120 .deg. C. However, sulfuric acid induced more xylose degradation compared to oxalic and maleic acid hydrolysis. The activation energy for xylan degradation was the highest when sulfuric acid was used

  20. Study on the Hydrolysis Kinetics of Xylan on Different Acid Catalysts

    Na, Byeong-Il; Lee, Jae-Won [Chonnam National University, Gwangju (Korea, Republic of)

    2014-04-15

    In this study, we investigated kinetic model for the acid-catalyzed xylan hydrolysis at temperature 120-150 .deg. C. Also, we analyzed the kinetic parameters for xylose production and furfural decomposition. The hydrolysis of xylan and the degradation of xylose were promoted by high reaction temperature and acid concentration. The optimal hydrolysis condition for the highest reaction rate constants (k{sub 1}) was different depending on the acid catalysts. Among sulfuric, oxalic and maleic acid, the xylan reaction rate constants (k{sub 1}) to xylose had the highest value of 0.0241 min{sup -1} when 100 mM sulfuric acid was used at 120 .deg. C. However, sulfuric acid induced more xylose degradation compared to oxalic and maleic acid hydrolysis. The activation energy for xylan degradation was the highest when sulfuric acid was used.

  1. Thermodynamics and kinetics of thermal decomposition of dibutylalkyl and dipentylalkyl phosphonate-nitric acid systems

    Highlights: • Thermal stability of neat and nitric acid solvated DBalP and DPalP have been studied for the first time. • Incompressible gases and reddish viscous or black solid residues were formed on decomposition. • Decomposition of acid solvated phosphonates was found to be exothermic and follows first order kinetics. • The thermodynamic and kinetic parameters were derived wherever possible. - Abstract: Thermal stability of neat and nitric acid-solvated dibutylalkyl and dipentylalkyl phosphonates was studied under closed air ambience using an adiabatic calorimeter. Enthalpies and kinetic parameters for the decomposition reaction were derived wherever possible and are reported for the first time. The neat compounds were found to be stable up to 555 K while the nitric acid-solvated phosphonates decomposed at lower temperatures (370–403 K) with exothermic rise in temperature and pressure invariably producing incompressible gases. Decomposition of all these acid-solvates followed first order kinetics. The rise in temperature and pressure was found to be strongly dependent on nitric acid content of the acid-solvate. While the neat phosphonates produced solid black residue, the acid-solvates produced a viscous reddish-brown residue on decomposition. Heat capacities (Cp), of acid-solvates (DBPrP·0.6HNO3, DBBP·0.6HNO3 and DBPP·0.6HNO3) were measured at constant pressure using a heat flux type differential scanning calorimeter in the temperature range 305–350 K

  2. Esterification of oleic acid with ethanol catalyzed by sulfonated cation exchange resin: Experimental and kinetic studies

    Graphical abstract: - Highlights: • Esterification of oleic acid with ethanol was investigated in the presence of sulfonated cation exchange resin. • We studied kinetic model of the esterification of oleic acid with ethanol according to experimental data. • The proposed kinetic model can well predict oleic acid conversion. - Abstract: This paper investigated the effects of ethanol to oleic acid molar ratio, reaction temperature, catalyst loading, water content and catalyst recycling on sulfonated cation exchange resin in a stirred batch reactor under atmospheric pressure. When the esterification was carried out with an ethanol to oleic acid (42.4 g) molar ratio of 9:1, reflux of ethanol at 82 °C, 20 g of catalyst and 8 h of reaction time, the oleic acid conversion rate reached approximately 93%. A pseudo-homogeneous kinetic model for describing the esterification of oleic acid with ethanol by the sulfonated cation exchange resin was developed on the basis of laboratorial results. The kinetic model can well predict the oleic acid conversion

  3. Kinetics of sulfuric acid decomposition of pre-baked danburite of Ak-Arkhar deposit

    The results of studies of kinetics of sulfuric acid decomposition of pre-baked danburite of Ak-Arkhar deposit by means of first-order equation is given. It is defined that reaction passes in mixed area. The activation energy of sulfuric acid decomposition of pre-baked danburite is evaluated.

  4. A kinetic study on the decomposition of 5-hydroxymethylfurfural into levulinic acid

    Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.

    2006-01-01

    Levulinic acid (LA), accessible by the acid catalyzed degradation of biomass, is potentially a very versatile green intermediate chemical for the synthesis of various (bulk) chemicals for applications like fuel additives, polymers, and resin precursors. We report here a kinetic study on one of the k

  5. Kinetic study of hexavalent plutonium reduction by hydrogen peroxide in acid solution

    The kinetics of the reduction of hexavalent plutonium by hydrogen peroxide has been studied in perchloric, sulphuric and nitric acids. The rate of reduction is proportional to the initial concentrations of plutonium and of hydrogen peroxide and is inversely proportional to the acidity. The values of the proportionality constant k have been determined. They are very dependent on the temperature, on the ionic force and on the nature of the anion of the acid medium. An interpretation is put forward, based on the experimental results, attributing an important role to the hydrolysed species PuO2(OH)+ in the reduction kinetics. (author)

  6. 5.3. The kinetics of acetic acid decomposition of calcined borosilicate concentrate

    Present article is devoted to kinetics of acetic acid decomposition of calcined borosilicate concentrate. The experimental data of kinetics of boron oxide extraction from the calcined danburite concentrate at acetic acid decomposition was obtained at 30-90 deg C temperature ranges and 15-60 minutes process duration. It was defined that at temperature increasing the extraction rate of boron oxide from the calcined danburite concentrate significantly increases. The influence of extraction rate of boron oxide on process duration at acetic acid decomposition was studied.

  7. Carbon-13 kinetic isotope effects in the decarbonylation of lactic acid of natural isotopic composition in phosphoric acid medium

    The 13C kinetic isotope effect fractionation in the decarbonylation of lactic acid (LA) of natural isotopic composition by concentrated phosphoric acids (PA) and by 85% H3PO4 has been studied in the temperature interval of 60-150 deg C. The values of the 13C(1) isotope effects in the decarbonylation of lactic acid in 100% H3PO4, in pyrophosphoric acid and in more concentrated phosphoric acids are intermediate between the values calculated assuming that the C(1)-OH bond is broken in the rate-controlling step of dehydration and those calculated for rupture of the carbon-carbon bond in the transition state. In the temperature interval of 90-130 deg C the experimental 13C fractionation factors determined in concentrated PA approach quite closely the 13C fractionation corresponding to C(2)-C(1) bond scission. The 13C(1) kinetic isotope effects in the decarbonylation of LA in 85% orthophosphoric acid in the temperature range of 110-150 deg C coincide with the 13C isotope effects calculated assuming that the frequency corresponding to the C(1)-OH vibration is lost in the transition state of decarbonylation. A change of the mechanism of decarbonylation of LA in going from concentrated PA medium to 85% H3PO4 has been suggested. A possible secondary 18O and a primary18O kinetic isotope effect in decarbonylation of lactic acid in phosphoric acids media have been discussed, too. (author) 21 refs.; 3 tabs

  8. Kinetic modelling of the demineralization of shrimp exoskeleton using citric acid

    Alewo Opuada AMEH

    2014-11-01

    Full Text Available Citric acid was used in the demineralization of shrimp exoskeleton and the kinetics of the demineralization process was studied. Kinetic data was obtained by demineralisation using five acid concentrations (0.1, 0.2, 0.3, 0.4 and 0.5M. The obtained kinetic data were fitted to the shrinking core model for fluid particle reactions. The concentration of calcium was found to decrease with time. For all acid concentrations considered, the best predictive mechanism for the demineralization process was determined to be Ash Layer Diffusion Control Mechanism. This was indicated by the high R2 values obtained (0.965 with 150% excess of citric acid.

  9. Kinetics of Reductive Acid Leaching of Cadmium-Bearing Zinc Ferrite Mixture Using Hydrazine Sulfate

    Zhang, Chun; Zhang, Jianqiang; Min, Xiaobo; Wang, Mi; Zhou, Bosheng; Shen, Chen

    2015-09-01

    The reductive acid leaching kinetics of synthetic cadmium-bearing zinc ferrite was investigated, and the influence of reaction temperature, sulfuric acid and hydrazine sulfate were studied. The results illustrated that an increase in the reaction temperature, initial sulfuric acid and hydrazine sulfate significantly enhanced the extraction efficiencies of cadmium, zinc and iron. The leaching kinetics were controlled by a surface chemical reaction based on a shrinking core model. The empirical equation applied was found to fit well with the kinetics analysis; the leaching processes of cadmium, zinc and iron were similar and the activation energies were 79.9 kJ/mol, 77.9 kJ/mol and 79.7 kJ/mol, respectively. The apparent orders of cadmium-bearing zinc ferrite dissolution with respect to sulfuric acid concentration were 0.83, 0.83 and 0.84 for Cd, Zn and Fe, respectively.

  10. Kinetics Studies on citric acid production by gamma ray induced mutant of Aspergillus niger

    Effect of cultural pH and incubation temperature on citric acid yield and kinetic patterns of citric acid fermentation by a natural isolate of aspergillus niger as CA16 and one of its gamma ray induced mutants were studied using cane molasses as growth and fermentation substrate. Mutant strain, 277/30 gave maximum citric acid yield of 85 g/l at pH 3.5 and 28 degree centigrade in molasses medium adjusted to 16% sugar and 25% prescott salt in the medium. Parent strain, CA16 gave a maximum yield of 34 g/l at pH 4.0 and 26 degree centigrade in molasses medium adjusted to 16% sugar and 100% prescott salt in the medium. In kinetic studies, strains showed combination kinetics of citric acid fermentation where product formation is directly related to growth and cell mass and indirectly related to carbohydrate uptake

  11. Affinity and kinetics study of anthranilic acids as HCA2 receptor agonists.

    van Veldhoven, Jacobus P D; Liu, Rongfang; Thee, Stephanie A; Wouters, Yessica; Verhoork, Sanne J M; Mooiman, Christiaan; Louvel, Julien; IJzerman, Adriaan P

    2015-07-15

    Structure-affinity relationship (SAR) and structure-kinetics relationship (SKR) studies were combined to investigate a series of biphenyl anthranilic acid agonists for the HCA2 receptor. In total, 27 compounds were synthesized and twelve of them showed higher affinity than nicotinic acid. Two compounds, 6g (IC50=75nM) and 6z (IC50=108nM) showed a longer residence time profile compared to nicotinic acid, exemplified by their kinetic rate index (KRI) values of 1.31 and 1.23, respectively. The SAR study resulted in the novel 2-F, 4-OH derivative (6x) with an IC50 value of 23nM as the highest affinity HCA2 agonist of the biphenyl series, although it showed a similar residence time as nicotinic acid. The SAR and SKR data suggest that an early compound selection based on binding kinetics is a promising addition to the lead optimization process. PMID:25737085

  12. Kinetics of free radical decay reactions in lactic acid homo and copolymers irradiated to sterilization dose

    The kinetics of free radical decay reactions of poly(L-Lactic acid), poly(DL-Lactic acid) and random copolymer of lactic and glycolic acid have been investigated for decays taking place in air and in vacuum. The change in ESR lines of γ-irradiated polymers have been followed over a long time period. The decay has been found to follow neither simple first-order nor second-order kinetics. Various kinetic approaches including composite first or second-order mechanisms and diffusion-controlled first or second-order equations were determined to be also unsatisfactory. The decay of radicals in bulk irradiated lactic acid homo and copolymers was found to be best described when the second-order non-classical equation with time dependent rate constant approach was used. (Author)

  13. Dissolution kinetics of nickel laterite ore using different secondary metabolic acids

    S. Sahu

    2011-06-01

    Full Text Available The dissolution kinetics of nickel laterite ore in aqueous acid solutions of three metabolic acids, i.e., citric acid, oxalic acid and acetic acid were investigated in a batch reactor individually. It was determined that experimental data comply with a shrinking core model. The diffusion coefficients for citric acid, oxalic acid and acetic acid were found to be 1.99×10-9 cm²/s, 2.59×10-8 cm²/s and 1.92×10-10 cm²/s respectively. The leaching ability of each acid was observed and it was found that oxalic acid was better than the other two.

  14. 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.

  15. 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)

  16. Kinetic theory of the shear viscosity of a strongly coupled classical one-component plasma

    We present an approximation to the linearized collision operator or memory function of the exact kinetic equation obeyed by the correlation function of the phase-space density of a classical one-component plasma. This approximate collision operator generalizes the well known Balescu-Guernsey-Lenard (BGL) operator to finite wavelengths, finite frequencies, and finite coupling constants. It, moreover, satisfies the necessary symmetry relations, leads to appropriate conservation laws, and fulfills its first sum rule exactly. Next we use this operator to compute the shear viscosity eta for a series of coupling constants spanning the whole fluid phase. For weak coupling we make contact with the BGL theory, while for strong coupling we confirm, at least qualitatively, the results of Vieillefosse and Hansen, who predicted a minimum in eta as a function of temperature. We also demonstrate the important role played by the sum rules in the quantitative evaluation of a transport coefficient such as eta

  17. Carbon-14 kinetic isotope effect in the decarbonylation of lactic acid [1-14C

    The carbon-14 kinetic isotope effect for the decarbonation of lactic acid[1-14C] in sulfuric acid has been measured in the temperature interval of 20-90 deg C. The experimental values of (k12C/k14C) are compared with the theoretical 14C kinetic isotope effect calculated assuming that one carbon-oxygen stretching vibration is lost in the rate-determining step. The discrepancy between experimentally observed temperature dependence of the 14C kinetic isotope effect and the theoretical one is explained by the possible side reactions wich change the apparent degrees of decarbonylation and isotopic composition of CH3CHOHCOOH[1-14C] used in experiments aiming at the determination of carbon-14 kinetic isotope effect in the decarbonylation process itself. (author) 6 refs.; 1 tab

  18. Effect of Ascorbic Acid on the Degradation of Cyanocobalamin and Hydroxocobalamin in Aqueous Solution: A Kinetic Study

    Ahmad, Iqbal; Qadeer, Kiran; Zahid, Saima; SHERAZ, MUHAMMAD ALI; Ismail, Tehmina; Hussain, Waqar; Ansari, Izhar Ahmad

    2014-01-01

    The degradation kinetics of 5 × 10−5 M cyanocobalamin (B12) and hydroxocobalamin (B12b) in the presence of ascorbic acid (AH2) was studied in the pH range of 1.0–8.0. B12 is degraded to B12b which undergoes oxidation to corrin ring cleavage products. B12b alone is directly oxidized to the ring cleavage products. B12 and B12b in degraded solutions were simultaneously assayed by a two-component spectrometric method at 525 and 550 nm without interference from AH2. Both degrade by first-order kin...

  19. RESEARCH ON THE POLYCONDENSATION KINETICS OF ω-AMINO-ACIDS

    WANG Baoren; SHI Manli; QIAN Chunqing

    1983-01-01

    In our previous report, it was discovered that the polycondensation of 9-amino-nonanoic acid follows second order from the beginning up to the extent of reaction, p, around 99%, and after which the reaction changes rapidly to third order. In this paper, we wish to report that this change of the reaction order from second to third occurred also in the polycondensation of 6aminocaproic acid and 11-amino-undecanoic acid. The transition region lay again at p around 99%.It may be concluded that this is a general rule in the polycondensation of the ω-amino-acids (monomers of the A-B type), and the controversial results that appeared in the literature may be cleared up by our experiments.

  20. Reaction Kinetics Between Acetic Acid and Ag2+

    2008-01-01

    <正>The application of the salt-free reagents in the spent fuel reprocessing process has been investigated so much in the last years. Preferable result was obtained in the application of acetohydroxamic acid in the

  1. Conjugated Linoleic Acid Production by Bifidobacteria: Screening, Kinetic, and Composition

    Raimondi, Stefano; Amaretti, Alberto; Leonardi, Alan; Quartieri, Andrea; Gozzoli, Caterina; Rossi, Maddalena

    2016-01-01

    Conjugated linoleic acids (CLA) are positional and geometric isomers of linoleic acid involved in a number of health aspects. In humans, CLA production is performed by gut microbiota, including some species of potential probiotic bifidobacteria. 128 strains of 31 Bifidobacterium species were screened with a spectrophotometric assay to identify novel CLA producers. Most species were nonproducers, while producers belonged to B. breve and B. pseudocatenulatum. GC-MS revealed that CLA producer st...

  2. Optimization of Process of Methacrylic Acid Obtaining by Aldol Condensation of Propionic Acid with Formaldehyde Using a Kinetic Model

    Nebesnyi, Roman; Ivasiv, Volodymyr; Dmytruk, Yulia; Lapychak, Nazar

    2013-01-01

    Methacrylic acid is widely used industrial monomer. An alternative method of its obtaining is aldol condensation of propionic acid with formaldehyde in the gas phase. It has been found that catalyst based on oxides of boron and phosphorus and promoted by oxide of tungsten is effective for this process. The purpose of this work is to find out optimal parameters of this process (temperature and contact time) using a kinetic model. The optimal parameters of this process have been found and techn...

  3. 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.

  4. Dissolution kinetics of nickel ferrite in amino poly carboxylic acids

    Nickel ferrite is one of the important corrosion products of PHWR's where Monel and carbon steel are used as the constructional materials in the primary heat transport system. The dissolution of synthetically prepared nickel ferrite was studied in low concentrations (< 10 mmol/l) of HEDTA, DTPA, NTA and HIDA. The dependence of the dissolution rate on the ligand concentration was found to be langmuirian in all these cases. The effect of the addition of low concentrations of citric acid, oxalic acid, ascorbic acid and Fe(II)-ligand complex, individually, to each of the above chelating agents was also studied. The effect of pH and temperature on the dissolution rate was determined. (author)

  5. Kinetic stability of indium(3) complexes with azaporphyrins in aqueous sulfuric acid

    Kinetic stability of octaphenyltetraazaporphynatochloroindium(3) and 3,7,13,17-tetramethyl-2,8,12,18-tetrabutyl-5,15-diazaporphynatochloroindium (3)= (ClInDAP) in aqueous 90-98% sulfuric acid was studied by the method of spectrophotometric titration. Kinetic parameters of solvo-protolytic dissociation of indium complexes were determined, the reaction mechanism being suggested. The state of ClInDAP in proton-donor medium was studied by the method of absorption spectroscopy and it was shown that two mesoatoms of nitrogen enter the interaction in series. Dissociation constants of the acid forms formed were determined

  6. Kinetic Model of Biomass Pyrolysis Based on Three-component Independent Parallel First-order Reactions

    王新运; 万新军; 陈明强; 王君

    2012-01-01

    The pyrolysis behavior of two kinds of typical biomass (pine wood and cotton stalk) was studied in nitrogen atmosphere at various heating rates by thermogravimetric analysis (TGA).The pyrolysis process can be divided into three stages:evolution of moisture (<200 ℃),devolatilization (200~400 ℃) and carbonization (>400 ℃).The comparison of DTG curves of two biomass materials show that the higher the hemicellulose content of biomass,the more evident the shoulder peak of DTG curve.The weight loss process of two materials was simulated by the kinetic model assuming cellulose,hemicellulose and lignin pyrolyzing independently and in parallel,obeying first-order reactions.The pyrolysis kinetic parameters corresponding to the three components were estimated by the nonlinear least square algorithm.The results show that their fitting curves are in good agreement with the experimental data.Their activation energy values for pine wood and cotton stalk are in the range of 188~215,90~102,29~49 and 187~214,95~101,30~38 kJ/mol,respectively.The corresponding pre-exponential factors are in the range of 1.8×1015~2.0×1016,1.6×107~7.1×108,9.3×101~l.5×103 and 1.2× 1015~6.7×1017,1.2× 108~1.4×109,1.4× 102~4.6× 102 min-1,respectively.In addition,the activation energy of cellulose and lignin increased and their contributions to volatile tended to fall,whereas the activation energy of herricellulose decreased and its contribution to volatile tended to rise with increasing of heating rate.

  7. Conjugated Linoleic Acid Production by Bifidobacteria: Screening, Kinetic, and Composition

    Amaretti, Alberto; Leonardi, Alan; Quartieri, Andrea; Gozzoli, Caterina; Rossi, Maddalena

    2016-01-01

    Conjugated linoleic acids (CLA) are positional and geometric isomers of linoleic acid involved in a number of health aspects. In humans, CLA production is performed by gut microbiota, including some species of potential probiotic bifidobacteria. 128 strains of 31 Bifidobacterium species were screened with a spectrophotometric assay to identify novel CLA producers. Most species were nonproducers, while producers belonged to B. breve and B. pseudocatenulatum. GC-MS revealed that CLA producer strains yielded 9cis,11trans-CLA and 9trans,11trans-CLA, without any production of other isomers. Hydroxylated forms of LA were absent in producer strains, suggesting that the myosin-cross-reactive antigen (MCRA) protein that exerts hydratase activity is not involved in LA isomerization. Moreover, both CLA producer and nonproducer species bear a MCRA homologue. The strain B. breve WC 0421 was the best CLA producer, converting LA into 68.8% 9cis,11trans-CLA and 25.1% 9trans,11trans-CLA. Production occurred mostly during the lag and the exponential phase. For the first time, production and incorporation of CLA in biomass were assessed. B. breve WC 0421 stored CLA in the form of free fatty acids, without changing the composition of the esterified fatty acids, which mainly occurred in the plasmatic membrane. PMID:27429985

  8. Phase separation kinetic studies for uranium recovery from phosphoric acid by solvent extraction

    Wet process phosphoric acid (WPA) contains uranium in the range 80-120 mg/LU3O8 while in the Merchant Grade Acid (MGA) it is in the range 220-240 mg/L .Based on the experimental work, a two cycle solvent extraction process for uranium separation from phosphoric acid has been developed at REDS and patented. While the equilibrium extraction behaviour and reaction mechanisms have been studied, the kinetic aspect of uranium extraction from phosphoric acid with particular reference to rate of mass transfer and phase disengagement time has not been studied

  9. Kinetics of Hydrochloric Acid Leaching of Titanium from Titanium-Bearing Electric Furnace Slag

    Zheng, Fuqiang; Chen, Feng; Guo, Yufeng; Jiang, Tao; Travyanov, Andrew Yakovlevich; Qiu, Guanzhou

    2016-05-01

    The hydrochloric acid leaching of titanium from titanium-bearing electric furnace slag was investigated under different experimental conditions. The results indicate that particle size, hydrochloric acid concentration and reaction temperature were of significance to the leaching kinetics. Specifically, reaction temperature was the most important factor followed by hydrochloric acid concentration and particle size. The shrinking core model was used to describe the leaching process which was controlled by surface chemical reaction. The kinetic equation was obtained and the activation energy was found to be 43.16 kJ/mol. Iron and calcium species were almost completely dissolved in the acid when the extraction degree of titanium reached 99.84%. MgO (19.34 wt.%) and Al2O3 (32.45 wt.%) in the spinel were still in the leaching residue and SiO2 (43.53 wt.%) in the form of quartz remained in the leaching residue.

  10. Degradation Kinetics of Xylose and Glucose in Hydrolysate Containing Dilute Sulfuric Acid

    亓伟; 张素平; 许庆利; 任铮伟; 颜涌捷

    2008-01-01

    In preparation of fuel alcohol from biomass as feedstock,hydrolysis with dilute acid as catalyst iS one way to produce fermentable saccharide,xylose and glucose.However,the acid is also the catalyst in degradation of xylose and glucose and the yield of sacchride is dependent on the kinetic behaviors of saccharide.The degradation kinetics of xylose and glucose in the hydrolysate Was investigated under the conventional process conditions of hydrogen ion concentration from O.05 to 0.2 mol/L and temperature from 150 to 200℃.With a numerical calculation method,the kinetic parameters Were estimated,and the activation energy of xylose and glucose in the degradation reaction was obtained.The kinetic equations correlating the effect of hydrogen ion concentration on the rate constants of degradation reaction were established.Comparison between the calculated results from the equations and experimental ones proved that the established kinetic model could satisfactorily predict the degradation behavior of xylose and glucose in the acidic hydrolysate.

  11. Kinetics, intermediates and acute toxicity of arsanilic acid photolysis.

    Zhu, Xiang-Dong; Wang, Yu-Jun; Liu, Cun; Qin, Wen-Xiu; Zhou, Dong-Mei

    2014-07-01

    Arsanilic acid (4-amino phenyl arsenic acid, ASA) is widely used in poultry production as feed additives, while most of ASA in the feed is excreted in the animal manure and released into the environment. However, the environmental behaviors of ASA were not well understood. In the present study, the photolysis behaviors of ASA and the toxicity of its metabolites to luminescent bacterium were studied. The results showed that ASA could be photodegraded and this process was strongly affected by solution pH, humic acid and dissolved oxygen. Upon UV irradiation for 360 min, ASA could be completely eliminated, but the reduction of total organic carbon (TOC) was not significant. In addition, NH4(+) ions and inorganic arsenic including arsenite and arsenate were identified as the predominant end-products. The conversion of ASA included both direct and indirect photolysis involving radicals, and its possible photolysis pathways were proposed on the basis of the identified intermediates. Unfortunately, higher adverse effects of the conversion products of ASA on bacteria were observed during the photolysis reaction. The results of present study might be helpful for assessing the environmental persistence and risks of ASA. PMID:24405966

  12. 2.2. The kinetics of hydrochloric-acid decomposition of calcined borosilicate ore

    Present article is devoted to kinetics of hydrochloric-acid decomposition of calcined borosilicate ore. The experimental data of dependence of hydrochloric-acid decomposition of calcined borosilicate ore for boron oxide extraction on temperature (30-95 deg C) and process duration (15-60 min) were considered. It was defined that at temperature increasing the boron oxide extraction increases from 28.9 till 53.2%. The constants of decomposition rate of calcined ore were calculated.

  13. Effect of retinoic acid on cell proliferation kinetics and retinoic acid receptor expression of colorectal mucosa

    Hong-Bo Wei; Xiao-Yan Han; Wei Fan; Gui-Hua Chen; Ji-Fu Wang

    2003-01-01

    AIM: To investigate the effect of retinoic acid (RA) on cell proliferation kinetics and retinoic acid receptor (RAR)expression of colorectal mucosa.METHODS:One hundred sixty healthy male Wistar rats were randomly divided into 4 groups. Rats in groups Ⅰ and Ⅱ were subcutaneously injected with dimethylhydrazine (DMH) (20 mg/kg, once a week,) for 7 to 13 weeks, while groups Ⅲ and Ⅳ were injected with normal saline. Rats in groups Ⅱ and Ⅲ were also treated with RA (50 mg/kg,every day, orally) from 7th to 15th week, thus group Ⅳ was used as a control. The rats were killed in different batches.The expressions of proliferating cell nuclear antigen (PCNA),nucleolar organizer region-associated protein (AgNOR) and RAR were detected.RESULTS: The incidence of colorectal carcinoma was different between groupsⅠ(100 %) and Ⅱ (15 %) (P<0.01).The PCNA indices and mean AgNOR count in group Ⅱ were significantly lower than those in group Ⅰ(F=5.418 and 4.243,P<0.01). The PCNA indices and mean AgNOR count in groups Ⅰ and Ⅱ were significantly higher than those in the groups Ⅲ and Ⅳ (in which carcinogen was not used) (F=5.927and 4.348, P<0.01). There was a tendency in group Ⅰ that the longer the induction with DMH the higher PCNA index and AgNOR count expressed (F=7.634 and 6.826, P<0.05).However, there was no such tendency in groups Ⅱ, Ⅲ and Ⅳ(F=1.662 and 1.984, P>0.05). The levels of RAR in normal and cancerous tissues in groups treated with RA were significantly higher than those in groups not treated with RA (F=6.343 and 6.024, P<0.05).CONCLUSION: RA decreases the incidence of colorectal carcinoma induced by DMH. Coiorectal cancer tissue is associated with abnormal expression of PCNA, AgNOR and RAR. RA inhibits the expression of PCNA and AgNOR, and increases RAR concentration in colorectal tissues.

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

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

    2016-05-01

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

  15. Kinetics of sulfuric acid decomposition of solid fluorine containing wastes of aluminium production

    The results of researches of kinetics of sulfuric acid decomposition of solid fluorine containing wastes of aluminium production were considered in this work. The apparent activation energy was determined. The rate constant and pre-exponential factor of Arrhenius equation were defined as well.

  16. Phospholipids and poly(glutamic acid)/hydrolyzed gluten: interaction and kinetics

    The effect of poly (glutamic acid) (PGA) and Hydrolyzed wheat gluten (HG) on the thermal and kinetics properties of lysophosphatidylcholine (LPC) was determined using Differential Scanning Calorimetry (DSC). A model system containing 3, 6 and 10% PGA or HG was added to 40% LPC aqueous suspension. ...

  17. Synthesis and photopolymerization kinetics of benzophenone sesamol one-component photoinitiator.

    Yang, Jinliang; Shi, Suqing; Xu, Fei; Nie, Jun

    2013-02-01

    A benzodioxole derivative, 4-(2-(benzodioxol-5-yloxy)ethoxy)benzophenone (BPC2BDO), based on 4-hydroxybenzophenone and sesamol was synthesized, and used as a one-component Type II photoinitiator. The structure of BPC2BDO was characterized by elementary analysis, APCI-MS, (1)H NMR, and (13)C NMR. The rate of decomposition (R(d)) of BPC2BDO in acetonitrile was studied by UV-Vis spectroscopy and found that R(d) was proportional to light intensity. Real-time near-IR was used to study the kinetics of photopolymerization of the photoinitiator. As the benzophenone (BP) moiety and hydrogen donor were introduced into one molecule in BPC2BDO, radicals could be generated through intra-molecular reaction due to the close vicinity of the hydrogen donor and BP, which might be faster than inter-molecular reaction. The results also showed that the rate of polymerization of acrylates was significantly higher than that of methacrylates at the same polymerization conditions; the functionality of acrylates, concentration of BPC2BDO, and light intensity affected the polymerization rate and the final conversion. PMID:23047776

  18. Reactive extraction of lactic acid using alamine 336 in MIBK: equilibria and kinetics.

    Wasewar, Kailas L; Heesink, A Bert M; Versteeg, Geert F; Pangarkar, Vishwas G

    2002-07-17

    Lactic acid is an important commercial product and extracting it out of aqueous solution is a growing requirement in fermentation based industries and recovery from waste streams. The design of an amine extraction process requires (i) equilibrium and (ii) kinetic data for the acid-amine (solvent) system used. Equilibria for lactic acid extraction by alamine 336 in methyl-iso-butyl-ketone (MIBK) as a diluent have been determined. The extent to which the organic phase (amine +MIBK) may be loaded with lactic acid is expressed as a loading ratio, z=[HL](o)/[B](i,o). Calculations based on the stoichiometry of the reactive extraction and the equilibria involved indicated that more lactic acid is transferred to the organic phase than would be expected from the (1:1) stoichiometry of the reaction. The extraction equilibrium was interpreted as a result of consecutive formation of two acid-amine species with stoichiometries of 1:1 and 2:1. Equilibrium complexation constant for (1:1) and (2:1) has been estimated. Kinetics of extraction of lactic acid by alamine 336 in MIBK has also been determined. In a first study of its kind, the theory of extraction accompanied by a chemical reaction has been used to obtain the kinetics of extraction of lactic acid by alamine 336 in MIBK. The reaction between lactic acid and alamine 336 in MIBK in a stirred cell falls in Regime 3, extraction accompanied by a fast chemical reaction occurring in the diffusion film. The reaction has been found to be zero order in alamine 336 and first order in lactic acid with a rate constant of 1.38 s(-1). These data will be useful in the design of extraction processes. PMID:12052683

  19. Asymmetric Synthesis of 1,3-Oxazolidine Derivatives with Multi-Component Reaction and Research of Kinetic Resolution

    Xiao-Wei Hong

    2015-09-01

    Full Text Available An efficient multi-component reaction to synthesize multi-substituted 1,3-oxazolidine compounds of high optical purity was described. All the products were well-characterized and the absolute configuration of one chiral center was determined. The plausible mechanism was proposed and a kinetic resolution of epoxides process was confirmed.

  20. Dilute Acid Hydrolysis of Cowpea Hulls: A Kinetic Study

    Chioma M. Onyelucheya

    2016-08-01

    Full Text Available In this study, dilute acid hydrolysis of cowpea hulls was carried out in two stages under the following conditions: pre-hydrolysis (4%v/v H2SO4, 121˚C, 30 minutes and hydrolysis ( at 10% and 15% v/v H2SO4,varied at different temperatures 150 oC, 160 oC, 170 oC and 180 oC for 2.5 hrs.. The substrate was characterized using both Fourier transform infrared spectroscopy and proximate analysis. The percentage lignocellulosic composition of the substrate was obtained for cellulose, hemicellulose and lignin as 34%, 14% and 4.7% respectively. Maximum glucose concentration of 8.09g was obtained using 10%v/v acid concentration at 170˚C after a reaction time of 90min. Saeman’s model gave a good fit for the experimental data. Activation energy for glucose formation using 10%v/v and 15%v/v H2SO4 was obtained as 38.28KJ and 82.204KJ respectively. From the results obtained it can be concluded that cowpea hulls can be converted to a useful product.

  1. Removal of 5-Amino-2-chlorotoluene-4-sulfonic and Chlorhydric Acids From Wastewater by Weakly Basic Resin: Equilibrium and Kinetics

    2007-01-01

    To study the adsorption of 5-Amino-2-chlorotoluene-4-sulfonic (CLT) and chlorhydric (HCl) acids from wastewater by weakly basic resin.Methods The kinetics and isotherm were studied. Thermodynamic parameters for the adsorption of acids were calculated and discussed.Results The adsorption of CLT and HCl acids followed Langmuir isotherm and the first-order kinetics model.Conclusion The adsorptive affinity of the two acids on D301R is in the order of CLT acid > HCl acid. CLT and HCl acids can be separated.

  2. Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes

    Casale, Mia T.; Richman, Aviva R.; Elrod, Matthew J.; Garland, Rebecca M.; Beaver, Melinda R.; Tolbert, Margaret A.

    Field observations of atmospheric aerosols have established that organic compounds compose a large fraction of the atmospheric aerosol mass. However, the physical/chemical pathway by which organic compounds are incorporated into atmospheric aerosols remains unclear. The potential role of acid-catalyzed reactions of organic compounds on acidic aerosols has been explored as a possible chemical pathway for the incorporation of organic material into aerosols. In the present study, ultraviolet-visible (UV-vis) spectroscopy was used to monitor the kinetics of formation of the products of the acid-catalyzed aldol condensation reaction of a range of aliphatic aldehydes (C 2-C 8). The experiments were carried out at various sulfuric acid concentrations and a range of temperatures in order to estimate the rate constants of such reactions on sulfuric acid aerosols under tropospheric conditions. The rate constants were generally found to decrease as the chain length of the aliphatic aldehyde increased (except for acetaldehyde, which had an unusually small rate constant), increase as a function of sulfuric acid concentration as predicted by excess acidity theory, and showed normal Arrhenius behavior as a function of temperature. While the kinetic data are generally consistent with previous laboratory reports of aldehyde reactivity in various sulfuric acid media, the aldol condensation reactions involving aliphatic aldehydes do not appear fast enough to be responsible for significant transfer of organic material into atmospheric aerosols.

  3. 4-Hydroxy cinnamic acid as mushroom preservation: Anti-tyrosinase activity kinetics and application.

    Hu, Yong-Hua; Chen, Qing-Xi; Cui, Yi; Gao, Huan-Juan; Xu, Lian; Yu, Xin-Yuan; Wang, Ying; Yan, Chong-Ling; Wang, Qin

    2016-05-01

    Tyrosinase is a key enzyme in post-harvest browning of fruit and vegetable. To control and inhibit its activity is the most effective method for delaying the browning and extend the shelf life. In this paper, the inhibitory kinetics of 4-hydroxy cinnamic acid on mushroom tyrosinase was investigated using the kinetics method of substrate reaction. The results showed that the inhibition of tyrosinase by 4-hydroxy cinnamic acid was a slow, reversible reaction with fractional remaining activity. The microscopic rate constants were determined for the reaction on 4-hydroxy cinnamic acid with tyrosinase. Furthermore, the molecular docking was used to simulate 4-hydroxy cinnamic acid dock with tyrosinase. The results showed that 4-hydroxy cinnamic acid interacted with the enzyme active site mainly through the hydroxy competed with the substrate hydroxy group. The cytotoxicity study of 4-hydroxy cinnamic acid indicated that it had no effects on the proliferation of normal liver cells. Moreover, the results of effects of 4-hydroxy cinnamic acid on the preservation of mushroom showed that it could delay the mushroom browning. These results provide a comprehensive underlying the inhibitory mechanisms of 4-hydroxy cinnamic acid and its delaying post-harvest browning, that is beneficial for the application of this compound. PMID:26812105

  4. Kinetic study on the photocatalytic degradation of salicylic acid using ZnO catalyst

    The photocatalytic degradation of salicylic acid was studied by a batch process using ZnO as the catalyst on irradiation with UV light. The effect of process parameters such as pH, catalyst loading and initial concentration of salicylic acid on the extent of degradation was investigated. The degradation of salicylic acid was found to be effective in the neutral pH range. The optimum catalyst loading was observed at 2.0 g/L. The process followed first order kinetics and the apparent rate constant decreased with increase in the initial concentration of salicylic acid. The mechanism for the degradation of salicylic acid could be explained on the basis of Langmuir-Hinshelwood mechanism. The complete mineralization of salicylic acid was observed in the presence of ZnO photocatalyst. The ZnO was found to be quite stable and undergoes photocorrosion only to a negligible extent.

  5. Study of kinetics of scandium extraction by di(2-ethylhexyl)phosphoric acid

    Kinetics of extracting scandium with (2-ethylhexyl)phosphoric acid (D2EHPA) from 0.5 and 8 mol/l solutions of hydrochloric acid has been studied. At [Sc]:[D2EHPA] ratio equal to 1:2.6 and 1:3.2 equilibrium is attained in strongly acid solutions after 40 and 10 minutes periods of contacting and in weakly acid solutions after 60 and 20 minutes. At [Sc]:[D2EHPA] ratio more than 1:4.6 the equilibrium is attained for less than two minutes. The rate constant of scandium extraction by cation-exchange mechanism is 0.0293 cm/min and by solvate mechanism 0.0415 cm/min. The activation energy upon extracting from weakly acid solutions is 5.4 kcal/mol, from strongly acid solutions - 1.8 kcal/mol

  6. Kinetics of acetic acid synthesis from ethanol over a Cu/SiO2 catalyst

    Voss, Bodil; Schjødt, Niels Christian; Grunwaldt, Jan-Dierk;

    2011-01-01

    The dehydrogenation of ethanol via acetaldehyde for the synthesis of acetic acid over a Cu based catalyst in a new process is reported. Specifically, we have studied a Cu on SiO2 catalyst which has shown very high selectivity to acetic acid via acetaldehyde compared to competing condensation routes....... The dehydrogenation experiments were carried out in a flow through lab scale tubular reactor. Based on 71 data sets a power law kinetic expression has been derived for the description of the dehydrogenation of acetaldehyde to acetic acid. The apparent reaction order was 0.89 with respect to water and...

  7. Kinetics of the Esterification Reaction between Pentanoic Acid and Methanol Catalyzed by Noncorrosive Cation Exchange Resin

    Sharma, M.; Toor, A. P.; R. K. Wanchoo

    2014-01-01

    Methyl pentanoate, commonly known as methyl valerate, is the methyl ester of pentanoic acid (valeric acid) with a fruity odour. Methyl pentanoate is commonly used in fragrances, beauty care, soap, laundry detergents at levels of 0.1 – 1 %. In its very pure form (purity 99.5 %) it is used as a plasticizer in the manufacture of plastics. In the present investigation, kinetics of esterification of pentanoic acid with methanol catalyzed by heterogeneous catalyst in a batch-type reactor is reporte...

  8. New method for spectrophotometric determination of quinones and barbituric acid through their reaction. A kinetic study

    Medien, H. A. A.

    1996-11-01

    A new and sensitive spectrophotometric method is described for the determination of p-benzoquinone, p-chloranil and 1.4-naphthoquinone. The method is based on the reaction between quinones and barbituric acid, by which a color is developed with maximum absorption between 485 and 555 nm in 50% methyl alcohol-water mixture. The absorption of the product obeys Beer's law within the concentration range 0.025-05 mM of orginal quinone. The kinetics of the reaction between p-benzoquinone and barbituric acid was studied in a range of methyl alcohol-water mixtures. The reaction follows overall second order kinetics, first order in each of the reactants. The rate increases with increasing dielectric constant. The method was applied for determination of barbituric acid with p-benzoquinone in the concentration range of 0.025-0.345 mM. Other barbiturates do not interfere.

  9. β-methyl-15-p-iodophenylpentadecanoic acid metabolism and kinetics in the isolated rat heart

    The use of 15-p-iodophenyl-β-methyl-pentadecanoic acid (βMe-IPPA) as an indicator of long chain fatty acid (LCFA) utilization in nuclear medicine studies was evaluated in the isolated, perfused, working rat heart. Time courses of radioactivity (residue curves) were obtained following bolus injections of both βMe-IPPA and its straight chain counterpart 15-p-iodophenyl-pentadecanoic acid (IPPA). IPPA kinetics clearly indicated flow independent impairment of fatty acid oxidation caused by the carnitine palmitoyltransferase I inhibitor 2[5(4-chlorophenyl)pentyl]oxirane-2-carboxylate (POCA). In contrast, βMe-IPPA kinetics were insensitive to changes in fatty acid oxidation rate and net utilization of long chain fatty acid. Analysis of radiolabeled species in coronary effluent and heart homogenates showed the methylated fatty acid to be readily incorporated into complex lipids but a poor substrate for oxidation. POCA did not significantly alter metabolism of the tracer, suggesting that the tracer is poorly metabolized beyond βMe-IPPA-CoA in the oxidative pathway. (orig.)

  10. Kinetics of bromide catalysed oxidation of dextrose by cerium (IV) in aqueous sulphuric acid solution

    Kinetics of bromide catalysed oxidation of dextrose by CeIV in aqueous sulphuric acid medium show first order dependence each in dextrose and cerium(IV). The reaction rate decreases on increasing the concentration of hydrogen ion. The increase in [HSO4-] or [SO42-] decreases the rate. The bromide ion shows positive catalytic effect on the reaction rate. The value of activation energy has been calculated and a suitable mechanism confirming to the kinetic data is proposed. (author). 3 refs., 3 tabs

  11. Reaction kinetics of free fatty acids esterification in palm fatty acid distillate using coconut shell biochar sulfonated catalyst

    Hidayat, Arif; Rochmadi, Wijaya, Karna; Budiman, Arief

    2015-12-01

    Recently, a new strategy of preparing novel carbon-based solid acids has been developed. In this research, the esterification reactions of Palm Fatty Acid Distillate (PFAD) with methanol, using coconut shell biochar sulfonated catalyst from biomass wastes as catalyst, were studied. In this study, the coconut shell biochar sulfonated catalysts were synthesized by sulfonating the coconut shell biochar using concentrated H2SO4. The kinetics of free fatty acid (FFA) esterification in PFAD using a coconut shell biochar sulfonated catalyst was also studied. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%w, and reaction temperature of 60°C. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.

  12. Kinetics of sulfuric acid leaching of cadmium from Cd-Ni zinc plant residues.

    Safarzadeh, Mohammad Sadegh; Moradkhani, Davood; Ojaghi-Ilkhchi, Mehdi

    2009-04-30

    Cd-Ni filtercakes are produced continuously at the third purification step in the electrolytic production of zinc in the National Iranian Lead and Zinc Company (NILZ) in northwestern Iran. In this research, the dissolution kinetics of cadmium from Cd-Ni residues produced in NILZ plant has been investigated. Hence, the effects of temperature, sulfuric acid concentration, particle size and stirring speed on the kinetics of cadmium dissolution in sulfuric acid were studied. The dissolution kinetics at 25-55 degrees C and tshrinking core model, with inter-diffusion of cadmium and sulfate ions through the porous region of alloying layer (Cd(5)Ni, Cd(2)Ni(1.9) and Cd(10)Cu(3)) as the rate determining step. This finding is in accordance with the apparent activation energy (E(a)) of 13.363 kJ/mol and a linear relationship between the rate constant and the reciprocal of squared particle size. Arrhenius constant was calculated as 6.3942 min(-1). The order of reaction with respect to sulfuric acid concentration, solid/liquid ratio and particle size were also achieved. The rate of reaction at first 5 min based on diffusion-controlled process can be expressed by a semi-empirical equation as:It was determined that the dissolution rate increased with increasing sulfuric acid concentration and decreasing particle size. PMID:18755541

  13. Kinetic studies for sorption of some metal ions from aqueous acid solutions onto TDA impregnated resin

    Kinetic studies for sorption of uranium, thorium and cobalt ions from hydrochloric acid solutions using tri-dodecyl amine (TDA) loaded on Amberlite XAD4 (polystyrene resin supplied by Rohm and Haas) using the batch technique, have been evaluated and assessed. Analysis of the respective data in accordance with three kinetic models revealed that the particle diffusion mechanism is the rate determining step, and the sorption for each metal ion on the impregnated sorbent follows the first order reversible kinetics. Values of the first order rate constants, rate constants of intraparticle transport, and the particle diffusion coefficients for the studied ions were determined. Sorption isotherms, which have been evaluated from the distribution coefficients for these ions, were found in good fit with the Langmuir and Freundlich isotherms. (author)

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

    Krishna K. Yerneni

    2015-12-01

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

  15. Kinetic investigation of the immobilization of chromotropic acid derivatives onto anion exchange resin

    Savić Jasmina

    2007-01-01

    Full Text Available The adsorption kinetics of pyrazol- (РАСА and imidazol-azo-chromo-tropic acid (IACA onto Dowex 1-X8 resin, as a function of the dye concentration and temperature were investigated at pH 4.5. The pseudo-first- and second-order kinetic models and intraparticle diffusion model were used to describe the obtained kinetic data. The adsorption rate constants were found to be in the order of magnitude 10-2 min-1 for all of the used kinetics models. The adsorption capacity increases with increasing initial dye concentration. The study of adsorption kinetics at different temperatures (in the range from 5 to 25 °C reveals an increase in the rate of adsorption and adsorption capacity with increasing temperature. The activation energy (in the case of РАСА 16.6 kJ/mol, and for IACA 11.3 kJ/mol was determined using the Arrhenius dependence. Electrostatic interactions between the dye and resin beads were shown to be the adsorption mechanism.

  16. Lewis acidic metal catalysed organic transformations by designed multi-component structures and assemblies

    Afsar Ali; Amit P Singh; Rajeev Gupta

    2010-05-01

    This paper presents the recent developments in designing multi-component structures including metal-organic frameworks containing Lewis acidic metal ions. The emphasis has been given to understand the design elements adopted to synthesize such structures bearing Lewis acidic metal ion. Further, few important Lewis acidic metal catalysed organic transformation reactions have been discussed demonstrating the importance of such materials for practical purposes.

  17. Adsorption of rhodamine B by acid activated carbon-Kinetic, thermodynamic and equilibrium studies

    Shanmugam Arivoli; M. Thenkuzhali; P. Martin Deva Prasath

    2009-01-01

    A carbonaceous adsorbent prepared from an indigenous waste by acid treatment was tested for its efficiency in removing Rhodamine B (RDB). The parameters studied include agitation time, initial dye concentration, carbon dose, pH and temperature. The adsorption followed first order kinetics and the rate is mainly controlled by intra-particle diffusion. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The adsorption capacity (Qm) obtained from the Langmuir isotherm p...

  18. Kinetics and mechanism of sphalerite leaching by sodium nitrate in sulphuric acid solution

    Sokić M.; Marković B.; Matković V.; Živković D.; Štrbac N.; Stojanović J.

    2012-01-01

    Interest for application of hydrometallurgical processes in a processing of complex sulphide ores and concentrates has increased in recent years. Their application provides better metal recoveries and reduced emission of gaseous and toxic ageneses in the environment. The kinetics and mechanism of sphalerite leaching from complex sulphide concentrate with sulphuric acid and sodium nitrate solution at standard conditions was presented in this paper. The influences of temperature and time ...

  19. Kinetics of Sawdust Hydrolysis with Dilute Hydrochloric Acid and Ferrous Chloride

    袁传敏; 颜涌捷; 任铮伟; 李庭琛; 曹建勤

    2004-01-01

    With dilute hydrochloric acid as catalyst and promoted by ferrous chloride, hydrolysis of waste sawdust to produce monosaccharides was conducted by using an one-step method in a batch-wise operation reactor. Based on the model of first order consecutive irreversible reactions, the kinetics equation incorporating the term of catalyst concentration was obtained that is suitable for describing the hydrolysis of sawdust. Activation energies were calculated for hydrolysis of sawdust and decomposition of monosaccharides.

  20. Kinetic Modelling for Flavonoid Recovery from Red Grape (Vitis vinifera) Pomace with Aqueous Lactic Acid

    Katerina Tzima; Stamatina Kallithraka; Yorgos Kotseridis; Dimitris P. Makris

    2014-01-01

    This study was undertaken with the aim of establishing a correlation between the extraction yield in total flavonoids from red grape pomace and the extraction temperature, using 0.5% (w/v) aqueous lactic acid as the solvent system. Extraction of flavonoids was found to obey second-order kinetics, and on such a basis, the yield in total flavonoids at saturation could be very effectively determined and correlated with temperature using non-linear regression. The results indicated that the extr...

  1. 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)

  2. Kinetics and Thermodynamics of Oil Extraction from Sun ower Seeds in the Presence of Aqueous Acidic

    TOPALLAR, Hüseyin

    2000-01-01

    Oil extraction was performed in aqueous HCl, H2SO4 and H3PO4 solutions with n-hexane (C6H14) at 30, 40, 50 and 60 oC using 10 gr of sunflower seeds over 1 h with 10-min. sampling intervals. The optimum acid concentration was wt. 10% for each acid, and the highest oil yield was obtained in the extraction procedure with n-hexane containing H2SO4. The extraction process was observed with regard to the percent oil yield versus time, and the reaction order was found to be first-order kinetics by t...

  3. Kinetic energy releases of small amino acids upon interaction with keV ions

    In chromatin, DNA is tightly packed into one complex together with histone and non-histone proteins. These proteins are known to protect the DNA against indirect and to some extent even direct radiation damage. Radiation action upon amino acids is thus one of the primary steps in biological radiation action. In this paper we investigate the ionization and fragmentation of the gas-phase amino acids glycine, alanine and valine upon interaction with keV α-particles. High resolution coincidence time-of-flight mass spectrometry is used to determine the dominant fragmentation channels as well as fragment kinetic energies. (authors)

  4. Kinetic energy releases of small amino acids upon interaction with keV ions

    Bari, S.; Alvarado, F.; Postma, J.; Sobocinski, P.; Hoekstra, R.; Schlatholter, T. [Groningen Univ., KVI Atomic Physics (Netherlands); Schlatholter, T. [Universites P. et M. Curie and D. Diderot, INSP, CNRS UMR 75-88, 75 - Paris (France)

    2009-01-15

    In chromatin, DNA is tightly packed into one complex together with histone and non-histone proteins. These proteins are known to protect the DNA against indirect and to some extent even direct radiation damage. Radiation action upon amino acids is thus one of the primary steps in biological radiation action. In this paper we investigate the ionization and fragmentation of the gas-phase amino acids glycine, alanine and valine upon interaction with keV {alpha}-particles. High resolution coincidence time-of-flight mass spectrometry is used to determine the dominant fragmentation channels as well as fragment kinetic energies. (authors)

  5. Thermodynamics and kinetics of lutetium extraction with HEH(EHP) in hydrochloric acid medium

    DONG Jinshi; XU Yang; WANG Liangshi; HUANG Xiaowei; LONG Zhiqi; WU Shengxi

    2016-01-01

    Solvent extraction has been the most widely used technique for rare earths separation. In this study, thermodynamics and kinetics of lutetium extraction with HEH (EHP) in hydrochloric acid medium were investigated. The extraction mechanism and the relevant parameters were determined by experiment research which can guide the practical extraction process. The data indicated that chloride ion had no effect on lutetium extraction, the rate constant increased when stirring speed was enhanced. Effects of temperature, HEH (EHP) concentration, acidity, and chloride concentration were also studied. Thickness of the diffusion film was also calculated to be 4.66×10–3 cm at 150 r/min.

  6. Equilibrium and Kinetic Studies on the Adsorption of Acid Yellow 36 Dye by Pinecone

    Amir Sheikh Mohammadi

    2013-11-01

    Full Text Available Background & Aims of the Study: Dyes have significant role in environmental problems, due to their toxic effects on the food chain and sources of water. The purpose of this research was to study the adsorption of acid yellow 36 dye onto pinecone using batch system. Materials & Methods: This research was performed at laboratory scale and batch system. Equilibrium isotherms were modeled using Langmuir, Freundlich, and D-R models. Also kinetic studies were done by three models of pseudo first order, pseudo second order, and intra-particle diffusion. Results: The maximum adsorption was achieved at pH 5.0, adsorbent dose 0.7 g/l and contact time 20 min. The equilibrium adsorption capacity (mg/g increased with increasing initial dye concentration. The Langmuir model (R2=0.99 provided the best fit for the experimental data. The adsorption kinetics were studied and best fit was achieved by pseudo- second order model (R2= 0.96. Conclusions: According to the results obtained of equilibrium and kinetic studies on the adsorption of acid yellow 36, pinecone can be a suitable and efficient adsorbent in the removal of yellow acid 36 dye from industrial wastewater.

  7. 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.

  8. Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

    Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-06-01

    Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

  9. Kinetic Study and Mathematical Model of Hemimorphite Dissolution in Low Sulfuric Acid Solution at High Temperature

    Xu, Hongsheng; Wei, Chang; Li, Cunxiong; Deng, Zhigan; Li, Minting; Li, Xingbin

    2014-10-01

    The dissolution kinetics of hemimorphite with low sulfuric acid solution was investigated at high temperature. The dissolution rate of zinc was obtained as a function of dissolution time under the experimental conditions where the effects of sulfuric acid concentration, temperature, and particle size were studied. The results showed that zinc extraction increased with an increase in temperature and sulfuric acid concentration and with a decrease in particle size. A mathematical model able to describe the process kinetics was developed from the shrinking core model, considering the change of the sulfuric acid concentration during dissolution. It was found that the dissolution process followed a shrinking core model with "ash" layer diffusion as the main rate-controlling step. This finding was supported with a linear relationship between the apparent rate constant and the reciprocal of squared particle radius. The reaction order with respect to sulfuric acid concentration was determined to be 0.7993. The apparent activation energy for the dissolution process was determined to be 44.9 kJ/mol in the temperature range of 373 K to 413 K (100 °C to 140 °C). Based on the shrinking core model, the following equation was established:

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

    J. E. N. Brainer

    2014-12-01

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

  11. A kinetic model for impact/sliding wear of pressurized water reactor internal components. Application to rod cluster control assemblies

    A new concept of industrial wear model adapted to components of nuclear plants is proposed. Its originality is to be supported, on one hand, by experimental results obtained via wear machines of relatively short operational times, and, on the other hand, by the information obtained from the operating feedback over real wear kinetics of the reactors components. The proposed model is illustrated by an example which corresponds to a specific real situation. The determination of the coefficients permitting to cover all assembly of configurations and the validation of the model in these configurations have been the object of the most recent work. (author)

  12. A kinetic model for impact/sliding wear of pressurized water reactor internal components. Application to rod cluster control assemblies

    Zbinden, M.; Durbec, V.

    1996-12-01

    A new concept of industrial wear model adapted to components of nuclear plants is proposed. Its originality is to be supported, on one hand, by experimental results obtained via wear machines of relatively short operational times, and, on the other hand, by the information obtained from the operating feedback over real wear kinetics of the reactors components. The proposed model is illustrated by an example which corresponds to a specific real situation. The determination of the coefficients permitting to cover all assembly of configurations and the validation of the model in these configurations have been the object of the most recent work. (author). 34 refs.

  13. Solid-state NMR studies of nucleic acid components

    Dračínský, Martin; Hodgkinson, P.

    2015-01-01

    Roč. 5, č. 16 (2015), s. 12300-12310. ISSN 2046-2069 R&D Projects: GA ČR GA13-24880S Institutional support: RVO:61388963 Keywords : NMR spectroscopy * nucleic acids * solid-state NMR Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.840, year: 2014 http://pubs.rsc.org/en/content/articlepdf/2015/ra/c4ra14404j

  14. Lipid clustering in bilayers detected by the fluorescence kinetics and anisotropy of trans-parinaric acid.

    C. Reyes Mateo; Brochon, J C; M Pilar Lillo; Ulises Acuña, A.

    1993-01-01

    Fluid heterogeneity in lipid bilayers and shows a simple and useful method to quantify this heterogeneity. Taking advantage of the maximum entropy method, we have resolved the probe fluorescence lifetime distributions in homogeneous solutions and in single and two-component lipid bilayers at different temperatures. A precise description of the emission kinetics was obtained as a function of viscosity in the homogeneous solution and as a function of the phase composition (gel/fluid) in the lip...

  15. Esterification of oleic acid for biodiesel production catalyzed by SnCl{sub 2}: a kinetic investigation

    Cardoso, A. L.; Gonzaga Neves, S. C.; Silva, M. J. da [Departament of Chemistry, Federal University of Vicosa, Vicosa, Minas Gerais, 36570-000 (Brazil)

    2008-07-01

    The production of biodiesel from low-cost raw materials which generally contain high amounts of free fatty acids (FFAs) is a valuable alternative that would make their production costs more competitive than petroleum-derived fuel. Currently, the production of biodiesel from this kind of raw materials comprises a two-stage process, which requires an initial acid-catalyzed esterification of the FFA, followed by a basecatalyzed transesterification of the triglycerides. Commonly, the acid H{sub 2}SO{sub 4} is the catalyst on the first step of this process. It must be said, however, that major drawbacks such as substantial reactor corrosion and the great generation of wastes, including the salts formed due to neutralization of the mineral acid, are negative and virtually unsurmountable aspects of this protocol. In this paper, tin(II) chloride dihydrate (SnCl{sub 2}{center_dot}2H{sub 2}O), an inexpensive Lewis acid, was evaluated as catalyst on the ethanolysis of oleic acid, which is the major component of several fat and vegetable oils feedstocks. Tin chloride efficiently promoted the conversion of oleic acid into ethyl oleate in ethanol solution and in soybean oil samples, under mild reaction conditions. The SnCl{sub 2} catalyst was shown to be as active as the mineral acid H{sub 2}SO{sub 4}. Its use has relevant advantages in comparison to mineral acids catalysts, such as less corrosion of the reactors and as well as avoiding the unnecessary neutralization of products. Herein, the effect of the principal parameters of reaction on the yield and rate of ethyl oleate production has been investigated. Kinetic measurements revealed that the esterification of oleic acid catalyzed by SnCl{sub 2}{center_dot}2H{sub 2}O is first-order in relation to both FFAs and catalyst concentration. Experimentally, it was verified that the energy of activation of the esterification reaction of oleic acid catalyzed by SnCl{sub 2} was very close to those reported for H{sub 2}SO{sub 4

  16. A novel diffusion-biphasic hydrolysis coupled kinetic model for dilute sulfuric acid pretreatment of corn stover.

    Chen, Longjian; Zhang, Haiyan; Li, Junbao; Lu, Minsheng; Guo, Xiaomiao; Han, Lujia

    2015-02-01

    Kinetic experiments on the dilute sulfuric acid pretreatment of corn stover were performed. A high xylan removal and a low inhibitor concentration were achieved by acid pretreatment. A novel diffusion-hydrolysis coupled kinetic model was proposed. The contribution to the xylose yield was analyzed by the kinetic model. Compared with the inhibitor furfural negatively affecting xylose yield, the fast and slow-hydrolyzing xylan significantly contributed to the xylose yield, however, their dominant roles were dependent on reaction temperature and time. The impact of particle size and acid concentration on the xylose yield were also investigated. The diffusion process may significantly influence the hydrolysis of large particles. Increasing the acid concentration from 0.15 M to 0.30 M significantly improved the xylose yield, whereas the extent of improvement decreased to near-quantitative when further increasing acid loading. These findings shed some light on the mechanism for dilute sulfuric acid hydrolysis of corn stover. PMID:25479388

  17. Study on the kinetics and transformation products of salicylic acid in water via ozonation.

    Hu, Ruikang; Zhang, Lifeng; Hu, Jiangyong

    2016-06-01

    ozonation of salicylic acid in water, in terms of transformation products, kinetic, mechanism, as well as degradation pathways. PMID:27031802

  18. Kinetics of Reaction Between Tc(Ⅶ) and Monomethylhydrazine or Dimethylhydroxylamine in Nitric Acid Medium Containing Plutonium

    2008-01-01

    <正>The chemical reaction kinetics research of Tc(Ⅶ) with monomethylhydrazine or dimethylhydroxy-lamine in nitric acid medium demonstrated that Tc(Ⅶ) hardly reacts with the salt-free reagents during the

  19. Comparison of palmitic acid kinetics during glucose or ketone body infusions

    Birkhahn, R.H.; Block, D.J.; Birkhahn, G.C.; Thomford, N.R.

    1986-03-05

    Ketone body interactions can be observed for extended ketosis by infusion by monoacetoacetin (the monoglyceride of acetoacetic acid). Palmitic acid kinetics were compared on the 5th day of glucose or ketone body-glucose infusions. 20 rats were fed complete diets intravenously at the rate of 50 ml/day. All diets contained vitamins, trace minerals, electrolytes, amino acids and 1 kcal/ml of non-protein energy. Rats were divided by energy source: Group A (n = 10) received energy from glucose and Group B (n = 10) from 72% monoacetoacetin plus 28% glucose. Diets were given at 1/2 and 3/4 rats on days 1 and 2, respectively and at full rate for days 3-5. Urinary nitrogen losses, body weight and dietary intake were measured daily. Palmitate kinetics was measured on day 5 using a continuous infusion of (1-/sup 14/C) palmitate and measuring C-14 in breath and plasma and plasma palmitate by GC. The two groups had similar body weight changes and urinary nitrogen losses over the 3 days of full intake Group A had lower plasma palmitate (88 +/- 7 vs 105 +/- 6 micromol/l) but similar turnover (17.1 +/- 2.4 vs 15.0 +/- 1.9 mmol/hr) and oxidation 2.3 +/- 0.3 vs 2.2 +/- 0.05 mmol/hr) compared to Group B. These data show that feeding monoacetoacetin intravenously does not stimulate fatty acid metabolism in the well nourished rat.

  20. Dissolution kinetics of Si and Al from montmorillonite in carbonic acid solution

    Xiaoming Ni; Quanzhong Li; Wenxue Chen

    2014-01-01

    The reaction between carbonic acid and montmorillonite minerals was studied in order to provide a theoretical basis for analyzing changes in the physical properties of coal seams after CO2 injection and for optimizing CO2 pumping parameters. A single montmorillonite mineral of purity [90%was selected and subjected to reactions at 25, 35, and 45 ?C in carbonic acid solutions of varying acidity. The Si and Al concentrations in the solutions and the structure and elemental compositions of the montmorillonite before and after the reactions were analyzed using a spectrophotometer, an X-ray diffractometer, and an energy-dispersive X-ray spectrometer;kinetic reaction models were established for the dissolution of Si and Al in carbonic acid solutions in order to estimate the apparent activation energy of Si dissolution under different acidity conditions. The results indicate that Al dissolved rapidly and soon reached solubility equilibrium. On the other hand, Si concentration in the solutions increased rapidly and then gradually declined with vibrations, with maximum values at 25, 35, and 45 ?C, which were observed at approximately 96, 72, and 48 h, respectively. In addition, Si dissolution fitted the diffusion-controlled reaction model well;as the pH value decreased, the apparent activation energy of Si dissolution decreased, and Si became easier to dissolve. Furthermore, it was concluded that as a weak acid, carbonic acid causes little damage to the mineral structure of montmorillonite.

  1. Transesterification of canola, palm, peanut, soybean and sunflower oil with methanol, ethanol, isopropanol, butanol and tert-butanol to biodiesel: Modelling of chemical equilibrium, reaction kinetics and mass transfer based on fatty acid composition

    Graphical abstract: Modelling of chemical equilibrium, reaction kinetics and mass transfer for triglyceride transesterification with different alcohols based on fatty acid composition. - Highlights: • Catalysed transesterification to biodiesel with various oils, alcohols and catalysts. • Analysis of components and reactivity based on fatty acid composition of all species. • Simultaneous modelling of mass transfer, reaction kinetics and chemical equilibrium. • Diffusivities, distribution and mass transfer coefficients for individual components. • Correlation of kinetic parameters with molecular structure of reactants and products. - Abstract: Mechanism of alcoholysis (e.g. methanolysis) using different oils, alcohols and homogeneous base catalysts was utilized to devise chemical kinetics and thermodynamics based on fatty acid composition, differentiating among triglycerides, diglycerides, monoglycerides and fatty acid alkyl esters (e.g. fatty acid alkyl esters, FAME) with bonded gadoleic, linoleic, linolenic, oleic, palmitic and stearic acid-originating substituents. Their concentrations were measured using an optimized high-performance liquid chromatography (HPLC) method. Hydrodynamics and diffusion limitations in emulsion were considered in overall model by determining diffusivities, distribution coefficients, molar volumes, boiling points and viscosities of individual components. Pre-exponential factors and activation energies were related with structure of reactants, intermediates and products acknowledging number of carbons, double bonds and alkyl branches by linear and mixed response surface methodology. Developed model may be used with batch and continuous flow reactors, e.g. for novel micro-structured or industrial-scale process intensification, different vegetable or non-edible oils (waste cooking Jatropha or microalgae lipids)

  2. Are the Crystal Structures of Enantiopure and Racemic Mandelic Acids Determined by Kinetics or Thermodynamics?

    Hylton, Rebecca K; Tizzard, Graham J; Threlfall, Terence L; Ellis, Amy L; Coles, Simon J; Seaton, Colin C; Schulze, Eric; Lorenz, Heike; Seidel-Morgenstern, Andreas; Stein, Matthias; Price, Sarah L

    2015-09-01

    Mandelic acids are prototypic chiral molecules where the sensitivity of crystallized forms (enantiopure/racemic compound/polymorphs) to both conditions and substituents provides a new insight into the factors that may allow chiral separation by crystallization. The determination of a significant number of single crystal structures allows the analysis of 13 enantiopure and 30 racemic crystal structures of 21 (F/Cl/Br/CH3/CH3O) substituted mandelic acid derivatives. There are some common phenyl packing motifs between some groups of racemic and enantiopure structures, although they show very different hydrogen-bonding motifs. The computed crystal energy landscape of 3-chloromandelic acid, which has at least two enantiopure and three racemic crystal polymorphs, reveals that there are many more possible structures, some of which are predicted to be thermodynamically more favorable as well as slightly denser than the known forms. Simulations of mandelic acid dimers in isolation, water, and toluene do not differentiate between racemic and enantiopure dimers and also suggest that the phenyl ring interactions play a major role in the crystallization mechanism. The observed crystallization behavior of mandelic acids does not correspond to any simple "crystal engineering rules" as there is a range of thermodynamically feasible structures with no distinction between the enantiopure and racemic forms. Nucleation and crystallization appear to be determined by the kinetics of crystal growth with a statistical bias, but the diversity of the mandelic acid crystallization behavior demonstrates that the factors that influence the kinetics of crystal nucleation and growth are not yet adequately understood. PMID:26244445

  3. Temperature-controlled structure and kinetics of ripple phases in one- and two-component supported lipid bilayers

    Kaasgaard, Thomas; Leidy, Chad; Crowe, J.H.; Mouritsen, Ole G.; Jørgensen, Kent

    2003-01-01

    ripples was seen. From height profiles of the AFM images, estimates of the amplitudes of the different ripple phases are reported. To elucidate the processes of ripple formation and disappearance, a ripple-phase DPPC lipid bilayer was taken through the pretransition in the cooling and the heating......Temperature-controlled atomic force microscopy (AFM) has been used to visualize and study the structure and kinetics of ripple phases in one-component dipalmitoylphosphaticlylcholine (DPPC) and two-component dimyristoylphosphatidylcholine-distearoylphosphatidylcholine (DMPC-DSPC) lipid bilayers....... The lipid bilayers are mica-supported double bilayers in which ripple-phase formation occurs in the top bilayer. In one-component DPPC lipid bilayers, the stable and metastable ripple phases were observed. In addition, a third ripple structure with approximately twice the wavelength of the metastable...

  4. Effect of a Previous Acid Adaptation of Zygosaccharomyces bailii on its Growth Kinetic in Acidic Media

    Alex Tchuenchieu

    2014-11-01

    Full Text Available The growth response of Zygosaccharomyces bailii acid adapted cells was assessed in acidified media. Yeast cells were first pre-cultured in nutrient broth adjusted with hydrochloric, citric and malic acid to pH 4; 4.5; 5; 5.5; 6 and 6.5. Moreover, they were also grown in two controls consisting of nutrient broth and nutrient broth supplemented with 1% of glucose both adjusted at pH 7. The variation of pH before and after the growth along with yeast concentration was measured. The cells pre-cultured in controls conditions and in the three conditions at pH 5 were then each inoculated in six BHI medium consisting of BHI adjusted with hydrochloric, citric and malic acid at pH 5.5 and 3.5. The growth was monitored by spectrophotometry and the yeast concentration after incubation was obtained by microscopy using a Thoma cell chamber. DMFit 2.1 was used to plot the growth curves and to estimate the growth parameters. All the pre-cultures and cultures were made at 37°C during 24 hours. During the pre-cultures, an important decrease of pH was noted in nutrient broth supplemented with glucose, moving from 7 to 3.81. In all the other pre-cultures, just a little variation was observed ranging from -0.57 to 0.50. Growth was observed in all the conditions, except at pH4. By growing the cells coming from the selected pre-cultures conditions in the different acidic BHI media, it appears that acid adaptation enhance the growth at pH 5.5 no matter the acid contains in the medium and the acid to which the cells were adapted. However, this acid adaptation was not sufficient to initiate growth at pH 3.5 after 24 hours of incubation at 37°C. Growth rate was significantly affected by the pH of the pre-culture medium and the acid present in the culture medium. Pre-culture with glucose supplementation was the only parameter studied affecting the latency.

  5. Oxidation of Chalcones by Morpholinium Chlorochromate with Oxalic Acid as Catalyst: Kinetic and Mechanistic Study

    K. Rajalakshmi

    2013-01-01

    Full Text Available The kinetics of oxidation of chalcones by morpholinium chlorochromate (MCC has been studied in 55% acetic acid-water (v/v medium. The reaction showed unit order dependence each with respect to oxidant and catalyst and fractional order with respect to substrate and H+ ion. Increased ionic strength has no effect on the reaction rate. In the case of substituted chalcones, the order with respect to substrate varies depending upon the nature of the substituent present in the ring. In general, the electron withdrawing substituents retard the reaction rate while the electron releasing substituents enhance the rate of the reaction. From the kinetic data obtained, the activation parameters have been calculated and a suitable mechanism has been proposed.

  6. Kinetic studies on the carboxylation of 6-amino-penicillanic acid to 8-hydroxy-penillic acid

    Henriksen, Claus Maxel; Holm, SS; Schipper, D.;

    1997-01-01

    The carboxylation in aqueous solution of 6-amino-penicillanic acid (6-APA) to 8-hydroxy-penillic acid (8-HPA) was studied at 25 degrees C and pH 6.5. During sparging with either a citrate buffer or a chemically defined cultivation medium containing 6-APA with mixtures of carbon dioxide and air (2.......7-41% (v/v) CO2), the kinetics for conversion of 6-APA was followed by HPLC. In the citrate buffer 6-APA was converted by two competitive reactions each following first order kinetics with respect to the concentration of 6-APA: 1. carboxylation into 8-HPA; and 2. slow conversion into an unknown compound....... Formation of the unknown compound was not observed in the cultivation medium. The carboxylation of 6-APA was also found to be first order with respect to the concentration of dissolved carbon dioxide. The rate constant for formation of 8-HPA did not differ significantly in the cultivation medium compared to...

  7. Super phosphoric acid catalyzed esterification of Palm Fatty Acid Distillate for biodiesel production: physicochemical parameters and kinetics

    Metre Anand V.

    2015-03-01

    Full Text Available In the present study the esterification of palm fatty acid distillate (PFAD, a by-product from palm oil industry, in the presence of super phosphoric acid (SPA catalyst was studied. The effects of various physico-chemical parameters such as temperature, PFAD to methanol molar ratio and amount of catalyst on the conversion of biodiesel were investigated. The percent conversion of FFA and properties of the biodiesel were determined following standard methodologies. Percent conversion of biodiesel was found to increase with the increase in PFAD to methanol molar ratio and at 1:12 molar ratio and 70°C temperature 95% conversion was achieved. Thermodynamic parameters were also evaluated in terms of Gibbs free energy, enthalpy and entropy at different molar ratio and temperatures. Both pseudo first and second order irreversible kinetics were applied to a wide range of experimental data. However, according to regression coefficient (R2 the second order described better experimental behavior of kinetic data.

  8. System-level understanding of the potential acid-tolerance components of Acidithiobacillus thiooxidans ZJJN-3 under extreme acid stress.

    Feng, Shoushuai; Yang, Hailin; Wang, Wu

    2015-09-01

    In previous study, two extremely acidophilic strains Acidithiobacillus thiooxidans ZJJN-3 (collection site: bioleaching leachate) and ZJJN-5 (collection site: bioleaching wastewater) were isolated from a typical industrial bio-heap in China. Here, we unraveled the potential acid-tolerance components of ZJJN-3 by comparing the physiological differences with ZJJN-5 under different acid stresses. The parameters used for comparison included intracellular pH (pHin), capsule morphology, fatty acid composition of cell membrane, transcription of key molecular chaperones, H(+)-ATPase activities and NAD(+)/NADH ratio. It was indicated that the acid-tolerance of A. thiooxidans ZJJN-3 was systematically regulated. Capsule first thickened and then shed off along with increased acid stress. Cell membrane maintained the intracellular stability by up-regulating the proportion of unsaturated fatty acid and cyclopropane fatty acids. Meanwhile, the transcription of key repair molecular chaperones (GrpE-DnaK-DnaJ) was up-regulated by 2.2-3.5 folds for ensuring the proper folding of peptide. Moreover, low pHin promoted ZJJN-3 to biosynthesize more H(+)-ATPase for pumping H(+) out of cells. Furthermore, the NAD(+)/NADH ratio increased due to the decreased H(+) concentration. Based on the above physiological analysis, the potential acid-tolerance components of A. thiooxidans ZJJN-3 were first proposed and it would be useful for better understanding how these extremophiles responded to the high acid stress. PMID:26264736

  9. Quantitative analysis of myocardial kinetics of 15-p-[iodine-125] iodophenylpentadecanoic acid

    Myocardial extraction and the characteristic tissue clearance of radioactivity following bolus injections of a radioiodinated (125I) long chain fatty acid (LCFA) analog 15-p-iodophenylpentadecanoic acid (IPPA) were examined in the isolated perfused working rat heart. Radioactivity remaining in the heart was monitored with external scintillation probes. A compartmental model which included nonesterified tracer, catabolite, and complex lipid compartments successfully fitted tissue time-radioactivity residue curves, and gave a value for the rate of IPPA oxidation 1.8 times that obtained from steady-state release of tritiated water from labeled palmitic acid. The technique was sensitive to the impairment of LCFA oxidation in hearts of animals treated with the carnitine palmitoyltransferase I inhibitor, 2[5(4-chlorophenyl)pentyl]oxirane-2-carboxylate (POCA). IPPA or similar modified fatty acids may be better than 11C-labeled physiological fatty acids such as palmitate in this type of study, because efflux of unoxidized tracer and catabolite(s) from the heart are kinetically more distinct, and their contributions to the early data can be reliably separated. This technique may be suitable for extension to in vivo measurements with position tomography and appropriate modified fatty acids

  10. Kinetics of liquid-solid reactions in naphthenic acid conversion and Kraft pulping

    Yang, Ling

    Two liquid-solid reactions, in which the morphology of the solid changes as the reactions proceeds, were examined. One is the NA conversion in oil by decarboxylation on metal oxides and carbonates, and the other is the Kraft pulping in which lignin removal by delignification reaction. In the study of the NA conversion, CaO was chosen as the catalyst for the kinetic study from the tested catalysts based on NA conversion. Two reaction mixtures, carrier oil plus commercial naphthenic acids and heavy vacuum gas oil (HVGO) from Athabasca bitumen, were applied in the kinetic study. The influence of TAN, temperature, and catalyst loading on the NA conversion and decarboxylation were studied systematically. The results showed that the removal rate of TAN and the decarboxylation of NA were both independent of the concentration of NA over the range studied, and significantly dependent on reaction temperature. The data from analyzing the spent catalyst demonstrated that calcium naphthenate was an intermediate of the decarboxylation reaction of NA, and the decomposition of calcium naphthenate was a rate-determining step. In the study on the delignification of the Kraft pulping, a new mechanism was proposed for the heterogeneous delignification reaction during the Kraft pulping process. In particular, the chemical reaction mechanism took into account the heterogeneous nature of Kraft pulping. Lignin reacted in parallel with sodium hydroxide and sodium sulfide. The mechanism consists of three key kinetic steps: (1) adsorption of hydroxide and hydrosulfide ions on lignin; (2) surface reaction on the solid surface to produce degraded lignin products; and (3) desorption of degradation products from the solid surface. The most important step for the delignification process is the surface reaction, rather than the reactions occurring in the liquid phase. A kinetic model has, thus, been developed based on the proposed mechanism. The derived kinetic model showed that the mechanism

  11. Kinetics of pyrite oxidation by hydrogen peroxide in phosphoric acid solutions

    VALENTINA DIMITRIJEVIC

    1999-12-01

    Full Text Available The kinetics of pyrite oxidation by hydrogen peroxide in phosphoric acid solutions were investigated. The effects of stirring, temperature, and particle size, as well as of the hydrogen peroxide and phosphoric acid concentrations were studied. The effect of phosphate ion addition was also examined. The oxidation kinetics was found to follow a shrinking core model, with the surface chemical reaciton as the rate-controlling step. This is in accord with an activation energy of 57 kJ mol-1 and a linear relationship between the rate constant and the reciprocal of the particle radius. The reaction order with respect to the hydrogen peroxide concentration was found to be equal to unity. Variation of the phosphoric acid concentration had practically no effect on the rate of pyrite oxidation. Addition of the phosphate ion in the relatively low concentration range (0.005-0.1 mol dm-3 had a highly negative influence on the rate of pyrite oxidation, indicating that this ion has an inhibiting effect on the oxidation of pyrite by hydrogen peroxide.

  12. Kinetics of Non-Catalytic Esterification of Free Fatty Acids Present in Jatropha Oil.

    Prasanna Rani, Karna Narayana; Ramana Neeharika, Tulasi Sri Venkata; Kumar, Thella Prathap; Satyavathi, Bankupalli; Sailu, Chintha

    2016-05-01

    Non-catalytic esterfication of free fatty acids (FFA) present in vegetable oils is an alternative pretreatment process for the biodiesel production. Biodiesel, consists of long-chain fatty acid methyl esters (FAME) and is obtained from renewable sources such as vegetable oils or animal fat. This study presents kinetics of thermal esterification of free fatty acids present in jatropha oil with methanol. The effect of process parameters like reaction time (1-5 h), temperature (170-190°C) and oil to methanol ratio (1:3-1:5) at constant pressure was investigated. The optimal conditions were found to be oil to methanol ratio of 1:4, 190°C, at 27.1 bar and 5 h which gave a maximum conversion of 95.1%. A second order kinetic model for both forward and backward reactions was proposed to study the reaction system. A good agreement was observed between the experimental data and the model values. The activation energy for forward reaction and the heat of reaction were found to be 36.364 Kcal/mol and 1.74 Kcal/mol respectively. PMID:27086997

  13. Thermodynamic and kinetic modelling of the reduction of concentrated nitric acid

    This research thesis aimed at determining and quantifying the different stages of the reduction mechanism in the case of concentrated nitric acid. After having reported the results of a bibliographical study on the chemical and electrochemical behaviour of concentrated nitric media (generalities, chemical equilibriums, NOx reactivity, electrochemical reduction of nitric acid), the author reports the development and discusses the results of a thermodynamic simulation of a nitric environment at 25 C. This allowed the main species to be identified in the liquid and gaseous phases of nitric acid solutions. The author reports an experimental electrochemical investigation coupled with analytic techniques (infrared and UV-visible spectroscopy) and shows that the reduction process depends on the cathodic overvoltage, and identifies three potential areas. A kinetic modelling of the stationary state and of the impedance is then developed in order to better determine, discuss and quantify the reduction process. The application of this kinetic model to the preliminary results of an electrochemical study performed on 304 L steel is then discussed

  14. Kinetics and Quantitative Structure—Activity Relationship Study on the Degradation Reaction from Perfluorooctanoic Acid to Trifluoroacetic Acid

    Chen Gong

    2014-08-01

    Full Text Available Investigation of the degradation kinetics of perfluorooctanoic acid (PFOA has been carried out to calculate rate constants of the main elementary reactions using the multichannel Rice-Ramsperger-Kassel-Marcus theory and canonical variational transition state theory with small-curvature tunneling correction over a temperature range of 200~500 K. The Arrhenius equations of rate constants of elementary reactions are fitted. The decarboxylation is role step in the degradation mechanism of PFOA. For the perfluorinated carboxylic acids from perfluorooctanoic acid to trifluoroacetic acid, the quantitative structure–activity relationship of the decarboxylation was analyzed with the genetic function approximation method and the structure–activity model was constructed. The main parameters governing rate constants of the decarboxylation reaction from the eight-carbon chain to the two-carbon chain were obtained. As the structure–activity model shows, the bond length and energy of C1–C2 (RC1–C2 and EC1–C2 are positively correlated to rate constants, while the volume (V, the energy difference between EHOMO and ELUMO (ΔE, and the net atomic charges on atom C2 (QC2 are negatively correlated.

  15. Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study

    Amrit P. Toor

    2011-05-01

    Full Text Available The kinetic behavior of esterification of lactic acid with isopropanol over an acidic cation exchange resin, Amberlyst 15, was studied under isothermal condition. Isopropyl lactate synthesized in this reaction is an important pharmaceutical intermediate. The experiments were carried out in a stirred batch reactor in the temperature range of 323.15 to 353.15 K. The effect of various parameters such as temperature, molar ratio and catalyst loading was studied. Variation in parameters on rate of reaction demonstrated that the reaction was intrinsically controlled. Kinetic modeling was performed using Eley-Rideal model which acceptably fits the experimental data. The activation energy was found to be 22.007 kJ/mol and frequency factor was 0.036809 l2 g-1 mol-1 min-1 for forward reaction. The value of entropy for the forward reaction was found to be 182.317 J K-1 mol-1 . © 2011 BCREC UNDIP. All rights reserved(Received: 19th January 2011, Revised: 16th March 2011; Accepted: 16th March 2011[How to Cite: A.P. Toor, M. Sharma, S. Thakur, and R. K. Wanchoo. (2011. Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 39-45. doi:10.9767/bcrec.6.1.791.39-45][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.791.39-45 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/791 ] | View in  

  16. Analysis of embryo, cytoplasm and maternal effects on fatty acid components in soybean (Glycine max Merill.)

    NING Hailong; LI Wenxia; LI Wenbin

    2007-01-01

    The quality of oil determined by the constituents and proportion of fatty acid components,and the understanding of heredity of fatty acid components are of importance to breeding good quality soybean varieties.Embryo,cytoplasmic and maternal effects and genotype×environment interaction effects for quality traits of soybean [Glycine max (L.) Merrill.] seeds were analyzed using a general genetic model for quantitative traits of seeds with parents,F1 and F2,of 20 crosses from a diallel mating design of five parents planted in the field in 2003 and 2004 in Harbin,China.The interaction effects of palmitic,stearic,and linoleic acid contents were larger than the genetic main effects,while the genetic main effects were equal to interaction effects for linolenic and oleic acid content.Among all kinds of genetic main effects,the embryo effects were the largest for palmitic,stearic,and linoleic acids,while the cytoplasm effects were the largest for oleic and linolenic acids.Among all kinds of interaction effects,the embryo interaction effects were the largest for fatty acids.The sum of additive and additive× environment effects were larger than that of dominance and dominance×environment effects for the linolenic acid content,but not for other quality traits.The general heritabilities were the main parts of heritabilities for palmitic and oleic acid contents,but the interaction was more important for stearic,linoleic,and linolenic acid contents.For the general heritability,maternal and cytoplasm heritabilities were the main components for palmitic,oleic,and linolenic acid contents.It was shown for the interaction heritabilities that the embryo interaction heritabilities were more important for oleic and linolenic acid contents,while the maternal interaction heritabilities were more important for linoleic acid content.Among selection response components,the maternal and cytoplasm general responses and/or interaction responses were more important for palmitic

  17. Kinetics of Acid-Catalyzed Dehydration of Cyclic Hemiacetals in Organic Aerosol Particles in Equilibrium with Nitric Acid Vapor.

    Ranney, April P; Ziemann, Paul J

    2016-04-28

    Previous studies have shown that 1,4-hydroxycarbonyls, which are often major products of the atmospheric oxidation of hydrocarbons, can undergo acid-catalyzed cyclization and dehydration in aerosol particles to form highly reactive unsaturated dihydrofurans. In this study the kinetics of dehydration of cyclic hemiacetals, the rate-limiting step in this process, was investigated in a series of environmental chamber experiments in which secondary organic aerosol (SOA) containing cyclic hemiacetals was formed from the reaction of n-pentadecane with OH radicals in dry air in the presence of HNO3. A particle beam mass spectrometer was used to monitor the formation and dehydration of cyclic hemiacetals in real time, and SOA and HNO3 were quantified in filter samples by gravimetric analysis and ion chromatography. Measured dehydration rate constants increased linearly with increasing concentration of HNO3 in the gas phase and in SOA, corresponding to catalytic rate constants of 0.27 h(-1) ppmv(-1) and 7.0 h(-1) M(-1), respectively. The measured Henry's law constant for partitioning of HNO3 into SOA was 3.7 × 10(4) M atm(-1), ∼25% of the value for dissolution into water, and the acid dissociation constant was estimated to be SOA and that dehydration of cyclic hemiacetals was catalyzed by molecular HNO3 rather than by H(+). The Henry's law constant and kinetics relationships measured here can be used to improve mechanisms and models of SOA formation from the oxidation of hydrocarbons in dry air in the presence of NOx, which are conditions commonly used in laboratory studies. The fate of cyclic hemiacetals in the atmosphere, where the effects of higher relative humidity, organic/aqueous phase separation, and acid catalysis by molecular H2SO4 and/or H(+) are likely to be important, is discussed. PMID:27043733

  18. Kinetic modeling of multi‐component crystallization of industrial‐grade oils and fats

    Hjorth, Jeppe L.; Miller, Rasmus L.; Woodley, John M.;

    2015-01-01

    Transient crystallization kinetics is investigated for complex, industrial‐grade vegetable oils consisting of more than ten triacylglycerols (TAG). The classical nucleation model has been used to describe primary nucleation, while secondary nucleation has been described by a semi‐empirical approach...... describe how higher cooling rates lead to formation of more meta‐stable crystals and smaller mean‐crystal sizes. : The model provides a good starting point for developing more realistic, transient models for TAG crystallization with the ability to accommodate processing conditions and complex chemical...

  19. Thermodynamics and kinetics of thermal decomposition of diamylamyl phosphonate-nitric acid systems

    Highlights: ► The thermal hazard characteristics of DAAP has been evaluated for the first time. ► The thermodynamic and kinetic parameters have also been derived wherever possible. ► The onset of decomposition of the acid-solvates depended on the nitric acid content. ► A clear trend was seen in the decomposition of acid-solvates of TBP, TiAP and DAAP. - Abstract: Thermal decomposition of neat diamylamyl phosphonate (DAAP), nitric acid-solvates of DAAP and 1.1 M DAAP/n-dodecane was studied calorimetrically in heat-wait-search mode for the first time. The neat DAAP decomposed beyond 500 K while DAAP·0.7HNO3, DAAP·HNO3 and DAAP·2.1HNO3 decomposed exothermally at 386, 381 and 366 K respectively, indicating the role of amount of nitric acid on decomposition. Mixture of DAAP and 8 M nitric acid decomposed at a lower temperature than the acid solvates with a larger excursion in temperature and pressure yielding hydrocarbons, CO2, CO, NOx and a reddish liquid or a black solid residue. Enthalpy of decomposition of DAAP·0.7HNO3, DAAP·HNO3 and DAAP·2.1HNO3 were found to be −237.7 ± 4.8, −348.9 ± 3.4 and −1002.1 ± 2.6 kJ mol−1 and the activation energy and pre-exponential factors were 127.5 ± 1.5, 121.8 ± 0.8 and 105.3 ± 1.2 kJ mol−1 and 9.0 × 1013, 1.4 × 1012 and 2.2 × 1010 lit mol−1 s 1, respectively. Heat capacity (Cp) of acid solvates were measured and used for deriving the enthalpy change.

  20. Thermodynamics and kinetics of thermal decomposition of dibutylalkyl and dipentylalkyl phosphonate-nitric acid systems

    Tributyl phosphate (TBP) is used in the reprocessing industry for the separation of uranium and plutonium from the spent nuclear fuels by PUREX process. A variety of dialkylalky/phosphonates were synthesised and their extraction behaviour on actinides was studied in this laboratory. The superior extraction characteristics of phosphonates make them useful for several metal recovery applications in the nuclear fuel cycle. However, higher solubility of phosphonates in aqueous phase as compared to TBP, introduces higher chances of the formation of thermally active 'red oil' like substances during the evaporation of aqueous streams. Thermal stability of neat and nitric acid solvated homologues of four dibutylalkyl phosphonates namely, dibutylpropyl phosphonate (DBPrP), dibutylbutyl phosphonate (DBBP), dibutylpentyl phosphonate (DBPP), dibutylhexyl phosphonate (DBHeP), and two dipentylalkyl phosphonates viz. dipentylbutyl phosphonate (DPBP), dipentylhexyl phosphonate (DPHeP) were studied. Experiments were conducted using an adiabatic calorimeter in heat-wait-search mode. Various stoichiometry of nitric acid-solvated DBalP and DPalP were prepared by equilibrating the respective organic with 4-15.6 M nitric acid followed by separation. Neat DBalP and DPalP are stable up to the temperature of ∼ 555 K while their acid-solvates decomposed in the temperature range 380-403 K. The results also indicated that the presence of nitric acid accelerated the decomposition of phosphonates. Decomposition of these acid solvated phosphonates is found to be exothermic and follows first order kinetics. The onset temperature, adiabatic temperature rise, pressure rise, decomposition enthalpy and activation energy were found to strongly depend on the nitric acid content of the acid-solvates. The studies also indicate that dibutylalkyl and dipentylalkyl phosphonates are also prone to form 'red oil' like substances under extreme conditions and can lead to run-away reactions

  1. Mechanism and Kinetics for the Dissolution of Apatitic Materials in Acid Solutions

    Calmanovici C.E.

    1997-01-01

    Full Text Available Abstract - This work concerns the study of the digestion step in the production process of phosphoric acid. Some qualitative experiments indicate that the difference between the pH at the surface of the phosphate and that in the bulk of the solution is negligible and that the dissolution is controlled by diffusion of products away from the phosphate particle. In further experiments, to isolate the dissolution phenomenon from the formation of calcium sulfate, the sulfuric acid normally used industrially is replaced by hydrochloric acid. The phosphate material used in our experiments is a model apatitic material: synthetic hydroxyapatite (HAP. The dissolution of calcium hydroxyapatite was studied with increasing amounts of calcium and phosphate at different temperatures. A simple method was developed for this observation based on the time required for complete dissolution of the HAP powder. The results confirm that the dissolution is controlled by a diffusional process through an interface of calcium and phosphate ions released from the solid surface. A kinetic model for the dissolution of apatitic materials is proposed which assumes a shrinking particle behaviour controlled by diffusion of calcium ions. The experimental results are fitted to this model to determine the mass transfer constant for HAP dissolution in acid solutions. The activation energy of the reaction is about 14kJ/mol. This study was carried on in conditions similar to the industrial ones for the production of phosphoric acid by the dihydrate-process

  2. Kinetics of D-lactic acid production by Sporolactobacillus sp. strain CASD using repeated batch fermentation.

    Zhao, Bo; Wang, Limin; Li, Fengsong; Hua, Dongliang; Ma, Cuiqing; Ma, Yanhe; Xu, Ping

    2010-08-01

    D-lactic acid was produced by Sporolactobacillus sp. strain CASD in repeated batch fermentation with one- and two-reactor systems. The strain showed relatively high energy consumption in its growth-related metabolism in comparison with other lactic acid producers. When the fermentation was repeated with 10% (v/v) of previous culture to start a new batch, D-lactic acid production shifted from being cell-maintenance-dependent to cell-growth-dependent. In comparison with the one-reactor system, D-lactic acid production increased approximately 9% in the fourth batch of the two-reactor system. Strain CASD is an efficient D-lactic acid producer with increased growth rate at the early stage of repeated cycles, which explains the strain's physiological adaptation to repeated batch culture and improved performance in the two-reactor fermentation system. From a kinetic point of view, two-reactor fermentation system was shown to be an alternative for conventional one-reactor repeated batch operation. PMID:20374976

  3. Competitive kinetics as a tool to determine rate constants for reduction of ferrylmyoglobin by food components.

    Jongberg, Sisse; Lund, Marianne N; Pattison, David I; Skibsted, Leif H; Davies, Michael J

    2016-05-15

    Competitive kinetics were applied as a tool to determine apparent rate constants for the reduction of hypervalent haem pigment ferrylmyoglobin (MbFe(IV)O) by proteins and phenols in aqueous solution of pH 7.4 and I=1.0 at 25°C. Reduction of MbFe(IV)O by a myofibrillar protein isolate (MPI) from pork resulted in kMPI=2.2 ± 0.1 × 10(4)M(-1)s(-1). Blocking of the protein thiol groups on the MPI by N-ethylmaleimide (NEM) markedly reduced this rate constant to kMPI-NEM=1.3 ± 0.4 × 10(3)M(-1)s(-1) consistent with a key role for the Cys residues on MPI as targets for haem protein-mediated oxidation. This approach allows determination of apparent rate constants for the oxidation of proteins by haem proteins of relevance to food oxidation and should be applicable to other systems. A similar approach has provided approximate apparent rate constants for the reduction of MbFe(IV)O by catechin and green tea extracts, though possible confounding reactions need to be considered. These kinetic data suggest that small molar excesses of some plant extracts relative to the MPI thiol concentration should afford significant protection against MbFe(IV)O-mediated oxidation. PMID:26775941

  4. Plasma kinetics of complement component C4: comparison of three models

    Plasma C4 kinetics were studied in members of a kindred with hereditary incomplete C4 deficiency and in control subjects. Test subjects received iodine 125-labeled C4 intravenously, and plasma disappearance curves for 125I-C4 were plotted. By nonlinear least-squares analysis, we fit two-, three-, and four-exponential models of plasma disappearance to the plasma curves of each subject. Goodness of fit was significantly better for all subjects with the three-exponential versus the two-exponential model (p less than 0.0005). No further improvement in curve fit was accomplished by using a four-exponential model (p greater than 0.5). Metabolic rates and extravascular/plasma ratios calculated from the two- and three-exponential models were significantly different. As judged by extravascular/plasma ratio, the two-exponential model underestimated the amount of extravascular C4. Furthermore, the two-exponential model significantly over-estimated catabolic and synthetic rates. Hence, our results show that C4 kinetics are not optimally described by a conventional, two-exponential model. A possible explanation for our findings is that in previous studies of C4 metabolism, the analysis of plasma radioactivity disappearance curves was done by inspection, whereas we used least-squares analysis, a method that determines the number of exponentials with greater reliability

  5. Kinetics and mechanism of sphalerite leaching by sodium nitrate in sulphuric acid solution

    Sokić M.

    2012-01-01

    Full Text Available Interest for application of hydrometallurgical processes in a processing of complex sulphide ores and concentrates has increased in recent years. Their application provides better metal recoveries and reduced emission of gaseous and toxic ageneses in the environment. The kinetics and mechanism of sphalerite leaching from complex sulphide concentrate with sulphuric acid and sodium nitrate solution at standard conditions was presented in this paper. The influences of temperature and time on the leaching degree of zinc were investigated and kinetic analysis of the process was accomplished. With temperature increasing from 60 to 90°C, the zinc leaching increased from 25.23% to 71.66% after 2 hours, i.e. from 59.40% to 99.83% after 4 hours. The selected kinetic model indicated that the diffusion through the product layer was the rate-controlling step during the sphalerite leaching. The activation energy was determined to be 55 kJ/mol in the temperature range 60-90°C. XRD, light microscopy and SEM/EDX analyses of the complex concentrate and leach residue confirmed formation of elemental sulphur and diffusion-controlled leaching mechanism.

  6. Kinetics of enzymatic synthesis of liquid wax ester from oleic acid and oleyl alcohol.

    Radzi, Salina Mat; Mohamad, Rosfarizan; Basri, Mahiran; Salleh, Abu Bakar; Ariff, Arbakariya; Rahman, Mohammad Basyaruddin Abdul; Rahman, Raja Noor Zaliha Raja Abdul

    2010-01-01

    The kinetics of wax ester synthesis from oleic acid and oleyl alcohol using immobilized lipase from Candida antartica as catalyst was studied with different types of impeller (Rushton turbine and AL-hydrofoil) to create different mixing conditions in 2l stirred tank reactor. The effects of catalyst concentration, reaction temperature, and impeller tip speed on the synthesis were also evaluated. Rushton turbine impeller exhibited highest conversion rate at lower impeller tip speed as compared to AL-hydrofoil impeller. A second-order reversible kinetic model from single progress curve for the prediction of fractional conversion at given reaction time was proposed and the corresponding kinetic parameter values were calculated by non-linear regression method. The results from the simulation using the proposed model showed satisfactory agreement with the experimental data. Activation energy shows a value of 21.77 Kcal/mol. The thermodynamic parameters of the process, enthalpy and entropy, were 21.15 Kcal/mol and 52.07 cal/mol.K, respectively. PMID:20124754

  7. Complexes between ovalbumin nanoparticles and linoleic acid: Stoichiometric, kinetic and thermodynamic aspects.

    Sponton, Osvaldo E; Perez, Adrián A; Carrara, Carlos R; Santiago, Liliana G

    2016-11-15

    Stoichiometric, kinetic and thermodynamic aspects of complex formation between heat-induced aggregates of ovalbumin (ovalbumin nanoparticles, OVAn) and linoleic acid (LA) were evaluated. Extrinsic fluorescence data were fitted to modified Scatchard model yielding the following results: n: 49±2 LA molecules bound per OVA monomer unit and Ka: 9.80±2.53×10(5)M. Kinetic and thermodynamic properties were analyzed by turbidity measurements at different LA/OVA monomer molar ratios (21.5-172) and temperatures (20-40°C). An adsorption approach was used and a pseudo-second-order kinetics was found for LA-OVAn complex formation. This adsorption process took place within 1h. Thermodynamic parameters indicated that LA adsorption on OVAn was a spontaneous, endothermic and entropically-driven process, highlighting the hydrophobic nature of the LA and OVAn interaction. Finally, Atomic Force Microscopy imaging revealed that both OVAn and LA-OVAn complexes have a roughly rounded form with size lower than 100nm. PMID:27283701

  8. Kinetic study of the reduction of Np(VI) with humic acid

    237Np is one of the most long-life and toxic nuclides in the high level nuclear waste, and will become the primary hazard in the final nuclear waste disposal after a long time of storage, so it is important to study the chemical behaviour of Np. Humic acid is a kind of organic compound reduction in nature. The study of the kinetics of the reduction of Np(VI) with humic acid will afford a basis for further study of the chemical behaviour of Np in the environmental water. Considering the rapid exchange of Np valences during this experiment, extractants TTA and TOPO are used to analyze simultaneously three Np valences (VI), (V) and (IV)

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

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

    2003-01-01

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

  10. Hydrophobic amino acids as a new class of kinetic inhibitors for gas hydrate formation

    Sa, Jeong-Hoon; Kwak, Gye-Hoon; Lee, Bo Ram; Park, Da-Hye; Han, Kunwoo; Lee, Kun-Hong

    2013-08-01

    As the foundation of energy industry moves towards gas, flow assurance technology preventing pipelines from hydrate blockages becomes increasingly significant. However, the principle of hydrate inhibition is still poorly understood. Here, we examined natural hydrophobic amino acids as novel kinetic hydrate inhibitors (KHIs), and investigated hydrate inhibition phenomena by using them as a model system. Amino acids with lower hydrophobicity were found to be better KHIs to delay nucleation and retard growth, working by disrupting the water hydrogen bond network, while those with higher hydrophobicity strengthened the local water structure. It was found that perturbation of the water structure around KHIs plays a critical role in hydrate inhibition. This suggestion of a new class of KHIs will aid development of KHIs with enhanced biodegradability, and the present findings will accelerate the improved control of hydrate formation for natural gas exploitation and the utilization of hydrates as next-generation gas capture media.

  11. Kinetics of the Leaching Process of an Australian Gibbsitic Bauxite by Hydrochloric Acid

    Aichun Zhao

    2016-01-01

    Full Text Available Gibbsitic bauxite from Australia was leached by hydrochloric acid in this work. Analysis on kinetics for the extraction of Al2O3 was quantitatively studied. It was concluded that the hydrochloric acid leaching process of gibbsitic bauxite was controlled by chemical reaction. Moreover, the mechanism for the dissolution followed the equation, ln⁡k=39.44-1.66×104(1/T, with an apparent activation energy of 137.90 kJ/mol, according to the equation of k=Ae-Ea/RT. This work aims to provide a good theory support for the process control by using a new method of alumina production from the low grade bauxite.

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

    2003-01-01

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

  13. A kinetic study of the oxidation of some amino acids by peroxydisulphate

    The present work deals with the study of redox reactions of some amino-acids (Leucine, Aspartic and Arganine) with peroxydisulphate. The kinetic study of the above reactions showed that these reactions followed first order with respect to peroxydisulphate and silver ion as catalyst and zero order with respect to the amino-acids. For these reactions, the activation energies and other thermodynamic parameters, namely entropy (ΔS≠) and free energy of activation (ΔG≠) were evaluated. The analysis of the reaction products by the (IR) revealed the presence of 2-butanone in the case of leucine, propanone in the case of aspartic and 2-3 butanone in the case of arganine. Plausible mechanisms were proposed for there are reactions in accordance with the experimentally observed rate law and the products formed. (Author)

  14. Quantitative evaluation of dichloroacetic acid kinetics in human--a physiologically based pharmacokinetic modeling investigation.

    Li, Ting; Schultz, Irv; Keys, Deborah A; Campbell, Jerry L; Fisher, Jeffrey W

    2008-03-12

    Dichloroacetic acid is a common disinfection by-product in surface waters and is a probable minor metabolite of trichloroethylene. Dichloroacetic acid (DCA) liver carcinogenicity has been demonstrated in rodents but epidemiological evidence in humans is not available. High doses of DCA ( approximately 50mg/kg) are used clinically to treat metabolic acidosis. Biotransformation of DCA by glutathione transferase zeta (GSTzeta) in the liver is the major elimination pathway in humans. GSTzeta is also inactivated by DCA, leading to slower systemic clearance and nonlinear pharmacokinetics after multiple doses. A physiologically based pharmacokinetic (PBPK) model was developed to quantitatively describe DCA biotransformation and kinetics in humans administered DCA by intravenous infusion and oral ingestion. GSTzeta metabolism was described using a Michaelis-Menten equation coupled with rate constants to account for normal GSTzeta synthesis, degradation and irreversible covalent binding and inhibition by the glutathione-bound-DCA intermediate. With some departures between observation and model prediction, the human DCA PBPK model adequately predicted the DCA plasma kinetics over a 20,000-fold range in administered doses. Apparent inhibition of GSTzeta mediated metabolism of DCA was minimal for low doses of DCA (microg/kg day), but was significant for therapeutic doses of DCA. Plasma protein binding of DCA was assumed to be an important factor influencing the kinetics of low doses of DCA (microg/kg day). Polymorphisms of GSTzeta may help explain inter-individual variability in DCA plasma kinetics and warrants evaluation. In conclusion, using a previously published rodent DCA PBPK model (Keys, D.A., Schultz, I.R., Mahle, D.A., Fisher, J.W., 2004. A quantitative description of suicide inhibition of dichloroacetic acid in rats and mice. Toxicol. Sci. 82, 381-393) and this human DCA PBPK model, human equivalent doses (HEDs) were calculated for a 10% increase in mice hepatic

  15. Evaluation of medium components by Plackett-Burman statistical design for lipase production by Candida rugosa and kinetic modeling.

    Rajendran, Aravindan; Palanisamy, Anbumathi; Thangavelu, Viruthagiri

    2008-03-01

    Lipase production by Candida rugosa was carried out in submerged fermentation. Plackett-Burman statistical experimental design was applied to evaluate the fermentation medium components. The effect of twelve medium components was studied in sixteen experimental trials. Glucose, olive oil, peptone and FeCl3.6H2O were found to have more significance on lipase production by Candida rugosa. Maximum lipase activity of 3.8 u mL(-1) was obtained at 50 h of fermentation period. The fermentation was carried out at optimized temperature of 30 degrees C, initial pH of 6.8 and shaking speed of 120 r/min. Unstructured kinetic models were used to simulate the experimental data. Logistic model, Luedeking-Piret model and modified Luedeking-Piret model were found suitable to efficiently predict the cell mass, lipase production and glucose consumption respectively with high determination coefficient(R2). From the estimated values of the Luedeking-Piret kinetic model parameters, alpha and beta, it was found that the lipase production by Candida rugosa is growth associated. PMID:18589820

  16. Evaluation of Medium Components by Plackett-Burman Statistical Design for Lipase Production by Candida rugosa and Kinetic Modeling

    Aravindan Rajendran; Anbumathi Palanisamy; Viruthagiri Thangavelu

    2008-01-01

    Lipase production by Candida rugosa was carried out in submerged fermentation. Plackett-Burman statistical experimental design was applied to evaluate the fermentation medium components. The effect of twelve medium components was studied in sixteen experimental trials.Glucose,olive oil,peptone and FeCl3·6H2O were found to have more significance on lipase production by Candida rugosa. Maximum lipase activity of 3.8 u mL-1 was obtained at 50 h of fermentation period. The fermentation was carried out at optimized temperature of 30℃, initial pH of 6.8 and shaking speed of 120 r/min. Unstructured kinetic models wereused to simulate the experimental data. Logistic model, Luedeking-Piret model and modified Luedeking-Piret model were foundsuitable to efficiently predict the cell mass, lipase production and glucose consumption respectively with high determination coefficient(R2). From the estimated values of the Luedeking-Piret kinetic model parameters, α and β, it was found that the lipase production by Candida rugosa is growth associated.

  17. Ionizing radiation induced attachment reactions of nucleic acids and their components

    An extensive bibliographic review is given of experimental and theoretical data on radiation-induced attachment reactions of nucleic acids and their components. Mechanisms of these reactions are reviewed. The reactions with water, formate, and alcohols, with amines and other small molecules, and with radiation sensitizers and nucleic acid-nucleic acid reactions are discussed. Studies of the reaction mechanisms show that many of the reactions occur by radical-molecule reactions, but radical-radical reactions also occur. Radiation modifiers become attached to nucleic acids in vitro and in vivo and there are indications that attachment may be necessary for the action of some sensitizers. (U.S.)

  18. Slow component of VO2 kinetics: Mechanistic bases and practical applications

    Jones, Andrew M; Grassi, Bruno; Christensen, Peter Møller; Krustrup, Peter; Bangsbo, Jens; Poole, David C

    2011-01-01

    with the progressive recruitment of additional (type II) muscle fibers that are presumed to have lower efficiency. Recent studies, however, indicate that muscle efficiency is also lowered (resulting in a 'mirror-image'V¿O2 slow component) during fatiguing, high-intensity exercise in which additional...... fiber recruitment is unlikely or impossible. Therefore, it appears that muscle fatigue underpins the V¿O2 slow component, although the greater fatigue-sensitivity of recruited type II fibers might still play a crucial role in the loss of muscle efficiency in both situations.Several interventions can...

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

    Zhaksyntay Kairbekov; Dina Akbayeva; Zhaniya Eshova; M. Bazhanovа

    2012-01-01

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

  20. Effect of preliminary mechanical manganese tungstate activation on the kinetics of its decomposition by sulfuric acid

    Effect of mechanical manganese tungstate activation on the rate of its decomposition by the sulfuric acid has been investigated. Activation is carried out in the laboratory centrifugal planetary grinder (CPG) of periodic action operating under the impact-wearing down mode with centrifugal acceleration of balls with ∼ 5 mm in diameter (alloy VK-8) ∼ 25 g. ''Dry'' activation (grinding in the air) has been carried out at the ratio of balls to the concentrate by mass 1050:50 g; ''wet'' activation (grinding in water pulp) - at the ratio of balls : concentrate : water by mass 1000:50:50 g. Time of activation varies from 5 to 15 min. Grinding of manganese tungstate concentrates in the apparatuses of the CPG type both in the air and in water pulp is shown to lead to deep structure changes in manganese tungstate activated the further process of concentrate decomposition by the sulfuric acid. Sharp increase of rate and degree of manganese tungstate concentrates decomposition by sulfuric acid solutions has been established on the basis of the kinetics investigation that opens the way for application of decomposition by the sulfuric acid during tungsten raw material reprocessing

  1. 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

  2. Carbon-13 kinetic isotope effects in the decarbonylations of lactic acid containing 13C at the natural abundance level

    The 13C kinetic isotope fractionation in the decarbonylation of lactic acid of natural isotopic composition by sulfuric acid has been studied in the temperature range of 20-80 deg C. The 13C(1) isotope separation in the decarbonylation of lactic acid by concentrated sulfuric acid depends strongly on the temperature above 40 deg C. Below this temperature the 13C isotope effect in the decarbonylation of lactic acid by concentrated sulfuric acid is normal similarly as has been found in the decarbonylation of lactic [1-14C] acid. The experimental values of k(12C)/k(13C) ratios of isotopic rate constants for 12C and 13C are close to, but slightly higher than theoretical 13C-kinetic isotope effects calculated (neglecting tunneling) under the asumption that the C(1)-OH bond is broken in the rate-controlling step of the dehydration reaction. Dilution of concentrated sulfuric acid with water up to 1.4 molar (H2O)/(H2SO4) ratio caused the increase of the 13C isotope fractionation from 1.0273 found in concentrated sulfuric acid at 80.5 deg C to 1.0536±0.0008 (at 80.6 deg C). A discussion of the abnormally high temperature dependence of 14C and 13C isotope fractionation in this reaction and the discussion of the problem of relative 14C/13C kinetic isotope effects is given. (author) 18 refs.; 2 tabs

  3. Shikimic acid ozonolysis kinetics of the transition from liquid aqueous solution to highly viscous glass.

    Steimer, Sarah S; Berkemeier, Thomas; Gilgen, Anina; Krieger, Ulrich K; Peter, Thomas; Shiraiwa, Manabu; Ammann, Markus

    2015-12-14

    Ageing of particulate organic matter affects the composition and properties of atmospheric aerosol particles. Driven by temperature and humidity, the organic fraction can vary its physical state between liquid and amorphous solid, or rarely even crystalline. These transitions can influence the reaction kinetics due to limitations of mass transport in such (semi-) solid states, which in turn may influence the chemical ageing of particles containing such compounds. We have used coated wall flow tube experiments to investigate the reaction kinetics of the ozonolysis of shikimic acid, which serves as a proxy for oxygenated, water-soluble organic matter and can form a glass at room temperature. Particular attention was paid to how the presence of water influences the reaction, since it acts a plasticiser and thereby induces changes in the physical state. We analysed the results by means of a traditional resistor model, which assumes steady-state conditions. The ozonolysis rate of shikimic acid is strongly increased in the presence of water, a fact we attribute to the increased transport of O3 and shikimic acid through the condensed phase at lower viscosities. The analysis using the resistor model suggests that the system undergoes both surface and bulk reaction. The second-order rate coefficient of the bulk reaction is 3.7 (+1.5/-3.2) × 10(3) L mol(-1) s(-1). At low humidity and long timescales, the resistor model fails to describe the measurements appropriately. The persistent O3 uptake at very low humidity suggests contribution of a self-reaction of O3 on the surface. PMID:26536455

  4. The Effect of Oxygen Supply on the Dual Growth Kinetics of Acidithiobacillus thiooxidans under Acidic Conditions for Biogas Desulfurization

    Hyeong-Kyu Namgung; JiHyeon Song

    2015-01-01

    In this study, to simulate a biogas desulfurization process, a modified Monod-Gompertz kinetic model incorporating a dissolved oxygen (DO) effect was proposed for a sulfur-oxidizing bacterial (SOB) strain, Acidithiobacillus thiooxidans, under extremely acidic conditions of pH 2. The kinetic model was calibrated and validated using experimental data obtained from a bubble-column bioreactor. The SOB strain was effective for H2S degradation, but the H2S removal efficiency dropped rapidly at DO ...

  5. Atomic kinetic Monte Carlo modeling of multi-component Fe dilute alloys under irradiation

    The ageing of pressure vessel steels under radiation has been correlated with the formation of more or less dilute solute clusters which are investigated in this work using a multi-scale approach based on ab initio and atomistic kinetic Monte Carlo (AKMC) simulations. The microstructure evolution of Fe alloys is modeled by AKMC on a lattice, using pair interactions adjusted on DFT (Density Functional Theory) calculations. Several substitutional elements (Cu, Ni, Mn, Si, P) and foreign interstitials (C, N) are taken into account to describe the alloy. The point defect created by the irradiation, i.e. the vacancies and self interstitials have a tendency to form clusters. The evolution of these clusters is governed by the migration energy of the individual point defects which is very heavy in terms of computing time due to the large number of AKMC steps required. The structure of all the possible objects that can form is complex and some optimized and accelerated methods will be presented. The results obtained are in agreement with the experimental trends and indicate that the formation of solute clusters takes place via segregation mechanisms on the point defect clusters

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

    G P Panigrahi; Jagannath Panda

    2000-12-01

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

  7. Labelling of nucleic acid components with tritium by hydrogenolysis of corresponding precursors

    To desalt the luates of liquid column chromatography containing components of the nucleic acids different types of activated carbons are used: AG-5, Ou-4, KAD, BAU (SU), Norit (GB) and Carboafin (CS). The Carborafin (CS) carbon proved to be the most efficient for the purpose. Dependences of the adsorption degree on pH, the time of the phases contact, temperature, concentration of the salt background (ammonium formite, lithium chloride) as well as adsorption isotherm are determined for the activated carbon. Desorption conditions of the nucleic acids components from the carbon are studied. It is shown that quantitative desorption is achieved when 1n solution of ammonia is used in 50% ethanole for 50-60 min. Data on practical application of the method to desalt the eluates containing tritiated nucleic acid components with a high activity are presented

  8. An Analytical Model Approach for the Dissolution Kinetics of Magnesite Ore Using Ascorbic Acid as Leaching Agent

    Nadeem Raza

    2013-01-01

    Full Text Available Ascorbic acid was used as leaching agent to investigate the dissolution kinetics of natural magnesite ore. The effects of various reaction parameters such as acid concentration, liquid-solid ratio, particle size, stirring speed, and temperature were determined on dissolution kinetics of the magnesite ore. It was found that the dissolution rate increased with increase in acid concentration, liquid-solid ratio, stirring speed, and temperature and decrease in the particle size of the ore. The graphical and statistical methods were applied to analyze the kinetic data, and it was evaluated that the leaching process was controlled by the chemical reaction, that is, . The activation energy of the leaching process was found to be 57.244 kJ mol−1 over the reaction temperature range from 313 to 343 K.

  9. Spectrophotometric method for fast quantification of ascorbic acid and dehydroascorbic acid in simple matrix for kinetics measurements.

    Gómez Ruiz, Braulio; Roux, Stéphanie; Courtois, Francis; Bonazzi, Catherine

    2016-11-15

    A simple, rapid and reliable method was developed for quantifying ascorbic (AA) and dehydroascorbic (DHAA) acids and validated in 20mM malate buffer (pH 3.8). It consists in a spectrophotometric measurement of AA, either directly on the solution added with metaphosphoric acid or after reduction of DHAA into AA by dithiothreitol. This method was developed with real time measurement of reactions kinetics in bulk reactors in mind, and was checked in terms of linearity, limits of detection and quantification, fidelity and accuracy. The linearity was found satisfactory on the range of 0-6.95mM with limits of detection and quantification of 0.236mM and 0.467mM, respectively. The method was found acceptable in terms of fidelity and accuracy with a coefficient of variation for repeatability and reproducibility below 6% for AA and below 15% for DHAA, and with a recovery range of 97-102% for AA and 88-112% for DHAA. PMID:27283671

  10. Kinetics of Glycoxidation of Bovine Serum Albumin by Glucose, Fructose and Ribose and Its Prevention by Food Components

    Izabela Sadowska-Bartosz

    2014-11-01

    Full Text Available The aim of this study was to compare the kinetics of the glycoxidation of bovine serum albumin (BSA as a model protein by three sugars: glucose, fructose and ribose, using fluorometric measurements of the content of advanced glycation end products (AGEs, protein-bound fructosamine, dityrosine, N'-formylkynurenine, kynurenine, tryptophan, the content of advanced oxidation protein products (AOPP, protein carbonyl groups, as well as thiol groups. Moreover, the levels of glycoalbumin and AGEs were determined by using an enzyme-linked immunosorbent assay. Based on the kinetic results, the optimal incubation time for studies of the modification of the glycoxidation rate by additives was chosen, and the effects of 25 compounds of natural origin on the glycoxidation of BSA induced by various sugars were examined. The same compounds were found to have different effects on glycoxidation induced by various sugars, which suggests caution in extrapolation from experiments based on one sugar to other sugars. From among the compounds tested, the most effective inhibitors of glycoxidation were: polyphenols, pyridoxine and 1-cyano-4-hydroxycinnamic acid.

  11. KINETIC STUDY OF PALMITIC ACID ESTERIFICATION CATALYZED BY Rhizopus oryzae RESTING CELLS

    RAMON CANELA

    2009-04-01

    Full Text Available

    ABSTRACT

    In the present study, a kinetic model for the biocatalytic synthesis of esters using Rhizopus oryzae resting cells is proposed. The kinetic study has been made in a range of 30-50 °C and atmospheric pressure. The Influence of operating variables, water content, pH, amount of mycelium was studied. Different values of temperature, initial mycelium concentration and acid/alcohol molar ratio were tested. Initial rates were estimated from the slope of the concentration of palmitic acid, or their corresponding ester at conversions of less than 10%, versus time and reported as mmol l-1 min -1. The values of kinetic constants were computed using the freeware program SIMFIT (http:\\www.simfit.man.ac.uk.

    Key words: bound lipase, esterification, fungal resting cells, Rhizopus oryzae, palmitic acid, propanol.


    RESUMEN

    En el presente estudio, un modelo cinético para la síntesis de esteres usando Rhizopus oryzae resting cells es propuesto. El estudio cinético fue realizado en un rango de temperatura de 30-50 ºC a presión atmosférica reducida. La influencia de las variables de operación tales como temperatura, pH y contenido de agua fueron estudiadas. Diferentes valores de concentración de micelio y relación molar de ácido/alcohol son ensayadas, Las velocidades iníciales se estimaron de la curva de concentración de acido palmítico, y su correspondiente conversión a ester en menos del 10%, frente a tiempo y reportadas en mmol I-1 min -1. Los valores de las constantes cinéticas fueron calculados usando el programa freeware SIMFIT (http:\\www.simfit.man.ac.uk.

    Palabras clave: Lipasas, esterificación, resting cells, Rhizopus oryzae, acido palmítico, propanol.

  12. Kinetic Studies on Wheat Straw Hydrolysis to Levulinic Acid%小麦秸秆制备乙酰丙酸的动力学研究

    常春; 马晓建; 岑沛霖

    2009-01-01

    Levulinic acid is considered as a promising green platform chemical derived from biomass. The kinetics of levulinic acid accumulation in the hydrolysis process of wheat straw was investigated in the study. Using dilute sulfuric acid as a catalyst, the kinetic experiments were performed in a temperature range of 190-230℃ and an acid concentration range of 1%-5% (by mass). A simple model of first-order series reactions was developed, which provided a satisfactory interpretation of the experimental results. The kinetics of main intermediates including sugar and 5-hydroxymethylfurfural (5-HMF) were also established. The kinetic parameters provided useful information for understanding the hydrolysis process.

  13. Accumulation and kinetics of 90Sr in fishes and other components of an artificial aquatic system

    Regularities are described of 90Sr transfer from water into the particular components of a simplified experimental aquatic system - the sediments, algae, invertebrates (gastropods) and fish - based on a model experiment simulating conditions of a section of the Jihlava River as influenced by the release of liquid wastes from the Dukovany nuclear power plant. Owing to their high abundance, both in nature and in the experiment, the aquatic algae and sediments are the most important accumulators of 90Sr. Nevertheless, the highest increase in the specific radionuclide concentrations and in the accumulation coefficients were found in aquatic gastropods and in fish bones. (author). 1 tab., 12 refs

  14. Catalytic Kinetic Determination of Micro Amounts of Oxalic Acid by Second-Order Derivative Oscillopolarography

    2001-01-01

    It was found that micro amounts of oxalate showed a very strong catalytic effect on the slow reaction between K2Cr2O7 and Orange Ⅳ in a diluted sulfuric acid medium in a water bath at 70 ℃. Orange Ⅳ exhibited a sensitive second-order derivative polarographic wave at -0.50 V(vs. SCE). This provides the basis for a sensitive and selective catalytic kinetic method for oxalate determination with second-order derivative oscillopolarography. The effects of sulphuric acid, K2Cr2O7, and orange Ⅳ concentrations, reaction temperature and reaction time were investigated. A calibration curve of oxalate in the range of 0.1—2.0 μg/mL was obtained by the fixed-time procedure. The detection limit was 0.03 μg/ mL. The possible interference from co-existing substances or ions was examined. The new method has a high sensitivity and a good selectivity compared to other existing methods for oxalic acid determination. It has been applied to the determination of micro amounts of oxalate in real urine samples with satisfactory results.

  15. The Inherent Reactor Kinetics for Transformation of Geniposidic Acid from Geniposide in a Microreactor

    Chiu-Lan Hsieh

    2015-01-01

    Full Text Available The ripe fruits of Gardenia jasminoides Ellis (Rubiaceae (GJ are widely used in chemical, food and medicinal industries. Crocin and geniposide, the main constituents of GJ, have shown a diversity of biological activities including sedative, anti-inflammatory and antipyretic. We propose some new bioactive chemicals could be derived from geniposide. The optimum transformation condition of geniposide into geniposidic acid still remains unclear. In order to develop a reactor, the information about the inherent reaction kinetics is required. In a microreactor (V =62.8 mL, geniposide (0.01 mole/L, 20 mL and NaOH (0.1 equivalent/L, pH=13, 10mL were left to react at 80, 70, 60, 50, and 40 oC and tracked with HPLC. Results indicated that the reaction obeyed the pseudo-first order kinetics, the corresponding pseudo-first order rate constants ( 1 k ' were 11.064 h -1 , 8.682 h -1 , 2.400 h -1 , 1.021 h -1 , and 0.750 h-1 , and the fractional conversions were 73.4%, 60.5%, 38.6%, 43.6%, and 51.8% at 0.50, 0.50, 0.833, 1.00, and 2.00 h. The energy of activation was 8.751 kJ mol-1 . Conclusively, this transformation obeys the pseudo-first order kinetics with a low energy of activation, 8.751 kJ mol-1 . The optimum transformations at 80oC and 70oC for 0.5 h were 73.4% and 60.5%, respectively.

  16. THE EFFECT OF EMI EHF ON ELECTRO - KINETIC POTENTIAL OF CELL NUCLEAR MEMBRANES OF WHEAT SEEDLINGS TREATED WITH HYBBERELLIC ACID

    Vardevanyan Poghos O

    2013-09-01

    Full Text Available The effect of hybberellic acid and EMI EHF on electro kinetic potential changes of cell nuclear membrane of wheat seedlings has been investigated. It was revealed that electro kinetic potential value depends on functional state of plant organism. It was reported that the treatment of wheat germs with hybberellic acid and EMI EHF induces a change of nuclear membrane surface charge. It was revealed that the combined influence of chemical as well as physical factors induces more pronounced response on biological systems as compared to separately. It was also observed that the effect of EMI EHF has significant effect on water resonant frequencies as compared to water non- resonant frequencies.

  17. Dynamic modeling of in vitro lipid digestion: individual fatty acid release and bioaccessibility kinetics.

    Giang, T M; Gaucel, S; Brestaz, P; Anton, M; Meynier, A; Trelea, I C; Le Feunteun, S

    2016-03-01

    The aim of this study was to gain knowledge about the role of triacylglycerol (TAG) composition in fatty acids (FA) of o/w emulsions on both the pancreatic lipolysis kinetics and the bioaccessibility of released products (i.e. contained within the bile salt micellar phase). A mathematical model was developed and its predictions were compared to a set of experimental data obtained during an in vitro digestion of a whey protein stabilized emulsion. Modeling results show that FA residues of TAG were hydrolyzed at specific rates, inducing different bioaccessibility kinetics. The estimated lipolysis rate constants of the studied FA (C8:0, C10:0≫C18:1 n-9≫C12:0>C14:0>C16:0≈C16:1 n-7>C22:6 n-3) were in close agreement with the available literature on the substrate specificity of pancreatic lipase. Results also suggest that lipolysis products are very rapidly solubilized in the bile salt mixed micelles with no fractionation according to the FA carbon chain. PMID:26471670

  18. Aqueous chlorination of mefenamic acid: kinetics, transformation by-products and ecotoxicity assessment.

    Adira Wan Khalit, Wan Nor; Tay, Kheng Soo

    2016-05-18

    Mefenamic acid (Mfe) is one of the most frequently detected nonsteroidal anti-inflammatory drugs in the environment. This study investigated the kinetics and the transformation by-products of Mfe during aqueous chlorination. The potential ecotoxicity of the transformation by-products was also evaluated. In the kinetic study, the second-order rate constant (kapp) for the reaction between Mfe and free available chlorine (FAC) was determined at 25 ± 0.1 °C. The result indicated that the degradation of Mfe by FAC is highly pH-dependent. When the pH was increased from 6 to 8, it was found that the kapp for the reaction between Mfe and FAC was decreased from 16.44 to 4.4 M(-1) s(-1). Characterization of the transformation by-products formed during the chlorination of Mfe was carried out using liquid chromatography-quadrupole time-of-flight accurate mass spectrometry. Four major transformation by-products were identified. These transformation by-products were mainly formed through hydroxylation, chlorination and oxidation reactions. Ecotoxicity assessment revealed that transformation by-products, particularly monohydroxylated Mfe which is more toxic than Mfe, can be formed during aqueous chlorination. PMID:27062128

  19. Formic Acid Decomposition on Au catalysts: DFT, Microkinetic Modeling, and Reaction Kinetics Experiments

    Singh, Suyash; Li, Sha; Carrasquillo-Flores, Ronald; Alba-Rubio, Ana C.; Dumesic, James A.; Mavrikakis, Manos

    2014-04-01

    A combined theoretical and experimental approach is presented that uses a comprehensive mean-field microkinetic model, reaction kinetics experiments, and scanning transmission electron microscopy imaging to unravel the reaction mechanism and provide insights into the nature of active sites for formic acid (HCOOH) decomposition on Au/SiC catalysts. All input parameters for the microkinetic model are derived from periodic, self-consistent, generalized gradient approximation (GGA-PW91) density functional theory calculations on the Au(111), Au(100), and Au(211) surfaces and are subsequently adjusted to describe the experimental HCOOH decomposition rate and selectivity data. It is shown that the HCOOH decomposition follows the formate (HCOO) mediated path, with 100% selectivity toward the dehydrogenation products (CO21H2) under all reaction conditions. An analysis of the kinetic parameters suggests that an Au surface in which the coordination number of surface Au atoms is 4 may provide a better model for the active site of HCOOH decomposition on these specific supported Au catalysts.

  20. Kinetic Modelling for Flavonoid Recovery from Red Grape (Vitis vinifera Pomace with Aqueous Lactic Acid

    Katerina Tzima

    2014-12-01

    Full Text Available This study was undertaken with the aim of establishing a correlation between the extraction yield in total flavonoids from red grape pomace and the extraction temperature, using 0.5% (w/v aqueous lactic acid as the solvent system. Extraction of flavonoids was found to obey second-order kinetics, and on such a basis, the yield in total flavonoids at saturation could be very effectively determined and correlated with temperature using non-linear regression. The results indicated that the extraction yield at saturation is highly correlated with temperature, following a quadratic function. The extract obtained at 40 °C had an optimal predicted total flavonoid yield of 13.27 mg rutin equivalents per gram of dry weight, and it was further analyzed by liquid chromatography-mass spectrometry to characterize its major constituents. The polyphenols detected were flavanols, flavonols and an anthocyanin. The outcome of this study outlined that temperatures above 40 °C are rather unfavorable for flavonoid extraction from red grape pomace, as suggested by the model established through kinetics.

  1. Dissolution kinetics of manganese dioxide ore in sulfuric acid in the presence of ferrous ion

    In this paper, kinetics of reductive leaching of manganese dioxide ore by ferrous ion in sulfuric acid media has been examined. Experimental results show that increasing temperature from 20 to 60 degC and decreasing are particle size from -16+20 to -60+100 mesh considerably enhance both the dissolution rate and efficiency. Molar ratios of Fe2+/MnO2 and H2SO4/MnO2 in excess to the stoichiometric amounts were needed for successful manganese dissolution. Under the optimum condition (are particle size of -60+100 mesh, Fe2+/MnO2 molar ratio of 3.0, H2SO4/MnO2 molar ratio of 2.0) manganese could be extracted with 95% efficiency by 20 minutes leaching at room temperature. A kinetic analysis based on dimensionless time method showed that shrinking core -ash diffusion control model fits the experimental results reasonably well. Value of activation energy was found to be 28.1 kJ/mole for the proposed mechanism

  2. Kinetic studies of acid inactivation of alpha-amylase from Aspergillus oryzae

    Carlsen, Morten; Nielsen, Jens Bredal; Villadsen, John

    1996-01-01

    The stability of alpha-amylase from Aspergillus oryzae has been studied at different pH. The enzyme is extremely stable at neutral pH (pH 5-8), whereas outside this pH-range a substantial loss of activity is observed. The acid-inactivation of alpha-amylase from A. oryzae was monitored on-line by a...... regains part of its activity, and the reactivation process also follows first-order kinetics. The irreversible loss of activity is found not to result from a protease contamination of the protein samples. A proposed model, where irreversibly inactivated a-amylase is formed both directly from the active...

  3. Kinetics of oxidation and dissolution of uranium dioxide in aqueous acid solutions

    The oxidation and dissolution of UO2 has been studied using electrochemical methods with an UO2 rotating disc electrode in acidic (pH 3) and non-complexing (trifluoromethanesulfonate: 0.1 mol L−1 NaCF3SO3) media. The effect of the experimental parameters such as scan rate (v) and rotation rate (ω) on the electrochemical signal has been studied. The rotation rate of the electrode does not influence the resulting signal, which indicates that only a charge transfer is involved in the UO2 oxidation kinetic. However, scan rate variations show different reactions involved in the UO2 oxidation. Linear sweep voltammetry and cyclic voltammetry coupled to X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS) measurements suggest two successive electrochemical reactions with an exchange of one electron for each of them and the formation of one intermediate species of U(V).

  4. Dissolution kinetics of uranium from a low grade uranium ore in acid lixiviant

    Kinetic studies on uranium dissolution were carried out on an uranium ore sample from Narwapahar, Jharkhand and a pre-concentrate obtained by physical beneficiation of the ore sample. The dissolution was effected by leaching the feed sample with sulphuric acid at a pH of 1.6-1.8 at 50 deg C with pyrolusite (MnO2) as the oxidant. The uranium dissolution was monitored at fixed time intervals by drawing samples and analyzing for the U3O8 content. It was continued up to a cumulative contact time of 12 hours. The experimental data was analyzed using 'shrinking unreacted core' (SUC) model. During the initial stages, the leaching was found to be chemical-reaction controlled and subsequently diffusion controlled. The rate constants for the uranium dissolution under the two different mechanisms have been estimated. (author)

  5. Kinetics and mechanism of the reaction of fluorine atoms with pentafluoropropionic acid.

    Vasiliev, E S; Knyazev, V D; Karpov, G V; Morozov, I I

    2014-06-12

    The kinetics of the reaction between fluorine atoms and pentafluoropropionic acid has been studied experimentally at T = 262-343 K. The overall reaction rate constant decreases with temperature: k1(T) = 6.1 × 10(-13) exp(+1166 K)/T) cm(3) molecule(-1) s(-1). The potential energy surface of the reaction has been studied using quantum chemistry. The results were used in transition state theory calculations of the temperature dependences of the rate constants of the two channels of the reaction. The abstraction channel ultimately producing HF, C2F5, and CO2 is dominant at the experimental temperatures; the addition-elimination channel producing C2F5 and CF(O)OH becomes important above 1000 K. PMID:24819330

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

    2009-01-01

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

  7. Kinetics of oxidation of pentavalent neptunium by pentavalent vanadium in solutions of nitric acid

    Precek, Martin; Paulenova, Alena

    2010-03-01

    Management of the oxidation state of neptunium in the reprocessing of spent nuclear fuel by solvent extraction is very important. The kinetics of the oxidation of neptunium(V) by vanadium(V) in solutions of nitrate acid was investigated at constant ionic strength 4M. The reaction rate is first order with respect to Np(V) and V(V). The effects of proton concentration on the apparent second order rate constant k1" was determined for temperature 25°C as k1" = (0.99±0.03)·[H+]1.21M-1s-1. Activation parameters associated with the overall reaction have been calculated; the standard reaction enthalpy and entropy were 52.6±0.9 kJ/mol and -55.8±0.9 J/K/mol respectively.

  8. Kinetic of the COLUMBO-TANTALITE dissolution in aqueous solutions of hydrofluoric acid

    The dissolution rate of a columbo-tantalite of the San Luis Province in aqueous solutions of hydrofluoric acid has been studied.Experiments at different temperatures were carried out in a pressure reactor.The experimental results show that the mineral dissolution increases with the reaction time.This effect is greater when the temperature increases from 348 up to 396 K, but it is little 493 K. The experimental data were treated with different models, which have been deduced for the kinetic study of solid-fluid non-catalytic heterogeneous reactions. As a result, the better model that fit the experimental data is a model based on the nucleation and growth theory.This model is physically according to the attack observed by means of scanning electron microscopy (SEM) and energy-dispersive X-ray spectrometry (EDXS) on the mineral residues.These residues show an irregular located-type attack

  9. Kinetic study of enzymatic hydrolysis of acid-pretreated coconut coir

    Fatmawati, Akbarningrum; Agustriyanto, Rudy

    2015-12-01

    Biomass waste utilization for biofuel production such as bioethanol, has become more prominent currently. Coconut coir is one of lignocellulosic food wastes, which is abundant in Indonesia. Bioethanol production from such materials consists of more than one step. Pretreatment and enzymatic hydrolysis is crucial steps to produce sugar which can then be fermented into bioethanol. In this research, ground coconut coir was pretreated using dilute sulfuric acid at 121°C. This pretreatment had increased the cellulose content and decreased the lignin content of coconut coir. The pretreated coconut coir was hydrolyzed using a mix of two commercial cellulase enzymes at pH of 4.8 and temperature of 50°C. The enzymatic hydrolysis was conducted at several initial coconut coir slurry concentrations (0.1-2 g/100 mL) and reaction times (2-72 hours). The reducing sugar concentration profiles had been produced and can be used to obtain reaction rates. The highest reducing sugar concentration obtained was 1,152.567 mg/L, which was produced at initial slurry concentration of 2 g/100 mL and 72 hours reaction time. In this paper, the reducing sugar concentrations were empirically modeled as a function of reaction time using power equations. Michaelis-Menten kinetic model for enzymatic hydrolysis reaction is adopted. The kinetic parameters of that model for sulfuric acid-pretreated coconut coir enzymatic hydrolysis had been obtained which are Vm of 3.587×104 mg/L.h, and KM of 130.6 mg/L.

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

    Zhaksyntay Kairbekov; Dina Akbayeva; Zh. Eshova

    2012-01-01

    It was established that in mild conditions (50-70 oC, РО2= 1 atm) white phosphorus effectively is oxidized by oxygen in water-toluene solutions of copper(II) chloride modified by humic (fulvo-) acid to give mainly phosphoric acid. Humic (fulvo-) acid was extracted from brown coal of domestic deposit Kiyakty. For determination of optimum parameters of fulvo-acid extraction the laboratory experiments were carried out using the method of experiment planning. The kinetics, intermediate and final ...

  11. A component of platypus (Ornithorhynchus anatinus) venom forms slow-kinetic cation channels.

    Kourie, J I

    1999-11-01

    The lipid bilayer technique is used to examine the biophysical properties of anion and cation channels frequently formed by platypus (Ornithorhynchus anatinus) venom (OaV). The OaV-formed anion channel in 250/50 mm KCl cis/trans has a maximum conductance of 857 +/- 23 pS (n = 5) in 250/50 mm KCl cis/trans. The current-voltage relationship of this channel shows strong inward rectification. The channel activity undergoes time-dependent inactivation that can be removed by depolarizing voltage steps more positive than the reversal potential for chloride, E(Cl), (+40 mV). The reversal potential of the OaV-formed slow current activity in 250/50 mm KCl cis/trans is close to the potassium equilibrium potential (E(K)) of -40 mV. The conductance values for the slow channel are 22.5 +/- 2.6 pS and 41.38 +/- 4.2 pS in 250/50 and 750/50 mm cis/trans, respectively. The gating kinetics of the slow ion channels are voltage-dependent. The channel open probability (P(o)) is between 0.1 and 0.8 at potentials between 0 and +140 mV. The channel frequency (F(o)) increases with depolarizing voltages between 0 and +140 mV, whereas mean open time (T(o)) and mean closed time (T(c)) decrease. Ion substitution experiments of the cis solution show that the channel has conductance values of 21.47 +/- 2. 3 and 0.53 +/- 0.1 pS in 250 mm KCl and choline Cl, respectively. The amplitude of the single channel current is dependent on [K(+)](cis) and the current reversal potential (E(rev)) responds to increases in [K(+)](cis) by shifting to more negative voltages. The increase in current amplitude as a function of increasing [K(+)](cis) can be best described by a third order polynomial fit. At +140 mV, the values of the maximal single channel conductance (gamma(max)) and the concentration for half maximal gamma (K(s)) are 38.6 pS and 380 mm and decline to 15.76 pS and 250 mm at 0 mV, respectively. The ion selectivity of the channel to K(+), Na(+), Cs(+) and choline(+) was determined in ion substitution

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

    Zhaksyntay Kairbekov

    2012-12-01

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

  13. Effects of Fructus Psoraleae Extract on the Intestinal Absorption Kinetics of Geniposide and Geniposidic Acid in Rat

    Yan Huo

    2014-06-01

    Full Text Available Cortex Eucommia has been used as a kidney-tonifying herbal medicine with a long history of compatibility with Fructus Psoraleae. Geniposide (GP and geniposidic acid (GPA are the two main chemical components in Cortex Eucommia. In the present study, the effects of Fructus Psoraleae extract (FPE on intestinal absorption kinetics of GP and GPA in rat were investigated. Twenty four male Sprague-Dawley rats were randomly assigned into four groups which were treated with GP, GPA, GP mixed with FPE and GPA mixed with FPE, respectively, by in situ intestinal perfusion for 3 h. The samples of intestinal perfusion solutions were collected every 30 min, and analyzed by ultra high performance liquid chromatography (UPLC. The curves of time and residual quantities of GP and GPA (lnx in the intestinal perfusion solution and the cumulative absorption rate were obtained. The results showed that FPE exhibited different effects on the intestinal absorption of GP and GPA in rat: it increased the intestinal absorption of GP (p < 0.05, while demonstrated no significant effect on the absorption of GPA.

  14. 4.2. The kinetics of nitric acid decomposition of calcined borosilicate raw material of Ak-Arkhar Deposit

    Present article is devoted to kinetics of nitric acid decomposition of calcined borosilicate raw material of Ak-Arkhar Deposit. The dependence of nitric acid decomposition of calcined boric raw material for extraction of boron oxide on temperature (20-100 deg C) and process duration (15-60 minutes) was defined. It was defined that at temperature increasing the extraction rate of boron oxide increases from 20.8 to 78.6%.

  15. Potential origin and formation for molecular components of humic acids in soils

    DiDonato, Nicole; Chen, Hongmei; Waggoner, Derek; Hatcher, Patrick G.

    2016-04-01

    Soil humic acids are the base soluble/acid insoluble organic components of soil organic matter. Most of what we know about humic acids comes from studies of their bulk molecular properties or analysis of individual fractions after extraction from soils. This work attempts to better define humic acids and explain similarities and differences for several soils varying in degrees of humification using advanced molecular level techniques. Our investigation using electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) and nuclear magnetic resonance spectroscopy (NMR) has given new insight into the distinctive molecular characteristics of humic acids which suggest a possible pathway for their formation. Humic acids from various ecosystems, climate regions and soil textural classes are distinguished by the presence of three predominant molecular components: lignin-like molecules, carboxyl-containing aliphatic molecules and condensed aromatic molecules that bear similarity to black carbon. Results show that humification may be linked to the relative abundance of these three types of molecules as well as the relative abundance of carboxyl groups in each molecular type. This work also demonstrates evidence for lignin as the primary source of soil organic matter, particularly condensed aromatic molecules often categorized as black carbon and is the first report of the non-pyrogenic source for these compounds in soils. We also suggest that much of the carboxyl-containing aliphatic molecules are sourced from lignin.

  16. KINETIC MODELING AND ISOTHERM STUDIES ON A BATCH REMOVAL OF ACID RED 114 BY AN ACTIVATED PLANT BIOMASS

    N. RAJAMOHAN

    2013-12-01

    Full Text Available In this paper, the dye Acid Red 114(AR 114 was removed from aqueous solutions using Acid-Activated Eichornia Crassipes (AAEC under batch conditions. The optimum conditions for AR 114 removal were found to be pH 1.5, adsorbent dosage = 1.25 g/L of solution and equilibrium time = 3 h. The equilibrium data were evaluated for compliance with Langmuir, Freundlich and Temkin isotherms and Langmuir isotherm was found to fit well. The maximum sorption capacity was estimated as 112.34 mg/g of adsorbent. Also, adsorption kinetics of the dye was studied and the rates of sorption were found to follow pseudo-second order kinetics with good correlation (R2 ≥ 0.997.The kinetic study at different temperatures revealed that the sorption was an endothermic process. The activation energy of the sorption process was estimated as 9.722 kJ/mol.

  17. Adsorption of rhodamine B by acid activated carbon-Kinetic, thermodynamic and equilibrium studies

    Shanmugam Arivoli

    2009-08-01

    Full Text Available A carbonaceous adsorbent prepared from an indigenous waste by acid treatment was tested for its efficiency in removing Rhodamine B (RDB. The parameters studied include agitation time, initial dye concentration, carbon dose, pH and temperature. The adsorption followed first order kinetics and the rate is mainly controlled by intra-particle diffusion. Freundlich and Langmuir isotherm models were applied to the equilibrium data. The adsorption capacity (Qm obtained from the Langmuir isotherm plots were 40.161, 35.700, 38.462 and 37.979 mg/g respectively at an initial pH of 7.0 at 30, 40, 50 and 60 0C. The temperature variation study showed that the RDB adsorption is endothermic and spontaneous with increased randomness at the solid solution interface. Significant effect on adsorption was observed on varying the pH of the RDB solutions. Almost 85% removal of RDB was observed at 60 0C. The Langmuir and Freundlich isotherms obtained, positive ?H0 value, pH dependent results and desorption of dye in mineral acid suggest that the adsorption of RDB by Banana bark carbon involves physisorption mechanism.

  18. Mathematic modelling of kinetics for the crystallization of tungstic acid from electrolytically treated sodium tungstate solution

    The nucleation and growth rate kinetics for the continuous crystallization of tungstic acid from solution was studied in a 0.8 1 evaporative mixed suspension, mixed product removal crystallizer. The crystallizer included a draft tube which improved the uniformity of the suspension. Experimental conditions which were varied during the experimental runs were drawdown time of the crystallizer, stirrer speed of the stirrer in solution, heat flux to the crystallizing solution and the suspension density of the crystallizing magma. X-ray diffraction patterns of the tungstic acid material produced confirmed that the material was crystalline and that it was in the tungsten monohydrate (WO3.H2O) form. The crystal size distribution of the crystallizer magma was obtained under steady state conditions and used to calculate the crystal nucleation and growth rates. The main nucleation mechanism in the crystallizing system was contact secondary nucleation and the crystal growth rates were found to be crystal size dependent. A size dependent growth rate model was proposed which was incorporated in the population balance equation. Good fits of the model to the data were obtained using this population balance equation. Analysis of the expressions derived for the nucleation and nuclei sized crystal growth rates indicated that the nucleation rate was a linear function of crystallizer magma suspension density and that there existed an inverse relationship between the nucleation rate and the crystal growth rate of the nuclei sized crystals

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

    Jayachamarajapura Pranesh Shubha

    2014-01-01

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

  20. Kinetics of chronic inflammation in Nile tilapia fed n‑3 and n‑6 essential fatty acids

    Róberson Sakabe

    2013-03-01

    Full Text Available The objective of this work was to investigate the effect of dietary supplementation with essential fatty acids on the kinetics of macrophage accumulation and giant cell formation in Nile tilapia (Oreochromis niloticus. The supplementation sources were soybean oil (SO, source of omega 6, n‑6 and linseed oil (LO, source of omega 3, n‑3, in the following proportions: 100% SO; 75% SO + 25% LO; 50% SO + 50% LO; 25% SO + 75% LO; and 100% LO (four replicates per treatment. After a feeding period of three months, growth performance was evaluated, and glass coverslips were implanted into the subcutaneous connective tissue of fish, being removed for examination at 2, 4, 6, and 8 days after implantation. Growth performance did not differ between treatments. Fish fed 100% linseed oil diet had the greatest macrophage accumulation and the fastest Langhans cell formation on the sixth day. On the eighth day, Langhans cells were predominant on the coverslips implanted in the fish feed 75 and 100% linseed oil. n‑3 fatty acids may contribute to macrophage recruitment and giant cell formation in fish chronic inflammatory response to foreign body.

  1. Kinetics and Mechanistic Chemistry of Oxidation of Butacaine Sulfate by Chloramine-B in Acid Medium

    Shubha, Jayachamarajapura Pranesh; Kotabagi, Vinutha [Bosco Institute of Technology, Bangalore (India); Puttaswamy [Bangalore Univ., Bangalore (India)

    2012-11-15

    Butacaine sulfate is an ester of p-aminobenzoic acid which has been widely used as a local anaesthetic and it is a long standing agent particularly for spinal anaesthesia. For this reason, a kinetic study of oxidation of butacaine sulfate by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried out in HClO{sub 4} medium at 303 K in order to explore this redox system mechanistic chemistry. The rate shows a first-order dependence on both [CAB]{sub o}, and [substrate]{sub o}, and a fractional-order dependence on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increases the rate of the reaction. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction has been found to be 1:2 and the oxidation products have been identified by spectral analysis. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

  2. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

    Birdsall, A. W.; Miner, C. R.; Mael, L. E.; Elrod, M. J.

    2014-12-01

    Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters, and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied with experimental methods. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of similar magnitudes, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

  3. Kinetic studies on the extraction of uranium(VI) from phosphoric acid medium by bulk liquid membrane containing di-2-ethylhexyl phosphoric acid

    To go through the first stage of industrial solvent extraction process in order to recover uranium from phosphate rocks by liquid membrane techniques, as a simple model, the kinetics of facilitated transport of uranium(VI) from a dilute phosphoric acid medium into more concentrated phosphoric acid media as a receiving phase through a bulk liquid membrane containing di-2-ethylhexyl phosphoric acid as a carrier was studied. The influence of phosphoric acid concentration in the source and receiving phases, carrier concentration, type of solvent, stirring speed and temperature were investigated. The kinetic parameters (ke, ks, tmax, Jmax) were calculated for the interface reactions assuming two consecutive, irreversible first-order reactions. The activation energy values were calculated as 29.40 and 19.51 kJ mol-1 for extraction and stripping, respectively. The values of calculated activation energy indicated that both the extraction and stripping processes were controlled by mixed regime (both kinetic and diffusion). In addition, the influence of adding trioctyl-phosphine oxide into the membrane phase as a synergic agent on the transport kinetics was determined. (author)

  4. Kinetic properties of two Rhizopus exo-polygalacturonase enzymes hydrolyzing galacturonic acid oligomers using isothermal titration calorimetry

    The kinetic characteristics of two Rhizopus oryzae exo-polygalacturonases acting on galacturonic acid oligomers (GalpA) were determined using isothermal titration calorimetry (ITC). RPG15 hydrolyzing (GalpA)2 demonstrated a Km of 55 uM and kcat of 10.3 s^-1^ while RPG16 was shown to have greater af...

  5. Effects of inorganic components in acid rain on tube elongation of Camellia pollen

    Masaru, N.; Katsuhisa, F.; Sankichi, T.; Yutaka, W.

    1980-01-01

    Pollen grains of Camellia japonica were cultivated in culture plates containing individual inorganic components found in acid rain (SO/sub 4//sup 2 -/, NO/sub 3//sup -/, Cl/sup -/, H/sup +/, Pb/sup +2/, Mg/sup +2/ or Mn/sup +2/). In the case of three acids (HNO/sub 3/, HCl or H/sub 2/SO/sub 4/), a promotion of pollen tube elongation due to nitric acid or hydrogen chloride occurred in the range 0-0.5 millimole/litre and a marked inhibition was observed when the acid concentrations were above 0.6 millimole/litre (pH<3.2). Sulphuric acid promoted tube elongation in the range 0-0.2 millimole/litre and markedly inhibited tube elongation above 0.3 millimole/litre (pH<3.2). Nitric acid promoted tube elongation more than hydrogen chloride and sulphuric acid. However, individual inhibitions due to the three acids were similar to each other. In the case of three metallic salts (Pb(NO/sub 3/)/sub 2/, Mg(NO/sub 3/)/sub 2/ or Mn(NO/sub 3/)/sub 2/), those of lead and manganese showed a slight promotion of tube elongation at low concentrations (0.005-0.015 millimole/litre). However, the salt of magnesium had no effect in this range. Interaction of various combinations of three acids (HNOHNO/sub 3/, HCl and H/sub 2/SO/sub 4/) or three ammonium salts (NH/sub 4/NO/sub 3/, NH/sub 4/Cl and (NH/sub 4/)/sub 2/SO/sub 4/) were studied. A marked inhibition of tube elongation occurred above 0.47 millimole/litre (pH<3.2) with a combination of the three acids. However, no inhibition occurred in the same concentration range with a combination of the three ammonium salts.

  6. Characterization and mapping of the multi-component release kinetics of a Traditional Chinese Medicine dosage form using a modified LC/MS/MS method and chemomic release kinetic theory

    Hai-yan Li; Xiang-yong Cui; Feng Gao; Peter York; Qun Shao; Xian-zhen Yin; Tao Guo; Zhen Guo; Jing-kai Gu; Ji-wen Zhang

    2011-01-01

    It is essential to develop effective methods for the quality control of the traditional medicine with multiple components. However, few researches on the quality control have been conducted to interpret the holistic characteristics of the traditional medicine in terms of dissolution/release. In this study, the multi-component release kinetics of Traditional Chinese Medicine (TCM) dosage forms was characterized and mapped by multivariate analysis techniques in the field of “-omics”. The Liuwei...

  7. Impact of individual acid flue gas components on mercury capture by heat-treated activated carbon

    Jian-ming ZHENG; Jin-song ZHOU; Zhong-yang LUO; Ke-fa CEN

    2012-01-01

    Elemental mercury capture on heat-treated activated carbon (TAC) was studied using a laboratory-scale fixed bed reactor.The capability of TAC to perform Hg0 capture under both N2 and baseline gas atmospheres was studied and the effects of common acid gas constituents were evaluated individually to avoid complications resulting from the coexistence of multiple components.The results suggest that surface functional groups (SFGs) on activated carbon (AC) are vital to Hg0 capture in the absence of acid gases.Meanwhile,the presence of acid gas components coupled with defective graphitic lattices on TAC plays an important role in effective Hg0 capture.The presence of HCl,NO2,and NO individually in basic gases markedly enhances Hg0 capture on TAC due to the heterogeneous oxidation of Hg0 on acidic sites created on the carbon surface and catalysis by the defective graphitic lattices on TAC.Similarly,the presence of SO2 improves Hg0 capture by about 20%.This improvement likely results from the deposition of sulfur groups on the AC surface and oxidation of the elemental mercury by SO2 due to catalysis on the carbon surface.Furthermore,O2 exhibits a synergistic effect on Hg0 oxidation and capture when acid gases are present in the flue gases.

  8. 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

  9. Kinetic observation of rapid electron transfer between thymine and thymidine anion radicals and caffeic acid: a pulse radiolysis study

    Rapid electron transfer from thymine or thymidine anion radicals to caffeic acid with rate constant of 1 x 109 M-1s-1 was observed by pulse radiolysis, leading to the formation of anion radicals of caffeic acid which is characterized with absorption maximum at 360nm. Caffeic acid has a higher one-electron reduction potential than the target molecule (thymine or thymidine) and acts as a electrophilic protector which prevent the target anion radical from its irreversible protonation at C6 leading to its 5-yl radical via fast electron transfer. The kinetic demonstrations have provided dynamic evidence of charge transfer protection mechanism. (author)

  10. Kinetic models of reaction systems for the in situ epoxidation of unsaturated fatty acid esters and triglycerides

    Janković Milovan R.

    2004-01-01

    Full Text Available Mathematical models that describe the kinetics of reaction systems for the in situ epoxidation of unsaturated fatty acid esters or triglycérides with organic peracids are reviewed in this paper. The advantages and inadequacies of each model are discussed. A mono-phase pseudo-first order kinetic model was compared with a two phase model based on the Langmuir-Hinshelwood-Hougen-Watson (LHHW postulates proposed by the authors of this paper. The comparison was performed on the experimentally determined values for the in situ epoxidation of soybean oil by peracetic acid in the presence of different quantities of ion exchange resin used as the catalyst. It was concluded that a complete model for in situ epoxidation in the presence of ion exchange resin as the catalyst was still not given for perorganic acid formation. In particular, we report here the possibilities of the creation of an "ideal" model for in situ epoxidation.

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

    Zhaksyntay Kairbekov

    2012-12-01

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

  12. Magnetic vinylphenyl boronic acid microparticles for Cr(VI) adsorption: Kinetic, isotherm and thermodynamic studies

    Highlights: • Cr(VI) can oxidize biological molecules and be one of the most harmful substance. • Magnetic seperation techniques are used on different applications in many fields. • Magnetic systems can be used for rapid and selective removal as a magnetic processor. • We investigate properties of both new material and other magnetic adsorbents reported in the literatures on the adsorption of Cr(VI) ions. • No researchments were reported on adsorption of Cr(VI) with magnetic vinylphenyl boronic acid microparticles. - Abstract: Magnetic vinylphenyl boronic acid microparticles, poly(ethylene glycol dimethacrylate(EG)–vinylphenyl boronic acid(VPBA)) [m-poly(EG–VPBA)], produced by suspension polymerization and characterized, was found to be an efficient solid polymer for Cr(VI) adsorption. The m-poly(EG–VPBA) microparticles were prepared by copolymerizing of ethylene glycol dimethylacrylate (EG) with 4-vinyl phenyl boronic acid (VPBA). The m-poly(EG–VPBA) microparticles were characterized by N2 adsorption/desorption isotherms, electron spin resonance (ESR), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), elemental analysis, scanning electron microscope (SEM) and swelling studies. The m-poly(EG–VPBA) microparticles were used at adsorbent/Cr(VI) ion ratios. The influence of pH, Cr(VI) initial concentration, temperature of the removal process was investigated. The maximum removal of Cr(VI) was observed at pH 2. Langmuir isotherm and Dubinin–Radushkvich isotherm were found to better fit the experiment data rather than Fruendlich isotherm. The kinetics of the adsorption process of Cr(VI) on the m-poly(EG–VPBA) microparticles were investigated using the pseudo first-order, pseudo-second-order, Ritch-second-order and intraparticle diffusion models, results showed that the pseudo-second order equation model provided the best correlation with the experimental results. The thermodynamic

  13. Esterification with ethanol to produce biodiesel from high acidity raw materials. Kinetic studies and analysis of secondary reactions

    Pisarello, M.L.; Dalla Costa, B.; Mendow, G.; Querini, C.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE)-(FIQ-UNL, CONICET), Santiago del Estero 2654-Santa Fe, S3000AOJ (Argentina)

    2010-09-15

    In this work, the esterification reaction of free fatty acids (FFA) in sunflower oil, coconut oil and concentrated FFA, with ethanol, methanol and ethanol 96%, using homogeneous acid catalysts to produce biodiesel is studied. Kinetic parameters are estimated with a simplified model, and then used to predict the reaction behavior. Reactions other than the reversible esterification are considered to explain the behavior that this system displays. Such reactions are the triglycerides conversion by acid catalyzed transesterification and hydrolysis. In addition, we include kinetic studies of the reaction that occur between the sulphuric acid and methanol (or ethanol), forming mono and dialkylsulphates. This reaction produces water and consumes methanol (or ethanol), and consequently has a direct impact in the esterification reaction rate and equilibrium conversion. The concentration of sulphuric acid decreases to less than 50% of the initial value due to the reaction with the alcohol. A minimum in the acidity due to the free fatty acids as a function of time was clearly observed during the reaction, which has not been reported earlier. This behavior is related to the consecutive reactions that take place during the esterification of FFA in the presence of triglycerides. The phase separation due to the presence of water, which is generated during the reaction, is also studied. (author)

  14. Uranium from phosphoric acid: kinetics studies of the solvent extraction processes for separation based on statistical data analysis

    Uranium is recovered from wet process phosphoric acid, an important secondary source, by solvent extraction technique. Kinetics of the mass transfer processes involved in extraction, scrubbing and stripping, solvent recovery operations are important for process equipment design. In this investigation we have reported results on the kinetics of separation of entrained solvent by diluent washing. The effect of stirring speed, O/A ratio and temperature has been studied. Experiments at elevated temperature (45 deg C) were carried out by preheating the WPA and Petrofin and then mixing the required volume before stirring for different time periods. (author)

  15. Temperature dependence of relaxation times in proton components of fatty acids

    We examined the temperature dependence of relaxation times in proton components of fatty acids in various samples in vitro at 11 tesla as a standard calibration data for quantitative temperature imaging of fat. The spin-lattice relaxation time, T1, of both the methylene (CH2) chain and terminal methyl (CH3) was linearly related to temperature (r>0.98, P2 signal for calibration and observed the signal with 18% of CH3 to estimate temperature. These findings suggested that separating the fatty acid components would significantly improve accuracy in quantitative thermometry for fat. Use of the T1 of CH2 seems promising in terms of reliability and reproducibility in measuring temperature of fat. (author)

  16. Biosorption of the metal-complex dye Acid Black 172 by live and heat-treated biomass of Pseudomonas sp. strain DY1: Kinetics and sorption mechanisms

    Du, Lin-Na; Wang, Bing [College of Life Science, Zhejiang University, 310058, Hangzhou, Zhejiang Province (China); Li, Gang [Department of Agriculture and Biotechnology, Wenzhou Vocational College of Science and Technology, 325006 Wenzhou, Zhejiang Province (China); Wang, Sheng [College of Life Science, Zhejiang University, 310058, Hangzhou, Zhejiang Province (China); Crowley, David E., E-mail: crowley@ucr.edu [Department of Environmental Science, University of California, Riverside, CA 92521 (United States); Zhao, Yu-Hua, E-mail: yhzhao225@zju.edu.cn [College of Life Science, Zhejiang University, 310058, Hangzhou, Zhejiang Province (China)

    2012-02-29

    Highlights: Black-Right-Pointing-Pointer The maximum amount of Acid Black 172 sorption was about 2.98 mmol/g biomass. Black-Right-Pointing-Pointer Amine groups played a major role in the biosorption of Acid Black 172. Black-Right-Pointing-Pointer The reasons of increased dye sorption by heat-treated biomass were proposed. - Abstract: The ability of Pseudomonas sp. strain DY1 to adsorb Acid Black 172 was studied to determine the kinetics and mechanisms involved in biosorption of the dye. Kinetic data for adsorption fit a pseudo-second-order model. Increased initial dye concentration could significantly enhance the amount of dye adsorbed by heat-treated biomass in which the maximum amount of dye adsorbed was as high as 2.98 mmol/g biomass, whereas it had no significant influence on dye sorption by live biomass. As treated temperature increased, the biomass showed gradual increase of dye sorption ability. Experiments using potentiometric titration and Fourier transform infrared spectroscopy (FTIR) indicated that amine groups (NH{sub 2}) played a prominent role in biosorption of Acid Black 172. Scanning electron microscopy (SEM), atomic force microscopy (AFM) and transmission electron microscopy (TEM) analysis indicated that heat treatment of the biomass increased the permeability of the cell walls and denatured the intracellular proteins. The results of biosorption experiments by different cell components confirmed that intracellular proteins contributed to the increased biosorption of Acid Black 172 by heat-treated biomass. The data suggest that biomass produced by this strain may have application for removal of metal-complex dyes from wastewater streams generated from the dye products industry.

  17. Biosorption of the metal-complex dye Acid Black 172 by live and heat-treated biomass of Pseudomonas sp. strain DY1: Kinetics and sorption mechanisms

    Highlights: ► The maximum amount of Acid Black 172 sorption was about 2.98 mmol/g biomass. ► Amine groups played a major role in the biosorption of Acid Black 172. ► The reasons of increased dye sorption by heat-treated biomass were proposed. - Abstract: The ability of Pseudomonas sp. strain DY1 to adsorb Acid Black 172 was studied to determine the kinetics and mechanisms involved in biosorption of the dye. Kinetic data for adsorption fit a pseudo-second-order model. Increased initial dye concentration could significantly enhance the amount of dye adsorbed by heat-treated biomass in which the maximum amount of dye adsorbed was as high as 2.98 mmol/g biomass, whereas it had no significant influence on dye sorption by live biomass. As treated temperature increased, the biomass showed gradual increase of dye sorption ability. Experiments using potentiometric titration and Fourier transform infrared spectroscopy (FTIR) indicated that amine groups (NH2) played a prominent role in biosorption of Acid Black 172. Scanning electron microscopy (SEM), atomic force microscopy (AFM) and transmission electron microscopy (TEM) analysis indicated that heat treatment of the biomass increased the permeability of the cell walls and denatured the intracellular proteins. The results of biosorption experiments by different cell components confirmed that intracellular proteins contributed to the increased biosorption of Acid Black 172 by heat-treated biomass. The data suggest that biomass produced by this strain may have application for removal of metal-complex dyes from wastewater streams generated from the dye products industry.

  18. The radiation crosslinking of poly(vinyl chloride) with trimethylolpropanetrimethacrylate. III. Effect of diundecyl phthalate: chemical kinetics of a three-component system

    The radiation chemistry of poly(vinyl chloride) (PVC) blended with trimethylolpropanetrimethacrylate (TMPTMA) and diundecyl phthalate (DUP) has been examined. This three-component mixture contains a base resin (PVC), a crosslinking sensitizer (TMPTMA), and a physical modifier (DUP). These are the basic components in any radiation-curable coating. The kinetics and mechanism of the crosslinking reactions were studied with reference to the dependence on radiation dose and blend composition. The polyfunctional TMPTMA underwent polymerization incorporating the PVC into a 3-dimensional network. DUP remained chemically inert during the irradiation, not being bound to the network. However, DUP by plasticizing the macromolecules and diluting the monomer, changed the kinetics extensively. DUP enhanced TMPTMA homopolymerization, TMPTMA grafting, and PVC crosslinking reaction rates. The effect of the competition between polymerization, grafting, and degradation reactions was examined in terms of enhanced mobility of the reacting species. The influence of these kinetics considerations in selecting a blend composition for a coating application was discussed

  19. The radiation crosslinking of poly(vinyl chloride) with trimethylolpropanetrimethacrylate. III. Effect of diundecyl phthalate: chemical kinetics of a three-component system

    Bowmer, T.N.; Vroom, W.I.; Hellman, M.Y.

    1983-08-01

    The radiation chemistry of poly(vinyl chloride) (PVC) blended with trimethylolpropanetrimethacrylate (TMPTMA) and diundecyl phthalate (DUP) has been examined. This three-component mixture contains a base resin (PVC), a crosslinking sensitizer (TMPTMA), and a physical modifier (DUP). These are the basic components in any radiation-curable coating. The kinetics and mechanism of the crosslinking reactions were studied with reference to the dependence on radiation dose and blend composition. The polyfunctional TMPTMA underwent polymerization incorporating the PVC into a 3-dimensional network. DUP remained chemically inert during the irradiation, not being bound to the network. However, DUP by plasticizing the macromolecules and diluting the monomer, changed the kinetics extensively. DUP enhanced TMPTMA homopolymerization, TMPTMA grafting, and PVC crosslinking reaction rates. The effect of the competition between polymerization, grafting, and degradation reactions was examined in terms of enhanced mobility of the reacting species. The influence of these kinetics considerations in selecting a blend composition for a coating application was discussed.

  20. Free fatty acids as a major component of the chlorosulfolipid membrane of Ochromonas danica

    Winicov, I.

    1985-01-01

    This work is an attempt to determine whether or not free fatty acids are components of the natural membrane of Ochromonas danica. If the FFAs were artifacts, they would most likely have been produced during solvent extraction or during the procedure for flagellar detachment. Attempts to denature putative solvent-activated lipase(s) through exposure to boiling isopropanol or by crosslinking the flagella with glutaraldehyde prior to extraction failed to eliminate the free fatty acid fraction, nor to significantly alter its composition. Exposure of flagella to albumin resulted in the net transfer of FFAs to the supernatant phase, showing their presence is not caused by solvent activated lipolysis. Finally levels of labelled free fatty acids failed to rise as a function of time after deflagellation in cells grown in the presence of (10-/sup 14/C)-oleic acid. Acid hydrolysis of the total labelled lipid at elevated temperature increased the percentage of counts occurring as unesterified fatty acids (from 2.6% to 64.8%). This, taken together with a corresponding loss of the more polar labelled material (66.8% to 8.2%) indicates that some esterified lipids were present, but probably not broken down during the isolation procedure.

  1. Free fatty acids as a major component of the chlorosulfolipid membrane of Ochromonas danica

    This work is an attempt to determine whether or not free fatty acids are components of the natural membrane of Ochromonas danica. If the FFAs were artifacts, they would most likely have been produced during solvent extraction or during the procedure for flagellar detachment. Attempts to denature putative solvent-activated lipase(s) through exposure to boiling isopropanol or by crosslinking the flagella with glutaraldehyde prior to extraction failed to eliminate the free fatty acid fraction, nor to significantly alter its composition. Exposure of flagella to albumin resulted in the net transfer of FFAs to the supernatant phase, showing their presence is not caused by solvent activated lipolysis. Finally levels of labelled free fatty acids failed to rise as a function of time after deflagellation in cells grown in the presence of [10-14C]-oleic acid. Acid hydrolysis of the total labelled lipid at elevated temperature increased the percentage of counts occurring as unesterified fatty acids (from 2.6% to 64.8%). This, taken together with a corresponding loss of the more polar labelled material (66.8% to 8.2%) indicates that some esterified lipids were present, but probably not broken down during the isolation procedure

  2. Soil Components Affecting Phosphate Sorption Parameters of Acid Paddy Soils in Guangdong Province

    2000-01-01

    Soil components affecting phosphate sorption parameters were studied using acid paddy soils derived from basalt, granite, sand-shale and the Pearl River Delta sediments, respectively, in Guangdong Province.For each soil, seven 2.50 g subsamples were equilibrated with 50 mL 0.02 mol L-1 (pH=7.0) of KCl containing 0, 5, 10, 15, 25, 50 and 100 ng P kg-1, respectively, in order to derive P sorption parameters (P sorption maximum, P sorption intensity factor and maximum buffer capacity) by Langmuir isotherm equation. It was shown that the main soil components influencing phosphate sorption maximum (Xm) included soil clay, pH,amorphous iron oxide (Feo) and amorphous aluminum oxide (Alo), with their effects in the order of Alo >Feo > pH > clay. Among these components, pH had a negative effect, and the others had a positive effect.Organic matter (OM) was the only soil component influencing P sorption intensity factor (K). The main components influencing maximum phosphate buffer capacity (MBC) consisted of soil clay, OM, pH, Feo and Alo, with their effects in the order of Alo > OM > pH > Feo > clay. Path analysis indicated that among the components with positive effects on maximum phosphate buffer capacity (MBC), the effect was in the order of Alo > Feo > Clay, while among the components with negative effects, OM > pH. OM played an important role in mobilizing phosphate in acid paddy soils mainly through decreasing the sorption intensity of phosphate by soil particles.

  3. Sorption of a branched nonylphenol and perfluorooctanoic acid on Yangtze River sediments and their model components

    Li, C L; R. Ji; Schaffer, A.; Sequaris, J.M.; Amelung, W.; H. Vereecken; E. Klumpp

    2012-01-01

    Many metabolites of organic surfactants such as nonylphenol (NP) and perfluorooctanoic acid (PFOA) are ubiquitously found in the environment and are toxic if not sorbed on soils and sediments. In this study, we quantified the sorption of the NP isomer with the highest endocrine activity, [4-(1-ethyl-1,3-dimethylpentyl) phenol] (NP111), and that of PFOA on Yangtze River sediments and its model components illite, goethite and natural organic matter. The sorption experiments were performed with ...

  4. Model Compounds for Heavy Crude Oil Components and Tetrameric Acids: Characterization and Interfacial Behaviour

    Nordgård, Erland Løken

    2009-01-01

    The tendency during the past decades in the quality of oil reserves shows that conventional crude oil is gradually being depleted and the demand being replaced by heavy crude oils. These oils contain more of a class high-molecular weight components termed asphaltenes. This class is mainly responsible for stable water-in-crude oil emulsions. Both heavy and lighter crude oils in addition contain substantial amounts of naphthenic acids creating naphthenate deposits in topside facilities.The asph...

  5. Optimization of medium components using orthogonal arrays for Linolenic acid production by Spirulina platensis

    This work describes the medium optimization of '-Linolenic acid (GLA) production by Spirulina platensis using one-factor and orthogonal array design methods. In the one-factor experiments, NaHCO3 (9 mg L-1), NaNO3 (13.5 mg L-1) and MgSO4•7H2O (11.85 mg L-1) proved to be the best components for GLA p...

  6. The kinetics of process dependent ammonia inhibition of methanogenesis from acetic acid.

    Wilson, Christopher Allen; Novak, John; Takacs, Imre; Wett, Bernhard; Murthy, Sudhir

    2012-12-01

    Advanced anaerobic digestion processes aimed at improving the methanization of sewage sludge may be potentially impaired by the production of inhibitory compounds (e.g. free ammonia). The result of methanogenic inhibition is relatively high effluent concentrations of acetic acid and other soluble organics, as well as reduced methane yields. An extreme example of such an advanced process is the thermal hydrolytic pretreatment of sludge prior to high solids digestion (THD). Compared to a conventional mesophilic anaerobic digestion process (MAD), THD operates in a state of constant inhibition driven by high free ammonia concentrations, and elevated pH values. As such, previous investigations of the kinetics of methanogenesis from acetic acid under uninhibited conditions do not necessarily apply well to the modeling of extreme processes such as THD. By conducting batch ammonia toxicity assays using biomass from THD and MAD reactors, we compared the response of these communities over a broad range of ammonia inhibition. For both processes, increased inhibitor concentrations resulted in a reduction of biomass growth rate (r(max) = μ(max)∙X) and a resulting decrease in the substrate half saturation coefficient (K(S)). These two parameters exhibited a high degree of correlation, suggesting that for a constant transport limited system, the K(S) was mostly a linear function of the growth rate. After correcting for reactor pH and temperature, we found that the THD and MAD biomass were both able to perform methanogenesis from acetate at high free ammonia concentrations (equivalent to 3-5 g/L total ammonia nitrogen), albeit at less than 30% of their respective maximum rates. The reduction in methane production was slightly less pronounced for the THD biomass than for MAD, suggesting that the long term exposure to ammonia had selected for a methanogenic pathway less dependent on those organisms most sensitive to ammonia inhibition (i.e. aceticlastic methanogens). PMID

  7. [Photocatalytic degradation kinetics of perfluorooctanoic acid (PFOA) in TiO2 dispersion and its mechanism].

    Li, Ming-Jie; Yu, Ze-Bin; Chen, Ying; Wang, Li; Liu, Qing; Liu, Yu-Xin; He, Li-Li

    2014-07-01

    Decomposition of perfluorooctanoic acid (PFOA) is of prime importance since it is recognized as a persistent organic pollutant and is widespread in the environment. Heterogeneous photocatalytic decomposition of PFOA by TiO2 (P25) was investigated under 254 nm UV light. Experimental conditions including initial pH, TiO2 content and PFOA concentration, were varied to demonstrate their effects on the decomposition of PFOA. It was observed that the photocatalytic degradation kinetics of PFOA could be fitted to the quasi-first-order equation. The pH played a determinant role in the decomposition of PFOA and the presence of O2 increased the degradation rate. Optimal conditions for a complete removal were obtained using 1.5 g x L(-1) TiO2 at pH 3 in air atmosphere, with a rate constant of 0.420 6 h(-1). The contribution experiments of various reactive species produced during the photocatalysis were also investigated with the addition of different scavengers and it was found that photogenerated holes (h+) was the major reactive species which was responsible for 66.1% of the degradation rate, and the *OH was involved in PFOA degradation as well. In addition, the photocatalytic experiment with the addition of NaF indicated that the adsorption of PFOA was of primary importance for the photocatalytic decomposition. Perfluorocarboxylic acids (PFCAs) with shorter carbon chain length as intermediates and products were identified with UPLC-QTOF/MS, and a possible mechanism for PFOA decomposition was proposed. PMID:25244845

  8. Lactic acid bacteria in dairy food: surface characterization and interactions with food matrix components.

    Burgain, J; Scher, J; Francius, G; Borges, F; Corgneau, M; Revol-Junelles, A M; Cailliez-Grimal, C; Gaiani, C

    2014-11-01

    This review gives an overview of the importance of interactions occurring in dairy matrices between Lactic Acid Bacteria and milk components. Dairy products are important sources of biological active compounds of particular relevance to human health. These compounds include immunoglobulins, whey proteins and peptides, polar lipids, and lactic acid bacteria including probiotics. A better understanding of interactions between bioactive components and their delivery matrix may successfully improve their transport to their target site of action. Pioneering research on probiotic lactic acid bacteria has mainly focused on their host effects. However, very little is known about their interaction with dairy ingredients. Such knowledge could contribute to designing new and more efficient dairy food, and to better understand relationships between milk constituents. The purpose of this review is first to provide an overview of the current knowledge about the biomolecules produced on bacterial surface and the composition of the dairy matter. In order to understand how bacteria interact with dairy molecules, adhesion mechanisms are subsequently reviewed with a special focus on the environmental conditions affecting bacterial adhesion. Methods dedicated to investigate the bacterial surface and to decipher interactions between bacteria and abiotic dairy components are also detailed. Finally, relevant industrial implications of these interactions are presented and discussed. PMID:25277266

  9. Combined Kinetic Studies and Computational Analysis on Kojic Acid Analogs as Tyrosinase Inhibitors

    Carlyle Ribeiro Lima

    2014-07-01

    Full Text Available Tyrosinase is a key enzyme in melanin synthesis and widely distributed in plants and animals tissues. In mammals, this enzyme is related to pigment production, involved in wound healing, primary immune response and it can also contribute to catecholamines synthesis in the brain. Consequently, tyrosinase enzyme represents an attractive and selective target in the field of the medicine, cosmetics and bio-insecticides. In this paper, experimental kinetics and computational analysis were used to study the inhibition of tyrosinase by analogous of Kojic acid. The main interactions occurring between inhibitors-tyrosinase complexes and the influence of divalent cation (Cu2+ in enzymatic inhibition were investigated by using molecular docking, molecular dynamic simulations and electrostatic binding free energy by using the Linear Interaction Energy (LIE method. The results showed that the electrostatic binding free energy are correlated with values of constant inhibition (r2 = 0.97.Thus, the model obtained here could contribute to future studies of this important system and, therefore, eventually facilitate development of tyrosinase inhibitors.

  10. Preparation and Kinetics of a Novel Glutathione Peroxidase Mimic——Selenium-modified Hyaluronic Acid

    CHEN Jia; HONG Shui-sheng; AN Yang; JIANG Guang-zhi; ZHANG Bo-xun; FANG Xiang-yang; LIU Lan-ying; TENG Li-rong

    2007-01-01

    A selenium-modified hyaluronic acid(HA) compound(SeHA) was synthesized as a mimic of glutathione peroxidase(GPX). IR and NMR spectra of SeHA predict that the -CH2OH group of the N-acetyl-D-glucosamine in HA was modified by group -SeH. There are averagely 152 -SeH groups in one SeHA molecule. The GPX activities are 103.88, 32.15 and 152.71 U/μmol, respectively, when the substrates were H2O2, BuOOH and CuOOH. Ping-pong mechanism was observed in the steady-state kinetic studies of the reactive oxygen species(ROS) consuming reaction. Result of reactions of SeHA with free radical capturer 2,6-di-tert-butyl-4-methylphenol(BHT) shows that the catalysis is based on a non-free radical-mechanism and the SeHA can not be inhibited by iodoacetate, an enzyme inhibitor.

  11. The viability of a nonenzymatic reductive citric acid cycle--kinetics and thermochemistry.

    Ross, David S

    2007-02-01

    The likelihood of a functioning nonenzymatic reductive citric acid cycle, recently proposed as the precursor to biosynthesis on early Earth, is examined on the basis of the kinetics and thermochemistry of the acetate --> pyruvate --> oxaloacetate --> malate sequence. Using data derived from studies of the Pd-catalyzed phosphinate reduction of carbonyl functions it is shown that the rate of conversion of pyruvate to malate with that system would have been much too slow to have played a role in the early chemistry of life, while naturally occurring reduction systems such as the fayalite-magnetite-quartz and pyrrhotite-pyrite-magnetite mineral assemblages would have provided even slower conversions. It is also shown that the production of pyruvate from acetate is too highly endoergic to be driven by a naturally occurring energy source such as pyrophosphate. It is thus highly doubtful that the cycle can operate at suitable rates without enzymes, and most unlikely that it could have participated in the chemistry leading to life. PMID:17136437

  12. Enzymatic Synthesis of Furfuryl Alcohol Ester with Oleic Acid by Candida antarctica Lipase B and Its Kinetic Study

    Sengupta, Avery; Dey, Tanmoy; Ghosh, Mahua; Ghosh, Jaydip; Ghosh, Santinath

    2012-08-01

    This study investigated the successful enzymatic production of furfuryl oleate and its detailed kinetic study by Michaelis-Menten model. Esterification of oleic acid and furfuryl alcohol by Candida antarctica lipase B (Novozym 435 preparation) in a solvent free system was studied in the present work at 1:1 molar ratio of furfuryl alcohol and oleic acid. About 99 % conversion (on the basis of oleic acid) has been achieved within 6 h at 5 % enzyme concentration. Ping-pong bi-bi mechanism (inhibition phenomenon taken into account) was applied to describe the ratios as a complex kinetic model. The kinetic parameters were determined using MATLAB language programme. The two initial rate constants KA and KB respectively were found out by different progress curves plotted with the help of MATLAB language programme. It was concluded from the results that furfuryl alcohol considerably inhibited the enzymatic reaction while oleic acid had negligible inhibitory effect. It was clearly seen that the initial rate was increased with the increase in the furfuryl alcohol concentration until 2 M/L after which there was a drop in the initial rate depicting the inhibitory effect of furfuryl alcohol. Surprisingly, it has been observed that addition of 0.1 mol of product activated the esterification reaction. Finally, the model was found to be statistically fitting well with the experimental data.

  13. Dynamic Acid/Base Equilibrium in Single Component Switchable Ionic Liquids and Consequences on Viscosity

    Cantu Cantu, David; Lee, Jun Taek; Lee, Mal Soon; Heldebrant, David J.; Koech, Phillip K.; Freeman, Charles J.; Rousseau, Roger J.; Glezakou, Vassiliki Alexandra

    2016-05-05

    The deployment of transformational non-aqueous CO2-capture solvent systems is encumbered by high viscosity even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we identify the key molecular features controlling bulk liquid viscosity and CO2 uptake kinetics. Fast uptake kinetics arise from close proximity of the alcohol and amine sites that are involved in CO2 binding. This process results in the concerted formation of a Zwitterion containing both an alkylcarbonate and a protonated amine. The hydrogen bonding between the two functional groups ultimately determines the solution viscosity. Based on molecular simulation, this work reveals options to significantly reduce viscosity with molecular modifications that shift the proton transfer equilibrium towards a neutral acid/amine species as opposed to the ubiquitously accepted Zwitterionic state. The molecular design concepts proposed here, for the alkyl-carbonate systems, are readily extensible to other CO2 capture technologies, such as the carbamate- or imidazole-based solvent chemistries.

  14. Evaluation of a new protocol for enzymatic dynamic kinetic resolution of 3-hydroxy-3-(aryl)propanoic acids.

    Koszelewski, Dominik; Zysk, Małgorzata; Brodzka, Anna; Żądło, Anna; Paprocki, Daniel; Ostaszewski, Ryszard

    2015-12-01

    The application of tandem metal-enzyme dynamic kinetic resolution (DKR) is a powerful tool for the manufacture of high-value chemical commodities. A new protocol of kinetic resolution based on irreversible enzymatic esterification of carboxylic acids with orthoesters was introduced to obtain optically active β-hydroxy esters. This procedure was combined with metal catalyzed racemization of the target substrate providing both (R) and (S) enantiomers of ethyl 3-hydroxy-3-(4-nitrophenyl)propanoate with a high yield of 89% at 40 °C. A substantial influence of the enzyme type, organic co-solvent, and metal catalyst on the conversion and enantioselectivity of the enzymatic dynamic kinetic resolution was noted. PMID:26383530

  15. Mutual azo prodrug of 5-aminosalicylic acid for colon targeted drug delivery: Synthesis, kinetic studies and pharmacological evaluation

    Nagpal Deepika

    2006-01-01

    Full Text Available Mutual azo prodrug of 5-aminosalicylic acid with histidine, was synthesized by coupling L-histidine with salicylic acid, for targeted drug delivery to the inflamed gut tissue, in inflammatory bowel disease. In vitro kinetic studies in HCl buffer (pH 1.2 showed negligible release of 5-aminosalicylic acid, whereas in phosphate buffer (pH 7.4, only 14% release was observed over a period of 6h. In rat fecal matter, the release of 5-aminosalicylic acid was almost complete (85.6%, with a half life of 163 min, following zero order kinetics. The azo conjugate was evaluated for its ulcerogenic potential by Rainsford′s cold stress method. Therapeutic efficacy of the carrier system and the mitigating effect of the azo conjugate were evaluated in trinitrobenzenesulphonic acid- induced experimental colitis model. The synthesized prodrug was found to be equally effective in mitigating the colitis in rats, as that of sulfasalazine, without the ulcerogenicity of 5-aminosalicylic acid, and adverse effects of sulfasalazine.

  16. Kinetic study of acid depolymerization of chitosan and effects of low molecular weight chitosan on erythrocyte rouleaux formation.

    Tsao, Ching Ting; Chang, Chih Hao; Lin, Yu Yung; Wu, Ming Fung; Han, Jin Lin; Hsieh, Kuo Huang

    2011-01-01

    In this study, the depolymerization of chitosan was carried out in an acetic acid aqueous solution and was followed by viscometry for molecular weight determination. It was found that the depolymerization rate increased with elevated temperatures and with high acid concentrations. Based on FTIR analysis, the chitosan was depolymerized randomly along the backbone; no other structural change was observed during the acid depolymerization process. Revealed in the TGA study, the degradation temperature and char yield of LMWCs (low molecular weight chitosan) were molecular weight dependent. The blood compatibility of LMWCs was also investigated: rouleaux formation was observed when erythrocyte contacted with LMWCs, which showed that LMWCs are able to interfere with the negatively charged cell membrane through its polycationic properties. Furthermore, as regards a kinetics investigation, the values of M(n) (number-average molecular weight) were obtained from an experimentally determined relationship. The kinetics study showed that the complex salt, formed by amine on chitosan and acetic acid, acted as catalyst. Finally, the activation energy for the hydrolysis of the glycosidic linkage on chitosan was calculated to be 40kJ/mol; the mechanism of acid depolymerization is proposed. In summary, LMWCs could be easily and numerously generated with acid depolymerization for further biological applications. PMID:21075360

  17. Kinetics and mechanism of catalytic hydroprocessing of components of coal-derived liquids. Seventh quarterly report, November 16, 1980-February 15, 1981

    Gates, B.C.; Katzer, J.R.; Kwart, H.; Olson, J.H.; Schuit, G.C.A.; Stiles, A.B.; Petrakis, L.

    1981-10-21

    An asphaltene-containing SRC-II coal liquid derived from Powhatan No. 5 coal and produced in the Ft. Lewis demonstration plant was selected for study of catalytic hydroprocessing reactions. Separation by liquid chromatography has been carried out to produce nine distinct fractions. Experiments have begun to determine the reactivities of these fractions in high-pressure catalytic hydroprocessing. Hydroprocessing experiments with aromatic hydrocarbons under industrially relevant conditions have shown that the reaction networks involve reversible hydrogenation and isomerization, and significant concentrations of hydroaromatic (hydrogen-donor) species are attainable under practical conditions. The least reactive class of aromatic hydrocarbons consists of substituted benzenes. Biphenyl has been selected for thorough study, and quantitative kinetics of the biphenyl hydrogenation to give cyclohexylbenzene has been determined. Kinetics of hydrodenitrogenation of indole was studied in an autoclave between 321 and 400/sup 0/C and 16.3 to 69 atm, using American Cyanamid HDS-9A catalyst. A reaction network with kinetics parameters was developed for the calculation of product distribution and nitrogen removal. Lumping of components in a reaction network simplifies the kinetics determination of fuel feedstocks. Component lumping simulations involving first-order kinetics were successfully carried out for certain schemes in the quinoline network. This network can be represented by the reactant, the hydrogenated intermediate (lumps), and the denitrogenated product.

  18. Preliminary Study on Kinetic Solid-Liquid Extraction and Bio-Active Components Analysis of Hibiscus rosa-sinensis Leaves

    Hibiscus rosa-sinensis or commonly known as 'Hibiscus' is a kind of decorative flowers which often grown in a subtropical countries. This plant is often used in the preparation of traditional medicine because of its pharmacological properties that are capable of treating number of health problems. The plant contains several essential bio-active substances and nutrients especially in its flowers and leaves. One of the bioactive substances is β-sitosterol which is abundant in the leaf crude extract. Hibiscus leaves water extract yielded mucilage which is widely used in lowering high body temperature due to fever (antipyretic). Therefore, the main objective of this paper was to determine the maximum concentration of mucilage and time of exhaustive extraction from fresh and dried leaves using a Peleq's mathematical model. Moreover, several analyses were conducted such as qualitative analysis to determine the presence of bioactive substances using high performance liquid chromatography (HPLC) and determination of functional groups by means of fourier transform infrared method (FTIR). Physical properties of the extracts were evaluated to determine its acidity and viscosity of the mucilage with respect to different shear stress. The result show that the extract of dried Hibiscus leaves exhibited high in its concentrations even though the achieved exhaustive extraction was relatively slow as compared to fresh leaves (p < 0.05). Based on the HPLC analysis, the main bio-active substances of β-sitosterol was only existed in fresh leaves samples. The absence of β-sitosterol in dried leaves extract was caused by the loss of other important bio-active substances which possess surfactant capability, due to thermal degradation of drying process or the component itself was deteriorated during the pre-preparation drying process. Furthermore, the FTIR analysis shows that the same composition of the absorption peaks for both extracts with the highest absorption of O-H bonds was

  19. Kinetics and Mechanism of Electron Transfer Reaction: Oxidation of Sulfanilic Acid by N-Chloro-p-Toluene Sulfonamide in Acid Perchlorate Medium

    Sailani, Riya; Bhasin, Meneka; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

    2014-01-15

    The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be (61.67 ± 0.47) kJ mol{sup -1} and (-62.71 ± 2.48) JK{sup -1}mol{sup -1} respectively employing Eyring equation.

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

    Puttaswamy; S Dakshayani

    2014-11-01

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

  1. Influence of microwaves on the leaching kinetics of uraninite from a low grade ore in dilute sulfuric acid.

    Madakkaruppan, V; Pius, Anitha; T, Sreenivas; Giri, Nitai; Sarbajna, Chanchal

    2016-08-01

    This paper describes a study on microwave assisted leaching of uranium from a low-grade ore of Indian origin. The host rock for uranium mineralization is chlorite-biotite-muscovite-quartzo-feldspathic schist. The dominant presence of siliceous minerals determined leaching of uranium values in sulfuric acid medium under oxidizing conditions. Process parametric studies like the effect of sulfuric acid concentration (0.12-0.50M), redox potential (400-500mV), particle size (600-300μm) and temperature (35°-95°C) indicated that microwave assisted leaching is more efficient in terms of overall uranium dissolution, kinetics and provide relatively less impurities (Si, Al, Mg and Fe) in the leach liquor compared to conventional conductive leaching. The kinetics of leaching followed shrinking core model with product layer diffusion as controlling mechanism. PMID:27045621

  2. Model compounds for heavy crude oil components and tetrameric acids: Characterization and interfacial behaviour

    Nordgaard, Erland Loeken

    2009-07-01

    The tendency during the past decades in the quality of oil reserves shows that conventional crude oil is gradually being depleted and the demand being replaced by heavy crude oils. These oils contain more of a class high-molecular weight components termed asphaltenes. This class is mainly responsible for stable water-in-crude oil emulsions. Both heavy and lighter crude oils in addition contain substantial amounts of naphthenic acids creating naphthenate deposits in topside facilities. The asphaltene class is defined by solubility and consists of several thousand different structures which may behave differently in oil-water systems. The nature of possible sub fractions of the asphaltene has been received more attention lately, but still the properties and composition of such is not completely understood. In this work, the problem has been addressed by synthesizing model compounds for the asphaltenes, on the basis that an acidic function incorporated could be crucial. Such acidic, poly aromatic surfactants turned out to be highly inter facially active as studied by the pendant drop technique. Langmuir monolayer compressions combined with fluorescence of deposited films indicated that the interfacial activity was a result of an efficient packing of the aromatic cores in the molecules, giving stabilizing interactions at the o/w interface. Droplet size distributions of emulsions studied by PFG NMR and adsorption onto hydrophilic silica particles demonstrated the high affinity to o/w interfaces and that the efficient packing gave higher emulsion stability. Comparing to a model compound lacking the acidic group, it was obvious that sub fractions of asphaltenes that contain an acidic, or maybe similar hydrogen bonding functions, could be responsible for stable w/o emulsions. Indigenous tetrameric acids are the main constituent of calcium naphthenate deposits. Several synthetic model tetra acids have been prepared and their properties have been compared to the indigenous

  3. Experimental and kinetic modelling studies on the acid-catalysed hydrolysis of the water hyacinth plant to levulinic acid

    Girisuta, B.; Danon, B.; Manurung, R.; Janssen, L. P. B. M.; Heeres, H. J.

    2008-01-01

    A comprehensive experimental and modelling study on the acid-catalysed hydrolysis of the water hyacinth plant (Eichhornia crassipes) to optimise the yield of levulinic acid (LA) is reported (T = 150-175 degrees C, C-H2SO4 - 0.1-1 M, water hyacinth intake = 1-5 wt%). At high acid concentrations (> 0.5 M), LA was the major organic acid whereas at low acid concentrations (

  4. Reaction of Chromium(III with 3,4-Dihydroxybenzoic Acid: Kinetics and Mechanism in Weak Acidic Aqueous Solutions

    Athinoula L. Petrou

    2009-02-01

    Full Text Available The interactions between chromium(III and 3,4-dihydroxybenzoic acid (3,4-DHBA were studied resulting in the formation of oxygen-bonded complexes upon substitution of water molecules in the chromium(III coordination sphere. The experimental results show that the reaction takes place in at least three stages, involving various intermediates. The first stage was found to be linearly dependent on ligand concentration k1(obs_=k0+k1(obs[3,4-DHBA], and the corresponding activation parameters were calculated as follows: ΔH1(obs≠=51.2±11.5 kJ mol−1, ΔS1(obs≠=−97.3±28.9 J mol−1 K−1 (composite activation parameters . The second and third stages, which are kinetically indistinguishable, do not depend on the concentrations of ligand and chromium(III, accounting for isomerization and chelation processes, respectively. The corresponding activation parameters are ΔH2(obs≠=44.5±5.0 kJ mol−1, ΔS2(obs≠=−175.8±70.3 J mol−1 K−1. The observed stages are proposed to proceed via interchange dissociative (Id, first stage and associative (second and third stages mechanisms. The reactions are accompanied by proton release, as is shown by the pH decrease.

  5. Extraction kinetics of uranium(VI) with di(2-ethylhexyl) phosphoric acid using a hollow fiber membrane extractor

    The kinetics of solvent extraction of U(VI) with di(2-ethylhexyl) phosphoric acid (HDEHP) using a microporous hydrophobic hollow fiber membrane extractor has been investigated. The effects of U(VI) and hydrogen ion concentrations in aqueous phase, HDEHP concentration in organic phase, flow velocities of aqueous and organic phase and temperature on extraction rate of U(VI) were examined. The experimental results suggest that the extraction rate of U(VI) is controlled by diffusion. (author)

  6. [Rapidly labelled low molecular weight components in nucleic acid preparations from plant cells].

    Richter, G; Grotha, R

    1974-09-01

    After pulse-labelling with [(3)H]nucleosides and [(3)H]orotic acid of freely suspended callus cells of Petroselinum sativum and tissue fragments of the liverwort Riella helicophylla, rapidly labelled low molecular weight components were detected among the total nucleic acids when these were extracted in the presence of Mg(2+) and finally precipitated with alcohol. These highly labelled species could clearly be distinguished from the 5 S- and 4 S-RNA on the basis of their migration in agarose-polyacrylamide gels (2.4%) and their elution from Sephadex G-150 columns. No degradation was obtained with DNase and RNase. By using [(14)C]ATP as a marker it was found that the low molecular components consisted mainly of nucleoside triphosphates. Only small amounts of nucleoside diphosphates were detected, which were obviously formed by degradation of the former. Nucleic acid preparations free of nucleoside phosphates were obtained by using Mg-free extraction buffers containing EDTA. PMID:24458196

  7. Characterization and mapping of the multi-component release kinetics of a Traditional Chinese Medicine dosage form using a modified LC/MS/MS method and chemomic release kinetic theory

    Hai-yan Li

    2011-08-01

    Full Text Available It is essential to develop effective methods for the quality control of the traditional medicine with multiple components. However, few researches on the quality control have been conducted to interpret the holistic characteristics of the traditional medicine in terms of dissolution/release. In this study, the multi-component release kinetics of Traditional Chinese Medicine (TCM dosage forms was characterized and mapped by multivariate analysis techniques in the field of “-omics”. The Liuweidihuang pill was used as a model formulation. The multi-component release kinetics of the concentrated and water-honeyed Liuweidihuang pills at rotation speeds of 50 and 100 rpm were analyzed by chemomic release kinetic theory and modified LC/MS/MS method. Mass features of 103 (concentrated pills and 101 (water-honeyed pills were selected with a linear correlation coefficient ≥0.99 between mass responses and concentrations. To compose the chemomic standard spectrum, the relative abundance of both mass features was no less than 1% as compared with an internal standard. The correlation coefficients between six samples of various solutions were in line with analytical requirements of precision (r≥0.985. The score plots of principal component analysis showed that the concentrated Liuweidihuang pills presented better chemomic release reproducibility than the water-honeyed pills. Conversely, the impact of rotation speed on the chemomic release was less obvious. The heat maps of hierarchical clustering analysis did not show significant changes in individual clusters of mass features along different time intervals, reflecting the release integrity of the mass features. Therefore, both multivariate analysis methods, the principal component analysis and the hierarchical clustering analysis, seemed to be effective techniques to demonstrate the multiple component release performance of TCM. The research provided the basis of a new strategy for the quality

  8. Kinetics of cytochrome P450 2E1-catalyzed oxidation of ethanol to acetic acid via acetaldehyde.

    Bell-Parikh, L C; Guengerich, F P

    1999-08-20

    The P450 2E1-catalyzed oxidation of ethanol to acetaldehyde is characterized by a kinetic deuterium isotope effect that increases K(m) with no effect on k(cat), and rate-limiting product release has been proposed to account for the lack of an isotope effect on k(cat) (Bell, L. C., and Guengerich, F. P. (1997) J. Biol. Chem. 272, 29643-29651). Acetaldehyde is also a substrate for P450 2E1 oxidation to acetic acid, and k(cat)/K(m) for this reaction is at least 1 order of magnitude greater than that for ethanol oxidation to acetaldehyde. Acetic acid accounts for 90% of the products generated from ethanol in a 10-min reaction, and the contribution of this second oxidation has been overlooked in many previous studies. The noncompetitive intermolecular kinetic hydrogen isotope effects on acetaldehyde oxidation to acetic acid ((H)(k(cat)/K(m))/(D)(k(cat)/K(m)) = 4.5, and (D)k(cat) = 1.5) are comparable with the isotope effects typically observed for ethanol oxidation to acetaldehyde, and k(cat) is similar for both reactions, suggesting a possible common catalytic mechanism. Rapid quench kinetic experiments indicate that acetic acid is formed rapidly from added acetaldehyde (approximately 450 min(-1)) with burst kinetics. Pulse-chase experiments reveal that, at a subsaturating concentration of ethanol, approximately 90% of the acetaldehyde intermediate is directly converted to acetic acid without dissociation from the enzyme active site. Competition experiments suggest that P450 2E1 binds acetic acid and acetaldehyde with relatively high K(d) values, which preclude simple tight binding as an explanation for rate-limiting product release. The existence of a rate-determining step between product formation and release is postulated. Also proposed is a conformational change in P450 2E1 occurring during the course of oxidation and the discrimination of P450 2E1 between acetaldehyde and its hydrated form, the gem-diol. This multistep P450 reaction is characterized by kinetic

  9. KINETIC STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A NOVEL COPOLYMER- BOUND CIS- DICARBONYLRHODIUM COMPLEX

    CHEN Yuying; YUAN Guoqing; CHEN Rongyao

    1989-01-01

    The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh)coordinated with the ethylene diacrylate (M')crosslinked copolymer of methyl acrylate (M) and 2 - vinylpyridine (V) shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex . Polar solvents can accelerate the reaction .Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system . A mechanism similar to that of soluble rhodium catalyst was proposed .

  10. STOPPED-FLOW SPECTROPHOTOMETRIC STUDIES OF THE KINETICS OF INTERACTION OF DIHYDROXYFUMARIC ACID WITH THE DPPH FREE RADICAL

    N. Secara

    2010-01-01

    The reaction of dihydroxyfumaric acid with the free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) was studied using the stopped-flow method, in order to describe the reaction kinetics. Dihydroxyfumaric acid reacts very rapidly with DPPH, the reaction being completed in several minutes. This 2-stoichiometric reaction proceeds in two stages, with reaction orders of 1 and 0.76 with respect to DPPH, and 0.5 and 0.3 with respect to DHF, respectively. The rate constant of the two stages of the react...

  11. Kinetics of rapid covalent bond formation of aniline with humic acid: ESR investigations with nitroxide spin labels

    Glinka, Kevin; Matthies, Michael; Theiling, Marius; Hideg, Kalman; Steinhoff, Heinz-Jürgen

    2016-04-01

    Sulfonamide antibiotics used in livestock farming are distributed to farmland by application of slurry as fertilizer. Previous work suggests rapid covalent binding of the aniline moiety to humic acids found in soil. In the current work, kinetics of this binding were measured in X-band EPR spectroscopy by incubating Leonardite humic acid (LHA) with a paramagnetic aniline spin label (anilino-NO (2,5,5-Trimethyl-2-(3-aminophenyl)pyrrolidin-1-oxyl)). Binding was detected by a pronounced broadening of the spectral lines after incubation of LHA with anilino-NO. The time evolution of the amplitude of this feature was used for determining the reaction kinetics. Single- and double-exponential models were fitted to the data obtained for modelling one or two first-order reactions. Reaction rates of 0.16 min-1 and 0.012 min-1, were found respectively. Addition of laccase peroxidase did not change the kinetics but significantly enhanced the reacting fraction of anilino-NO. This EPR-based method provides a technically simple and effective method for following rapid binding processes of a xenobiotic substance to humic acids.

  12. Kinetic Determination of Uric Acid in Human Serum by Using the Uncatalyzed BZ Reaction in Non-equilibrium Steady State

    Ren, Jie; Yang, Wu; Niu, Xiuli; Gao, Jinzhang

    2012-01-01

    A novel kinetic method for determination of uric acid in human serum by means of an uncatalyzed BZ system consisting of potassium bromate and p-hydroxybenzaldehyde (p-HBA) in sulfuric acid medium was proposed, in which the analyte perturbation to the system was recorded close to the bifurcation point. The potential change was directly proportional to the logarithm of concentration of uric acid in the range of 3.73 × 10 8--7.48 × 10-4 mol.L-1 (r=0.9983) with a detection limit of 7.45 × 10-9mol.L-I and a recovery from 98.9% to 101.1%. A comparison between the proposed technique and other methods indicated that results obtained were in agreement with those in clinical detection. In addition, the possible mechanism of action of uric acid on the uncatalyzed BZ reaction was also discussed briefly.

  13. Laboratory study on OH-initiated degradation kinetics of dehydroabietic acid.

    Lai, Chengyue; Liu, Yongchun; Ma, Jinzhu; Ma, Qingxin; He, Hong

    2015-04-28

    Dehydroabietic acid (DHAA) is a specific organic tracer for the pyrolysis of conifer resin. To understand its atmospheric stability, the degradation behavior of particulate DHAA in the presence of hydroxyl radicals (OH) was investigated under different environmental conditions using a stainless steel reactor with volume of 30 cm(3), in the dark. At 25 °C and 40% relative humidity (RH), the second-order rate constant (k2) of pure DHAA with OH was measured to be 5.72 ± 0.87 × 10(-12) cm(3) molecule(-1) s(-1). The influence of temperature, RH and mixing state on the degradation kinetics of DHAA were also investigated. At 40% RH, k2 of pure DHAA increases with increasing temperature and follows the Arrhenius equation k2 = (8.9 ± 1.9) × 10(-10) exp[-(1508.2 ± 64.2)/T], while RH does not have significant impact on k2 at 25 °C. At 25 °C and 40% RH, compared with pure DHAA, the corresponding k2 for DHAA mixed with (NH4)2SO4 decreased to 4.58 ± 0.95 × 10(-12) cm(3) molecule(-1) s(-1), while the value was 3.30 ± 0.79 × 10(-12) cm(3) molecule(-1) s(-1) when mixed with soot. The atmospheric lifetime of DHAA varied from 2.3 ± 0.2 to 4.4 ± 0.8 days under different environmental conditions. This study indicates that degradation of DHAA by OH radicals is appreciable, and a significant error in source apportionment should be introduced if the contribution of degradation to DHAA concentration is not considered during air mass aging. PMID:25824374

  14. Kinetics properties of cations absorption by ion exchangers on the base of antimonic acid

    This article is devoted to study of kinetics of sorption one- and two-charge elements by antimony-silicon sorbent. Kinetic studies are conducted at ph=0-5 and temperature interval 10-50 deg C. Data on X-ray analysis of ion exchangers is considered.

  15. Developments in bile acid kinetic measurements using C-13 and H-2 : 10(5) times improved sensitivity during the last 40 years

    Stellaard, Frans; Brufau, Gemma; Boverhof, Renze; Jonkers, Elles Zwanet; Boer, Theo; Kuipers, Folkert

    2009-01-01

    Bile acid kinetics involve the measurement of pool sizes and turnover rates of individual bile acids. The technique is based on isotope dilution and was first described in the 1950s using radioactive C-14-labelled cholic acid (CA). It took until the 1970s before stable isotopes were introduced for t

  16. Analysis of volatile components, fatty acids, and phytosterols of Abies koreana growing in Poland.

    Wajs-Bonikowska, Anna; Olejnika, Karol; Bonikowski, Radosław; Banaszczakb, Piotr

    2013-09-01

    Extracts and essential oils from seeds as well as essential oils from cone scales and needles with twigs of the Abies koreana population were studied. An analysis of Korean fir essential oils allowed us to determine 147 volatile compounds. The identified compounds constituted 97-99% of the seed, cone and needle oils. The main volatile in the seed and needle oils was limonene (56.6% and 23.4%, respectively), while the predominant volatile in cone oils was alpha-pinene (51.2%). Korean fir seeds provided a rich source of both essential oil (3.8-8.5%) and extract, which was isolated with a 24.5% yield and contained numerous groups of fatty acids and phytosterols (414 microg/100g extract). The most prominent fatty acids were unsaturated, among which linoleic (41.2%) and oleic (31.2%) fatty acid were the main ones while the dominant sterols were isomers of ergostadienol and beta-sitosterol. A. koreana seeds, cones and needles are a source of many volatile bioactive compounds while the seed extract, with a pleasant scent, contained not only volatiles, but also fractions rich in fatty acids and phytosterols. These facts make A. koreana essential oils and especially the seed extract potential components of cosmetics. PMID:24273870

  17. The effect of particulate matter components on the acidity of rain in upper Silesia (Poland)

    Analysis of data characterizing the chemical composition of atmospheric precipitation was presented, with an emphasis on components responsible for neutralization of rain acidity. For this purpose, chemometric methods were applied. Based on a principal component analysis (PCA) a strong correlation between precipitation pH and potassium and ammonium ions in the heating period (October-March) and potassium and sodium ions in the non-heating period (April-September) was observed. Additionally, a classification of eight variables, i.e., Na+, K+, Mg2+, Ca2+, SO42-, NO3-, Cl-, and NH4+ according to their similarities was made using a cluster analysis. Based on this study, two ions, potassium and ammonium, together with the pH value were classified into one group (cluster) in the heating period while in the non-heating period ions of potassium and sodium were clustered together with the pH. The results of the cluster analysis indicated that the selected ions contributed the most to the neutralization of the atmospheric precipitation acidity. This relationship was confirmed by a discriminant analysis in which potassium and ammonium ions were selected as components of the highest potential for precipitation classification according to its acidity degree. The relationship between the precipitation pH and the number of non-precipitation days preceding the precipitation was also analyzed. It was found that although the observed an increase of the pH value was not very high, nevertheless, the effect of the duration of the period preceding the precipitation on the pH value recorded on the day of the precipitation occurrence was quite evident. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  18. Polyethylene Glycols as Efficient Media for Decarboxylative Nitration of α,β-Unsaturated Aromatic Carboxylic Acids by Ceric Ammonium Nitrate in Acetonitrile Medium: A Kinetic and Mechanistic Study

    K.Ramesh; S. Shylaja; K. C. Rajanna; P. Giridhar Reddy; P. K. Saiprakash

    2013-01-01

    Polyethylene glycols (PEGs) were found to be efficient media for decarboxylative nitration of α,β-unsaturated aromatic carboxylic acids by ceric ammonium nitrate (CAN) in acetonitrile to give β-nitrostyrene derivatives. Kinetics of the reaction exhibited second order kinetics with a first order dependence on [CAN] and [substrate]. Reactions were too sluggish to be studied in the absence of PEG; therefore detailed kinetics were not taken up. Reaction times were reduced from 24 hrs to few hours...

  19. Continuous cultivations of a Penicillium chrysogenum strain expressing the expandase gene from Streptomyces clavuligerus: Kinetics of adipoyl-7-aminodeacetoxycephalosporanic acid and byproduct formations

    Robin, Jarno Jacky Christian; Bruheim, P.; Nielsen, M.L.;

    2003-01-01

    The production kinetics of a transformed strain of Penicillium chrysogenum expressing the expandase gene from Streptomyces clavuligerus was investigated in chemostat cultivations. The recombinant strain produces adipoyl-7-aminodeacetoxycephalosporanic acid (ad-7-ADCA) as the major product; howeve...

  20. Callus Growth Kinetics of Physic Nut (Jatropha curcas L.) and Content of Fatty Acids from Crude Oil Obtained In Vitro.

    da Luz Costa, Jefferson; da Silva, André Luís Lopes; Bier, Mário César Jucoski; Brondani, Gilvano Ebling; Gollo, André Luiz; Letti, Luiz Alberto Junior; Erasmo, Eduardo Andrea Lemus; Soccol, Carlos Ricardo

    2015-06-01

    The callus growth kinetics allows identifying the appropriate moment for callus pealing and monitoring the accumulation of primary and secondary metabolites. The physic nut (Jatropha curcas L.) is a plant species used for biofuel production due to its high oil content; however, this plant presents a great amount of bioactive compounds which can be useful for industry. The aim of this research was to establish a calli growth curve and to evaluate the fatty acid profile of crude oil extracted from callus. The callus growth kinetics presented a sigmoid standard curve with six distinct phases: lag, exponential, linear, deceleration, stationary, and decline. Total soluble sugars were higher at the inoculation day. Reducing sugars were higher at the inoculation day and at the 80th day. The highest percentage of ethereal extract (oil content) was obtained at the 120th day of culture, reaching 18 % of crude oil from the callus. The calli produced medium-chain and long-chain fatty acids (from 10 to 18 carbon atoms). The palmitic acid was the fatty acid with the highest proportion in oil (55.4 %). The lipid profile obtained in callus oil was different from the seed oil profile. PMID:25917545

  1. Development of Acid Functional Groups and Lactones During the Thermal Degradation of Wood and Wood Components

    Rutherford, David W.; Wershaw, Robert L.; Reeves, James B., III

    2008-01-01

    Black carbon (pyrogenic materials including chars) in soils has been recognized as a substantial portion of soil organic matter, and has been shown to play a vital role in nutrient cycling; however, little is known concerning the properties of this material. Previous studies have largely been concerned with the creation of high-surface-area materials for use as sorbents. These materials have been manufactured at high temperature and have often been activated. Chars occurring in the environment can be formed over a wide range of temperature. Because it is extremely difficult to isolate black carbon once it has been incorporated in soils, chars produced in the laboratory under controlled conditions can be used to investigate the range of properties possible for natural chars. This report shows that charring conditions (temperature and time) have substantial impact on the acid functional group and lactone content of chars. Low temperatures (250?C) and long charring times (greater than 72 hours) produce chars with the highest acid functional group and lactone content. The charring of cellulose appears to be responsible for the creation of the acid functional group and lactones. The significance of this study is that low-temperature chars can have acid functional group contents comparable to humic materials (as high as 8.8 milliequivalents per gram). Acid functional group and lactone content decreases as charring temperature increases. The variation in formation conditions expected under natural fire conditions will result in a wide range of sorption properties for natural chars which are an important component of soil organic matter. By controlling the temperature and duration of charring, it is possible to tailor the sorption properties of chars, which may be used as soil amendments.

  2. Effect of Humic Acid on As Redox Transformation and Kinetic Adsorption onto Iron Oxide Based Adsorbent (IBA

    Hoda Fakour

    2014-10-01

    Full Text Available Due to the importance of adsorption kinetics and redox transformation of arsenic (As during the adsorption process, the present study elucidated natural organic matter (NOM effects on As adsorption-desorption kinetics and speciation transformation. The experimental procedures were conducted by examining interactions of arsenate and arsenite with different concentrations of humic acid (HA as a model representative of NOM, in the presence of iron oxide based adsorbent (IBA, as a model solid surface in three environmentally relevant conditions, including the simultaneous adsorption of both As and HA onto IBA, HA adsorption onto As-presorbed IBA, and As adsorption onto HA-presorbed IBA. Experimental adsorption-desorption data were all fitted by original and modified Lagergren pseudo-first and -second order adsorption kinetic models, respectively. Weber’s intraparticle diffusion was also used to gain insight into the mechanisms and rate controlling steps, which the results suggested that intraparticle diffusion of As species onto IBA is the main rate-controlling step. Different concentrations of HA mediated the redox transformation of As species, with a higher oxidation ability than reduction. The overall results indicated the significant effect of organic matter on the adsorption kinetics and redox transformation of As species, and consequently, the fate, transport and mobility of As in different environmentally relevant conditions.

  3. Kinetic and equilibrium studies of the removal of cadmium ions from acidic chloride solutions by hydrophobic pyridinecarboxamide extractants

    Liquid-liquid extraction of cadmium(II) from acidic chloride solutions was carried out with alkyl derivatives of pyridinecarboxamide in toluene with addition of 2-ethylhexan-1-ol as modifier. Equilibrium as well as kinetic studies was performed. The kinetic studies of a Cd(II) extraction process were carried out with a Lewis cell having a constant interfacial area. Cadmium(II) concentration in the aqueous phases was determined by atomic absorption spectroscopy (Varian SPECTR AA800). The results of equilibrium experiments showed that cadmium(II) was quantitatively extracted with N,N-dihexylpyridine-3-carboxamide whereas the derivative N,N-dihexylpyridine-2-carboxamide was not able to transfer Cd(II) ions from the aqueous phase to the organic one. Thus, the kinetics of extraction and the initial extraction rate were examined only in the systems with N,N-dihexylpyridine-3-carboxamide. The obtained experimental data as well as the calculated values of mass transfer coefficients suggest that the investigated process of extraction of Cd(II) by means of pyridinecarboxamide as extractant occurs in the mixed diffusion-kinetic region. Moreover, the results of adsorption studies indicated that the extraction of Cd(II) with a hydrophobic extractant should be considered as an interfacial process.

  4. Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

    Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Abuin, Senen Paz, E-mail: senen@gairesa.com [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Soulé, Ezequiel R. [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina); Williams, Roberto J.J., E-mail: williams@fi.mdp.edu.ar [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina)

    2015-09-20

    Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.

  5. Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

    Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted

  6. Hydroxyalkylation of phenol to bisphenol F over heteropolyacid catalysts: The effect of catalyst acid strength on isomer distribution and kinetics.

    Wu, Xianzhang; Liu, Yutang; Liu, Ran; Wang, Longlu; Lu, Yanbing; Xia, Xinnian

    2016-11-01

    Hydroxyalkylation of phenol with formaldehyde to bisphenol F over heteropolyacid impregnated on clay was investigated. These catalysts displayed excellent catalytic performance for this reaction, especially that the effects of acid sites on the isomer distribution are obvious. Various solid catalysts were prepared by impregnating heteropolyacid on different kind of clay matrices, and their chemical compositions, textural properties, and acid strength of the heteropolyacid catalysts were characterized by EDX, BET, NH3-TPD, XRD, and FT-IR. Moreover, the effects of acid sites and reaction temperature on the yield and 4,4'-isomer distribution were launched by comparing the data obtained from the two kinds of catalysts. Furthermore, the kinetics of the hydroxyalkylation of phenol to BPF was established. PMID:27451037

  7. Kinetic characterization for hemicellulose hydrolysis of corn stover in a dilute acid cycle spray flow-through reactor at moderate conditions

    The kinetic characterization of hemicellulose hydrolysis of corn stover was investigated using a new reactor of dilute acid cycle spray flow-through (DCF) pretreatment. The primary purpose was to obtain kinetic data for hemicellulose hydrolysis with sulfuric acid concentrations (10-30 kg m-3) at relatively low temperatures (90-100 oC). A simplified kinetic model was used to describe its performance at moderate conditions. The results indicate that the rates of xylose formation and degradation are sensitive to flow rate, temperature and acid concentration. Moreover, the kinetic data of hemicellulose hydrolysis fit a first-order reaction model and the experimental data with actual acid concentration after accounting for the neutralization effect of the substrates at different temperatures. Over 90% of the xylose monomer yield and below 5.5% of degradation product (furfural) yield were observed in this reactor. Kinetic constants for hemicellulose hydrolysis models were analyzed by an Arrhenius-type equation, and the activation energy of xylose formation were 111.6 kJ mol-1, and 95.7 kJ mol-1 for xylose degradation, respectively. -- Highlights: → Investigating a novel pretreatment reactor of dilute acid cycle spray flow-through. → Xylose yield is sensitive to flow rate, temperature and acid concentration. → Obtaining relatively higher xylose monomer yield and lower fermentation inhibitor. → Lumping hemicellulose and xylan oligmers together in the model is a valid way. → The kinetic model as a guide for reactor design, and operation strategy optimization.

  8. Development of new chiral ligand exchange capillary electrophoresis system with amino acid ionic liquids ligands and its application in studying the kinetics of L-amino acid oxidase

    Sun, Bingbing [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); College of Food Sciences and Engineering, Shandong Agricultural University, Tai’an, Shandong 271018 (China); Mu, Xiaoyu [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Qi, Li, E-mail: qili@iccas.ac.cn [Beijing National Laboratory for Molecular Sciences, Key Lab of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)

    2014-04-01

    Highlights: • Novel amino acid ionic liquids with pyridinium as cations and L-lysine as anion were synthesized. • These synthesized AAILs have been explored as the ligands coordinated with Zn(II) in CLE-CE system. • The developed CLE-CE method could be used for the enantioseparation of Dns-D, L-amino acids. • The kinetic contents of L-amino acid oxidase were investigated with the proposed CLE-CE system. - Abstract: New kinds of amino acid ionic liquids (AAILs) with pyridinium as cations and L-lysine (L-Lys) as anion have been developed as the available chiral ligands coordinated with Zn(II) in chiral ligand-exchange capillary electrophoresis (CLE-CE). Four kinds of AAILs, including [1-ethylpyridinium][L-lysine], 1-butylpyridinium][L-lysine], [1-hexylpyridinium][L-lysine] and 1-[octylpyridinium][L-lysine], were successfully synthesized and characterized by nuclear magnetic resonance and mass spectrometry. Compared with other AAILs, the best chiral separation of Dns-D, L-amino acids could be achieved when [1-ethylpyridinium][L-lysine] was chosen as the chiral ligand. It has been found that after investigating the influence of key factors on the separation efficiency, such as pH of buffer solution, the ratio of Zn(II) to ligand and complex concentration, eight pairs of Dns-D, L-AAs enantiomers could be baseline separated and three pairs were partly separated under the optimum conditions. The proposed CLE-CE method also exhibited favorable quantitative analysis property of Dns-D, L-Met with good linearity (r{sup 2} = 0.998) and favorable repeatability (RSD ≤ 1.5%). Furthermore, the CLE-CE system was applied in investigating the kinetic contents of L-amino acid oxidase, which implied that the proposed system has the potential in studying the enzymatic reaction mechanism.

  9. Specific catalysis of asparaginyl deamidation by carboxylic acids: kinetic, thermodynamic, and quantitative structure-property relationship analyses.

    Connolly, Brian D; Tran, Benjamin; Moore, Jamie M R; Sharma, Vikas K; Kosky, Andrew

    2014-04-01

    Asparaginyl (Asn) deamidation could lead to altered potency, safety, and/or pharmacokinetics of therapeutic protein drugs. In this study, we investigated the effects of several different carboxylic acids on Asn deamidation rates using an IgG1 monoclonal antibody (mAb1*) and a model hexapeptide (peptide1) with the sequence YGKNGG. Thermodynamic analyses of the kinetics data revealed that higher deamidation rates are associated with predominantly more negative ΔS and, to a lesser extent, more positive ΔH. The observed differences in deamidation rates were attributed to the unique ability of each type of carboxylic acid to stabilize the energetically unfavorable transition-state conformations required for imide formation. Quantitative structure property relationship (QSPR) analysis using kinetic data demonstrated that molecular descriptors encoding for the geometric spatial distribution of atomic properties on various carboxylic acids are effective determinants for the deamidation reaction. Specifically, the number of O-O and O-H atom pairs on carboxyl and hydroxyl groups with interatomic distances of 4-5 Å on a carboxylic acid buffer appears to determine the rate of deamidation. Collectively, the results from structural and thermodynamic analyses indicate that carboxylic acids presumably form multiple hydrogen bonds and charge-charge interactions with the relevant deamidation site and provide alignment between the reactive atoms on the side chain and backbone. We propose that carboxylic acids catalyze deamidation by stabilizing a specific, energetically unfavorable transition-state conformation of l-asparaginyl intermediate II that readily facilitates bond formation between the γ-carbonyl carbon and the deprotonated backbone nitrogen for cyclic imide formation. PMID:24620787

  10. Assay of amoxicillin and clavulanic acid, the components of Augmentin, in biological fluids with high-performance liquid chromatography.

    Foulstone, M; Reading, C

    1982-01-01

    Augmentin is a new antibacterial formulation comprised of amoxicillin and the beta-lactamase inhibitor clavulanic acid. In the present paper, the use of high-performance liquid chromatography (HPLC) to provide a rapid assay of the components of Augmentin in body fluids is described. Clavulanic acid was assayed by reacting the sample with imidazole, which readily produces a derivative absorbing at 311 nm. This derivative chromatographs on reverse-phase HPLC columns clear of interfering compone...

  11. The kinetics of the solidification of highly supersaturated solutions of palmitic acid in oleic acid: a comparison between two models

    RAMIRO RICO-MARTINEZ; JOSE ALBERTO GALLEGOS-INFANTE

    1999-01-01

    The crystallization of fatty acids is very important in industrial applications and biological systems. A comparison between theoretical models and experimental data helps in clarifying mechanistic aspects of these systems. In this contribution, we compare the performance of two models in fitting data from the crystallization of supersaturated solutions of palmitic acid in oleic acid. One of the models was developed by Avrami and the other is based on considering diffusion as limiting (the D-...

  12. The regioselective synthesis of spirooxindolo pyrrolidines and pyrrolizidines via three-component reactions of acrylamides and aroylacrylic acids with isatins and α-amino acids.

    Pavlovskaya, Tatyana L; Yaremenko, Fedor G; Lipson, Victoria V; Shishkina, Svetlana V; Shishkin, Oleg V; Musatov, Vladimir I; Karpenko, Alexander S

    2014-01-01

    The regioselective three-component condensation of azomethine ylides derived from isatins and α-amino acids with acrylamides or aroylacrylic acids as dipolarophiles has been realized through a one-pot 1,3-dipolar cycloaddition protocol. Decarboxylation of 2'-aroyl-2-oxo-1,1',2,2',5',6',7',7a'-octahydrospiro[indole-3,3'-pyrrolizine]-1'-carboxylic acids is accompanied by cyclative rearrangement with formation of dihydropyrrolizinyl indolones. PMID:24454564

  13. Characterization of Fatty Acid, Amino Acid and Volatile Compound Compositions and Bioactive Components of Seven Coffee (Coffea robusta) Cultivars Grown in Hainan Province, China

    Wenjiang Dong; Lehe Tan; Jianping Zhao; Rongsuo Hu; Minquan Lu

    2015-01-01

    Compositions of fatty acid, amino acids, and volatile compound were investigated in green coffee beans of seven cultivars of Coffea robusta grown in Hainan Province, China. The chlorogenic acids, trigonelline, caffeine, total lipid, and total protein contents as well as color parameters were measured. Chemometric techniques, principal component analysis (PCA), hierarchical cluster analysis (HCA), and analysis of one-way variance (ANOVA) were performed on the complete data set to reveal chemic...

  14. Dynamic Acid/Base Equilibrium in Single Component Switchable Ionic Liquids and Consequences on Viscosity.

    Cantu, David C; Lee, Juntaek; Lee, Mal-Soon; Heldebrant, David J; Koech, Phillip K; Freeman, Charles J; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

    2016-05-01

    The deployment of transformational nonaqueous CO2-capture solvent systems is encumbered by high viscosities even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we present key molecular features that control bulk viscosity. Fast CO2-uptake kinetics arise from close proximity of the alcohol and amine sites involved in CO2 binding in a concerted fashion, resulting in a Zwitterion containing both an alkyl-carbonate and a protonated amine. The population of internal hydrogen bonds between the two functional groups determines the solution viscosity. Unlike the ion pair interactions in ionic liquids, these observations are novel and specific to a hydrogen-bonding network that can be controlled by chemically tuning single molecule CO2 capture solvents. We present a molecular design strategy to reduce viscosity by shifting the proton transfer equilibrium toward a neutral acid/amine species, as opposed to the ubiquitously accepted zwitterionic state. The molecular design concepts proposed here are readily extensible to other CO2 capture technologies. PMID:27019342

  15. Kinetics and mechanism of iridium (III) catalysed oxidation of tellurium (IV) by cerium (IV) in sulfuric acid medium

    The kinetics and mechanism of iridium (III) catalysed oxidation of tellurium (IV) by cerium (IV) have been studied in sulfuric acid medium. The reaction is first order in [Ir (III)] as well as in [Ce (IV)] and fractional order (0.23) in [Te (IV)]. Increase in [H3O+] accelerates the rate while that in ionic strength or [HSO4-] retards. Ce (III), one of the products, inhibits while the other, Te (VI), has negligible effect on the rate. The reaction is supposed to proceed via the formation of a complex between Te (IV) and Ir (III) which in turn reacts with active Ce (IV) species in a reversible step. A rate law, consistent with the observed kinetic data, has been derived basing on the proposed mechanism. (author)

  16. Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors

    Refat M. Hassan

    2013-06-01

    Full Text Available Corrosion inhibition of aluminum (Al in hydrochloric acid by anionic polyeletrolyte pectates (PEC as a water-soluble natural polymer polysaccharide has been studied using both gasometric and weight loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing inhibitor concentration and decrease with increasing temperature. The inhibition action of PEC on Al metal surface was found to obey the Freundlich isotherm. Factors such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and temperature affecting the corrosion rates were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the kinetic results is discussed in the paper.

  17. Relationship between uric acid and arterial stiffness in the elderly with metabolic syndrome components

    SUN Ning; ZHANG Yun; TIAN Jian-li; WANG Hui

    2013-01-01

    Background High uric acid (UA) levels and metabolic syndrome (MS) are risk factors for atherosclerotic diseases.Brachial-ankle pulse wave velocity (baPWV) is a valid and reproducible measurement by which to assess arterial stiffness and a surrogate marker of atherosclerosis.However,little is known about the relationship between them,especially in elderly Chinese with MS components who are at high risk for atherosclerotic diseases.Methods One thousand and twenty Chinese subjects (159 women) older than 60 years of age (mean age (70.6±5.7)years) with at least one MS component underwent routine laboratory tests,and baPWV measurements were analyzed.Results Participants were divided into four groups by MS components.The mean age did not significantly differ among the MS component groups.We found that not only the diagnostic factors (blood pressure,body mass index (BMI),lipids,glucose) of MS but also baPWV,UA,insulin,homeostasis model of assessment for insulin resistence index (HOMAIR) levels increased,and high density lipoprotein (HDL)-C decreased with an increased number of MS components (test for trend P<0.05).The association between UA and baPWV was observed after adjustment for gender,age,blood pressure,BMI,serum creatinine and high density lipoprotein,and insulin resistance (r=0.186,P<0.0001).There were increases in the odds ratios for the association between the number of components of MS,UA and baPWV,even after adjustment for traditional risk factors.However,after adjustment for insulin or HOMA-IR,there were no significant differences in the multivariate odds ratios among the number of MS components for UA.Conclusions The UA level is positively associated with baPWV and MS,but the association between UA and MS is dependent on insulin resistance.Furthermore,baPWV is independently associated with MS in our study population.

  18. Simultaneous Determination of Essential Oil Components and Fatty Acids in Fennel using Gas Chromatography with a Polar Capillary Column.

    Najdoska-Bogdanov, Menče; Bogdanov, Jane B; Stefova, Marina

    2015-09-01

    Cultivated and wild growing samples of fennel (Foeniculum vulgare Mill., Apiaceae) from R. Macedonia were studied for their volatiles and fatty acid composition. The main essential oil components isolated via hydrodistillation were: trans-anethole (>80%), estragole (hexane and dichloromethane (3:1, v/v) in a Soxhlet extraction followed by transesterification. The obtained extracts were then characterized and the dominant fatty acid was 18:1 (petroselinic and oleic acid) 75.0-82.8%, followed by 18:2 (linoleic acid) 10.8-16.2% and other fatty acids: palmitic (4.3-6.9%), stearic (1.2-1.7%) and myristic (0-2.9%). The results for the volatile fraction after Soxhlet extraction and transesterification did not significantly differ from results obtained after hydrodistillation, especially for the main components (trans-anethole, estragole, fenchone and limonene), implying that the developed method can be used for simultaneous determination of volatiles and fatty acids. PMID:26594773

  19. Intensification of conversion of glucose to lactic acid : equilibria and kinetics for back extraction of lactic acid using trimethylamine

    Wasewar, Kailas L.; Heesink, A. Bert M.; Versteeg, Geert F.; Pangarkar, Vishwas G.

    2004-01-01

    Alamine 336 is an effective extractant for the recovery of lactic acid from aqueous solutions. An approach for regeneration and product recovery from such extracts is to back extract lactic acid with a water soluble, volatile tertiary amine such as trimethyl amine. Equilibrium data are presented tha

  20. Kinetic Spectrophotometric Determination of Trace Titanium(Ⅳ) Based on Oxidation Discoloration of Acid Chrome Blue K with Hydrogen Peroxide

    XIONG Yan; ZHOU Zhi-rong; WU Fu-hai

    2007-01-01

    A simple and sensitive kinetic spectrophotometric method for the determination of trace amounts of titanium(IV), based upon the catalytic effect of Ti(IV) on the oxidation of acid chrome blue K (ACBK) by hydrogen peroxide in 0.002 mol/L sulfuric acid, is described. The reaction rate is monitored spectrophotometrically by measuring the decrease in absorbance of ACBK at 524 nm. The detection limit of the method is 1.01×10-9 g/mL, and the linear range is 0-0.048 mg/L. The influence of acidity, concentration of reactants, reaction time, reaction temperature and for-eign ions is also discussed. The optimum reaction conditions were established and some kinetic parameters determined. The apparent activation energy of the catalytic reaction is 5.32 kJ/mol. The relative standard deviation for the determi-nation of titanium(IV) at the concentration of 0.048 mg/L is calculated to be 1.31% (n = 11). In combination with sol-vent extraction separation, the method has been successfully applied to the determination of trace titanium(IV) in human hair, plant matter, tea and rock samples. The results are in good agreement with the certified values with the relative standard deviations (RSD) of 1.4%-3.5%.

  1. Foliar application of amino acids modulates aroma components of 'FUJI' apple (malus domestica L.)

    Volatile flavor compounds play a key role in determining the perception and acceptability as well as enhancing market competitiveness of apple (Malus domestica L.). In our study, we evaluated the effects of foliar-applied four different amino acids, i.e. leucine (Leu), isoleucine (Ile), valine (Val) and alanine (Ala), on aroma components and two key enzymes activities involved in aroma metabolism of Fuji apple. The total amount of aromatic components under Ala treatment was significantly higher than those under other treatments. There was a considerable increase in total aroma content, including hexanal, 2-methyl-butanol, nonanal, (E)-2-hexenal, methyleugenol, ethyl acetate, butanoic acid-pentyl ester, butanoic acid-hexyl ester, butyric acid ethyl ester, acetic acid-2-methyl-butyl ester, treated with spraying amino acids compared with the control. More specifically, hexanal, 2-methyl-butanol, methyleugenol and acetic acid-2-methyl-butyl ester exhibited a greater substantial increase of their contents than those of in other ingredients. However, butanoic acid-2-methyl-2-methyl butyl ester maintained a highest level among all aroma components regardless of different amino acids application. Furthermore, the activities of alcohol dehydrogenase (ADH) and alcohol acyltransferase (AAT) were much higher under Ala treatment than those under other treatments. We concluded that foliar-applied organic nitrogen (N), especially for Ala, can improve aroma metabolism and it could be used in production to enhance fruit quality on a commercial scale. (author)

  2. Kinetics and mechanism of oxidation of chloramphenicol by 1-chlorobenzotriazole in acidic medium

    R C Hiremath; R V Jagadeesh; Puttaswamy; S M Mayanna

    2005-07-01

    Chloramphenicol (CAP) is an antibiotic drug having a wide spectrum of activity. The kinetics of oxidation of chloramphenicol by 1-chlorobenzotriazole (CBT) in HClO4 medium over the temperature range 293-323 K has been investigated. The reaction exhibits first-order kinetics with respect to [CBT]o and zero-order with respect to [CAP]o. The fractional-order dependence of rate on [H+] suggests complex formation between CBT and H+. It fails to induce polymerization of acrylonitrile under the experimental conditions employed. Activation parameters are evaluated. The observed solvent isotope effect indicates the absence of hydride transfer during oxidation. Effects of dielectric constant and ionic strength of the medium on the reaction rate have been studied. Oxidation products are identified. A suitable reaction scheme is proposed and an appropriate rate law is deduced to account for the observed kinetic data.

  3. Whole-body DHA synthesis-secretion kinetics from plasma eicosapentaenoic acid and alpha-linolenic acid in the free-living rat.

    Metherel, Adam H; Domenichiello, Anthony F; Kitson, Alex P; Hopperton, Kathryn E; Bazinet, Richard P

    2016-09-01

    Whole body docosahexaenoic acid (DHA, 22:6n-3) synthesis from α-linolenic acid (ALA, 18:3n-3) is considered to be very low, however, the daily synthesis-secretion of DHA may be sufficient to supply the adult brain. The current study aims to assess whether whole body DHA synthesis-secretion kinetics are different when comparing plasma ALA versus eicosapentaenoic acid (EPA, 20:5n-3) as the precursor. Male Long Evans rats (n=6) were fed a 2% ALA in total fat diet for eight weeks, followed by surgery to implant a catheter into each of the jugular vein and carotid artery and 3h of steady-state infusion with a known amount of (2)H-ALA and (13)C-eicosapentaenoic acid (EPA, 20:5n3). Blood samples were collected at thirty-minute intervals and plasma enrichment of (2)H- and (13)C EPA, n-3 docosapentaenoic acid (DPAn-3, 22:5n-3) and DHA were determined for assessment of synthesis-secretion kinetic parameters. Results indicate a 13-fold higher synthesis-secretion coefficient for DHA from EPA as compared to ALA. However, after correcting for the 6.6 fold higher endogenous plasma ALA concentration, no significant differences in daily synthesis-secretion (nmol/day) of DHA (97.6±28.2 and 172±62), DPAn-3 (853±279 and 1139±484) or EPA (1587±592 and 1628±366) were observed from plasma unesterified ALA and EPA sources, respectively. These results suggest that typical diets which are significantly higher in ALA compared to EPA yield similar daily DHA synthesis-secretion despite a significantly higher synthesis-secretion coefficient from EPA. PMID:27263420

  4. Thermal Behavior and Non-isothermal Kinetics of the Polyoxometalate of Ciprofloxacin with Tungstophosphoric Acid

    WANG Dunjia; FANG Zhengdong; LU Lianying

    2007-01-01

    The polyoxometalate (CPFX-HCl)3H3PW12O40·8H2O was prepared and characterized by elemental analysis, IR spectra and TG-DTA-DTG. The thermal decomposition mechanism and non-isothermal kinetic parameters of the polyoxometalate were obtained from the analysis of TG-DTG data using the Achar equation, Coats-Redfern equation (CR), Madhusudanan-Krishnan-Ninan equation (MKN) and Horowitz-Metzger equation (HM). And their mathematical expressions of the kinetic compensation effect were also calculated.

  5. Principal component articial neural network calibration models for the simultaneous spectrophotometric estimation of mefenamic acid and paracetamol in tablets

    RAJAPPAN MANAVALAN; KAMARAJAN KANNAN; DONDETI SATYANARAYANA

    2006-01-01

    Simultaneous estimation of all drug components in a multicomponent analgesic dosage form with artificial neural networks calibration models using UV spectrophotometry is reported as a simple alternative to using separate models for each component. Anovel approach for calibration using a compund spectral dataset derived from three spectra of each component is described. The spectra of mefenamic acid and paracetamol were recorded as several concentrations within their linear range and used to c...

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

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

    2005-07-01

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

  7. Kinetics of mass transfer on a drop bundle in the system uranyl nitrate nitric acid/tributyl phosphate, kerosene

    The dissertation discusses the kinetics of the coupled exchange of nitric acid and uranyl nitrate between water and tributylphosphate-burdened kerosene. Preliminary to column design, mass exchange measurements were carried out on a monodisperse droplet bundle according to a method not described so far. The concentration range investigated, i.e. 1x10-5 2(NO3)2 -1 kmol/m3, HNO3 = 2,4 kmol/m3, TBP = 30 Vol.% (TBP-Tributylphosphat), meets the technical standards. (orig.)

  8. Identification of significant medium components that affect docosahexaenoic acid production by Schizochytrium sp. SW1

    Manikan, Vidyah; Hamid, Aidil A.

    2013-11-01

    Central composite design (CCD) was employed to investigate the significance of glucose, yeast extract, MSG and sea salt in affecting the amount of docosahexaenoic acid (DHA) accumulated by a locally isolated strain of Schizochytrium. Design Expert software was used to construct a set of experiments where each medium component mentioned above was varied over three levels. Cultivation was carried out in 250mL flasks containing 50mL of medium, incubated at 30°C with 200 rpm agitation for 96 hours. ANOVA was conducted to identify the influential factors and the level of their significance where factors that scored a probability value of less than 0.05 were considered significant. The level of influence for each independent variable was also interpreted using perturbation whereas pattern of interaction between the factors were interpreted using interaction plots. This experiment revealed that yeast extract and monosodium glutamate have significant influence on DHA accumulation process by Schizochytrium sp. SW1.

  9. Influence of Organic Acids on Diltiazem HCl Release Kinetics from Hydroxypropyl Methyl Cellulose Matrix Tablets.

    Sateesha, Sb; Rajamma, Aj; Narode, Mk; Vyas, Bd

    2010-07-01

    The matrix tablets of diltiazem hydrochloride were prepared by direct compression using hydroxypropyl methyl cellulose (HPMC) and various amounts (2.5%, 5.0%, 10% and 20%) of citric acid, malic acid and succinic acid. The characterization of physical mixture of drug and organic acids was performed by Infra-red spectroscopy. An organic acid was incorporated to set up a system bringing about gradual release of this drug. The influence of organic acids on the release rate were described by the Peppas equation: M (t) /M(∞) = Kt (n) and Higuchi's equation: Q (t) = K(1)t(1/2). The addition of organic acids and the pH value of medium could notably influence the dissolution behavior and mechanism of drug-release from matrices. Increasing amounts of organic acid produced an increase in drug release rate, which showed a good linear relationship between contents of organic acid and drug accumulate release (%) in phosphate buffer, pH 7.4. The drug release increased significantly (P < 0.05) with use of succinic acid in tablet formulation. Increasing amounts of succinic acid above 10% produced decreasing values of n and increasing values of k, in a linear relationship, which indicated there was a burst release of drug from the matrix. Optimized formulations are found to be stable upon 3-month study. PMID:21042476

  10. Mechanism of oxovanadium (IV)-catalysed and uncatalysed bromate oxidation of lactic acid in acid medium: evaluation of composite and individual kinetic and thermodynamic parameters

    Uncatalysed acid bromate oxidation of lactic acid (LA) exhibits fractional order (1.6) in [acid] and first order each in [Br(V)] and [LA]. Kinetic isotope effect (kH/kD=1) is absent, however an inverse solvent isotope effect (kH2O/kD2O=1.78 at 313 K) is observed. The mechanism proposed consists of a rate determining formation of bromate ester due to the nucleophilic attack by the alcoholic/hydroxyl group at the bromine atom of HOBrO2/H2O2Br+O, followed by a fast disproportionation of the ester through C-C bond cleavage to form products. Oxovanadium(IV)-catalysed LA-Br(V) reaction exhibits second order in [acid], fractional order in [lactic acid] and first order each in [VOSO4] and [oxidant]. The envisaged mechanism assumes a ternary complex formation involving a binary complex of LA and V(IV) and protonated bromate, which subsequently decomposes to the intermediate/products. The rate constants involved for each step of the reactions are evaluated along with their thermodynamic parameters. (author)

  11. Carbon-13 kinetic isotope effect and its temperature dependence in the decarboxylation of lactic acid of natural isotopic composition with aqueous sulphuric acid

    Carbon-13 kinetic isotope effect in the decarboxylation of lactic acid of natural isotopic composition in sulphuric acid diluted with water in M(H2O)/M(H2SO4) molar ratio equal to 2.2 has been studied in the temperature range 80-130 C and found to be normal. The absolute values and the temperature dependence of the experimental 13C-K.I.E. are in agreement with the absolute values and the temperature dependence of the theoretical 13C-K.I.E. calculated under the assumption that one frequency corresponding to the carbon-oxygen bound broken in the decarboxylation reaction is lost in the course of activation of lactic acid molecules. The chemical side reactions leading to the abnormal temperature dependence of the carbon-13 and carbon-14 isotope fractionation, observed in the course of decarboxylation of lactic acid in concentrated sulphuric acid, have been suggested. (author). 11 refs, 1 fig., 1 tab

  12. Comparative electrochemical degradation of salicylic and aminosalicylic acids: Influence of functional groups on decay kinetics and mineralization.

    Florenza, Xavier; Garcia-Segura, Sergi; Centellas, Francesc; Brillas, Enric

    2016-07-01

    Solutions of 100 mL with 1.20 mM of salicylic acid (SA), 4-aminosalicylic acid (4-ASA) or 5-aminosalicylic acid (5-ASA) have been comparatively degraded by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were carried out with a stirred tank reactor with a BDD anode and an air-diffusion cathode for continuous H2O2 production. A marked influence of the functional groups of the drugs was observed in their decay kinetics, increasing in the order SA H2O2 and 5-ASA H2O2 H2O2 at 100 mA cm(-2). The mineralization rate in EF and PEF grew in the order: 4-ASA 98% mineralization for all the drugs at 100 mA cm(-2). Oxalic and oxamic acids were detected as final short-linear aliphatic carboxylic acids by ion-exclusion HPLC, allowing the fast photolysis of their Fe(III) complexes by UVA light to justify the high power of PEF. PMID:27045634

  13. Synthesis and myocardial kinetics of N-13 and C-11 labeled branched-chain L-amino acids

    Glutamate dehydrogenase (GDH), immobilized on CNBr-activated Sepharose supports, was used with N-13 ammonia to aminate α-ketoisocaproic acid (KIC), and α-ketoisovaleric acid (KIV) to produce N-13-labeled branched-chain L-amino acids with radiochemical yields ranging from 29% to 35%. From kinetic and practical cosiderations, pH 7.5 to 8.0 was established to be optimal for the synthesis of N-13-labeled branched-chain-L-amino acids. Myocardial time-activity curves in dogs at control, during low-flow ischemia, reperfusion, and after transaminase inhibition following intracoronary bolus injection of the N-13 labeled amino acids were biexponential. Higher retention of N-13 activity was observed in ischemic segments both during low-flow ischemia (29.2%) and reperfusion (23.2%) when compared with controls (20.0%), (n-4). On the other hand, transaminase inhibition decreased residue fractions from 21.0% at control to 13.9% (n=4). The residual activity with L-[1-11C]leucine allows for the calculation of protein synthesis rates

  14. The kinetics of the solidification of highly supersaturated solutions of palmitic acid in oleic acid: a comparison between two models

    RAMIRO RICO-MARTINEZ

    1999-08-01

    Full Text Available The crystallization of fatty acids is very important in industrial applications and biological systems. A comparison between theoretical models and experimental data helps in clarifying mechanistic aspects of these systems. In this contribution, we compare the performance of two models in fitting data from the crystallization of supersaturated solutions of palmitic acid in oleic acid. One of the models was developed by Avrami and the other is based on considering diffusion as limiting (the D-model. The D-model fitted the data better than the Avrami model in all cases. The D-model has a low value of the regression coefficient (r2, lower than 0.9 in only three cases. For these points, the thermodynamic force was smaller. Differences in the parameter n (an index of dimensionality were observed; these differences indicate that clusters were present previous to the crystallization process. Furthermore, there appears to be a difference in the mechanism of crystallization of pure solutions of palmitic acid and solutions with a small fraction of oleic acid. Thus, one is lead to the conclusion that the rate of crystallization of fatty acids at high concentrations is limited by diffusion.

  15. Leaching Kinetics of Zinc from Metal Oxide Varistors (MOVs with Sulfuric Acid

    Youngjin Kim

    2016-08-01

    Full Text Available The leaching kinetics of zinc from zinc oxide-based metal oxide varistors (MOVs was investigated in H2SO4 at atmospheric pressure. Kinetics experiments were carried out at various agitation speeds, particle sizes, initial H2SO4 concentrations, and reaction temperatures. It was determined that the leaching rate of zinc was independent of agitation speed above 300 rpm and also independent of particle size below 105 μm, whereas it dramatically increased with an increasing H2SO4 concentration. Except for when the H2SO4 concentration was varied, the m-values were almost constant at varying agitation speeds (m-values: 0.554–0.579, particle sizes (m-values: 0.507–0.560 and reaction temperature (m-values: 0.530–0.560 conditions. All of the m-values in these experiments were found to be below 0.580. Therefore, it is proposed that the extraction of zinc is a diffusion-controlled reaction. The leaching kinetics followed the D3 kinetic equation with a rate-controlling diffusion step through the ash layers, and the corresponding apparent activation energy was calculated as 20.7 kJ/mol in the temperature range of 313 K to 353 K.

  16. Ferrate promoted oxidative cleavage of sulfonamides: Kinetics and product formation under acidic conditions

    Sulfonamide-based antibiotics are often detected in surface waters and secondary wastewater effluents and pose an eminent threat for the development of antibiotic resistance bacteria and genes in aquatic environment. This paper presents the kinetics and stoichiometry of the oxid...

  17. Kinetic analysis of waste activated sludge hydrolysis and short-chain fatty acids production at pH 10

    FENG Leiyu; YAN Yuanyuan; CHEN Yinguang

    2009-01-01

    The accumulation of short-chain fatty acids (SCFAs), a preferred carbon source for enhanced biological phosphorus removal microbes, was significantly improved when waste activated sludge (WAS) was fermented at pH 10. The kinetics of WAS hydrolysis and SCFAs production at pH 10 were investigated. It was observed that during WAS anaerobic fermentation at pH 10 the accumulation of SCFAs was limited by the hydrolysis process, and both the hydrolysis of WAS particulate COD and the accumulation of SCFAs followed first-order kinetics. The hydrolysis and SCFAs accumulation rate constants increased with a increasing of temperature from 10 to 35℃, which could be described by the Arrhenius equation. The kinetic data further indicated that SCFAs production at pH 10 was a biological process. Compared with the experiment of pH uncontrolled (blank test), both the rate constants of WAS hydrolysis and SCFAs accumulation at 20℃ were significantly improved when WAS was fermented at pH 10.

  18. Chapter 4. Uranium extraction technology from wastes of uranium industry. 4.1. Sulfuric acid leaching kinetics of residues from anthropogenic deposit Map 1-9

    Present article is devoted to sulfuric acid leaching kinetics of residues from anthropogenic deposit Map 1-9. Since residues from anthropogenic deposit Map 1-9 basically contain quartz (69%), it went through acid leaching. Results of laboratory investigations on the opening degree and uranium conversion to solution were summarized. The influence of sulfuric acid consumption on uranium extraction during leaching (U = 0,018%, t =20 deg C, t = 10 hours) was considered. The kinetic and energetic parameters of residues leaching of anthropogenic deposit Map 1-9 was discussed. The basic process flow diagram of uranium industry wastes reprocessing was proposed.

  19. Kinetics and mechanism of the acid-catalyzed decomposition of omega-diazoacetophenones and their o-carbomethyoxy derivatives

    Denisova, T.G.

    1988-01-01

    The kinetics of the acid-catalyzed decomposition of omega-diazoacetophenones and their o-carbomethoxy derivatives have been studied and their rate constants and activation energies measured in dioxane-H/sub 2/O (D/sub 2/O) and aqueous (D/sub 2/O)-dioxane mixtures (40:60 by volume) in the presence of H/sub 2/SO/sub 4/ (D/sub 2/SO/sub 4/), as well as in acetic and deuteroacetic acids, in the temperature range 290-328 K. Based on the results of k/sub H//k/sub D/ and ..delta..S not identical to measurements, assumptions have been made concerning the mechanism of the catalytic decomposition of the indicated diazoketones.

  20. Study of the kinetics and mechanism of the dissolution of PUO2 by Cr(II) ion in acidic medium

    The study of the dissolution of actinides oxides is a topic of particular importance in nuclear energy production. The present study deals with the understanding of the reductive dissolution of PuO2 in sulfuric acid media under the action of Cr2+aq ion. In the first chapter of the document, crystallographic and electronic properties of PuO2 are described, followed by informations related to its dissolution in acidic media. The second chapter concerns the presentation of the different theories usable to interpret the kinetics of heterogeneous reaction and those for the understanding of electronic transfer applied to semi-conductors. With the help of the above mathematical tools an empirical law rate is established and a reactional model proposed. It appears that the electronic transfer is purely of the heterogenous nature and that the limiting step of the overall process corresponds certainly to the rupture of plutonium oxygen bond

  1. Investigation of Thermal Decomposition of Ascorbic Acid by TG-FTIR and Thermal Kinetics Analysis Shi Jingyan

    史竞艳; LIU; Yuwen; WANG; Zhiyong; WANG; Cunxin

    2014-01-01

    The thermal behavior of dry solid ascorbic acid in nitrogen atmosphere in the temperature range of 25800℃was investigated by TG-FTIR.During the thermal decomposition process,five evolved gaseous species,including H2O,CO2,CO,CH4 and HCOOH,were identified and monitored,in which HCOOH was detected for the first time.The results indicated that ascorbic acid began to decompose at 191℃.Its decomposition process consisted of three stages,and dehydration and decarboxylation to form furfural were the possible principal mechanism.The kinetic analysis for the first decomposition stage was also carried out by the isoconversional method and the master plots method.The results indicated that this process can be described by the model of 1st order reaction.

  2. Kinetic study on microwave-assisted esterification of free fatty acids derived from Ceiba pentandra Seed Oil.

    Lieu, Thanh; Yusup, Suzana; Moniruzzaman, Muhammad

    2016-07-01

    Recently, a great attention has been paid to advanced microwave technology that can be used to markedly enhance the biodiesel production process. Ceiba pentandra Seed Oil containing high free fatty acids (FFA) was utilized as a non-edible feedstock for biodiesel production. Microwave-assisted esterification pretreatment was conducted to reduce the FFA content for promoting a high-quality product in the next step. At optimum condition, the conversion was achieved 94.43% using 2wt% of sulfuric acid as catalyst where as 20.83% conversion was attained without catalyst. The kinetics of this esterification reaction was also studied to determine the influence of factors on the rate of reaction and reaction mechanisms. The results indicated that microwave-assisted esterification was of endothermic second-order reaction with the activation energy of 53.717kJ/mol. PMID:27019128

  3. Kinetic Approach to the Mechanism of Redox Reaction of Pyrocatechol Violet and Nitrite Ion in Aqueous Hydrochloric Acid

    A. Adetoro

    2011-10-01

    Full Text Available The kinetics of the oxidation of Pyrocatechol violet (PCVH by nitrite ion (NO2- in aqueous acidic medium has been studied at 24±1ºC, I = 0.50 mol/dm3(NaCl, [H+] = 1.0×10-3 mol/dm3. The reaction is first order to [PCVH] and half order to [NO2-]. The redox reaction displayed a 1:1 stoichiometry and obeys the rate law: d[PCVH]/dt = (a + b[H+] [PCVH][NO2-]½. The second-order rate constant increases with increase in acid concentration and ionic strength. This system displayed positive salt effect while spectroscopic investigation and Michaelis-Menten plot showed evidence of intermediate complex formation in the course of the reaction. A plausible mechanism has been proposed for the reaction.

  4. Kinetics for the synthetic bile acid 75-selenohomocholic acid-taurine in humans: comparison with [14C]taurocholate

    The apparent fractional turnover rate of the gamma-labeled bile acid analogue 75-selenohomocholic acid-taurine (75-SeHCAT) was assessed from decline in radioactivity over the gallbladder area on 4 successive days using a gamma-camera, and was compared in the same subjects with the fractional turnover rate of the corresponding natural bile acid, cholic acid-taurine, labeled with 14C ([14C]CAT) using the classical Lindstedt technique. Very similar results were obtained in 5 healthy individuals (coefficient of variation 4.8%, medians 0.35 and 0.34, respectively). By contrast, the fractional deconjugation rate assessed from zonal scanning of glycine- and taurine-conjugated bile acids on thin-layer chromatography was much less for 75-SeHCAT than for [14C]CAT (0.02 and 0.13, respectively; p less than 0.05). The fractional rate for deconjugation plus dehydroxylation was also determined by zonal scanning, and gave lower values for 75-SeHCAT than for [14C]CAT (0.02 and 0.12, respectively; p less than 0.05). There was a striking similarity between the fractional rate for deconjugation alone and that for deconjugation plus dehydroxylation for both bile acids in individual samples (r = 0.999, p less than 0.001), suggesting that these two processes might occur simultaneously and probably involve the same bacteria. We conclude that our scintiscanning technique provides an accurate, noninvasive method of measuring fractional turnover rate of a bile acid in humans, and that the finding that 75SeHCAT remains conjugated with taurine during enterohepatic recycling means that absorption should be specific for the ileal active transport site, thus rendering it an ideal substance for assessing ileal function

  5. L-Lactate-mediated Dynamic Kinetic Resolution of α-Bromo Esters for Asymmetric Syntheses of α-Amino Acid Derivatives

    Kim, Yelim; Park, Kon Ji; Choi, Yun Soo; Lee, Myungsu; Park, Yong Sun [Konkuk Univ., Seoul (Korea, Republic of)

    2013-08-15

    We conclude that ethyl L-lactate is an effective and convenient chiral auxiliary for dynamic kinetic resolution of α-bromo esters in nucleophilic substitution with various amine nucleophiles. The methodology can provide a general procedure for asymmetric syntheses of dihydroquinoxalinones, dihydrobenzoxazinones and 1,1'-iminodicarboxylic acid derivatives. Simple and easy procedure in obtaining highly enantioenriched α-amino acid derivatives suggests that the dynamic kinetic resolution approach should be further developed. For asymmetric synthesis of α-substituted carboxylic acid derivatives, a variety of chiral auxiliaries have been used for the dynamic resolution of α-halo esters in nucleophilic substitution.1 For example, L-lactamide-mediated dynamic kinetic resolution of α-bromo esters was successfully used for the asymmetric preparation of α-aryloxy carboxylic acids and oxazin-2-ones.

  6. L-Lactate-mediated Dynamic Kinetic Resolution of α-Bromo Esters for Asymmetric Syntheses of α-Amino Acid Derivatives

    We conclude that ethyl L-lactate is an effective and convenient chiral auxiliary for dynamic kinetic resolution of α-bromo esters in nucleophilic substitution with various amine nucleophiles. The methodology can provide a general procedure for asymmetric syntheses of dihydroquinoxalinones, dihydrobenzoxazinones and 1,1'-iminodicarboxylic acid derivatives. Simple and easy procedure in obtaining highly enantioenriched α-amino acid derivatives suggests that the dynamic kinetic resolution approach should be further developed. For asymmetric synthesis of α-substituted carboxylic acid derivatives, a variety of chiral auxiliaries have been used for the dynamic resolution of α-halo esters in nucleophilic substitution.1 For example, L-lactamide-mediated dynamic kinetic resolution of α-bromo esters was successfully used for the asymmetric preparation of α-aryloxy carboxylic acids and oxazin-2-ones

  7. Esterification of Oleic Acid for Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation

    Marcio J. da Silva; Abiney L. Cardoso; Soraia Cristina Gonzaga Neves

    2008-01-01

    The production of biodiesel from low-cost raw materials which generally contain high amounts of free fatty acids (FFAs) is a valuable alternative that would make their production costs more competitive than petroleum-derived fuel. Currently, the production of biodiesel from this kind of raw materials comprises a two-stage process, which requires an initial acid-catalyzed esterification of the FFA, followed by a basecatalyzed transesterification of the triglycerides. Commonly, the acid H2SO4 i...

  8. Potential origin and formation for molecular components of humic acids in soils

    Hatcher, Patrick; DiDonato, Nicole; Waggoner, Derek

    2016-04-01

    humification. The less humified samples contain relatively more components having a relationship to lignin. The more humified samples are composed of relatively more molecular formulas in the CCAM and condensed aromatic regions and also contain relatively more carboxylated molecular formulas than the less humified samples. To explain the molecular formulas observed we propose a humification process that involves photo- or microbially-generated reactive oxygen species in soils which are responsible for transforming the materials supplied to soil as fresh organic matter, mainly lignin, to the molecules observed in ESI-FTICR-MS data. When plotted on the van Krevelen diagram, the H/C and O/C ratios of molecular formulas from humic acids predictably plot in the same regions as the newly produced formulas discovered by Chen, et al. (2014) when natural organic matter was photoirradiated or when lignin-derived humics were subjected to Fenton chemistry (Waggoner et al., 2015). References: Chen H., Abdulla H.A.N., Sanders R.L., Myneni S.C.B., Mopper K. and Hatcher P.G. (2014) Production of Black Carbon-like and Aliphatic Molecules from Terrestrial Dissolved Organic Matter in the Presence of Sunlight and Iron. Environmental Science & Technology Letters 1, 399-404. Waggoner D.C., Chen H., Willoughby A.S. and Hatcher P.G. (2015) Formation of black carbon-like and alicyclic aliphatic compounds by hydroxyl radical initiated degradation of lignin. Organic Geochemistry 82, 69-76.

  9. Light-absorbing aldol condensation products in acidic aerosols: Spectra, kinetics, and contribution to the absorption index

    Nozière, Barbara; Esteve, William

    The radiative properties of aerosols that are transparent to light in the near-UV and visible, such as sulfate aerosols, can be dramatically modified when mixed with absorbing material such as soot. In a previous work we had shown that the aldol condensation of carbonyl compounds produces light-absorbing compounds in sulfuric acid solutions. In this work we report the spectroscopic and kinetic parameters necessary to estimate the effects of these reactions on the absorption index of sulfuric acid aerosols in the atmosphere. The absorption spectra obtained from the reactions of six different carbonyl compounds (acetaldehyde, acetone, propanal, butanal, 2-butanone, and trifluoroacetone) and their mixtures were compared over 190-1100 nm. The results indicated that most carbonyl compounds should be able to undergo aldol condensation. The products are oligomers absorbing light in the 300-500 nm region where few other compounds absorb, making them important for the radiative properties of aerosols. Kinetic experiments in 96-75 wt% H 2SO 4 solutions and between 273 and 314 K gave an activation energy for the rate constant of formation of the aldol products of acetaldehyde of -(70±15) kJ mol -1 in 96 wt% solution and showed that the effect of acid concentration was exponential. A complete expression for this rate constant is proposed where the absolute value in 96 wt% H 2SO 4 and at 298 K is scaled to the Henry's law coefficient for acetaldehyde and the absorption cross-section for the aldol products assumed in this work. The absorption index of stratospheric sulfuric acid aerosols after a 2-year residence time was estimated to 2×10 -4, optically equivalent to a content of 0.5% of soot and potentially significant for the radiative forcing of these aerosols and for satellite observations in channels where the aldol products absorb.

  10. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid

    Andri Cahyo Kumoro

    2015-03-01

    Full Text Available Acetylation is one of the common methods of modifying starch properties by introducing acetil (CH3CO groups to starch molecules at low temperatures. While most acetylation is conducted using starch as anhidroglucose source and acetic anhydride or vinyl acetate as nucleophilic agents, this work employ reactants, namely flour and glacial acetic acid. The purpose of this work are to study the effect of pH reaction and GAA/GF mass ratio on the rate of acetylation reaction and to determine its rate constants. The acetylation of gadung flour with glacial acetic acid in the presence of sodium hydroxide as a homogenous catalyst was studied at ambient temperature with pH ranging from 8-10 and different mass ratio of acetic acid : gadung flour (1:3; 1:4; and 1:5. It was found that increasing pH, lead to increase the degree of substitution, while increasing GAA/GF mass ratio caused such decreases in the degree of substitution, due to the hydrolysis of the acetylated starch. The desired starch acetylation reaction is accompanied by undesirable hydrolysis reaction of the acetylated starch after 40-50 minutes reaction time. Investigation of kinetics of the reaction observed that the value of mass transfer rate constant (Kcs is smaller than the surface reaction rate constant (k. Thus, it can be concluded that rate controlling step is mass transfer.  © 2015 BCREC UNDIP. All rights reservedReceived: 7th August 2014; Revised: 8th September 2014; Accepted: 14th September 2014How to Cite: Kumoro, A.C., Amelia, R. (2015. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 30-37. (doi:10.9767/bcrec.10.1.7181.30-37Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7181.30-37

  11. Membrane omega-3 fatty acids modulate the oligomerisation kinetics of adenosine A2A and dopamine D2 receptors

    Guixà-González, Ramon; Javanainen, Matti; Gómez-Soler, Maricel; Cordobilla, Begoña; Domingo, Joan Carles; Sanz, Ferran; Pastor, Manuel; Ciruela, Francisco; Martinez-Seara, Hector; Selent, Jana

    2016-01-01

    Membrane levels of docosahexaenoic acid (DHA), an essential omega-3 polyunsaturated fatty acid (ω-3 PUFA), are decreased in common neuropsychiatric disorders. DHA modulates key cell membrane properties like fluidity, thereby affecting the behaviour of transmembrane proteins like G protein-coupled receptors (GPCRs). These receptors, which have special relevance for major neuropsychiatric disorders have recently been shown to form dimers or higher order oligomers, and evidence suggests that DHA levels affect GPCR function by modulating oligomerisation. In this study, we assessed the effect of membrane DHA content on the formation of a class of protein complexes with particular relevance for brain disease: adenosine A2A and dopamine D2 receptor oligomers. Using extensive multiscale computer modelling, we find a marked propensity of DHA for interaction with both A2A and D2 receptors, which leads to an increased rate of receptor oligomerisation. Bioluminescence resonance energy transfer (BRET) experiments performed on living cells suggest that this DHA effect on the oligomerisation of A2A and D2 receptors is purely kinetic. This work reveals for the first time that membrane ω-3 PUFAs play a key role in GPCR oligomerisation kinetics, which may have important implications for neuropsychiatric conditions like schizophrenia or Parkinson’s disease.

  12. Polarographic study of electroreduction kinetics of molybdenum(6) complexes in acid solutions of sodium sulfate

    Electroreduction kinetics of molybdenum(6) complexes under 0.6-4.1 pH at presence of 1 MNa2SO4 is studied by means of polarographic technique. Three polarographic wave are obtained at CMo(6) = 2x10-5 - 2x10-4 mole/l concentration. First one of them is corresponded by adsorption limiting current on the basis of which the value of surface per one molybdenum (5) complex adsorbed on mercury is calculated. The second one is corresponded by diffusion limiting current on the basis of which diffusion factor of single-nuclear complex of molybdenum(5) participating in single-electron reaction is calculated. The third wave is a kinetic one. Effect of molybdenum(5) concentration and pH solution on the character of the first and the second waves is discussed

  13. Kinetics of tetracycline, oxytetracycline, and chlortetracycline adsorption and desorption on two acid soils

    Fernandez Calviño, David; Bermúdez-Couso, Alipio; Arias-Estévez, Manuel;

    2015-01-01

    The purpose of this work was to quantify retention/release of tetracycline, oxytetracycline, and chlortetracycline on two soils, paying attention to sorption kinetics and to implications of the adsorption/desorption processes on transfer of these pollutants to the various environmental compartments...... tetracycline > oxytetracycline > chlortetracycline in soil 1, with similar values for the three antibiotics and the sequence tetracycline > chlortetracycline > oxytetracycline in soil 2. The desorption sequences were oxytetracycline > tetracycline > chlortetracycline in soil 1 and oxytetracycline...... > chlortetracycline > tetracycline in soil 2. In conclusion, the SFC technique has yielded new kinetic data regarding tetracycline, oxytetracycline, and chlortetracycline adsorption/desorption on soils, indicating that it can be used to shed further light on the retention and transport processes affecting antibiotics...

  14. Observation of the Unusual Aggregation Kinetics of Colloidal Minerals in Acidic Solutions

    Rui Tian; Gang Yang; Xinmin Liu; Chengzhi Huang; Xiaodan Gao; Hang Li

    2015-06-01

    Hofmeister (Specific ion) effects have been considered as important to chemical science as Mendel’s work was to genetics. In this work, the aggregation kinetics of montmorillonite colloids in H+, Ag+, NH$^{+}_{4}$, K+ and Na+ solutions were measured in situ, detecting the unusual kinetics and ion specificity for H+. Activation energies that can quantitatively estimate the underlying specific ion effects change in the order of H+ < Ag+ < NH$^{+}_{4}$ < K+ < Na+. Meanwhile, it was found that although the aggregation of montmorillonite colloids with lower particle densities results in higher activation energies, Hofmeister series will not be affected. It was sufficiently testified that interaction energies of colloidal particles with adsorbed ions show fine correlation with activation energies for colloidal aggregation, and larger interaction energy corresponds to lower activation energy. An attempt was made to quantitatively estimate the ion specificity for H+, and it was substantialized that the unusual ion specificity of H+ is caused by steric effect.

  15. Biodegradation kinetics of picric acid by Rhodococcus sp.NJUST16 in batch reactors

    Biological degradation of 2,4,6-trinitrophenol (TNP) by Rhodococcus sp.NJUST16 in mineral salt medium was investigated in shake-flask experiments at pH of 7.0 and 30oC, over a wide range of initial TNP concentration (20-800 mg l-1). The TNP was observed to be the inhibitory compound. For the studied concentration range, Haldane's model could be fitted to the growth kinetics data well with the kinetic constants μmax = 0.2362 h-1, Ks = 9.9131 mg l-1 and Ki = 362.7411 mg l-1. Further, the variation of observed yield coefficient Y with initial TNP concentration and the decay coefficient were investigated. It is our view that the above information would be useful for modeling and designing the units treating TNP-containing wastewaters.

  16. Kinetic modeling of dissolution of salicylic acid with in situ ATR UV-vis spectroscopy

    Hsieh, Chun; Billeter, Julien; McNally, Mary Ellen; Hoffman, Ronald; Gemperline, Paul

    2011-01-01

    Process Analytical Technologies (PAT) recommended by the Food and Drug Administration (FDA) have significantly increased during the past years in the design, control and monitoring of pharmaceutical manufacturing processes [1]. Nowadays PAT is also commonly used in Good Manufacturing Practices (GMP). Some PAT techniques employ on-line fiber-optic sensors to acquire non-destructive measurements of physical properties, kinetic information about dissolved molecule and solid fraction of particles...

  17. Seasonal changes of exogenic amino acids concentration and kinetics of their assimilation in the water of lake Drukshiai - the cooler of Ignalina NPP in 1994

    Concentration of free and combined amino acids in the surface water of lake Drukshiai - the cooler of Ignalina NPP was determined. The direct connection between the concentration of free amino acids and domination of blue-green algae in planktocenosis was observed. Accordingly to kinetic indices of 14C - glutaminic acid uptake maximum assimilation rate and circulation time - lake Drukshiai may be ascribed to mezotrophic type with distinct areas of eutrophication. (author). 6 refs., 1 tab., 5 figs

  18. Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin

    Amrit Pal Toor

    2011-05-01

    Full Text Available Esters are an important pharmaceutical intermediates and very useful perfumery agents. In this study the esterification of acetic acid with n-butanol and iso-butanol over an acidic cation exchange resin, Amberlyst 15 were carried out. The effects of certain parameters such as temperature, catalyst loading, initial molar ratio between reactants on the rate of reaction were studied. The experiments were conducted in a stirred batch reactor in the temperature range of 351.15 K to 366.15K.Variation of parameters on rate of reaction demonstrated that the reaction was intrinsically controlled.The activation energy for the esterification of acetic acid with n-butanol and iso butanol is found to be 28.45 k J/mol and 23.29 kJ/mol respectively. ©2011 BCREC UNDIP. All rights reserved.(Received: 16th December 2010, Revised: 19th March 2011; Accepted: 7th April 2011[How to Cite: A.P. Toor, M. Sharma, G. Kumar, and R. K. Wanchoo. (2011. Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 23-30. doi:10.9767/bcrec.6.1.665.23-30][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.6.1.665.23-30 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/665 ] | View in 

  19. Addition and elimination kinetics in OH radical induced oxidation of phenol and cresols in acidic and alkaline solutions

    The rates of the two consecutive reactions, OH radical addition and H2O/OH- elimination, were studied by pulse radiolysis in highly acidic (pH=1.3-1.9) and alkaline (pH∼11) solutions, respectively, for phenol and for the three cresol isomers. The rate coefficient of the addition as measured by the build-up of phenoxyl radical absorbance and by a competitive method is the same (1.4±0.1)x1010 mol-1 dm3 s-1 both in acidic and alkaline solution. The rate coefficient of the H2O elimination in acidic solution is (1.6±0.2)x106 s-1, whereas the coefficient of the OH- elimination in alkaline solutions is 6-8 times higher. The kinetics of the phenoxyl radical formation was described by the two-exponential equation of the consecutive reactions: the first exponential is related to the pseudo-first-order addition, while the second to the elimination reaction. No considerable structure dependence was found in the rate coefficients, indicating that the methyl substitutent in these highly acidic or alkaline solutions influences neither the addition nor the elimination rate

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

    Cetrizine dihydrochloride (CTZH) is widely used as an anti-allergic drug. Sodium N-bromo-p-toluenesulfonamide or bromamine-T (BAT) is the bromine analogue of chloramine-T (CAT) and is found to be a better oxidizing agent than CAT. In the present research, the kinetics of oxidation of CTZH with BAT in acid and alkaline media was studied at 313 K. The experimental rate laws obtained are: -d[BAT]/dt = k[BAT] [CTZH]0.80[H+]-0.48 in acid medium and -d[BAT]/dt = k[BAT][CTZH]0.48[OH-]0.52[PTS]-0.40 in alkaline medium where PTS is p-toluenesulfonamide. Activation parameters and reaction constants were evaluated. The solvent isotope effect was studied using D2O. The dielectric effect is positive. The stoichiometry of the reaction was found to be 1:1 and the oxidation products were identified as 4-chlorobenzophenone and (2-piperazin-1-yl-ethoxy)-acetic acid in both media. The rate of oxidation of CTZH is faster in acid medium. Suitable mechanisms and related rate laws have been worked out

  1. Equilibrium, kinetic and thermodynamic studies of acid Orange 52 dye biosorption by Paulownia tomentosa Steud. leaf powder as a low-cost natural biosorbent.

    Deniz, Fatih; Saygideger, Saadet D

    2010-07-01

    The biosorption of Acid Orange 52 onto the leaf powder of Paulownia tomentosa Steud. was studied in a batch adsorption system to estimate the equilibrium, kinetic and thermodynamic parameters as a function of solution pH, biosorbent concentration, dye concentration, biosorbent size, temperature and contact time. The Langmuir, Freundlich and Temkin isotherm models were used for modeling the biosorption equilibrium. The experimental equilibrium data could be well interpreted by the Temkin and Langmuir isotherms with maximum adsorption capacity of 10.5 mg g(-1). In order to state the sorption kinetics, the fits of pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion kinetic models were investigated. It was obtained that the biosorption process followed the pseudo-second order rate kinetics. Thermodynamic studies indicated that this system was exothermic process. The results revealed that P. tomentosa leaf powder could be an efficient biosorbent for the treatment of wastewater containing Acid Orange 52. PMID:20194017

  2. On-Chip Microfluidic Components for In Situ Analysis, Separation, and Detection of Amino Acids

    Zheng, Yun; Getty, Stephanie; Dworkin, Jason; Balvin, Manuel; Kotecki, Carl

    2013-01-01

    The Astrobiology Analytical Laboratory at GSFC has identified amino acids in meteorites and returned cometary samples by using liquid chromatography-electrospray ionization time-of-flight mass spectrometry (LCMS). These organic species are key markers for life, having the property of chirality that can be used to distinguish biological from non-biological amino acids. One of the critical components in the benchtop instrument is liquid chromatography (LC) analytical column. The commercial LC analytical column is an over- 250-mm-long and 4.6-mm-diameter stainless steel tube filled with functionized microbeads as stationary phase to separate the molecular species based on their chemistry. Miniaturization of this technique for spaceflight is compelling for future payloads for landed missions targeting astrobiology objectives. A commercial liquid chromatography analytical column consists of an inert cylindrical tube filled with a stationary phase, i.e., microbeads, that has been functionalized with a targeted chemistry. When analyte is sent through the column by a pressurized carrier fluid (typically a methanol/ water mixture), compounds are separated in time due to differences in chemical interactions with the stationary phase. Different species of analyte molecules will interact more strongly with the column chemistry, and will therefore take longer to traverse the column. In this way, the column will separate molecular species based on their chemistry. A lab-on-chip liquid analysis tool was developed. The microfluidic analytical column is capable of chromatographically separating biologically relevant classes of molecules based on their chemistry. For this analytical column, fabrication, low leak rate, and stationary phase incorporation of a serpentine microchannel were demonstrated that mimic the dimensions of a commercial LC column within a 5 10 1 mm chip. The microchannel in the chip has a 75- micrometer-diameter oval-shaped cross section. The serpentine

  3. Differential effect of impaired renal function on the kinetics of clavulanic acid and amoxicillin.

    Horber, F. F.; Frey, F J; Descoeudres, C; Murray, A T; Reubi, F C

    1986-01-01

    Amoxicillin and clavulanic acid are prescribed as a fixed drug combination. The purpose of the present study was to assess the influence of various degrees of renal insufficiency (glomerular filtration rate [GFR], less than 5 to greater than 75 ml/min per 1.73 m2) on the pharmacokinetics of amoxicillin and clavulanic acid following oral (500 and 125 mg of amoxicillin and clavulanic acid, respectively) and intravenous (1,000 and 200 mg, respectively) dosing. The volume of distribution and the ...

  4. A kinetic model for the competitive reactions of ozone with amino acid residues in proteins in reverse micelles

    Pryor, W.A.; Uppu, R.M. (Louisiana State Univ., Baton Rouge (United States))

    1993-02-15

    Lysozyme and 10 other proteins are solubilized in reverse micelles formed by 0.1 M sodium di-2-ethyl-hexylsulfosuccinate and 2.0-2.5 M water (pH 7.4) in isooctane solvent. Exposure of the protein-containing reverse micellar solutions to ozone causes oxidative damage to the proteins, as assessed by the oxidation of tryptophan residues. The oxidation product of the protein-bound tryptophan has a molar absorption coefficient of 3275 +/- 81 M-1 cm-1 (mean +/- S.D., n = 6) at 320 nm. The product is suggested to be a Criegee ozonide or a tautomer of the Criegee ozonide and not N-formylkynurenine. Ozonation of lysozyme in reverse micelles results in the formation of hydrogen peroxide in yields of only approximately 0.07 mol/mol of tryptophan residues oxidized. The recovery of hydrogen peroxide added as an internal standard to the lysozyme-containing reverse micellar solutions ranges from 84 to 88%, whether or not the samples are subjected to ozonation. This suggests that hydrogen peroxide is neither destroyed during the process of ozonation nor consumed by the protein to a significant extent in an adventitious reaction. A kinetic model for the overall reaction of ozone with the proteins is developed, taking into account the concentrations and the reactivities of individual amino acid residues toward ozone. The model predicts the fractional reaction of ozone with tryptophan residues in the proteins, despite differences in amino acid composition, molecular weight, and tertiary structures. The lack of influence of protein structure is confirmed further by the observation that the native lysozyme (with and without external S-carboxymethylcysteine) and S-carboxymethylated lysozyme give identical values of the fractional reaction of ozone with tryptophan residues. The kinetic equations for the competitive reactions of ozone with amino acid residues in proteins, with some minor modification, are applicable to ozonations on complex mixtures of lipids, proteins, and antioxidants.

  5. The thermal decomposition of N,N-dimethyl-3-oxa-glutaramic acid and the kinetics of its second-stage thermal decomposition reaction

    SUN DaZhi; CHEN Jing

    2008-01-01

    N,N-dimethyl-3-oxa-glutaramic acid was purified and characterized by 1H-NMR, Fourier transform in-frared spectroscopy (FT-IR) and elemental analysis. The thermal decomposition of the title compound was studied by means of thermogravimetry differential thermogravimetry (TG-DTG) and FT-IR. The ki-netic parameters of its second-stage decomposition reaction were calculated and the decomposition mechanism was discussed. The kinetic model function in a differential form, apparent activation energy

  6. Thermoanalytical Study and Kinetics of New 8-Hydroxyquinoline 5-sulphonic Acid-Oxamide-Formaldehyde Terpolymer Resins

    Singru, Rajesh N.; Anil B. Zade; Gurnule, Wasudeo B.

    2009-01-01

    The terpolymer resins (8-HQ5-SAOF) have been synthesized by the condensation of 8-hydroxyquinoline 5-sulphonic acid (8-HQ5-SA) and oxamide (O) with formaldehyde (F) in the presence of acid catalyst and using varied molar proportion of the reacting monomers. The synthesized terpolymer resins have been characterized by different physico-chemical techniques. Thermogravimetric analysis of all terpolymer resins in present study have been carried out by non-isothermal thermogravimetric analysis tec...

  7. Characterization of Fatty Acid, Amino Acid and Volatile Compound Compositions and Bioactive Components of Seven Coffee (Coffea robusta Cultivars Grown in Hainan Province, China

    Wenjiang Dong

    2015-09-01

    Full Text Available Compositions of fatty acid, amino acids, and volatile compound were investigated in green coffee beans of seven cultivars of Coffea robusta grown in Hainan Province, China. The chlorogenic acids, trigonelline, caffeine, total lipid, and total protein contents as well as color parameters were measured. Chemometric techniques, principal component analysis (PCA, hierarchical cluster analysis (HCA, and analysis of one-way variance (ANOVA were performed on the complete data set to reveal chemical differences among all cultivars and identify markers characteristic of a particular botanical origin of the coffee. The major fatty acids of coffee were linoleic acid, palmitic acid, oleic acid, and arachic acid. Leucine (0.84 g/100 g DW, lysine (0.63 g/100 g DW, and arginine (0.61 g/100 g DW were the predominant essential amino acids (EAAs in the coffee samples. Seventy-nine volatile compounds were identified and semi-quantified by HS-SPME/GC-MS. PCA of the complete data matrix demonstrated that there were significant differences among all cultivars, HCA supported the results of PCA and achieved a satisfactory classification performance.

  8. Characterization of Fatty Acid, Amino Acid and Volatile Compound Compositions and Bioactive Components of Seven Coffee (Coffea robusta) Cultivars Grown in Hainan Province, China.

    Dong, Wenjiang; Tan, Lehe; Zhao, Jianping; Hu, Rongsuo; Lu, Minquan

    2015-01-01

    Compositions of fatty acid, amino acids, and volatile compound were investigated in green coffee beans of seven cultivars of Coffea robusta grown in Hainan Province, China. The chlorogenic acids, trigonelline, caffeine, total lipid, and total protein contents as well as color parameters were measured. Chemometric techniques, principal component analysis (PCA), hierarchical cluster analysis (HCA), and analysis of one-way variance (ANOVA) were performed on the complete data set to reveal chemical differences among all cultivars and identify markers characteristic of a particular botanical origin of the coffee. The major fatty acids of coffee were linoleic acid, palmitic acid, oleic acid, and arachic acid. Leucine (0.84 g/100 g DW), lysine (0.63 g/100 g DW), and arginine (0.61 g/100 g DW) were the predominant essential amino acids (EAAs) in the coffee samples. Seventy-nine volatile compounds were identified and semi-quantified by HS-SPME/GC-MS. PCA of the complete data matrix demonstrated that there were significant differences among all cultivars, HCA supported the results of PCA and achieved a satisfactory classification performance. PMID:26389867

  9. Fundamental study of the mechanism and kinetics of cellulose hydrolysis by acids and enzymes

    Gong, C. S.; Chang, M.

    1981-02-01

    There are three basic enzymes e.g., endoglucanase (C/sub x/), exoglucanase (C1) and cellobiase comprising the majority of extracellular cellulase enzymes produced by the cellulolytic mycelial fungi, Trichoderma reesei, and other cellulolytic microorganisms. The kinetics of cellobiase were developed on the basis of applying the pseudo-steady state assumption to hydrolyze cellobiose to glucose. The results indicated that cellobiase was bjected to end-product inhibition by glucose. The kinetic modeling of exoglucanase (C1) with respect to cellodextrins was studied. Both glucose and cellobiose were found to be inhibitors of this enzyme with cellobiose being a stronger inhibitor than glucose. Similarly, endoglucanase (C/sub x) is subject to end-product inhibition by glucose. Crystallinity of the cellulose affects the rate of hydrolysis by cellulases. Hence, the changes in crystallinity of cellulose in relation to chemical pretreatment and enzyme hydrolysis was compared. The study of cellulase biosynthesis resulted in the conclusion that exo-and endo-glucanases are coinduced while cellobiase is synthesized independent of the other two enzymes.

  10. Kinetic Characterisation of a Single Chain Antibody against the Hormone Abscisic Acid: Comparison with Its Parental Monoclonal

    Badescu, George O.; Marsh, Andrew; Smith, Timothy R.; Thompson, Andrew J.; Napier, Richard M.

    2016-01-01

    A single-chain Fv fragment antibody (scFv) specific for the plant hormone abscisic acid (ABA) has been expressed in the bacterium Escherichia coli as a fusion protein. The kinetics of ABA binding have been measured using surface plasmon resonance spectrometry (BIAcore 2000) using surface and solution assays. Care was taken to calculate the concentration of active protein in each sample using initial rate measurements under conditions of partial mass transport limitation. The fusion product, parental monoclonal antibody and the free scFv all have low nanomolar affinity constants, but there is a lower dissociation rate constant for the parental monoclonal resulting in a three-fold greater affinity. Analogue specificity was tested and structure-activity binding preferences measured. The biologically-active (+)-ABA enantiomer is recognised with an affinity three orders of magnitude higher than the inactive (-)-ABA. Metabolites of ABA including phaseic acid, dihydrophaseic acid and deoxy-ABA have affinities over 100-fold lower than that for (+)-ABA. These properties of the scFv make it suitable as a sensor domain in bioreporters specific for the naturally occurring form of ABA. PMID:27023768

  11. Kinetics study on separation of cadmium from tellurium in acidic solution media using ion-exchange resins

    The feasibility of using ion-exchange resins to separate cadmium from tellurium in acidic solutions of the two metals was investigated. We studied the competitive adsorption of cadmium and tellurium in such resins under varying acid strengths and contact time. We found that low sulfuric acid strength (i.e., 0.5 M) was most effective in removing cadmium from solutions. Different ion-exchange resins were tested for their affinity for cadmium and tellurium ions. In the selected systems, the ion-exchange rate of cadmium was rapid in the first 20 min, and reached equilibrium within 2 h. The Lagergren first-order model described the kinetic data with high coefficient of determination and correlation values. At room temperatures the ion-exchange for cadmium onto the resin followed the Freundlich isotherm model. The maximum removal of cadmium obtained from batch studies using resin A was 91%. Column studies with the same resin showed a removal of cadmium of 99.99% or higher

  12. A kinetic study of plutonium dioxide dissolution in hydrochloric acid using iron (II) as an electron transfer catalyst

    Effective dissolution of plutonium dioxide has traditionally been accomplished by contact with strong nitric acid containing a small amount of fluoride at temperatures of ∼ 100 C. In spite of these aggressive conditions, PuO2 dissolution is sometimes incomplete requiring additional contact with the solvent. This work focused on an alternative to conventional dissolution in nitric acid where an electron transfer catalyst, Fe(II), was used in hydrochloric acid. Cyclic voltammetry was employed as an in-situ analytical technique for monitoring the dissolution reaction rate. The plutonium oxide selected for this study was decomposed plutonium oxalate with > 95% of the material having a particle diameter (< 70 microm) as determined by a scanning laser microscopy technique. Attempts to dry sieve the oxide into narrow size fractions prior to dissolution in the HCl-Fe(II) solvent system failed, apparently due to significant interparticle attractive forces. Although sieve splits were obtained, subsequent scanning laser microscopy analysis of the sieve fractions indicated that particle segregation was not accomplished and the individual sieve fractions retained a particle size distribution very similar to the original powder assemblage. This phenomena was confirmed through subsequent dissolution experiments on the various screen fractions which illustrated no difference in kinetic behavior between the original oxide assemblage and the sieve fractions

  13. Kinetic Studies on ferrocolumbite Concentrate by Sulfuric Acid Dissolution at Abu Rusheid Cataclastic Rocks, South Eastern Desert, Egypt

    A kinetic study of the leaching of Abu Rusheid ferrocolumbite concentrate sample in sulfuric acid media under atmospheric pressure has been investigated. The effects of reaction temperature, sulfuric acid concentration, stirring speed, particle size and solid/liquid mass ratio on the dissolution rate of ferrocolumbite were examined. It is found that the dissolution rate of ferrocolumbite significantly increases with increasing acid concentration, temperature, stirring speed and decreasing the particle size. By using 3M H2SO4 solution, about 89% of ferrocolumbite was dissolved within 140 minutes using < 0.053 mm particle size at a temperature of 75 °C and a stirring speed of 360 rpm. The experimental data were well interpreted with a shrinking core model under diffusion control through the product layer, where the following rate equation was established:1+2(1-X)-3(1-X)2/3=6uMDCAk/dr2=k2t The result of the study indicated that the leaching data fitted a diffusion model. Values of 0.7993,23.64 kJmol-1 and 1.24 X 10-3 min-1 were calculated as reaction order, activation energy and Arrhenius constant, respectively for the dissolution process.

  14. Kinetics of fast ligand exchange in excited lanthanide complexes with anions of salicylic and 5-sulfosalisylic acids

    The luminescent-kinetic spectroscopic method with a flash selective photoexcitation has been used for studying the reaction of ligand substitution with solvent molecules in complexes of electron-excited ions Tb3+(5D4) and Dysup(3+)(sup(4)Fsub(9/2) with anions of salicylic and 5-sulphosalicylic acids in water and methanol. The acidic-catalytic mechanism of this reaction in water has been established, the limiting stage of complex dissociation being the stage of proton addition to the -COO- group of the ligand proceeding at a rate of 1x1010 mol-1s-1 and 0.77x1010 mol-1xs-1 for complexes of Tb3+(5D4) in H2O and D2O. It has been shown that in an aqueous medium anions of salicylic and 5-sulphosalicylic acids behave with respect to r.e.e. ions as bidentate ligands coordinating these ions with the oxygen of the -COO- group and oxygroup whereas in methanol an additional coordination with oxygen of the oxygroup is absent

  15. The Effect of Oxygen Supply on the Dual Growth Kinetics of Acidithiobacillus thiooxidans under Acidic Conditions for Biogas Desulfurization

    Hyeong-Kyu Namgung

    2015-01-01

    Full Text Available In this study, to simulate a biogas desulfurization process, a modified Monod-Gompertz kinetic model incorporating a dissolved oxygen (DO effect was proposed for a sulfur-oxidizing bacterial (SOB strain, Acidithiobacillus thiooxidans, under extremely acidic conditions of pH 2. The kinetic model was calibrated and validated using experimental data obtained from a bubble-column bioreactor. The SOB strain was effective for H2S degradation, but the H2S removal efficiency dropped rapidly at DO concentrations less than 2.0 mg/L. A low H2S loading was effectively treated with oxygen supplied in a range of 2%–6%, but a H2S guideline of 10 ppm could not be met, even with an oxygen supply greater than 6%, when the H2S loading was high at a short gas retention time of 1 min and a H2S inlet concentration of 5000 ppm. The oxygen supply should be increased in the aerobic desulfurization to meet the H2S guideline; however, the excess oxygen above the optimum was not effective because of the decline in oxygen efficiency. The model estimation indicated that the maximum H2S removal rate was approximately 400 ppm/%-O2 at the influent oxygen concentration of 4.9% under the given condition. The kinetic model with a low DO threshold for the interacting substrates was a useful tool to simulate the effect of the oxygen supply on the H2S removal and to determine the optimal oxygen concentration.

  16. The effect of oxygen supply on the dual growth kinetics of Acidithiobacillus thiooxidans under acidic conditions for biogas desulfurization.

    Namgung, Hyeong-Kyu; Song, JiHyeon

    2015-02-01

    In this study, to simulate a biogas desulfurization process, a modified Monod-Gompertz kinetic model incorporating a dissolved oxygen (DO) effect was proposed for a sulfur-oxidizing bacterial (SOB) strain, Acidithiobacillus thiooxidans, under extremely acidic conditions of pH 2. The kinetic model was calibrated and validated using experimental data obtained from a bubble-column bioreactor. The SOB strain was effective for H2S degradation, but the H2S removal efficiency dropped rapidly at DO concentrations less than 2.0 mg/L. A low H2S loading was effectively treated with oxygen supplied in a range of 2%-6%, but a H2S guideline of 10 ppm could not be met, even with an oxygen supply greater than 6%, when the H2S loading was high at a short gas retention time of 1 min and a H2S inlet concentration of 5000 ppm. The oxygen supply should be increased in the aerobic desulfurization to meet the H2S guideline; however, the excess oxygen above the optimum was not effective because of the decline in oxygen efficiency. The model estimation indicated that the maximum H2S removal rate was approximately 400 ppm/%-O2 at the influent oxygen concentration of 4.9% under the given condition. The kinetic model with a low DO threshold for the interacting substrates was a useful tool to simulate the effect of the oxygen supply on the H2S removal and to determine the optimal oxygen concentration. PMID:25633028

  17. 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.)

  18. Kinetics studying and character of fraction of sulfur organic compounds on courses of acidic corrosion

    The effective inhibitors of acidic corrosion are organic sulphides. Specific adsorption of them passes with the participation of undivided electric pair of sulfur atom. Sour oils of South of Middle Asia in this aspect-the rich source of sulfur compounds. Sulfur compounds in the oil of South of Middle Asia presents basically as a cyclic sulfides. Sulfur compounds extracted from oil of South of Middle Asia as corrosion inhibitors didn't studies. Therefore by authors was carried out investigations on exposure of their anti corrosive nature in acid medium

  19. Kinetics of the hydrolysis of polysaccharide galacturonic acid and neutral sugars chains from flaxseed mucilage

    Happi Emaga, T.; Rabetafika, N.; Blecker, CS.; Paquot, M.

    2012-01-01

    Different hydrolysis procedures of flaxseed polysaccharides (chemical and enzymatic) were carried out with H2SO4, HCl and TFA at different acid concentrations (0.2, 1 and 2 M) and temperatures (80 and 100°C). Enzymatic and combined chemical and enzymatic hydrolyses of polysaccharide from flaxseed mucilage were also studied. Acid hydrolysis conditions (2 M H2SO4, 4 h, 100°C) are required to quantify total monosaccharide content of flaxseed mucilage. The enzymatic pathway (Pectinex™ Ultra SP) l...

  20. Kinetics and mechanisms of the acid-base reaction between NH$_3$ and HCOOH in interstellar ice analogs

    Bergner, Jennifer B; Rajappan, Mahesh; Fayolle, Edith C

    2016-01-01

    Interstellar complex organic molecules (COMs) are commonly observed during star formation, and are proposed to form through radical chemistry in icy grain mantles. Reactions between ions and neutral molecules in ices may provide an alternative cold channel to complexity, as ion-neutral reactions are thought to have low or even no energy barriers. Here we present a study of a the kinetics and mechanisms of a potential ion-generating acid-base reaction between NH$_{3}$ and HCOOH to form the salt NH$_{4}^{+}$HCOO$^{-}$. We observe salt growth at temperatures as low as 15K, indicating that this reaction is feasible in cold environments. The kinetics of salt growth are best fit by a two-step model involving a slow "pre-reaction" step followed by a fast reaction step. The reaction energy barrier is determined to be 70 $\\pm$ 30K with a pre-exponential factor 1.4 $\\pm$ 0.4 x 10$^{-3}$ s$^{-1}$. The pre-reaction rate varies under different experimental conditions and likely represents a combination of diffusion and or...

  1. Effect of humic acid on the adsorption/desorption behavior of glyphosate on goethite. Isotherms and kinetics.

    Arroyave, Jeison Manuel; Waiman, Carolina C; Zanini, Graciela P; Avena, Marcelo J

    2016-02-01

    The effects of humic acid (HA) on the adsorption/desorption of glyphosate (Gly) on goethite were investigated under pseudo equilibrium conditions by adsorption isotherms and under kinetic conditions by ATR-FTIR spectroscopy. Isotherms reveal that the attachment of Gly is almost completely inhibited by HA molecules. The opposite effect is not observed: HA adsorption is not affected by the presence of Gly. ATR-FTIR allowed the simultaneous detection of adsorbed HA and Gly during kinetic runs, revealing that HA at the surface decreases markedly the adsorption rate of Gly likely as a result of a decreased availability of sites for Gly adsorption and because of electrostatic repulsion. In addition, HA in solution increases the desorption rate of Gly. The rate law for Gly desorption could be determined giving important insights on the desorption mechanism. The herbicide is desorbed by two parallel processes: i) a direct detachment from the surface, which is first order in adsorbed Gly; and ii) a ligand exchange with HA molecules, which is first order in adsorbed Gly and first order in dissolved HA. Rate constants for both processes were quantified, leading to half-lives of 3.7 h for the first process, and 1.4 h for the second process in a 400 mg L(-1) HA solution. These data are important for modeling the dynamics of glyphosate in environmentally relevant systems, such as soils and surface waters. PMID:26657085

  2. Kinetic analysis of acid orange 7 degradation by pulsed discharge plasma combined with activated carbon and the synergistic mechanism exploration.

    Guo, He; Wang, Huijuan; Wu, Qiangshun; Zhou, Guangshun; Yi, Chengwu

    2016-09-01

    The synergistic technique of pulsed discharge plasma (PDP) and activated carbon (AC) was built to investigate the kinetics of acid orange 7 (AO7) degradation under different conditions of AC addition, electrode gap, initial pH value of solution, gas variety and gas flow rate. Emission spectra of OH and O, UV-vis absorption spectra of the AO7 solution and TOC removal were measured to illustrate the synergistic mechanism of the PDP and the AC. The obtained results indicated that the kinetic constant of AO7 degradation increased from 0.00947 min(-1) to 0.01419 min(-1) when 4 g AC was added into the PDP system; AO7 degradation was higher in the case of alkaline solution when oxygen was used as the flow gas in the PDP/AC system, 2 L/min oxygen flow was more favorable for the degradation. Results of the relative emission intensities of OH and O indicated the catalytic effect of the AC on the active species formation as well as the important role of the two radicals for the AO7 degradation. There was no new peaks appeared by the UV-vis analysis of the AO7 solution after 60 min treatment. The highest TOC removal in the PDP/AC system was 30.3%, which was achieved under the condition of 4 L/min air flow rate and 3 initial pH value. PMID:27295438

  3. Removal kinetics of antibodies against glutamic acid decarboxylase by various plasmapheresis modalities in the treatment of neurological disorders.

    Ohkubo, Atsushi; Okado, Tomokazu; Kurashima, Naoki; Maeda, Takuma; Miyamoto, Satoko; Nakamura, Ayako; Seshima, Hiroshi; Iimori, Soichiro; Sohara, Eisei; Uchida, Shinichi; Rai, Tatemitsu

    2014-06-01

    Plasmapheresis is one of the acute treatment modalities for neurological disorders associated with antibodies against glutamic acid decarboxylase (anti-GAD). However, there is little information about the removal kinetics of anti-GAD by various plasmapheresis modalities. Here, we investigated the removal rate of anti-GAD and fibrinogen (Fib) by immunoadsorption (IA), plasma exchange using a conventional plasma separator (OP-PE), and plasma exchange using a high cut-off selective membrane plasma separator (EC-PE) in two cases of anti-GAD-associated neurological diseases. In case 1, IA and OP-PE were used, and the percent reductions were as follows: anti-GAD: 38.2% and 69.1% and Fib: 67.7% and 68.2%, respectively. In case 2, OP-PE and EC-PE were used, and the percent reductions were as follows: anti-GAD: 65.8% and 48.5% and Fib: 68.5% and 19.8%, respectively. OP-PE could remove anti-GAD more efficiently than IA. Further, EC-PE could maintain coagulation factors such as Fib better than IA and OP-PE. It is important to select the appropriate plasmapheresis modality on the basis of the removal kinetics. PMID:24965288

  4. Impact of processing conditions on the kinetic of vitamin C degradation and 2-furoylmethyl amino acid formation in dried strawberries.

    Gamboa-Santos, Juliana; Megías-Pérez, Roberto; Soria, A Cristina; Olano, Agustín; Montilla, Antonia; Villamiel, Mar

    2014-06-15

    In this paper, a study on the usefulness of the determination of vitamin C together with indicators of the initial steps of Maillard reaction (2-furoylmethyl amino acids, 2-FM-AA) during the convective drying of strawberries has been carried out for the first time, paying special attention to the kinetics of degradation and formation, respectively, of both parameters. Formation of 2-FM-AA of Lys, Arg and GABA and vitamin C loss increased with time and temperature following, respectively, a zero and first-order kinetics. As supported by its lower activation energy, 2-FM-GABA (55.9 kJ/mol) and 2-FM-Lys+2-FM-Arg (58.2 kJ/mol) were shown to be slightly more sensitive indicators than vitamin C (82.1 kJ/mol). The obtained results, together with a complementary study on the rehydration ability and sensorial attributes of samples, pointed out the suitability of the convective drying system to obtain dried strawberries of high nutritive quality and bioactivity and good consumer acceptance. PMID:24491716

  5. The routes and kinetics of trichloroacetic acid uptake and elimination in Sitka spruce ( Picea sitchensis) saplings via atmospheric deposition pathways

    Heal, M. R.; Dickey, C. A.; Cape, J. N.; Heal, K. V.

    A major flux of trichloroacetic acid (TCA) to forests is via wet deposition, but the transfer of TCA into tree foliage may occur by an above- or below-ground pathway. To investigate the routes and kinetics of TCA uptake, two groups of 10 Sitka spruce saplings (with an equivalent number of controls) were exposed to a single application of 200 μg TCA in solution, either to the soil only, or sprayed as a mist to the foliage only. The needle foliage was subsequently analysed regularly for TCA for 3 months during the growing season. Significant uptake into current year ( C) needles was observed from both routes just a few days after application, providing direct evidence of an above-ground uptake route. Uptake of TCA was also observed in the previous year needle class ( C+1). Kinetic modelling of the data indicated that the half-life for within-needle elimination (during the growing season) was ˜50±30 days. Most of the applied TCA appeared to be degraded before uptake, either in the soil, or externally on the sapling foliage.

  6. Root-exuded acid phosphatase and 32Pi-uptake kinetics of wheat, rye and triticale under phosphorus starvation

    A nutrient culture experiment was conducted with cereal species viz., wheat (Triticum aestivum L.) cv. PBW-343), rye (Secale cereale L cv. R-308) and triticale (Triticale octoploide L. cv. DT-46), a hybrid of wheat and rye, to examine the genetic variation in root-exuded acid phosphatase (ACPase) activity and kinetics of 32Pi-uptake under P deficient condition. The ACPase activity was assayed in the extract (intra-) and on surface (extra-cellular) or root, using p-nitrophenyl phosphate as substrate. Significantly higher ACPase activity was observed in wheat followed by rye and triticale both on the root surface and in root extract. In general, root surface ACPase activity was 2.2-fold higher than that in root extract. A strong correlation (r2 = 0.87**) between extra and intra-cellular ACPase activity was observed. In terms of kinetic parameters, it was observed that 32Pi uptake and Imax values were significantly higher in rye while Cmin and Km were lowest compared to wheat and triticale. The dry weights of shoot, root and total plant were significantly higher in rye compared to wheat and triticale. Rye also had higher amount of total plant P content The superiority of rye over wheat and triticale in P uptake was observed mainly due to efficient Pi-uptake system, which needs further studies to ascertain the enhancement of Pi-induced high-affinity P transporter in these cereals. (author)

  7. Kinetics and microbial ecology of batch sulfidogenic bioreactors for co-treatment of municipal wastewater and acid mine drainage.

    Deng, Dongyang; Weidhaas, Jennifer L; Lin, Lian-Shin

    2016-03-15

    The kinetics and microbial ecology in sulfidogenic bioreactors used in a novel two-stage process for co-treatment of acid mine drainage (AMD) and municipal wastewater (MWW) were investigated. Michaelis-Menten modeling of COD oxidation by sulfate reducing bacteria (SRB) (Vmax=0.33mgL(-1)min(-1), Km=4.3mgL(-1)) suggested that the Vmax can be reasonably achieved given the typical COD values in MWW and anticipated mixing with AMD. Non-competitive inhibition modeling (Ki=6.55mgL(-1)) indicated that excessive iron level should be avoided to limit its effects on SRB. The COD oxidation rate was positively correlated to COD/sulfate ratio and SRB population, as evidenced by dsrA gene copies. Phylogenetic analysis revealed diverse microbial communities dominated by sulfate reducing delta-proteobacteria. Microbial community and relative quantities of SRB showed significant differences under different COD/sulfate ratios (0.2, 1 and 2), and the highest dsrA gene concentration and most complex microbial diversity were observed under COD/sulfate ratio 2. Major species were associated with Desulfovirga, Desulfobulbus, Desulfovibrio, and Syntrophus sp. The reported COD kinetics, SRB abundances and the phylogenetic profile provide insights into the co-treatment process and help identify the parameters of concerns for such technology development. PMID:26686479

  8. Biogeochemistry of the compost bioreactor components of a composite acid mine drainage passive remediation system

    The compost bioreactor ('anaerobic cell') components of three composite passive remediation systems constructed to treat acid mine drainage (AMD) at the former Wheal Jane tin mine, Cornwall, UK were studied over a period of 16 months. While there was some amelioration of the preprocessed AMD in each of the three compost bioreactors, as evidenced by pH increase and decrease in metal concentrations, only one of the cells showed effective removal of the two dominant heavy metals (iron and zinc) present. With two of the compost bioreactors, concentrations of soluble (ferrous) iron draining the cells were significantly greater than those entering the reactors, indicating that there was net mobilisation (by reductive dissolution) of colloidal and/or solid-phase ferric iron compounds within the cells. Soluble sulfide was also detected in waters draining all three compost bioreactors which was rapidly oxidised, in contrast to ferrous iron. Oxidation and hydrolysis of iron, together with sulfide oxidation, resulted in reacidification of processed AMD downstream of the compost bioreactors in two of the passive treatment systems. The dominant cultivatable microorganism in waters draining the compost bioreactors was identified, via analysis of its 16S rRNA gene, as a Thiomonas sp. and was capable of accelerating the dissimilatory oxidation of both ferrous iron and reduced sulfur compounds. Sulfate-reducing bacteria (SRB) were also detected, although only in the bioreactor that was performing well were these present in significant numbers. This particular compost bioreactor had been shut down for 10 months prior to the monitoring period due to operational problems. This unforeseen event appears to have allowed more successful development of AMD-tolerant and other microbial populations with critical roles in AMD bioremediation, including neutrophilic SRB (nSRB), in this compost bioreactor than in the other two, where the throughput of AMD was not interrupted. This study has

  9. Synthesis and Kinetics of a Novel Mimic with Glutathione Peroxidase Activity-Tellurium-containing Hyaluronic Acid (TeHA)

    Zhi Bo CHEN; Lan Ying LIU; Bo Xun ZHANG; Zhong Xiu HUANG; Qing Lin PENG; Jia CHEN; Yu WANG; Jian Guo ZHANG; Guang Zhi JIANG; Wen Shu LI

    2006-01-01

    A novel mimic was synthesized by modifying hyaluronic acid (HA) with tellurium,whose function is similar to that of glutathione peroxidase (GPX). The structure of TeHA was characterized by means of IR and NMR, the target-Te was located at -CH2OH of the N-acetyl-D-glucosamine of HA. The H2O2 reducing activity of TeHA, by glutathione (GSH), was 163.6U/μmol according to Wilson's method. In contrast to other mimics, TeHA displayed the highest activity. Moreover, TeHA accepted many hydroperoxides as its substrates, such as H2O2, cumenyl hydroperoxide (CuOOH) and tert-butyl hydroperoxide (t-BuOOH), and CuOOH was the optimal substrate of TeHA. A ping-pong mechanism was observed in the steady-state kinetic studies of the reactions catalyzed by TeHA.

  10. Equilibrium and kinetics study on the adsorption of perfluorooctanoic acid from aqueous solution onto powdered activated carbon

    Powdered activated carbon (PAC) was applied to remove perfluorooctanoic acid (PFOA) from the aqueous PFOA solution in this study. Contact time, adsorbent dose and temperature were analyzed as the effect factors in the adsorption reaction. The contact time of maximum PFOA uptake was around 1 h while the sorption removal efficiency increased with the PAC concentrations. And the process of adsorption increased from 303 K to 313 K and then decreased from 313 K to 323 K. Among four applied models, the experimental isotherm data were discovered to follow Langmuir isotherm model more closely. Thermodynamically, adsorption was endothermic because enthalpy, entropy and Gibbs constants were 198.5 kJ/mol, 0.709 kJ/mol/K and negative, respectively, which also indicated that the adsorption process was spontaneous and feasible. From kinetic analysis, the adsorption was suggested to be pseudo-second-order model. The adsorption of PFOA on the PAC was mainly controlled by particle diffusion.

  11. Kinetics of hydrogen evolution at tantalum electrode in sulfuric acid media: effects of pH and solution temperature

    The influence of temperature in the range of 20-80 deg C and sulfuric acid and potassium sulfate solution pH in the range of pH=1.81-3.0 on kinetics of electrochemical reaction of hydrogen evolution on tantalum, which is characterized by Ta-H high binding energy, has been studied. It has been ascertained that the reaction occurs on the surface of electrode covered by a thin film of tantalum oxide. The oxide is preserved during cathode polarization, only its electrophysical and adsorption al properties change at the expense of hydrogen atoms penetration to the oxide film volume and appearance of low-valency; tantalum cations in the oxide

  12. Effect of hydrodynamics on kinetics of gluconic acid enzymatic production in bubble column reactor

    Ramezani Mohammad

    2013-01-01

    Full Text Available Oxidation of glucose by homogeneous glucose oxidase was performed in rectangular bubble column reactor at 40°C, ambient pressure and pH of 5.5 while superficial gas (oxygen velocity was varied in the homogeneous and transition regime in the range of 0.0014 - 0.0112 m s-1. Effect of superficial gas (oxygen velocity on the apparent reaction rate and its parameters was determined and it was observed that the apparent reaction rate on the basis of volume of the liquid increased with increasing the superficial gas (oxygen velocity. The apparent reaction rate was assumed to be in the form of Michaelis-Menten equation and its apparent kinetic parameters were evaluated by the nonlinear regression method.

  13. Biodegradation of Acid Anthraquinone Dye in a Facultative-aerobic Process: Kinetics and Products

    LI Yin; LI Zai-lei

    2009-01-01

    The transformation of an anthraquinone dye blue 324 in a facultative-aerobic (F-A) system was investigated. Kinetic parameter study showed that higher Vmax coupled with more recalcitrant chemical oxygen demand (COD) were found in the facuitative biofilm reactor (FBR) than in the aerobic reactor (AR). Results of the product analyses indicated that most of dye molecular could be facultatively broken down into simple intermediates, which would be further degraded under subsequent aerobic condition. The main metabolites in each reactor were detected by infrared (FT-IR) and high performance liquid chromatography and mass spectrometry (HPLC-MS). Comparison of the toxicities among the dye and its metabolites was conducted, surprisingly, the colorless intermediates from FBR possessed less inhibitory than original dye and the median effective luminescence concentration (EC50) in 15 min for aerobic effluent could not be detected, showing that hardly toxic products existed in the aerobic process effluent.

  14. Effect of ions on sulfuric acid-water binary particle formation: 1. Theory for kinetic- and nucleation-type particle formation and atmospheric implications

    Merikanto, Joonas; Duplissy, Jonathan; Määttänen, Anni; Henschel, Henning; Donahue, Neil M.; Brus, David; Schobesberger, Siegfried; Kulmala, Markku; Vehkamäki, Hanna

    2016-02-01

    We derive a version of Classical Nucleation Theory normalized by quantum chemical results on sulfuric acid-water hydration to describe neutral and ion-induced particle formation in the binary sulfuric acid-water system. The theory is extended to treat the kinetic regime where the nucleation free energy barrier vanishes at high sulfuric acid concentrations or low temperatures. In the kinetic regime particle formation rates become proportional to sulfuric acid concentration to second power in the neutral system or first power in the ion-induced system. We derive simple general expressions for the prefactors in kinetic-type and activation-type particle formation calculations applicable also to more complex systems stabilized by other species. The theory predicts that the binary water-sulfuric acid system can produce strong new particle formation in the free troposphere both through barrier crossing and through kinetic pathways. At cold stratospheric and upper free tropospheric temperatures neutral formation dominates the binary particle formation rates. At midtropospheric temperatures the ion-induced pathway becomes the dominant mechanism. However, even the ion-induced binary mechanism does not produce significant particle formation in warm boundary layer conditions, as it requires temperatures below 0°C to take place at atmospheric concentrations. The theory successfully reproduces the characteristics of measured charged and neutral binary particle formation in CERN CLOUD3 and CLOUD5 experiments, as discussed in a companion paper.

  15. Kinetic study of the precipitation of radioactive elements in the production process of phosphoric acid

    In this engineering study we determined the activities of gamma emitting radionuclides belonging to the families of 238U ,232Th and 40K in phosphate, the acid derivatives and gypsum in Tunisian Chemical Group. The most important activities are those of 238U and 226Ra, which are located in the phosphate, gypsum and the precipitates formed in the pipes.

  16. Kinetic Spectrophotometric Method for Determination of Oxalic Acid and Its application in Lathyrus sativus

    YAN Ze-Yi; XING Geng-Mei; LI Zhi-Xiao

    2003-01-01

    @@ Oxalic acid is one of the most common nutrient chelators in the human diet found in many vegetables, such as mushroom, spinach, fresh kidney beans, rhubarb leaves and beet leaves. Some recent reports demonstrate that oxalate plays an important role in resistance stress metabolism and steady state regulation in plant. [1

  17. Kinetics, aggregation behavior and optimization of the fractionation of whey protein isolate with hydrochloric acid

    Concentrated WPI solutions (10% (w/w)) containing approximately 30% alpha-lactalbumin (alpha-LA) and 60% beta-lactoglobulin (beta-LG) were fractionated with HCl at acidic pH and moderate temperatures to denature alpha-LA and recover the alpha-LA aggregates via centrifugation. Aggregation behavior an...

  18. Association of adiponectin,free fatty acids,and insulin resistance with metabolic syndrome and its components in Uygur Xinjiang

    闫贻忠

    2014-01-01

    Objective To investigate the association of adiponectin(APN),free fatty acids(FFA),and insulin resistance(IR)with metabolic syndrome(MS)and its components.Methods In the baseline survey,the subjects were divided into MS group and the control group based

  19. Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and products identification

    M. Mendez

    2013-06-01

    Full Text Available The heterogeneous reaction of Cl. radicals with sub-micron palmitic acid (PA particles was studied in an aerosol flow tube in the presence or in the absence of O2. Fine particles were generated by homogeneous condensation of PA vapors and introduced in the reactor where chlorine atoms are produced by photolysis of Cl2 using UV lamps surrounding the reactor. The effective reactive uptake coefficient (γ has been determined from the rate loss of PA measured by GC/MS analysis of reacted particles as a function of the chlorine exposure. In the absence of O2, γ = 14 ± 5 indicates efficient secondary chemistry involving Cl2. GC/MS analyses have shown the formation of monochlorinated and polychlorinated compounds in the oxidized particles. Although, the PA particles are solid, the complete mass can be consumed. In the presence of oxygen, the reaction is still dominated by secondary chemistry but the propagation chain length is smaller than in the absence of O2 which leads to an uptake coefficient γ = 3 ± 1. In the particulate phase, oxocarboxylic acids and dicarboxylic acids are identified by GC/MS. Formation of alcohols and monocarboxylic acids are also suspected. All these results show that solid organic particles could be efficiently oxidized by gas-phase radicals not only on their surface, but also in bulk by mechanisms which are still unclear. Furthermore the identified reaction products are explained by a chemical mechanism showing the pathway of the formation of more functionalized products. They help to understand the aging of primary tropospheric aerosol containing fatty acids.

  20. Intrinsic surface hardening and precipitation kinetics of Al0.3CrFe1.5MnNi0.5 multi-component alloy

    Highlights: ► Al0.3CrFe1.5MnNi0.5 multi-component alloy with surface hardening was developed. ► By simple aging treatments, the surface hardness was markedly enhanced. ► Wear resistance was efficiently improved, and fracture toughness retained. ► The intrinsic surface hardening behaves similar to short-range decomposition. ► The intrinsic surface hardening has relatively low heterogeneous nucleation energy. - Abstract: An Al0.3CrFe1.5MnNi0.5 multi-component alloy with a very effective surface hardening ability attributed to intrinsic ρ phase precipitation and applicable to complex tool components was developed. Under a conventional aging treatment in a normal atmosphere at 550 °C for 2 h, the alloy with the surface precipitation hardening layer of 74 μm thick exhibited markedly enhanced surface hardness from HV 338 to HV 840 and efficiently improved wear resistance to 1.4 times the values of SUJ2 and SKD61 steels, while high fracture toughness close to that of ductile SKD61 steel was effectively retained. Precipitation thermodynamics and growth kinetics of the surface hardening layer were also investigated. The growth of the surface hardening layer was much faster than that of the precipitation in the bulk matrix; it did not follow typical long-distance diffusion kinetics but behaves more similar to a self-induced or reaction-accelerated short-range decomposition with a thickness increase proportional to the cube of aging time. On the surface, a lower heterogeneous nucleation energy and a reduced strain energy (total 55 kJ/mol) than the regular nucleation energy in the bulk matrix (78 kJ/mol) dominated the rapid formation and growth of the intrinsic surface precipitation with significant strain relaxations.

  1. Cr(VI) reduction capability of humic acid extracted from the organic component of municipal solid waste

    Barbara Scaglia; Fulvia Tambone; Fabrizio Adani

    2013-01-01

    The capacity of humic acid extracted from organic waste (HAw) to reduce Cr(Ⅵ) was tested at pH 2.5,4 and 6 and compared with coal-derived humic acid (HAc).HAw was more effective than HAc in reducing Cr(Ⅵ).The kinetics of Cr(Ⅵ) reductions depended strongly on pH.The calculation of the apparent rate coefficients indicated that HAw was more efficient at reducing Cr(Ⅵ) than HAc,but was also more efficient than HAs from soil and peat.The reduction capability of HAs depends on the type of functional groups (i.e.,thiols and phenols) present,rather than the free radicals.HAw was more efficient at reducing Cr(Ⅵ) than HAc because more reactive phenols were present,i.e.,methoxy-and methyl-phenols.

  2. Effect of myocardial perfusion and metabolic interventions on cardiac kinetics of phenylpentadecanoic acid (IPPA) I 123

    Reske, S.N.; Schoen, S.; Schmitt, W.; Knopp, R.; Winkler, C.; Machulla, H.J.

    1986-08-01

    The effect of regional myocardial perfusion and flow-independent adrenergic stimulation, as well as lactate-mediated inhibition of cardiac lipolysis, on cardiac IPPA uptake and metabolism was examined in canine hearts (flow studies) and in the isolated perfused Langendorff rat heart (metabolic interventions). In both normal and ischaemic myocardium, local perfusion is a major determinant of cardiac IPPA uptake. In pacing-induced hyperaemia, the strict flow-dependence of cardiac IPPA uptake is not preserved. Adrenergic stimulation raises the rate of oxidation of both palmitic acid /sup 14/C and IPPA. This change is reflected by increased metabolite production released into the perfusate and radioactivity clearance recorded externally. Lactate in high concentrations exerts the opposite effect on cardiac free fatty acid oxidation. IPPA is stored in this condition preferentially in tissue phospholipids and triglycerides.

  3. The Inherent Reactor Kinetics for Transformation of Geniposidic Acid from Geniposide in a Microreactor

    Chiu-Lan Hsieh; Wang-Chi Hsieh

    2015-01-01

    The ripe fruits of Gardenia jasminoides Ellis (Rubiaceae) (GJ) are widely used in chemical, food and medicinal industries. Crocin and geniposide, the main constituents of GJ, have shown a diversity of biological activities including sedative, anti-inflammatory and antipyretic. We propose some new bioactive chemicals could be derived from geniposide. The optimum transformation condition of geniposide into geniposidic acid still remains unclear. In order to develop a reactor, the in...

  4. Kinetics of the hydrolysis of polysaccharide galacturonic acid and neutral sugars chains from flaxseed mucilage

    Happi Emaga, T.

    2012-01-01

    Full Text Available Different hydrolysis procedures of flaxseed polysaccharides (chemical and enzymatic were carried out with H2SO4, HCl and TFA at different acid concentrations (0.2, 1 and 2 M and temperatures (80 and 100°C. Enzymatic and combined chemical and enzymatic hydrolyses of polysaccharide from flaxseed mucilage were also studied. Acid hydrolysis conditions (2 M H2SO4, 4 h, 100°C are required to quantify total monosaccharide content of flaxseed mucilage. The enzymatic pathway (Pectinex™ Ultra SP limits sugar destruction during hydrolysis, but it is also insufficient for complete depolymerization. The combination of the two treatments, i.e. moderate chemical hydrolysis (0.2 M H2SO4, 80°C, 48 h combined with enzymatic hydrolysis is not more effective compared to chemical hydrolysis in drastic conditions (2 M H2SO4 at 100°C. The strong interaction between the neutral and acid fractions of flaxseed mucilage may hinder total release of sugar residues. Physical treatment prior to the hydrolysis could be necessary to achieve complete depolymerisation of flaxseed mucilage.

  5. Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

    Highlights: • Acid sulfate dissolution of clay-rich sediments from inland acid sulfate site in flow-through reactor experiments at pH 1–4. • Enhanced Al and K release at the higher ionic strength of solutions compared to the lower ionic strength. • Acid neutralization capacity (ANC) of 1.11 kg H2SO4/tonne clay-rich sediment/day was provided at pH 1, 25 °C. • ANC provided at 45 °C by the same amount of clay-rich sediment was more than three times higher than the ANC at 25 °C. - Abstract: Significant amounts of sulfuric acid (H2SO4) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; RSi, RAl, RFe) increased with decreasing solution pH and increasing temperature. For example, the highest log RSi value was obtained at pH 1 and 45 °C (−9.07 mol g−1 s−1

  6. Polyethylene Glycols as Efficient Media for Decarboxylative Nitration of α,β-Unsaturated Aromatic Carboxylic Acids by Ceric Ammonium Nitrate in Acetonitrile Medium: A Kinetic and Mechanistic Study

    K. Ramesh

    2013-01-01

    Full Text Available Polyethylene glycols (PEGs were found to be efficient media for decarboxylative nitration of α,β-unsaturated aromatic carboxylic acids by ceric ammonium nitrate (CAN in acetonitrile to give β-nitrostyrene derivatives. Kinetics of the reaction exhibited second order kinetics with a first order dependence on [CAN] and [substrate]. Reactions were too sluggish to be studied in the absence of PEG; therefore detailed kinetics were not taken up. Reaction times were reduced from 24 hrs to few hours. The catalytic activity was found to be in the increasing order PEG-300 > PEG-400 > PEG-600 > PEG-200. Mechanism of PEG-mediated reactions was explained by Menger-Portnoy's scheme as applied in micellar kinetics.

  7. Anti-tyrosinase kinetics and antibacterial process of caffeic acid N-nonyl ester in Chinese Olive (Canarium album) postharvest.

    Jia, Yu-Long; Zheng, Jing; Yu, Feng; Cai, Yi-Xiang; Zhan, Xi-Lan; Wang, Hui-Fang; Chen, Qing-Xi

    2016-10-01

    Enzymatic browning and bacterial putrefaction are mainly responsible for quality losses of Chinese Olive (Canarium album) postharvest and lead to very short shelf life on average. Screening anti-browning and anti-bacterial agents is important for preservation of Chinese Olive. Caffeic acid N-nonyl ester (C-9) and caffeic acid N- Heptyl ester (C-7) was synthesized as inhibitors of tyrosinase, which is a key enzyme in browning process. The compound of C-9 could inhibit the activity of tyrosinase strongly and its IC50 value was determined to be 37.5μM, while the compound of C-7 had no inhibitory ability. Kinetic analyses showed that compound of C-9 has been a reversible inhibitory mechanism below 50μM and been irreversible mechanisms above 50μM. For the reversible inhibitory mechanism, the values of inhibitory constants (KI and KIS) were determined to be 24.6 and 37.4μM, respectively. The results of Chinese Olive fruit postharvest showed that the compound of C-9 could effectively anti-browning and anti-bacterial putrefaction. In addition, this compound had strong antibacterial activities against Staphylococcus aureus, Escherichia coli, Bacillus subtilis and Salmonella. Therefore, C-9 could be a potential anti-browning and anti-bacterial reagent. PMID:27246378

  8. Microencapsulation of H. pluvialis oleoresins with different fatty acid composition: Kinetic stability of astaxanthin and alpha-tocopherol.

    Bustamante, Andrés; Masson, Lilia; Velasco, Joaquín; del Valle, José Manuel; Robert, Paz

    2016-01-01

    Haematococcus pluvialis is a natural source of astaxanthin (AX). However, AX loses its natural protection when extracted from this microalga. In this study, a supercritical fluid extract (SFE) of H. pluvialis was obtained and added to oils with different fatty acid compositions (sunflower oil (SO) or high oleic sunflower oil (HOSO)). The oleoresins of H. pluvialis ((SO+SFE) and (HOSO+SFE)) were encapsulated with Capsul by spray drying. The stability of the oleoresins and powders were studied at 40, 50 and 70° C. AX and alpha-tocopherol (AT) degradation followed a zero-order and first-order kinetic model, respectively, for all systems. The encapsulation of oleoresins improved the stability of AX and AT to a greater extent in oleoresins with a monounsaturated fatty acid profile, as shown by the significantly lowest degradation rate constants and longest half-lives. Therefore, the encapsulation of H. pluvialis oleoresins is an alternative to developing a functional ingredient for healthy food design. PMID:26213069

  9. Exploring the high-mass components of humic acid by laser desorption ionization mass spectrometry.

    Chilom, Gabriela; Chilom, Ovidiu; Rice, James A

    2008-05-01

    Leonardite and Elliot soil humic acids have been analyzed by laser desorption ionization mass spectrometry (LDI MS) in the m/z 4000-200,000 range. Positive ion mass spectra for each humic acid obtained under optimum conditions showed a broad high-mass distribution between m/z 20,000 and 80,000. The dependence of the mass distribution on instrumental parameters and solution conditions was used to investigate the nature of the high-mass peaks from humic acid spectra. Our data suggests that macromolecular ions and humic acid aggregates have the same probability of occurrence while cluster ion formation has a low probability of occurrence. PMID:18421699

  10. Equilibrium and kinetics studies for the adsorption of direct and acid dyes from aqueous solution by soy meal hull

    This paper deals with the application of Soy Meal Hull (SMH), an agricultural by-product, for the removal of direct and acid dyes from aqueous solutions. Four textile dyes, C.I.Direct red 80 (DR80), C.I.Direct red 81 (DR81), C.I.Acid blue 92 (AB92) and C.I.Acid red 14 (AR14) were used as model compounds. Physical characteristics of SMH such as surface area, Fourier transform infra-red (FTIR) and scanning electron microscopy (SEM) were obtained. The surface area of SMH was found to be 0.7623 m2/g and the presence of functional groups such as hydroxyl, amine and carbonyl groups were detected. The effect of initial dye concentration, pH, contact time and SMH doses were elucidated at 20 ± 1 deg. C. Results show that the pH value of 2 is favorable for the adsorption of all four dyes. The data evaluated for compliance with the Langmuir, Freundlich and BET isotherm models. It was found that data for DR80 and DR81 fitted well with Langmuir isotherm, for AB92, BET isotherm is preferred, while for AR14, the Freundlich isotherm is the most applicable. The adsorption capacities of SMH for DR80, DR81, AB92 and AR14 were, 178.57, 120.48, 114.94 and 109.89 mg/g of adsorbent, respectively. Also, adsorption kinetics of dyes was studied and the rates of sorption were found to conform to pseudo-second order kinetics with good correlation (R 2 ≥ 0.9977). Maximum desorption of ≥99.8% was achieved for DR80, DR81 and AB92 and 86% for AR14 in aqueous solution at pH 10. Based on the data of present investigation, one could conclude that the SMH being a natural, eco-friendly and low-cost adsorbent with relatively large adsorption capacity might be a suitable local alternative for elimination of dyes from colored aqueous solutions

  11. Time-dependent extraction kinetics of infused components of different Indian black tea types using UV spectroscopy

    Asir Gani

    2016-12-01

    Full Text Available Time-dependent aqueous extraction of six tea types was carried out with leaf–water–ratio of 0.5 g/100 ml, temperature of extraction 90°C and time of extraction ranging from 1 to 10 min. UV–vis spectroscopic analysis in the range varying from 220 to 900 nm of the aqueous tea extracts showed a prominent peak at 273 nm in the ultraviolet region which can be associated with n → π* electronic transition of caffeine molecules. Parabolic diffusion, Power law, hyperbolic, Weibull’s and Elovich’s models were fitted to represent the aqueous soluble component extraction behaviour for time-dependent extraction of aqueous extractables. Parabolic diffusion model, Power law and Elovich’s model were a close fit to the experimental data for all the selected tea types with correlation coefficients (R2 ranging 0.8029–0.9953, whereas hyperbolic and Weibull’s models showed poor fitness to represent the extraction behaviour of fanning and AO leaf, LD, fanning and dust, respectively, with R2 < 0.8, for time-dependent aqueous soluble component extraction.

  12. Electrolytic deposition of calcium phosphate/chitosan coating on titanium alloy: Growth kinetics and influence of current density, acetic acid, and chitosan

    Wang, Jiawei; Apeldoorn, van Aart; Groot, de Klaas

    2006-01-01

    Electrolytically deposited calcium phosphate/chitosan coating demonstrated good bone marrow stromal cell attachment. The aim of this study was to understand the coating's growth kinetics as well as the effects of current density, acetic acid, and chitosan on the coating's formation. The scanning ele

  13. Development of a method for calculating the equilibrium and kinetics of ion exchange on a weak acid resin in a ternary system H+-Ca2+-Mg2+

    In technical applications ion exchange resins are applied in filters. The breakthrough behaviour of such filters can be calculated using mathematical relationships for equilibrium and kinetics. An according method has been developed for a ternary ion exchage problem on a weak acid resin. Theoretical results are verified by means of experimental data. (orig.)

  14. Kinetic study on the enzymatic esterification of octanoic acid and hexanol by immobilized Candida antarctica lipase B

    Lopresto, Catia Giovanna; Calabro, Vincenza; Woodley, John M.;

    2014-01-01

    tThis study investigates reaction kinetics of the esterification of octanoic acid and hexanol into hexyloctanoate, catalyzed by an immobilized Candida antarctica lipase (Novozym®435). The product is considered natural and used as a fresh vegetable and fruity flavour additive in food, cosmetic and...

  15. Kinetics and mechanism of photocatalytic aging of polyacrylic acid and polyacrylamide at 770K

    This work is aimed at elucidating the mechanism of photoradical aging of polyacrylic acid and polyacrylamide, at obtaining quantitative properties of the intermediate stages of this process, and at establishing a relationship between photochemical reactions of macroradicals and changes in molecular weight of the polymers. Radicals were generated by irradiation with a cobalt 60 source at 77 K. High-pressure mercury lamps were used as the light source. Molecular weights were determined by ebulliography and photometry. The accumulation of carbon monoxide and ketenes was monitored as a function of reaction time. ESR spectra and hyperfine structure were also assessed in determining the reaction pathways

  16. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    The interaction of caffeic acid with eaq-, (CH3)2(OH) CCH2·, CO2·-, H·, ·OH and N3· radicals were studied by γ-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/·OH adducts, semi-quinone radicals of caffeic ions, and the stable products from the reactions were derived. The rate constants were determined. The attacked sites and the most favorable structures of the transient radicals were predicted. Reaction mechanisms were proposed. (author)

  17. Pipa carvalhoi skin secretion profiling: absence of peptides and identification of kynurenic acid as the major constitutive component.

    Mariano, Douglas Oscar Ceolin; Yamaguchi, Lydia Fumiko; Jared, Carlos; Antoniazzi, Marta Maria; Sciani, Juliana Mozer; Kato, Massuo Jorge; Pimenta, Daniel Carvalho

    2015-01-01

    The presence of peptides has been identified in all African pipid genera; nevertheless, little is known about skin secretion of South American frog genus Pipa. Skin secretion from captive and wild Pipa carvalhoi were obtained in the presence or absence of norepinephrine stimulation. The <10 kDa fraction was analyzed by liquid chromatography and mass spectrometry, searching for peptides. Chromatographic profiles show the presence of a major component in this secretion, regardless of the stimulation method (norepinephrine or mechanical stimulation) and the origin of the animal (captivity or wild), as well as in the absence of any stimulus. The general mass distribution profile in P. carvalhoi skin secretion shows numerous components below 800 Da. Moreover, no peptide could be identified, regardless of the chromatographic approach. The major component was purified and identified as kynurenic acid, an L-tryptophan derivative. P. carvalhoi does not secrete peptides as toxins in its skin. In addition, we here report that kynurenic acid is the main component of P. carvalhoi skin secretion. Although no biological activity was associated with kynurenic acid, we propose that this molecule is a pheromone that signals the presence of a co-specific in the shady environment in which this animal lives. In this study we demonstrate the absence of peptidic toxins in the skin secretion of P. carvalhoi, a break of paradigm in the pipid family. PMID:25181950

  18. The Changes in Color, Soluble Sugars, Organic Acids, Anthocyanins and Aroma Components in "Starkrimson" during the Ripening Period in China.

    Liu, Yulian; Chen, Nianlai; Ma, Zonghuan; Che, Fei; Mao, Juan; Chen, Baihong

    2016-01-01

    "Starkrimson" is a traditional apple cultivar that was developed a long time ago and was widely cultivated in the arid region of the northern Wei River of China. However, little information regarding the quality characteristics of "Starkrimson" fruit has been reported in this area. To elucidate these characteristics, the color, soluble sugars, organic acids, anthocyanins and aroma components were measured during the ripening period through the use of high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). The results indicated that the changes in anthocyanin contents took place later than the changes in the Commission International Eclairage (CIE) parameters. Meanwhile, cyanidin 3-galactoside (cy3-gal), fructose, sucrose, glucose and malic acid were the primary organic compounds, and 1-butanol-2-methyl-acetate, 2-hexenal and 1-hexanol were the most abundant aroma components in the skin. Furthermore, rapidly changing soluble sugars and organic acid synchronization took place in the early ripening period, while rapidly changing aroma components occurred later, on the basis of fresh weight. This result suggested that the production of aroma components might be a useful index of apple maturity. PMID:27338331

  19. Normal solution and transport coefficients to the Enskog-Landau kinetic equation for a two-component system of charged hard spheres The Chapman-Enskog method

    Kobryn, A E; Tokarchuk, M V

    1999-01-01

    An Enskog-Landau kinetic equation for a many-component system of charged hard spheres is proposed. It has been obtained from the Liouville equation with modified boundary conditions by the method of nonequilibrium statistical operator. On the basis of this equation the normal solutions and transport coefficients such as bulk kappa and shear eta viscosities, thermal conductivity lambda, mutual diffusion D^{\\alpha\\beta} and thermal diffusion D_T^\\alpha have been obtained for a binary mixture in the first approximation using the Chapman-Enskog method. Numerical calculations of all transport coefficients for mixtures Ar-Kr, Ar-Xe, Kr-Xe with different concentrations of compounds have been evaluated for the cases of absence and presence of long-range Coulomb interactions. The results are compared with those obtained from other theories and experiment.

  20. Kinetic modeling of a bi-enzymatic system for efficient conversion of lactose to lactobionic acid.

    Van Hecke, Wouter; Bhagwat, Aditya; Ludwig, Roland; Dewulf, Jo; Haltrich, Dietmar; Van Langenhove, Herman

    2009-04-01

    A model has been developed to describe the interaction between two enzymes and an intermediary redox mediator. In this bi-enzymatic process, the enzyme cellobiose dehydrogenase oxidizes lactose at the C-1 position of the reducing sugar moiety to lactobionolactone, which spontaneously hydrolyzes to lactobionic acid. 2,2'-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt is used as electron acceptor and is continuously regenerated by laccase. Oxygen is the terminal electron acceptor and is fully reduced to water by laccase, a copper-containing oxidase. Oxygen is added to the system by means of bubble-free oxygenation. Using the model, the productivity of the process is investigated by simultaneous solution of the rate equations for varying enzyme quantities and redox mediator concentrations, solved with the aid of a numerical solution. The isocharts developed in this work provide an easy-to-use graphical tool to determine optimal process conditions. The model allows the optimization of the employed activities of the two enzymes and the redox mediator concentration for a given overall oxygen mass transfer coefficient by using the isocharts. Model predictions are well in agreement with the experimental data. PMID:18988269

  1. Oxidation of lactose to lactobionic acid by a Microdochium nivale carbohydrate oxidase: kinetics and operational stability.

    Nordkvist, Mikkel; Nielsen, Per Munk; Villadsen, John

    2007-07-01

    Oxidation of lactose to lactobionic acid by a Microdochium nivale carbohydrate oxidase was studied. The K(m)-value for lactose, obtained by a traditional enzymatic assay, was 0.066 mM at pH 6.4 and 38 degrees C. The effect of oxygen on the enzymatic rate of reaction as well as the operational stability of the enzyme was studied by performing reactions at constant pH and temperature in a stirred tank reactor. Catalase was included in all reactions to avoid inhibition and deactivation of the oxidase by hydrogen peroxide. At pH 6.4 and 38 degrees C, K(m) for oxygen was 0.97 mM, while the catalytical rate constant, k(cat), was 94 s(-1). Furthermore, we found that the operational stability of the oxidase was dependent on the type of base used for neutralization of the acid produced. Thus, when 2 M NaOH was used for neutralization of a reaction medium containing 50 mM phosphate buffer, significant deactivation of the oxidase was observed. Also, we found that the oxidase was protected against deactivation by base at high lactose concentrations. A simple model is proposed to explain the obtained results. PMID:17154316

  2. nC60 deposition kinetics: the complex contribution of humic acid, ion concentration, and valence.

    McNew, Coy P; LeBoeuf, Eugene J

    2016-07-01

    The demonstrated toxicity coupled with inevitable environmental release of nC60 raise serious concerns about its environmental fate and transport, therefore it is crucial to understand how nC60 will interact with subsurface materials including attached phase soil and sediment organic matter (AP-SOM). This study investigated the attachment of nC60 onto a Harpeth humic acid (HHA) coated silica surface under various solution conditions using a quartz crystal microbalance with dissipation monitoring. The HHA coating greatly enhanced nC60 attachment at low ion concentrations while hindering attachment at high ion concentrations in the presence of both mono and divalent cations. At low ion concentrations, the HHA greatly reduced the surface potential of the silica, enhancing nC60 deposition through reduction in the electrostatic repulsion. At high ion concentrations however, the reduced surface potential became less important due to the near zero energy barrier to deposition and therefore non-DLVO forces dominated, induced by compaction of the HHA layer, and leading to hindered attachment. In this manner, observed contributions from the HHA layer were more complex than previously reported and by monitoring surface charge and calculated DLVO interaction energy alongside attachment experiments, this study advances the mechanistic understanding of the variable attachment contributions from the humic acid layer. PMID:27061365

  3. Kinetics of uptake and distribution of arachidonic acid by rat alveolar macrophages

    The time course of uptake and distribution of 3H-arachidonic acid (3H-AA) into rat alveolar macrophage phospholipid pools was examined. Macrophages incubated with exogenous 3H-AA in RPMI-1640 containing 0.1% bovine serum albumin (BSA), incorporated this radiolabel into phosphatidylcholine and phosphatidylinositol (PI) with plateaus reached within 2 to 4 hours, which remained relatively constant for up to 18 hours. Incorporation of 3H-AA into phosphatidylethanolamine was small, but continued to increase for 14 hours. Analysis of phosphate content in phospholipid pools revealed that treatment with exogenous 5 nM arachidonic acid had no effect upon pool sizes, but there was a selective incorporation of 3H-AA into PI. Cells were incubated with 3H-AA in RPMI alone or medium containing either 0.2% lactalbumin, fetal calf serum at variable concentrations, 10% Nu Serum, or 0.1% BSA. Incubation of macrophages with 3H-AA in RPMI alone or containing 0.2% lactalbumin, resulted in approximately 70% of the radiolabel taken up by the cells being incorporated into triglyceride. The addition of BSA to RPMI-1640 medium was found to facilitate selective uptake of 3H-AA into phospholipids. Approximately 70% of incorporated 3H-AA was releasable through the action of exogenous phospholipase A2

  4. Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

    Eick, M. J.; Grossl, P. R.; Golden, D. C.; Sparks, D. L.; Ming, D. W.

    1996-01-01

    The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased

  5. Kinetics and thermodynamics of {beta}-carotene and chlorophyll adsorption onto acid-activated bentonite from Xinjiang in xylene solution

    Wu Zhansheng [School of Life Science and Technology, Beijing Institute of Technology, Beijing 100081 (China); School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003 (China); Li Chun, E-mail: lichun@bit.edu.cn [School of Life Science and Technology, Beijing Institute of Technology, Beijing 100081 (China); School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832003 (China)

    2009-11-15

    The kinetics and thermodynamics of {beta}-carotene and chlorophyll adsorption from xylene solution onto acid-activated bentonite (AAB) within the temperature range 65-95 deg. C were investigated. Adsorption of {beta}-carotene was described well with the Langmuir isotherm, whereas chlorophyll adsorption was determined well with the Freundlich isotherm, and the experimental data on chlorophyll adsorption were also fitted by the Langmuir isotherm to a certain extent, as reflected by correlation coefficients (R{sup 2}) over 0.9865. In addition, the adsorption of {beta}-carotene and chlorophyll onto AAB are favorable. The pseudo-second-order model was found to explain the kinetics of adsorption of both pigments more effectively. Increase of temperature enhanced the adsorption rate and equilibrium adsorption capacity of {beta}-carotene and chlorophyll on AAB. The activation energy for the sorption of {beta}-carotene and chlorophyll on AAB was 19.808 kJ/mol and 16.475 kJ/mol, respectively. The thermodynamic parameters {Delta}H{sup {theta}}, {Delta}S{sup {theta}} and {Delta}G{sup {theta}}, computed from K{sub F} of the adsorption isotherm constant, were 21.766 kJ/mol, 92.244 J/K mol and -9.554 kJ/mol respectively for the adsorption of {beta}-carotene on AAB at 65 deg. C, and for adsorption of chlorophyll on AAB at 65 deg. C were 31.051 kJ/mol, 93.549 J/K mol and -0.729 kJ/mol, respectively. The adsorption of {beta}-carotene and chlorophyll in xylene solution on AAB was a spontaneous and endothermic process with increasing in the randomness at the solid-solution interface.

  6. Kinetic modeling of tricarboxylic acid cycle and glyoxylate bypass in Mycobacterium tuberculosis, and its application to assessment of drug targets

    Ghosh Indira

    2006-08-01

    Full Text Available Abstract Background Targeting persistent tubercule bacilli has become an important challenge in the development of anti-tuberculous drugs. As the glyoxylate bypass is essential for persistent bacilli, interference with it holds the potential for designing new antibacterial drugs. We have developed kinetic models of the tricarboxylic acid cycle and glyoxylate bypass in Escherichia coli and Mycobacterium tuberculosis, and studied the effects of inhibition of various enzymes in the M. tuberculosis model. Results We used E. coli to validate the pathway-modeling protocol and showed that changes in metabolic flux can be estimated from gene expression data. The M. tuberculosis model reproduced the observation that deletion of one of the two isocitrate lyase genes has little effect on bacterial growth in macrophages, but deletion of both genes leads to the elimination of the bacilli from the lungs. It also substantiated the inhibition of isocitrate lyases by 3-nitropropionate. On the basis of our simulation studies, we propose that: (i fractional inactivation of both isocitrate dehydrogenase 1 and isocitrate dehydrogenase 2 is required for a flux through the glyoxylate bypass in persistent mycobacteria; and (ii increasing the amount of active isocitrate dehydrogenases can stop the flux through the glyoxylate bypass, so the kinase that inactivates isocitrate dehydrogenase 1 and/or the proposed inactivator of isocitrate dehydrogenase 2 is a potential target for drugs against persistent mycobacteria. In addition, competitive inhibition of isocitrate lyases along with a reduction in the inactivation of isocitrate dehydrogenases appears to be a feasible strategy for targeting persistent mycobacteria. Conclusion We used kinetic modeling of biochemical pathways to assess various potential anti-tuberculous drug targets that interfere with the glyoxylate bypass flux, and indicated the type of inhibition needed to eliminate the pathogen. The advantage of such an

  7. Kinetics of amino acid and glucose absorption following pancreatic diversion in the pig

    Rerat, A.; Calmes, R.; Corring, T.; Vaissade, P.

    1996-01-01

    An experiment was conducted in the pig to determine the consequences of deprivation of exocrine pancreatic secretion on the composition and quantity of nutrients absorbed after intake of a balanced diet. Five growing pigs (53.8 kg body weight) were fitted with permanent catheters in the portal vein and the carotid artery and with an electromagnetic flow probe around the portal vein to measure the exchanges between the blood and the intestinal lumen. They were also fitted with a permanent catheter in the duct of Wirsung to educe the exocrine pancreatic secretion and another one in the duodenum in order to reintroduce it. In each animal, glucose, amino-N and amino acid absorption as well as insulin and glucagon production were measured over a period of 10 h after the meal (semi-purified diet based on purified starch and containing 180 g fish meal/kg, DM content of the meal 731 g), either in the presence of pancreatic juice (group C: immediate reintroduction), or in the absence of pancreatic juice (group D: deprivation). The deprivation of pancreatic juice provoked a marked depression in the absorption of glucose (D 67.9 (SEM 27.9) g/10 h, C 437.7 (SEM 39.5) g/10 h, P < 0.001), and of amino-N (D 7.55 (SEM 0.54) g/10 h, C 15.80 (SEM 0.79) g/10 h, P < 0.001). The composition of the mixture of amino acids in the portal blood was only slightly modified: only the levels of histidine (P < 0.05) and of valine (P < 0.06, NS) decreased in the absence of pancreatic juice. Insulin production was much lower (by 64%, P < 0.05) in the absence of pancreatic juice whereas that of glucagon was not affected.

  8. Biogenic hydroxyapatite (Apatite II™) dissolution kinetics and metal removal from acid mine drainage

    Apatite II™ is a biogenic hydroxyapatite (expressed as Ca5(PO4)OH) derived from fish bone. Using grains of Apatite II™ with a fraction size between 250 and 500 μm, batch and flow-through experiments were carried out to (1) determine the solubility constant for the dissolution reaction Ca5(PO4)3(OH) ⇔ 5Ca2+ + 3PO43− + OH−, (2) obtain steady-state dissolution rates over the pH range between 2.22 and 7.14, and (3) study the Apatite II™’s mechanisms to remove Pb2+, Zn2+, Mn2+, and Cu2+ from metal polluted water as it dissolves. The log KS value obtained was −50.8 ± 0.82 at 25 °C. Far-from-equilibrium fish-bone hydroxyapatite dissolution rates decrease by increasing pH. Assuming that the dissolution reaction is controlled by fast adsorption of a proton on a specific surface site that dominates through the pH range studied, probably ≡P-O−, followed by a slow hydrolysis step, the dissolution rate dependence is expressed in mol m−2 s−1 as Rate25°C=−8.9×10−10×(9.96×105×aH+)/(1+9.96×105×aH+) where aH+ is the proton activity in solution. Removal of Pb2+, Zn2+, Mn2+ and Cu2+ was by formation of phosphate-metal compounds on the Apatite II™ substrate, whereas removal of Cd2+ was by surface adsorption. Increase in pH enhanced the removal of aqueous heavy metals. Using the kinetic parameters obtained (e.g., dissolution rate and pH-rate dependence law), reactive transport simulations reproduced the experimental variation of pH and concentrations of Ca, P and toxic divalent metal in a column experiment filled with Apatite II™ that was designed to simulate the Apatite II™–metal polluted water interaction.

  9. Recycling of metal-organic chemical vapor deposition waste of GaN based power device and LED industry by acidic leaching: Process optimization and kinetics study

    Swain, Basudev; Mishra, Chinmayee; Kang, Leeseung; Park, Kyung-Soo; Lee, Chan Gi; Hong, Hyun Seon; Park, Jeung-Jin

    2015-05-01

    Recovery of metal values from GaN, a metal-organic chemical vapor deposition (MOCVD) waste of GaN based power device and LED industry is investigated by acidic leaching. Leaching kinetics of gallium rich MOCVD waste is studied and the process is optimized. The gallium rich waste MOCVD dust is characterized by XRD and ICP-AES analysis followed by aqua regia digestion. Different mineral acids are used to find out the best lixiviant for selective leaching of the gallium and indium. Concentrated HCl is relatively better lixiviant having reasonably faster kinetic and better leaching efficiency. Various leaching process parameters like effect of acidity, pulp density, temperature and concentration of catalyst on the leaching efficiency of gallium and indium are investigated. Reasonably, 4 M HCl, a pulp density of 50 g/L, 100 °C and stirring rate of 400 rpm are the effective optimum condition for quantitative leaching of gallium and indium.

  10. Canine SPECT studies for cerebral amino acid transport by means of 123I-3-iodo-α-methyl-L-tyrosine and preliminary kinetic analysis

    We have already reported that 123I-3-iodo-α-methyl-L-tyrosine (123I-L-AMT) is superior as a single-photon emitter labeled radiopharmaceutical reflecting cerebral amino acid transport. In this study, we investigated the distribution of 123I-L-AMT in the canine head by means of SPECT and kinetically analyzed the data in the brain. As a result, clear SPECT images of the canine brain were obtained. Kinetic analysis with a 2-compartment model, including or expressing membrane transport of the amino acid, was performed with time-activity curves in the arterial blood and in the cerebral region. The results of the analysis coincided closely with the experimental data and the relevance of the model was strongly suggested. Therefore 123I-L-AMT is considered to be useful as a single photon radiopharmaceutical which enables us to measure the cerebral amino acid transport rate. (author)

  11. Capillary Electrophoresis Profiles and Fluorophore Components of Humic Acids in Nebraska Corn and Philippine Rice Soils

    As humic substances represent relatively high molecular mass polyelectrolytes containing aromatic, aliphatic and heterocyclic subunits, capillary electrophoresis (CE) has become an attractive method for “finger-print” characterization of humic acids. In addition, fluorescence excitation-emission ma...

  12. Orthogonal translation components for the in vivo incorporation of unnatural amino acids

    Schultz, Peter G.; Xie, Jianming; Zeng, Huaqiang

    2012-07-10

    The invention relates to orthogonal pairs of tRNAs and aminoacyl-tRNA synthetases that can incorporate unnatural amino acids into proteins produced in eubacterial host cells such as E. coli, or in a eukaryotic host such as a yeast cell. The invention provides, for example but not limited to, novel orthogonal synthetases, methods for identifying and making the novel synthetases, methods for producing proteins containing unnatural amino acids, and translation systems.

  13. Orthogonal translation components for the in vivo incorporation of unnatural amino acids

    Schultz, Peter G.; Alfonta, Lital; Chittuluru, Johnathan R.; Deiters, Alexander; Groff, Dan; Summerer, Daniel; Tsao, Meng -Lin; Wang, Jiangyun; Wu, Ning; Xie, Jianming; Zeng, Huaqiang; Seyedsayamdost, Mohammad; Turner, James

    2015-08-11

    The invention relates to orthogonal pairs of tRNAs and aminoacyl-tRNA synthetase that can incorporate unnatural amino acid into proteins produced in eubacterial host cells such as E. coli, or in a eukaryotic host such as a yeast cell. The invention provides, for example but not limited to, novel orthogonal synthetases, methods for identifying and making the novel synthetases, methods for producing proteins containing unnatural amino acids, and translation systems.

  14. Miscibility behavior of two-component monolayers at the air-water interface: perfluorocarboxylic acids and DMPE.

    Yokoyama, Hiroki; Nakahara, Hiromichi; Nakagawa, Takahiro; Shimono, Satoshi; Sueishi, Kunihiko; Shibata, Osamu

    2009-09-01

    Surface pressure (pi)-molecular area (A) and surface potential (DeltaV)-A isotherms have been measured for two-component monolayers of four different perfluorocarboxylic acids [FCn; perfluorododecanoic acid (FC12), perfluorotetradecanoic acid (FC14), perfluorohexadecanoic acid (FC16), and perfluorooctadecanoic acid (FC18)] and dimyristoylphosphatidylethanolamine (DMPE) on 0.15M NaCl (pH 2) at 298.2K. The present study is focused on the miscibility and the interfacial behavior for the binary DMPE/FCn monolayers upon compression. From the isotherms, the miscibility has been elucidated in terms of the additivity rule, the interaction parameter, and the interaction energy. The interaction parameter (or energy) is compared with that for the previous dipalmitoylphosphatidylcholine (DPPC)/FCn systems [Colloids Surf. B 41 (2005) 285-298] to understand the effect of phospholipids' polar headgroup on the binary miscibility. Furthermore, the phase behavior of the DMPE/FCn systems has been morphologically examined using fluorescence microscopy (FM) and atomic force microscopy (AFM). These images reveal the different interaction modes among the four systems; DMPE can be miscible with FC12 and FC14 and immiscible with FC16 and FC18 in the monolayer state. These systematic examinations indicate that the miscibility of perfluorocarboxylic acids and phospholipids depends on combination of hydrocarbon and fluorocarbon chain lengths and on phospholipids' polar headgroups within a monolayer. PMID:19481762

  15. Bacterial Wall Components such as Lipothecoid Acid, Peptidoglycan, Liposaccharide and Lipid A Stimulate Cell Proliferation in Intestinal Epithelial Cells

    Olaya, Jaime H.; Neopikhanov, Vadim; Söderman, Charlotte; Uribe, Andrés

    2011-01-01

    Earlier studies indicate that the microflora contains mitogens to intestinal epithelial cells. Our aim is to examine whether cell wall components of both Gram-negative and positive bacteria influence cell proliferation in small intestinal and colonic epithelial cells. A human colonic epithelial cell line from adenocarcinoma (IEC-6) and a nontransformed small intestinal cell line from germ-free rats (LS-123) were incubated with (a) lipothecoid acid from Streptococcus faecalis at 1.56–50 ...

  16. Determination of sugars, organic acids, aroma components, and carotenoids in grapefruit pulps.

    Zheng, Huiwen; Zhang, Qiuyun; Quan, Junping; Zheng, Qiao; Xi, Wanpeng

    2016-08-15

    The composition and content of sugars, organic acids, volatiles and carotenoids, in the pulps of six grapefruit cultivars, were examined by HPLC and GC-MS. The results showed that sucrose was the dominant sugar in grapefruit, making up 40.08-59.68% of the total sugars, and the ratio of fructose to glucose was almost 1:1. Citric acid was the major organic acid and represented 39.10-63.55% of the total organic acids, followed by quininic acid. The ratios of individual sugars and organic acids play an important role in grapefruit taste determination. Monoterpenes and sesquiterpenes were the predominant volatiles in grapefruit, in particular d-limonene and caryophyllene. Caryophyllene, α-humulene, humulen-(v1), β-linalool and tert-butyl 2-methylpropanoate are the characteristic aroma compounds of grapefruit. Although β-carotene is the primary carotenoid in grapefruit, the pulp color is mainly determined by the ratios of zeaxanthin, β-cryptoxanthin and lycopene. Our results provide the first complete chemical characterization of the taste, aroma and color of grapefruit. PMID:27006221

  17. Effect of 5-aminolevulinic acid on kinetics of protoporphyrin IX production in CHO cells.

    W Warchoł

    2004-07-01

    Full Text Available 5-aminolevulinic acid (ALA is utilized in a photodynamic therapy as a compound capable of augmenting intracellular pool of protoporphyrin IX (PpIX, which exhibits properties of a photosensitizer. The studies were aimed at monitoring accumulation of endogenous protoporphyrin IX in CHO cells under effect of various concentrations of ALA in culture medium and following removal of the compound from the culture medium. Cell content of PpIX was determined following incubation of the cells for 72 h in a culture medium containing different concentration of ALA. Moreover, the cells were preincubated for 2 h in ALA at various concentrations and separated from the compound by medium change and their PpIX content was monitored following incubation. PpIX content was defined by a fluorescent technique under the confocal microscope. In the course of continuous incubation of cells with ALA, biphasic alterations were noted in cellular PpIX concentration. Removal of ALA from the incubation medium resulted at first in a decrease in PpIX content in cells, which was followed by an evidently augmented accumulation of the compound in the cells. The results suggested that in the case of CHO cells, exogenous ALA was not an exclusive source of PpIX synthesis and that alterations in enzyme activities were responsible for production of PpIX.

  18. Intracellular self-assembly based multi-labeling of key viral components: Envelope, capsid and nucleic acids.

    Wen, Li; Lin, Yi; Zhang, Zhi-Ling; Lu, Wen; Lv, Cheng; Chen, Zhi-Liang; Wang, Han-Zhong; Pang, Dai-Wen

    2016-08-01

    Envelope, capsid and nucleic acids are key viral components that are all involved in crucial events during virus infection. Thus simultaneous labeling of these key components is an indispensable prerequisite for monitoring comprehensive virus infection process and dissecting virus infection mechanism. Baculovirus was genetically tagged with biotin on its envelope protein GP64 and enhanced green fluorescent protein (EGFP) on its capsid protein VP39. Spodoptera frugiperda 9 (Sf9) cells were infected by the recombinant baculovirus and subsequently fed with streptavidin-conjugated quantum dots (SA-QDs) and cell-permeable nucleic acids dye SYTO 82. Just by genetic engineering and virus propagation, multi-labeling of envelope, capsid and nucleic acids was spontaneously accomplished during virus inherent self-assembly process, significantly simplifying the labeling process while maintaining virus infectivity. Intracellular dissociation and transportation of all the key viral components, which was barely reported previously, was real-time monitored based on the multi-labeling approach, offering opportunities for deeply understanding virus infection and developing anti-virus treatment. PMID:27209260

  19. The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

    J. Zahardis

    2006-11-01

    Full Text Available The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS: the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the primary products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal is described. Anomalies in the relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide polymers. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, a series of atmospheric implications of oxidative processing of particulate containing fatty acids is presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semisolids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation. Other effects, including the potential

  20. An in situ EDXRD kinetic and mechanistic study of the hydrothermal crystallization of TiO2 nanoparticles from nitric acid peptized sol-gel

    Rehan, M.; Kale, GM; Lai, X

    2015-01-01

    In situ energy dispersive X-ray diffraction (EDXRD) has been used to monitor the crystallization of TiO2 nanoparticles from hydrothermal reactions of nitric acid (HNO3) peptized sol-gels at 210, 230, 250 and 270 °C. The EDXRD peaks revealed the formation of pure rutile phase TiO2 particles from all the hydrothermal reactions studied. The reaction kinetic data have been determined by monitoring changes in the integrated peak areas of the highest intensity diffraction peak (110). A kinetic and ...

  1. Hg (II) Catalysed Oxidation of D-Arabinose and D-Mannose by Acidic Solution of Potassium Permanganate: Kinetics and Mechanism

    R. Naz; *R. Azmat; Qamar, N; 3N. I. Siddiqi

    2014-01-01

    The kinetics of Hg (II) catalyzed oxidation of D-Arabinose (Ara) and D-Mannose (Man) by potassium permanganate in acidic medium have been studied spectrophotometrically in the temperature range 30-50oC. The reactions exhibit first order kinetics with respect to [Man] and [MnO4-] while second order with [Ara]. The reaction rates were found to be unaffected by the change in [H+]. It has been observed that Hg (II) catalyzed the reaction but as the [Hg(II)] increases, reaction rate becomes indepe...

  2. Leaching Kinetics of Praseodymium in Sulfuric Acid of Rare Earth Elements (REE) Slag Concentrated by Pyrometallurgy from Magnetite Ore

    Kim, Chul-Joo; Yoon, Ho-Sung; Chung, Kyung Woo; Lee, Jin-Young; Kim, Sung-Don; Shin, Shun Myung [Korea Institute of Geoscience and Mineral Resources, Daejeon (Korea, Republic of); Kim, Hyung-Seop; Cho, Jong-Tae; Kim, Ji-Hye; Lee, Eun-Ji; Lee, Se-Il; Yoo, Seung-Joon [Seonam University, Asan (Korea, Republic of)

    2015-02-15

    A leaching kinetics was conducted for the purpose of recovery of praseodymium in sulfuric acid (H{sub 2}SO{sub 4}) from REE slag concentrated by the smelting reduction process in an arc furnace as a reactant. The concentration of H{sub 2}SO{sub 4} was fixed at an excess ratio under the condition of slurry density of 1.500 g slag/L, 0.3 mol H{sub 2}SO{sub 4}, and the effect of temperatures was investigated under the condition of 30 to 80 .deg. C. As a result, praseodymium oxide (Pr{sub 6}O{sub 1}1) existing in the slag was completely converted into praseodymium sulfate (Pr{sub 2}(SO{sub 4}){sub 3}·8H{sub 2}O) after the leaching of 5 h. On the basis of the shrinking core model with a shape of sphere, the first leaching reaction was determined by chemical reaction mechanism. Generally, the solubility of pure REEs decreases with the increase of leaching temperatures in sulfuric acid, but REE slag was oppositely increased with increasing temperatures. It occurs because the ash layer included in the slag is affected as a resistance against the leaching. By using the Arrhenius expression, the apparent activation energy of the first chemical reaction was determined to be 9.195 kJmol{sup -1}. In the second stage, the leaching rate is determined by the ash layer diffusion mechanism. The apparent activation energy of the second ash layer diffusion was determined to be 19.106 kJmol{sup -1}. These relative low activation energy values were obtained by the existence of unreacted ash layer in the REE slag.

  3. Leaching Kinetics of Praseodymium in Sulfuric Acid of Rare Earth Elements (REE) Slag Concentrated by Pyrometallurgy from Magnetite Ore

    A leaching kinetics was conducted for the purpose of recovery of praseodymium in sulfuric acid (H2SO4) from REE slag concentrated by the smelting reduction process in an arc furnace as a reactant. The concentration of H2SO4 was fixed at an excess ratio under the condition of slurry density of 1.500 g slag/L, 0.3 mol H2SO4, and the effect of temperatures was investigated under the condition of 30 to 80 .deg. C. As a result, praseodymium oxide (Pr6O11) existing in the slag was completely converted into praseodymium sulfate (Pr2(SO4)3·8H2O) after the leaching of 5 h. On the basis of the shrinking core model with a shape of sphere, the first leaching reaction was determined by chemical reaction mechanism. Generally, the solubility of pure REEs decreases with the increase of leaching temperatures in sulfuric acid, but REE slag was oppositely increased with increasing temperatures. It occurs because the ash layer included in the slag is affected as a resistance against the leaching. By using the Arrhenius expression, the apparent activation energy of the first chemical reaction was determined to be 9.195 kJmol-1. In the second stage, the leaching rate is determined by the ash layer diffusion mechanism. The apparent activation energy of the second ash layer diffusion was determined to be 19.106 kJmol-1. These relative low activation energy values were obtained by the existence of unreacted ash layer in the REE slag

  4. Principal component articial neural network calibration models for the simultaneous spectrophotometric estimation of mefenamic acid and paracetamol in tablets

    RAJAPPAN MANAVALAN

    2006-11-01

    Full Text Available Simultaneous estimation of all drug components in a multicomponent analgesic dosage form with artificial neural networks calibration models using UV spectrophotometry is reported as a simple alternative to using separate models for each component. Anovel approach for calibration using a compund spectral dataset derived from three spectra of each component is described. The spectra of mefenamic acid and paracetamol were recorded as several concentrations within their linear range and used to compute a calibration mixture between the wavelengths 220 to 340 nm. Neural networks trained by a Levenberg–Marquardt algorithm were used for building and optimizing the calibration models using MATALAB® Neural Network Toolbox and were compared with the principal component regression model. The calibration models were throughly evaluated at several concentration levels using 104 spectra obtained for 52 synthetic binary mixtures prepared using orthogonal designs. The optimized model showed sufficient robustness even when the calibration sets were constructed from a different set of pure spectra of the components. The simultaneous prediction of both components by a single neural netwook with the suggested calibration approach was successful. The model could accurately estimate the drugs, with satisfactory precision and accuracy, in tablet dosage with no interference from excipients as indicated by the results of a recovery study.

  5. Acid Blue 25 adsorption on base treated Shorea dasyphylla sawdust: Kinetic,isotherm, thermodynamic and spectroscopic analysis

    Megat Ahmad Kamal Megat Hanafiah; Wan Saime Wan Ngah; Shahira Hilwani Zolkafly; Lee Ching Teong; Zafri Azran Abdul Majid

    2012-01-01

    The potential of base treated Shorea dasyphylla (BTSD) sawdust for Acid Blue 25 (AB 25) adsorption was investigated in a batch adsorption process.Various physiochemical parameters such as pH,stirring rate,dosage,concentration,contact time and temperature were studied.The adsorbent was characterized with Fourier transform infrared spectrophotometer,scanning electron microscope and Brunauer,Emmett and Teller analysis.The optimum conditions for AB 25 adsorption were pH 2,stirring rate 500 r/min,adsorbent dosage 0.10 g and contact time 60 min.The pseudo second-order model showed the best conformity to the kinetic,data.The equilibrium adsorption of AB 25 was described by Freundlich and Langmuir,with the latter found to agree well with the isotherm model.The maximum monolayer adsorption capacity of BTSD was 24.39 mg/g at 300 K,estimated from the Langmuir model.Thermodynamic parameters such as Gibbs free energy,enthalpy and entropy were determined.It was found that AB 25 adsorption was spontaneous and exothermic.

  6. Anodically generated manganese(III) sulphate for the oxidation of dipeptides in aqueous sulphuric acid medium: A kinetic study

    M N Kumara; D Channe Gowda; A Thimme Gowda; K S Rangappa

    2004-01-01

    The kinetic of oxidation of dipeptides (DP) namely valyl-glycine (Val-Gly), alanyl-glycine (Ala-Gly) and glycyl-glycine (Gly-Gly), by Mn(III) have been studied in the presence of sulphate ions in acid medium at 26°C. The reaction was followed spectrophotometrically at max = 500 nm. A firstorder dependence of the rate on both [Mn(III)]$_o$ and [DP]o was observed. The rate is independent of the concentration of reduction product, Mn(II) and hydrogen ions. The effects of varying the dielectric constant of the medium and addition of anions such as sulphate, chloride and perchlorate were studied. The activation parameters have been evaluated using Arrhenius and Eyring plots. The oxidation products were isolated and characterized. A mechanism involving the reaction of DP with Mn(III) in the ratelimiting step is suggested. An apparent correlation was noted between the rate of oxidation and the hydrophobicity of these dimers, where increased hyphobicity results in increased rate of oxidation.

  7. Adsorption and photodegradation kinetics of herbicide 2,4,5-trichlorophenoxyacetic acid with MgFeTi layered double hydroxides.

    Nguyen, Thi Kim Phuong; Beak, Min-wook; Huy, Bui The; Lee, Yong-Ill

    2016-03-01

    The calcined layered double hydroxides (cLDHs) Ti-doped and undoped MgFe for this study were prepared by co-precipitation method followed by calcination at 500 °C. The as-prepared samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer Emmett Teller (BET) and UV-Vis diffuse reflectance spectrum (DRS) techniques and tested for adsorption and photodegradation (including photocatalytic and photo-Fenton-like) of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous solutions under visible light irradiation. In the range of studied operating conditions, the as-prepared samples exhibited excellent photo-Fenton-like activity, leading to more than 80-95% degradation of 2,4,5-T at initial concentration of 100 mg L(-1) with 4 g calcined LDHs per liter, was accomplished in 360 min, while 2,4,5-T half-life time was as short as 99-182 min. The kinetics of adsorption and photodegradation of 2,4,5-T were also discussed. These results offered a green, low cost and high efficiency photocatalyst for environmental remediation. PMID:26706931

  8. Deposition kinetics and characterization of stable ionomers from hexamethyldisiloxane and methacrylic acid by plasma enhanced chemical vapor deposition

    Urstöger, Georg; Resel, Roland; Koller, Georg; Coclite, Anna Maria

    2016-04-01

    A novel ionomer of hexamethyldisiloxane and methacrylic acid was synthesized by plasma enhanced chemical vapor deposition (PECVD). The PECVD process, being solventless, allows mixing of monomers with very different solubilities, and for polymers formed at high deposition rates and with high structural stability (due to the high number of cross-links and covalent bonding to the substrate) to be obtained. A kinetic study over a large set of parameters was run with the aim of determining the optimal conditions for high stability and proton conductivity of the polymer layer. Copolymers with good stability over 6 months' time in air and water were obtained, as demonstrated by ellipsometry, X-Ray reflectivity, and FT-IR spectroscopy. Stable coatings showed also proton conductivity as high as 1.1 ± 0.1 mS cm-1. Chemical analysis showed that due to the high molecular weight of the chosen precursors, it was possible to keep the plasma energy-input-per-mass low. This allowed limited precursor fragmentation and the functional groups of both monomers to be retained during the plasma polymerization.

  9. Sugar beet waste and its component ferulic acid inhibits external mycelium of arbuscular mycorrhizal fungus

    Medina, Almudena; Jakobsen, Iver; Egsgaard, Helge

    2011-01-01

    External arbuscular mycorrhiza (AM) mycelium plays an important role in soil while interacting with a range of biotic and abiotic factors. One example is the soil organic amendment sugar beet waste. The fermented Aspergillus niger–sugar beet waste (ASB) increases growth and P uptake by the AM...... mycelium in soil whereas non-fermented waste (SB) had a strong inhibitory effect. The underlying mechanisms are not understood. We used gas chromatography–mass spectrometry to identify differences in composition of water extracts of ASB and SB. The chromatograms showed that ferulic acid was present in SB...... and absent in ASB. We compared the effects of the water extracts of SB and ASB and ferulic acid upon the growth of Glomus intraradices in in vitro monoxenic cultures. Hyphal growth of the AM fungus G. intraradices was extremely reduced in ferulic acid and SB treatments. Moreover, AM hyphae appeared...

  10. Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

    Fawzy, Ahmed

    2016-03-15

    The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated. PMID:26794772

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

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

    2015-05-01

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

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

    In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO2, ZnO and ZrO2) was obtained by applying kinetic Monte Carlo simulation. The values of the rate constants for each step of the suggested mechanism have been obtained by simulation. The effect of the initial concentration of mineral oxides and uric acid on the rate of uric acid photo-oxidation by irradiation of some sun care agents has been studied. The kinetic Monte Carlo simulation results agree qualitatively with the existing experimental data for the production of free radicals by sun care agents. - Highlights: • The mechanism and kinetics of uric acid photo-oxidation by irradiation of sun care agents has been obtained by simulation. • The mechanism has been used for free radical production of TiO2 (rutile and anatase), ZnO and ZrO2. • The ratios of photo-activity of ZnO to anastase, rutile and ZrO have been obtained. • By doubling the initial concentrations of mineral oxide, the rate of reaction was doubled. • The optimum ratio of initial concentration of mineral oxides to uric acid has been obtained

  13. Free radical damage of nucleic acids and their components. I. Direct absorption of energy

    An attempt is made to summarize our present understanding of free radical formation and reactions when energy from ionizing radiations is deposited directly in nucleic acids. The scope of the discussion is limited to recent progress, with reference to older work only when needed for coherence

  14. Kinetic and equilibrium study on formic acid decomposition in relation to the water-gas-shift reaction.

    Yasaka, Yoshiro; Yoshida, Ken; Wakai, Chihiro; Matubayasi, Nobuyuki; Nakahara, Masaru

    2006-09-28

    Kinetics and equilibrium are studied on the hydrothermal decarbonylation and decarboxylation of formic acid, the intermediate of the water-gas-shift (WGS) reaction, in hot water at temperatures of 170-330 degrees C, to understand and control the hydrothermal WGS reaction. (1)H and (13)C NMR spectroscopy is applied to analyze as a function of time the quenched reaction mixtures in both the liquid and gas phases. Only the decarbonylation is catalyzed by HCl, and the reaction is first-order with respect to both [H(+)] and [HCOOH]. Consequently, the reaction without HCl is first and a half (1.5) order due to the unsuppressed ionization of formic acid. The HCl-accelerated decarbonylation path can thus be separated in time from the decarboxylation. The rate and equilibrium constants for the decarbonylation are determined separately by using the Henry constant (gas solubility data) for carbon monoxide in hot water. The rate constant for the decarbonylation is 1.5 x 10(-5), 2.0 x 10(-4), 3.7 x 10(-3), and 6.3 x 10(-2) mol(-1) kg s(-1), respectively, at 170, 200, 240, and 280 degrees C on the liquid branch of the saturation curve. The Arrhenius plot of the decarbonylation is linear and gives the activation energy as 146 +/- 3 kJ mol(-1). The equilibrium constant K(CO) = [CO]/[HCOOH] is 0.15, 0.33, 0.80, and 4.2, respectively, at 170, 200, 240, and 280 degrees C. The van't Hoff plot results in the enthalpy change of DeltaH = 58 +/- 6 kJ mol(-1). The decarboxylation rate is also measured at 240-330 degrees C in both acidic and basic conditions. The rate is weakly dependent on the solution pH and is of the order of 10(-4) mol kg(-1) s(-1) at 330 degrees C. Furthermore, the equilibrium constant K(CO2) = [CO(2)][H(2)]/[HCOOH] is estimated to be 1.0 x10(2) mol kg(-1) at 330 degrees C. PMID:16986841

  15. Calibration of amino acid racemization (AAR) kinetics in United States mid-Atlantic Coastal Plain Quaternary mollusks using 87Sr/ 86Sr analyses: Evaluation of kinetic models and estimation of regional Late Pleistocene temperature history

    Wehmiller, J. F.; Harris, W.B.; Boutin, B.S.; Farrell, K.M.

    2012-01-01

    The use of amino acid racemization (AAR) for estimating ages of Quaternary fossils usually requires a combination of kinetic and effective temperature modeling or independent age calibration of analyzed samples. Because of limited availability of calibration samples, age estimates are often based on model extrapolations from single calibration points over wide ranges of D/L values. Here we present paired AAR and 87Sr/ 86Sr results for Pleistocene mollusks from the North Carolina Coastal Plain, USA. 87Sr/ 86Sr age estimates, derived from the lookup table of McArthur et al. [McArthur, J.M., Howarth, R.J., Bailey, T.R., 2001. Strontium isotopic stratigraphy: LOWESS version 3: best fit to the marine Sr-isotopic curve for 0-509 Ma and accompanying Look-up table for deriving numerical age. Journal of Geology 109, 155-169], provide independent age calibration over the full range of amino acid D/L values, thereby allowing comparisons of alternative kinetic models for seven amino acids. The often-used parabolic kinetic model is found to be insufficient to explain the pattern of racemization, although the kinetic pathways for valine racemization and isoleucine epimerization can be closely approximated with this function. Logarithmic and power law regressions more accurately represent the racemization pathways for all amino acids. The reliability of a non-linear model for leucine racemization, developed and refined over the past 20 years, is confirmed by the 87Sr/ 86Sr age results. This age model indicates that the subsurface record (up to 80m thick) of the North Carolina Coastal Plain spans the entire Quaternary, back to ???2.5Ma. The calibrated kinetics derived from this age model yield an estimate of the effective temperature for the study region of 11??2??C., from which we estimate full glacial (Last Glacial Maximum - LGM) temperatures for the region on the order of 7-10??C cooler than present. These temperatures compare favorably with independent paleoclimate information

  16. Leaching potential and changes in components of metals in two acidic ferrisols

    GUO Zhao-hui; LIAO Bo-han; HUANG Chang-yong

    2006-01-01

    Two acidic ferrisols, i.e., red soil (RS) and yellow red soil (YRS), from the vicinity regions of non-ferrous ores in Hunan province of China, were leached with simulated acid rain through artificial column experiments. The results show that the total leaching mass of metals are m(Zn)>m(Cu)>m(Cd) from the original soils and m(Cd)>m(Zn)>> m(Cu) from the contaminated soils with external metals after leaching for 60 d continuously, leaching quantities of Cd and Zn from the contaminated red soil (CRS)are more than that from the contaminated yellow red soil (CYRS), but for Cu, it is almost the same. The preferential fractions for leaching are mainly in exchangeable forms, and content of exchangeable forms decreases significantly in the contaminated soil profiles. The unstable fractions of Cd, Cu and Zn in the RS and YRS increase significantly with the decrease of pH value of simulated acid rain. Changes of fractions of external Cd, Cu, and Zn in the residual CRS and CYRS profiles are significantly affected by the acidity of acid rain, too. After leaching for 60 d continuously, Cd exists mostly in exchangeable form, Cu exists mainly in exchangeable, manganese oxide-occluded and organically bounding forms, and Zn exists in residual in CRS and CYRS profiles.Most of exchangeable Cd and Zn exist only small in surface layer (0-20 cm) and are transferred to the sub-layers, contrarily, Cu accumulates mostly in the topsoil (0-20 cm) with low translocation.

  17. Regulation of taste-active components of meat by dietary branched-chain amino acids; effects of branched-chain amino acid antagonism.

    Imanari, M; Kadowaki, M; Fujimura, S

    2008-05-01

    1. The effects of dietary branched-chain amino acids (BCAAs) including leucine (Leu), isoleucine (Ile) and valine (Val) on taste-active components, especially free glutamate (Glu), in meat were investigated. 2. Broiler chickens (28 d old) were given varied dietary BCAA levels for 10 d before marketing. Dietary BCAA content ratios were either 100:100:100 (Low Leu group), 150:100:100 (Control group) or 150:150:150 (High Ile + Val group) for Leu:Ile:Val (% of each BCAA requirement according to NRC, 1994). Taste-related components of meat (free amino acids and ATP metabolites) and sensory scores of meat soup were estimated. 3. Free Glu content, the main taste-active component of meat, was significantly increased by dietary BCAA. Compared to the Control group, free Glu content increased by 30% in the High Ile + Val group. However, the inosine monophosphate (IMP) content in meat did not change among groups. 4. Sensory evaluation of meat soups showed that Control and High Ile + Val groups had different meat flavours. The sensory score of overall taste intensity was significantly higher in the High Ile + Val group. 5. These results suggest that dietary BCAA concentrations regulate free Glu in meat. Increasing dietary Ile + Val induces an increase in free Glu content of meat, improves meat taste and is more effective for increasing free Glu content in meat than decreasing dietary Leu level. PMID:18568754

  18. Production of lactobionic acid and sorbitol from lactose/fructose substrate using GFOR/GL enzymes from Zymomonas mobilis cells: a kinetic study.

    Pedruzzi, Israel; da Silva, Eduardo A Borges; Rodrigues, Alírio E

    2011-07-10

    In this work, we have investigated the kinetics of the biotechnological production of lactobionic acid (LBA) and sorbitol by the catalytic action of glucose-fructose oxidoreductase (GFOR) and glucono-δ-lactonase (GL) enzymes. The cells of bacterium Zymomonas mobilis ATCC 29191 containing this enzymatic complex were submitted to permeabilization and reticulation procedures. The effect of the concentration of substrates on the rate of product formation using a mobilized cell system was investigated. The application of higher fructose concentration seems to not affect the initial rate of formation of the bionic acid. Under conditions of low initial concentration of lactose, the experimental kinetic data of the bi-substrate reaction were modelled by assuming a rate equation of the classical ping-pong mechanism. The found kinetic parameters displayed a low affinity of the GFOR enzyme for both substrates. The enzymatic system did not exhibit normal Michaelis-Menten kinetics in response to a change of concentration of lactose, when fructose was held constant, presenting a sigmoid relationship between initial velocity and substrate concentration. A rate equation based on Hill kinetics was used to describe the kinetic behaviour of this enzyme-substituted reaction at higher lactose concentrations. The results from batch experiments using immobilized cells within Ca-alginate beads revealed that there is no pronounced occurrence of mass transfer limitations on LBA production for beads with 1.2 mm in average diameter. This discussion aids for defining the best operating conditions to maximize the productivity for LBA and sorbitol in this bioconversion and also for reducing the complexity of downstream separation processes. PMID:22112407

  19. Discovery and Characterization of Bicereucin, an Unusual d-Amino Acid-Containing Mixed Two-Component Lantibiotic.

    Huo, Liujie; van der Donk, Wilfred A

    2016-04-27

    Lantibiotics are a group of ribosomally synthesized and post-translationally modified peptides (RiPPs) exhibiting antimicrobial activity. They are characterized by the presence of the thioether-containing bisamino acids lanthionine and methyllanthionine. Here, we report a two-component lantibiotic from Bacillus cereus SJ1 with unusual structural features that we named bicereucin. Unlike all previous two-component lantibiotics, only one of the two peptides of bicereucin contains a lanthionine. The second peptide lacks any cysteines but contains several d-amino acids. These are installed by the dehydrogenase BsjJB, the activity of which was successfully reconstituted in vitro. The proteolytic removal of the leader peptide was also performed in vitro. Bicereucin displayed synergistic antimicrobial activities against Gram-positive strains including methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococci as well as hemolytic activity. To illustrate the utility of the enzymes, an analog of the d-amino acid containing opioid dermorphin was successfully produced in E. coli by employing the dehydratase BsjM and the dehydrogenase NpnJA. PMID:27074593

  20. Effect of humic acid and transition metal ions on the debromination of decabromodiphenyl by nano zero-valent iron: kinetics and mechanisms

    E-waste sites are one of the main sources of the pollutant decabromodiphenyl ether (BDE209); contaminated farmland and water bodies urgently need to be remediated. As a potential in situ remediation technology, nano zero-valent iron (nZVI) technology effectively removes PBDEs. However, the humic acid (HA) and heavy metals in the contaminated sites affect the remediation effects. In this study, we explored the influence of HA and transition metals on the removal of PBDEs by nZVI. The specific surface area and average size of the nZVI particles we prepared were 35 m2/g and 50–80 nm, respectively. The results showed that HA inhibited the removal of PBDEs; as the concentration of HA increased, its inhibitory effect intensified and the kobs decreased. However, the three metal ions (Cu2+, Co2+, and Ni2+) enhanced the removal of PBDEs. The enhancement effect was followed the order Ni2+ > Cu2+ > Co2+. As the concentration of metal ions increased, the promotion effect improved. The synergistic effect of HA and the metal ions was manifested in the combination of the inhibitory effect and the enhancement effect. The values of the first-order kinetic constants (kobs) under the combined effect were between the values of the rate constants under the individual components. The inhibitory mechanism was the chemisorption of HA, i.e., the benzene carboxylic and phenolic hydroxyl groups in HA occupied the surfactant reactive sites of nZVI, thus inhibiting the removal of BDE209. The promotion mechanism of Cu2+, Co2+, and Ni2+ can be explained by their reduction to zero valence on the nZVI surface; furthermore, Ni2+ strongly affects the debromination and dehydrogenation of BDE209, leading to a stronger promotability than Cu2+or Co2+

  1. Optimization of growth media components for polyhydroxyalkanoate (PHA) production from organic acids by Ralstonia eutropha

    Yang, Yung-Hun; Brigham, Christopher J.; Budde, Charles F.; Boccazzi, Paolo; Willis, Laura B.; Hassan, Mohd Ali; Yusof, Zainal Abidin Mohd; Rha, ChoKyun; Sinskey, Anthony J.

    2010-01-01

    We employed systematic mixture analysis to determine optimal levels of acetate, propionate, and butyrate for cell growth and polyhydroxyalkanoate (PHA) production by Ralstonia eutropha H16. Butyrate was the preferred acid for robust cell growth and high PHA production. The 3-hydroxyvalerate content in the resulting PHA depended on the proportion of propionate initially present in the growth medium. The proportion of acetate dramatically affected the final pH of the growth medium. A model was ...

  2. Kinetic analyses of trans-1-amino-3-[18F]fluorocyclobutanecarboxylic acid transport in Xenopus laevis oocytes expressing human ASCT2 and SNAT2

    Introduction: Trans-1-amino-3-[18F]fluorocyclobutanecarboxylic acid (anti-[18F]FACBC) is a promising amino acid positron emission tomography (PET) radiotracer for visualizing prostate cancer. We previously showed that anti-FACBC is transported by amino acid transporters, especially by alanine-serine-cysteine transporter 2 (ASCT2), which is associated with tumor growth. We studied this affinity to assess the mechanism of anti-FACBC transport in prostate cancer cells. Methods: Kinetic assays for trans-1-amino-3-fluoro-[1-14C]cyclobutanecarboxylic acid ([14C]FACBC) were performed in Xenopus laevis oocytes over-expressing either ASCT2 or sodium-coupled neutral amino acid transporter 2 (SNAT2), both of which are highly expressed in prostate cancer cells. We also examined the kinetics of [14C]FACBC uptake using mammalian cell lines over-expressing system L amino acid transporter 1 or 2 (LAT1 or LAT2). Results: ASCT2 and SNAT2 transported [14C]FACBC with Michaelis–Menten kinetics Km values of 92.0 ± 32.3 μM and 222.0 ± 29.3 μM, respectively. LAT1 and LAT2 transported [14C]FACBC with Michaelis–Menten Km values of 230.4 ± 184.5 μM and 738.5 ± 87.6 μM, respectively. Conclusions: Both ASCT2 and SNAT2 recognize anti-FACBC as a substrate. Anti-FACBC has higher affinity for ASCT2 than for SNAT2, LAT1, or LAT2. The ASCT2-preferential transport of anti-[18F]FACBC in cancer cells could be used for more effective prostate cancer imaging

  3. A New Strategy for the Preparation of N-Aminopiperidine Using Hydroxylamine-O-Sulfonic Acid: Synthesis, Kinetic Modelling, Phase Equilibria, Extraction and Processes

    E. Labarthe; A. J. Bougrine; Véronique Pasquet; H. Delalu

    2013-01-01

    A new strategy for the synthesis of N-aminopiperidine (NAPP) was developed using hydroxylamine-O-sulfonic acid (HOSA). A systematic study of NAPP formation and degradation reactions was carried out in diluted medium, in order to identify products and to establish a kinetic modelling. Principal parameters have been defined, in particular, that obtaining high yields (>90%) requires non stoichiometric conditions. The extraction and purification processes were also studied. NAPP isolation and pi...

  4. Controlling the degradation kinetics of porous iron by poly(lactic-co-glycolic acid) infiltration for use as temporary medical implants

    Yusop, Abdul Hakim Md; Daud, Nurizzati Mohd; Nur, Hadi; Kadir, Mohammed Rafiq Abdul; Hermawan, Hendra

    2015-01-01

    Iron and its alloy have been proposed as biodegradable metals for temporary medical implants. However, the formation of iron oxide and iron phosphate on their surface slows down their degradation kinetics in both in vitro and in vivo scenarios. This work presents new approach to tailor degradation behavior of iron by incorporating biodegradable polymers into the metal. Porous pure iron (PPI) was vacuum infiltrated by poly(lactic-co-glycolic acid) (PLGA) to form fully dense PLGA-infiltrated po...

  5. Experimental validation of concentration profiles in an HCCI engine, modelled by a multi-component kinetic mechanism: Outline for auto-ignition and emission control

    Machrafi, Hatim, E-mail: hatim-machrafi@enscp.f [UPMC Universite Paris 06, Ecole Nationale Superieure de Chimie de Paris, 11, rue de Pierre et Marie Curie, 75005 Paris (France); Universite de Liege, Thermodynamique des Phenomenes Irreversibles, 17, Allee du Six-Aout, 4000 Liege (Belgium)

    2010-10-15

    In order to contribute to the auto-ignition and emission control for Homogeneous Charge Compression Ignition (HCCI), a kinetic multi-component mechanism, containing 62 reactions and 49 species for mixtures of n-heptane, iso-octane and toluene is validated in this work, comparing for the concentration profiles of the fuel, the total hydrocarbons, O{sub 2}, CO{sub 2}, CO, acetaldehyde and iso-butene. These species are sampled during the combustion and quantified. For these measurements an automotive exhaust analyser, a gas chromatograph, coupled to a mass spectrometer and a flame ionisation detector are used, depending on the species to be measured. The fuel, total hydrocarbons, O{sub 2}, CO{sub 2}, iso-butene and acetaldehyde showed a satisfactory quantitative agreement between the mechanism and the experiments. Both the experiments and the modelling results showed the same formation behaviour of the different species. An example is shown of how such a validated mechanism can provide for a set of information of the behaviour of the auto-ignition process and the emission control as a function of engine parameters.

  6. 2.4. The kinetics of hydrochloric-acid decomposition of calcined concentrate of boron raw material of Ak-Arkhar Deposit

    Present article is devoted to kinetics of hydrochloric-acid decomposition of calcined concentrate of boron raw material of Ak-Arkhar Deposit. The experimental data of dependence of hydrochloric-acid decomposition of calcined boron raw material for boron oxide extraction on temperature (20-80 deg C) and process duration (15-60 min) were considered. It was defined that at temperature increasing the boron oxide extraction from borosilicate raw material increases from 24.1 till 86.8%. The constants of decomposition rate of boron raw material were calculated.

  7. Myo-inositol esters of indole-3-acetic acid are endogenous components of Zea mays L. shoot tissue

    Chisnell, J. R.

    1984-01-01

    Indole-3-acetyl-myo-inositol esters have been demonstrated to be endogenous components of etiolated Zea mays shoots tissue. This was accomplished by comparison of the putative compounds with authentic, synthetic esters. The properties compared were liquid and gas-liquid chromatographic retention times and the 70-ev mass spectral fragmentation pattern of the pentaacetyl derivative. The amount of indole-3-acetyl-myo-inositol esters in the shoots was determined to be 74 nanomoles per kilogram fresh weight as measured by isotope dilution, accounting for 19% of the ester indole-3-acetic acid of the shoot. This work is the first characterization of an ester conjugate of indole-3-acetate acid from vegetative shoot tissue using multiple chromatographic properties and mass spectral identification. The kernel and the seedling shoot both contain indole-3-acetyl-myo-inositol esters, and these esters comprise approximately the same percentage of the total ester content of the kernel and of the shoot.

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

    Sanjay Kumar Singh

    2011-09-01

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

  9. Hg (II Catalysed Oxidation of D-Arabinose and D-Mannose by Acidic Solution of Potassium Permanganate: Kinetics and Mechanism

    *1R. Naz

    2014-09-01

    Full Text Available The kinetics of Hg (II catalyzed oxidation of D-Arabinose (Ara and D-Mannose (Man by potassium permanganate in acidic medium have been studied spectrophotometrically in the temperature range 30-50oC. The reactions exhibit first order kinetics with respect to [Man] and [MnO4-] while second order with [Ara]. The reaction rates were found to be unaffected by the change in [H+]. It has been observed that Hg (II catalyzed the reaction but as the [Hg(II] increases, reaction rate becomes independent. Negligible effect of ionic strength (μ on the rate of oxidation has also been noted which supports the presence of at least one neutral specie in the rate determining step. The rate of oxidation was influenced by the change in temperature. Various activation parameters have been calculated. Formic acid and erythronic acid were identified as main oxidation product in case of arabinose while for mannose formic acid and arabinonic acid were identified. A mechanism consistent with the above findings has also been proposed.

  10. Kinetics and mechanism of the reduction of hydroxylamine-O-sulfonic acid by the hexaaquochromium(II) ion

    Bakac, A.; Simunic, J.L.; Espenson, J.H. (Iowa State Univ., Ames (USA))

    1990-03-07

    The title reaction takes place with a 2:1 (Cr{sup 2+}):(HSA) stoichiometry (HSA = hydroxylamine-O-sulfonic acid) and yields CrNH{sub 3}{sup 3+}, Cr{sup 3+}, and CrSO{sub 4}{sup +} as the main products. The kinetics conform to the rate law {minus}d(HSA)/dt = {minus}d(Cr{sup 2+})/2(dt) = k{sub obs}(Cr{sup 2+})(HSA), where k{sub obs} = kK{sub a}/(K{sub a} + (H{sup +)}). At 25{degree}C and 1.0 M ionic strength (CHlO{sub 4} + LiClO{sub 4}) the parameter k has the value of 20.5 {plus minus} 0.3 M{sup {minus}1} s{sup {minus}1} when K{sub a} is set at the value (6.8 {plus minus} 0.8) {times} 10{sup {minus}2} M, as determined by pH titration. In the proposed mechanism, Cr{sup 2+} attacks at the nitrogen end of the anion, NH{sub 2}OSO{sub 3}{sup {minus}}, to form CrNH{sub 3}{sup 3+} and SO{sub 4}{sup {center dot}{minus}}. The sulfate radical anion then oxidizes rapidly the second mole of Cr{sup 2+} to yield Cr{sup 3+} and some CrSO{sub 4}{sup +}. In solutions containing Br{sup {minus}}, SO{sub 4}{sup {center dot}{minus}} oxidizes it to Br{sub 2}{sup {center dot}{minus}}. The latter reacts with Cr{sup 2+} to yield CrBr{sup 2+}. 19 refs., 2 figs.

  11. A study of the film formation kinetics on zinc in different acidic corrosion inhibitor solutions by quartz crystal microbalance

    Chromates conversion coatings provide very effective corrosion protection for many metals. However, the high toxicity of chromate leads to an increasing interest in using non-toxic alternatives such as molybdates, silicates, rare earth metal ions and etc. In this work, quartz crystal microbalance (QCM) was applied as an in-situ technique to follow the film formation process on zinc (plated on gold) in acidic solutions containing an inorganic inhibitor, i.e. potassium chromate, sodium silicate, sodium molybdate or cerium nitrate. Using an equation derived in this work, the interfacial mass change during the film formation process under different conditions was calculated, indicating three different film formation mechanisms. In the presence of K2CrO4 or Na2SiO3, the film growth follows a mix-parabolic law, showing a process controlled by both ion diffusion and surface reaction. The apparent kinetic equations are 0.4t = -17.4 + 20Δm f + (Δm f)2 and 0.1t = 19.0 + 8.4Δm f + 10(Δm f)2 respectively (t and Δm are in seconds and μg/cm2). In solutions containing Na2MoO4, a logarithmic law of Δm f = -24.7 + 6.6 ln t was observed. Changing the inhibitor to Ce(NO3)3, the film growth was found to obey an asymptote law that could be fit into the equation of Δm f = 55.1(1 - exp(-2.6 x 10-3 t))

  12. Conversion of lignocellulosic biomass into its molecular components by sequential combination of organic acid and base

    Noda, Yu

    The primary objective of this research is to explore a new concept of converting lignocellulosic biomass into liquid organic products via hydrolysis by sequentially combining acid and base treatments. The concept was examined by studying two-step hydrolytic reactions of biomass (spruce) using oxialic acid (OA) and tetramethylammonium hydroxide (TMAH) at moderate reaction temperatures below 200 °C. Different selectivity of C-O bond cleavage of hemicellulose, cellulose, and lignin between the reactions with OA and TMAH was demonstrated, and the sequential combination of OA and TMAH treatments exhibited an enhancing effect on conversion of biomass, which proves the promise of the proposed concept. A similar enhancing effect of combination was further confirmed in the reactions with mineral acid and base. Interestingly, characterization of solid residue from reactions of biomass and further investigation of the reactions of commercial cellulose revealed that the A-B sequence (the first reaction with OA and the second with TMAH) enhanced the conversion of cellulose at the second step with TMAH. It was suggested from the NMR and XRD study of solid residues that this enhancement was caused by the reduction of crystallinity of cellulose by the first reaction with OA. This effect was shown to be an interesting feature of A-B treatment sequence for converting lignocellulosic biomass. To improve the yield of monomeric sugars, the effect of adding organic solvents to the system was also studied. No improvement on sugar yield was observed under the explored conditions. However, it was shown that some furans and phenols can be directly formed from the reactions of biomass in the binary solvent system, which may be beneficial for producing more value-added chemicals from biomass.

  13. Asymmetric synthesis of quaternary aryl amino acid derivatives via a three-component aryne coupling reaction

    Elizabeth P. Jones

    2011-11-01

    Full Text Available A method was developed for the synthesis of α-alkyl, α-aryl-bislactim ethers in good to excellent yields and high diastereoselectivities, consisting of a facile one-pot procedure in which the aryl group is introduced by means of a nucleophilic addition to benzyne and the alkyl group by alkylation of a resultant benzylic anion. Hydrolysis of the sterically less hindered adducts gave the corresponding quaternary amino acids with no racemization, whereas hydrolytic ring opening gave the corresponding valine dipeptides from bulkier bislactims.

  14. Peak alignment and robust principal component analysis of gas chromatograms of fatty acid methyl esters and volatiles

    Frosch, Stina; Jørgensen, Bo

    2007-01-01

    Gas chromatograms of fatty acid methyl esters and of volatile lipid oxidation products from fish lipid extracts are analyzed by multivariate data analysis [principal component analysis (PCA)]. Peak alignment is necessary in order to include all sampled points of the chromatograms in the data set....... The ability of robust algorithms to deal with outlier problems, including both sample-wise and element-wise outliers, and the advantages and drawbacks of two robust PCA methods, robust PCA (ROBPCA) and robust singular value decomposition when analysing these GC data were investigated. The results show...

  15. Relations between basic milk components and free fatty acid content in Holstein cow milk as lipolysis parameter

    Luděk Stádník; Jaromír Ducháček; Renáta Toušová; Jan Beran; Martin Ptáček; Lenka Kouřimská

    2015-01-01

    The aim of this study was to evaluate in detail the relationship between the basic milk components (fat and protein percentage) and the free fatty acids (FFA) content, as indicators of spontaneous and/or induced lipolysis. The additional aim of the study was to compare the FFA content of milk with respect to spontaneous and induced lipolysis. Milking was carried out in herringbone parlour twice a day. In total, 540 milk samples were obtained for evaluation of spontaneous (n=240) and induced l...

  16. Influence of organic acids on kinetic release of chromium in soil contaminated with leather factory waste in the presence of some adsorbents.

    Taghipour, Marzieh; Jalali, Mohsen

    2016-07-01

    In this study, batch experiments were conducted to investigate the effects of nanoparticles (NPs) (MgO, ZnO, TiO2) and clay minerals (bentonite, zeolite) on the release of chromium (Cr) from leather factory waste (LFW) and LFW treated soil using organic acids. Chromium release from all treatments was studied in the presence of citric acid, oxalic acid and CaCl2 solutions. The results showed that, in all treatments, organic acids released more Cr than inorganic salt (CaCl2). The release of Cr by citric acid was higher than that by oxalic acid. In LFW treated soil and LFW, the release of Cr from the all treatments with NPs was less than that from the clay mineral treatments. On the other hand, in the presence of organic acids, Cr release by NPs and clay minerals decreased. Two kinetic models including pseudo-first- and pseudo-second-order model were tested to describe the time dependent Cr release data. Among the kinetic models used, the pseudo-second-order model generally gave the best fits to experimental data. Before and after release experiments, Cr in LFW, treated LFW, control soil and LFW treated soils were fractionated. In all treatments, the greatest amounts of Cr were found in the residual fraction (RES). The organic acids were effective in reducing the exchangeable (EXC), bound to organic matter (OM) and bound to carbonate (CAR) fractions of Cr in all treatments, whereas, after release of Cr from treated soils, Cr remained mainly in the RES fraction. The application of NPs and clay minerals in soil led to a significant transformation of Cr from mobile fractions to the RES fraction. Therefore, organic ligands played a dominant role in mobility and bioavailability of Cr and the removal of Cr by adsorbents. PMID:27139119

  17. Protective Effects of Dihydrocaffeic Acid, a Coffee Component Metabolite, on a Focal Cerebral Ischemia Rat Model

    Kyungjin Lee

    2015-06-01

    Full Text Available We recently reported the protective effects of chlorogenic acid (CGA in a transient middle cerebral artery occlusion (tMCAo rat model. The current study further investigated the protective effects of the metabolites of CGA and dihydrocaffeic acid (DHCA was selected for further study after screening using the same tMCAo rat model. In the current study, tMCAo rats (2 h of MCAo followed by 22 h of reperfusion were injected with various doses of DHCA at 0 and 2 h after onset of ischemia. We assessed brain damage, functional deficits, brain edema, and blood-brain barrier damage at 24 h after ischemia. For investigating the mechanism, in vitro zymography and western blotting analysis were performed to determine the expression and activation of matrix metalloproteinase (MMP-2 and -9. DHCA (3, 10, and 30 mg/kg, i.p. dose-dependently reduced brain infarct volume, behavioral deficits, brain water content, and Evans Blue (EB leakage. DHCA inhibited expression and activation of MMP-2 and MMP-9. Therefore, DHCA might be one of the important metabolites of CGA and of natural products, including coffee, with protective effects on ischemia-induced neuronal damage and brain edema.

  18. Influence of acid rain components on radiocesium-137 desorption from Cetraria islandica (L. Ach. lichen

    Miljanić Šćepan S.

    2012-01-01

    Full Text Available Desorption of 137Cs from Cetraria islandica (L. Ach. lichen was performed by five consecutive desorptions with five identical solution volumes. Solutions of H2SO4, HNO3 and their mixtures, with pH 4.61, 5.15 and 5.75 were used for desorption. The desorbed amount of 137Cs (average value, all solutions used from lichen, for a given pH value was 49.2% for pH 4.61; 47.0% for pH 5.15 and 47.6% for pH 5.75. The obtained values of the desorbed amount of 137Cs from lichen are in accordance with the data obtained in earlier work, when 46.2 % 137Cs was desorbed from lichen for pH 3.75, and 47.2% was desorbed for pH 2.87. A higher percentage of 59.8%, obtained for pH 2.00 indicates increased activity of H+ ions. The amount of desorbed 137Cs from lichen using solutions corresponding to acid rain cannot be lower than the stated values as they contain other substances besides the acid solutions used in this work.

  19. Two-Component Regulatory Systems – implication in the quorum sensing mechanisms and bacteriocin production in lactic acid bacteria

    Lia–Mara Ditu

    2014-08-01

    Full Text Available For lactic acid bacteria, the mechanisms of quorum sensing and response are mediated by peptides or pheromones that interfere with the synthesis of antimicrobial peptides (AMP called bacteriocins, when these molecules reach a certain critical level of concentration. Generally, the synthesis and activity of pheromones is adjusted by means of a two-component regulatory system. The observation that some microorganisms, in particular lactic acid bacteria, produce bacteriocins according to the cell density, has led to the discovery of the involvement of QS mechanisms in the synthesis of these peptides. Bacteriocins synthesis is inducible, the process requiring the extracellular accumulation of peptides that functions as chemical messengers activators of bacteriocins synthesis. This minireview presents the molecular architecture and functions of two-component regulatory systems and ABC transporters implicated in the synthesis and secretion of nisin, one of the most studied bacteriocin. The elucidation of the intimate mechanisms of bacteriocins synthesis is equally of biotechnological and medical importance, opening interesting perspectives for the development of improved technologies for the production of bacteriocins with good yields, and also, for increasing the beneficial anti-infective roles of probiotic bacteria when administered in vivo.

  20. Characterization of a two-component system in Streptococcus pyogenes which is involved in regulation of hyaluronic acid production.

    Bernish, B; van de Rijn, I

    1999-02-19

    Hyaluronic acid production by group A streptococci is regulated by transcriptional control. In this study, transposon mutagenesis of an unencapsulated strain yielded an encapsulated mutant. Two genes homologous to sensors and response regulators of bacterial two-component systems were identified downstream of the transposon insertion. Inactivation of the putative sensor gene, csrS, in three different unencapsulated strains yielded encapsulated mutant strains. Electrophoretic mobility shift assays determined factor(s) in a cytoplasmic extract of an unencapsulated group A streptococcal strain was binding to a double-stranded DNA fragment derived from the has operon promoter. In contrast, similarly prepared cytoplasmic extracts from a csrS deletion mutant did not shift the fragment. The putative response regulator, CsrR, was partially purified and was shown to bind the has operon promoter fragment. The affinity and specificity of CsrR for the fragment were increased significantly after incubation with acetyl phosphate. DNase I footprinting determined that the acetyl phosphate-treated CsrR was binding to key sequences in the promoter and the coding region of hasA. Therefore, a two-component system is repressing the production of hyaluronic acid in group A streptococci using a phosphorylation-dependent binding interaction between the response regulator CsrR and the promoter region of the has operon. PMID:9988717

  1. Identification and Kinetics Study on the Transformation of Mevinolin in Acidic Alcohol Solution by High-performance Liquid Chromatography with Photodiode Array Detector or Mass Spectrometry

    2006-01-01

    Mevinolin is one of the earlier statin drugs which is effective for the treatment of hypercholesterolemia, as an inhibitor of the HMG-CoA reductase. The transformations of mevinolin in acidic alcohol(such as ethanol, methanol and isopropanol) solutions caused by solvent effects were revealed in the present article. The solvates, that is, mevinolinic methyl ester, mevinolinic ethyl ester and mevinolinic isopropyl ester, were identified by LC/PDA and LC/MS. The kinetics parameters of the transformations caused by solvent effects, such as the observed rate constant of mevinolin(kobs), the maximum concentration(cmax), and its corresponding maximum time(tmax, time for the acid form to reach the maximum concentration) of mevinolinic acid, are discussed. The influencing factors, such as the kind of solvents, the acidic concentration, the initial mevinolin concentration, and the water content as well as temperature were investigated. Two kinds of comparative reactions, hydrolysis and alcoholysis, of mevinolin in solution were studied. This detailed study on the kinetics of mevinolin transformations is valuable and meaningful for the purification, preparation, injection manufacturing, extraction, storage, etc., of mevinolin or other similar compounds. This work provides useful information for the quality control of mevinolin and mevinolin-like drugs as well.

  2. Polar modified post-cross-linked resin and its adsorption toward salicylic acid from aqueous solution: Equilibrium, kinetics and breakthrough studies.

    Fu, Zhenyu; He, Chunlian; Huang, Jianhan; Liu, You-Nian

    2015-08-01

    A novel polar modified post-cross-linked resin PDMPA was synthesized, characterized and evaluated for adsorption of salicylic acid from aqueous solution. PDMPA was prepared by a suspension polymerization of methyl acrylate (MA) and divinylbenzene (DVB), a Friedel-Crafts reaction and an amination reaction. After characterization of the chemical and pore structure of PDMPA, the adsorption behaviors of salicylic acid on PDMPA were determined in comparison with the precursor resins. The equilibrium adsorption capacity of salicylic acid on PDMPA was much larger than the precursor resins and the equilibrium data were correlated by both of the Langmuir and Freundlich models. The pseudo-second-order rate equation fitted the kinetic data better than the pseudo-first-order rate equation, and the micropore diffusion model could characterize the kinetic data very well. The dynamic experimental results showed that the breakthrough point and saturated point of salicylic acid on PDMPA were 40.3 and 92.4BV (1BV=10mL) at a feed concentration of 995.8mg/L and a flow rate of 1.4mL/min, and the resin column could be regenerated by 16.0BV of a mixture desorption solvent containing 0.01mol/L of NaOH (w/v) and 50% of ethanol (v/v). PMID:25863446

  3. Kinetic model-based feed-forward controlled fed-batch fermentation of Lactobacillus rhamnosus for the production of lactic acid from Arabic date juice.

    Choi, Minsung; Al-Zahrani, Saeed M; Lee, Sang Yup

    2014-06-01

    Arabic date is overproduced in Arabic countries such as Saudi Arabia and Iraq and is mostly composed of sugars (70-80 wt%). Here we developed a fed-batch fermentation process by using a kinetic model for the efficient production of lactic acid to a high concentration from Arabic date juice. First, a kinetic model of Lactobacillus rhamnosus grown on date juice in batch fermentation was constructed in EXCEL so that the estimation of parameters and simulation of the model can be easily performed. Then, several fed-batch fermentations were conducted by employing different feeding strategies including pulsed feeding, exponential feeding, and modified exponential feeding. Based on the results of fed-batch fermentations, the kinetic model for fed-batch fermentation was also developed. This new model was used to perform feed-forward controlled fed-batch fermentation, which resulted in the production of 171.79 g l(-1) of lactic acid with the productivity and yield of 1.58 and 0.87 g l(-1) h(-1), respectively. PMID:24100793

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

    GOVINDASAMY RAJARAJAN

    2009-02-01

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

  5. A calorimetric study of the kinetics and thermodynamics of the attack of synthetic fluorapatite by mixtures of sulfuric and phosphoric acids is undertaken at 25 deg. C

    A calorimetric study of the kinetics and thermodynamics of the attack of synthetic fluorapatite by mixtures of sulfuric and phosphoric acids is undertaken at 25 deg.. C. The global enthalpy of the attack equals -407.0 kJ/mol. Interpretation of the calorimeteric results by Avrami model shows the existence of two steps. The first is attributed to the dissolution of the solid, and the second to precipitation of gypsum. The deconvoluted curves were analysed iteratively to obtain the kinetic parameters and the enthalpy of precipitation. The later quantity does not differ from the experimental value by more than 2.3% and the reaction order equals 2 and 0.5 for calcium and sulphate ions respectively

  6. The thermal decomposition of N,N-dimethyl-3-oxa-glutaramic acid and the kinetics of its second-stage thermal decomposition reaction

    2008-01-01

    N,N-dimethyl-3-oxa-glutaramic acid was purified and characterized by 1H-NMR, Fourier transform in-frared spectroscopy (FT-IR) and elemental analysis. The thermal decomposition of the title compound was studied by means of thermogravimetry differential thermogravimetry (TG-DTG) and FT-IR. The ki-netic parameters of its second-stage decomposition reaction were calculated and the decomposition mechanism was discussed. The kinetic model function in a differential form, apparent activation energy and pre-exponential constant of the reaction are 3/2 [(1-α) 1/3-1]-1, 203.75 kJ-mol-1 and 1017.95s-1, respec-tively. The values of ΔS≠, ΔH≠ andΔG≠ of the reaction are 94.28 J-mol-1-K-1, 203.75 kJ-mol-1 and 155.75 kJ-mol-1, respectively.

  7. Thermal degradation kinetics and solid state, temperature dependent, electrical conductivity of charge–transfer complex of phenothiazine with chloranil and picric acid

    M A Ashok; B N Achar

    2008-02-01

    Temperature dependent electrical conductivity and thermal degradation kinetics of charge–transfer (C–T) complexes of phenothiazine (PTZ) with -chloranil (CHL) and picric acid (PA), are reported. These C–T complexes exhibited semiconducting behaviour. The activation energies for PTZ–CHL and PTZ–PA complexes are calculated based on their electrical conductivities measured over the temperature ranges 30–110°C and 30–90°C, respectively. And these energies for PTZ–CHL and PTZ–PA are 0.54 eV and 0.75 eV, respectively. The complexes are analysed for the kinetic parameters like the activation energy for decomposition and the Arrhenius pre-exponential factors in their pyrolysis region using Broido’s, Coats–Redfern as well as Horowitz–Metzger methods. Using standard equations, thermodynamic parameters such as enthalpy, entropy and free energies, are calculated.

  8. Kinetics of Mo, Ni, V and Al leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide

    The kinetics of molybdenum, nickel, vanadium and aluminium leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide was investigated. The effects of temperature and particle size were examined. In addition, the reaction mechanism for the dissolution of the spent catalyst was discussed. The results of the kinetic analysis for various experimental conditions indicated that the reaction rate of leaching process is controlled by chemical reaction at the particle surface. The values of the activation energies of 31 ± 2, 36 ± 4, 30 ± 4 and 57 ± 3 kJ mol-1 for Mo, Ni, V and Al, respectively, are characteristic for mechanism controlled by chemical reaction.

  9. Kinetics of Mo, Ni, V and Al leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide.

    Szymczycha-Madeja, Anna

    2011-02-28

    The kinetics of molybdenum, nickel, vanadium and aluminium leaching from a spent hydrodesulphurization catalyst in a solution containing oxalic acid and hydrogen peroxide was investigated. The effects of temperature and particle size were examined. In addition, the reaction mechanism for the dissolution of the spent catalyst was discussed. The results of the kinetic analysis for various experimental conditions indicated that the reaction rate of leaching process is controlled by chemical reaction at the particle surface. The values of the activation energies of 31±2, 36±4, 30±4 and 57±3 kJ mol(-1) for Mo, Ni, V and Al, respectively, are characteristic for mechanism controlled by chemical reaction. PMID:21167639

  10. Palladium(II)-catalyzed oxidation of L-tryptophan by hexacyanoferrate(III) in perchloric acid medium: a kinetic and mechanistic approach

    Ahmed Fawzy

    2016-02-01

    The catalytic effect of palladium(II) on the oxidation of L-tryptophan by potassium hexacyanoferrate( III) has been investigated spectrophotometrically in aqueous perchloric acid medium. A first order dependence in [hexacyanoferrate(III)] and fractional-first order dependences in both [L-tryptophan] and [palladium(II)] were obtained. The reaction exhibits fractional-second order kinetics with respect to [H+]. Reaction rate increased with increase in ionic strength and dielectric constant of the medium. The effect of temperature on the reaction rate has also been studied and activation parameters have been evaluated and discussed. Initial addition of the reaction product, hexacyanoferrate(II), does not affect the rate significantly. A plausible mechanistic scheme explaining all the observed kinetic results has been proposed. The final oxidation products are identified as indole-3-acetaldehyde, ammonium ion and carbon dioxide. The rate law associated with the reaction mechanism is derived.

  11. Vapor-Liquid Equilibria of Systems Containing Acetic Acid and Gaseous Components. Measurements and Calculations by a Cubic Equiation of State

    Jonasson, Ari Jonas; Persson, Ole Hilding; Rasmussen, Peter;

    1998-01-01

    Isothermal pressure-composition VLE data have been measured for four systems containing acetic acid and a gaseous component. The gaseous components are carbon monoxide, carbon dioxide, hydrogen and methane. The measurements were made in a static cell and the compositions of the gas and the liquid...

  12. Kinetics of Cd2+ and Cr3+ Sorption from Aqueous Solutions Using Mercaptoacetic Acid Modified and Unmodified Oil Palm Fruit Fibre(Elaeis guineensis) Adsorbents

    2007-01-01

    The kinetics of the sorption of Cd2+ and Cr3+ from aqueous solutions by mercaptoacetic acid modified and unmodified oil palm fruit fibre adsorbents were investigated. The results indicate that sorption equilibrium was reached within 60 min for both metals. Also, the removal efficiency of the three adsorbents was observed to increase for both metals with stronger treatments with mercaptoacetic acid. This may be attributed to the influence of the thiolation of the adsorbents. Furthermore, Cr3+ had higher removal percentages than Cd2+ for all the adsorbents. The sorption mechanism based on the intraparticle diffusion model shows that Cd2+ sorption is better described than Cr3+. The intraparticle diffusion rate constants, K1d, for Cd2+are 62.04 min-1 (untreated), 67.01 min-1 (treated with 0.5 mol/L mercaptoacetic acid), and 71.43 min-1(treated with 1.0 mol/L mercaptocacetic acid) while those for Cr3+ are 63.41 min-1 (untreated), 65.79 min-1(0.5 mol/L acid treated), and 66.25 min-1 (1.0 mol/L acid treated).

  13. Kinetic analysis of the antibacterial activity of probiotic lactobacilli towards Salmonella enterica serovar Typhimurium reveals a role for lactic acid and other inhibitory compounds.

    Makras, Lefteris; Triantafyllou, Vagelis; Fayol-Messaoudi, Domitille; Adriany, Tom; Zoumpopoulou, Georgia; Tsakalidou, Effie; Servin, Alain; De Vuyst, Luc

    2006-04-01

    Six Lactobacillus strains including commercial probiotic ones (L. acidophilus IBB 801, L. amylovorus DCE 471, L. casei Shirota, L. johnsonii La1, L. plantarum ACA-DC 287 and L. rhamnosus GG) were investigated, through batch fermentations under controlled conditions, for their capacity to inhibit Salmonella enterica serovar Typhimurium SL1344. All lactobacilli displayed strong antibacterial activity toward this Gram-negative pathogen and significantly inhibited invasion of the pathogen into cultured human enterocyte-like Caco-2/TC7 cells. By studying the production kinetics of antibacterial activity and applying the appropriate acid and pH control samples during a killing assay, we were able to distinguish between the effect of lactic acid and other inhibitory compounds produced. The antibacterial activity of L. acidophilus IBB 801, L. amylovorus DCE 471, L. casei Shirota and L. rhamnosus GG was solely due to the production of lactic acid. The antibacterial activity of L. johnsonii La1 and L. plantarum ACA-DC 287 was due to the production of lactic acid and (an) unknown inhibitory substance(s). The latter was (were) only active in the presence of lactic acid. In addition, the lactic acid produced was responsible for significant inhibitory activity upon invasion of Salmonella into Caco-2/TC7 cells. PMID:16266797

  14. Purification of Peptide Components including Melittin from Bee Venom using gel filtration chromatography and propionic acid/urea polyacrylamide gel electrophoresis

    Young Chon Choi; Ki Rok, Kwon; Suk Ho, Choi

    2006-01-01

    Objectives : This study was conducted to carry out Purification of Melittin and other peptide components from Bee Venom using gel filtration chromatography and propionic acid/urea polyacrylamide gel electrophoresis Methods : Melittin and other peptide components were separated from bee venom by using gel filtration chromatography on Sephadex G-50 column in 0.05M ammonium acetate buffer. Results : Melittin and other peptide components were separated from bee venom by using gel filtration...

  15. Interrelationships among hydrologic-budget components of a northern Wisconsin seepage lake and implications for acid-deposition modeling

    Wentz, D.A.; Rose, W.J.

    1989-01-01

    Components of the hydrologic budget for a northern Wisconsin seepage lake were analyzed by applying correlation and regression techniques to monthly data. Analyses for the 1981-83 water years revealed a statistically significant, direct relationship between storage change and precipitation-evaporation balance. Ground-water outflow was negatively correlated with ground-water inflow, and this relationship was influenced by similar relationships for both hydraulic gradients and cross-sectional areas in outflow versus inflow regions of the lake. Neither ground-water outflow nor inflow was significantly related to precipitation, evaporation, storage change, or lake stage; this may reflect a lag in response time of the ground-water system compared to the lake. The results (1) emphasize the complexity of factors that influence ground-water interactions with seepage lakes and (2) suggest the importance of completing detailed hydrologic studies of these systems before mechanistic models, such as those developed to predict effects of acid deposition, are applied.

  16. Effect of humic acid and transition metal ions on the debromination of decabromodiphenyl by nano zero-valent iron: kinetics and mechanisms

    Tan, Lei; Liang, Bin; Fang, Zhanqiang, E-mail: sunmoon124@163.com; Xie, Yingying [South China Normal University, School of Chemistry and Environment (China); Tsang, Eric Pokeung [Guangdong Technology Research Centre for Ecological Management and Remediation of Water System (China)

    2014-12-15

    E-waste sites are one of the main sources of the pollutant decabromodiphenyl ether (BDE209); contaminated farmland and water bodies urgently need to be remediated. As a potential in situ remediation technology, nano zero-valent iron (nZVI) technology effectively removes PBDEs. However, the humic acid (HA) and heavy metals in the contaminated sites affect the remediation effects. In this study, we explored the influence of HA and transition metals on the removal of PBDEs by nZVI. The specific surface area and average size of the nZVI particles we prepared were 35 m{sup 2}/g and 50–80 nm, respectively. The results showed that HA inhibited the removal of PBDEs; as the concentration of HA increased, its inhibitory effect intensified and the k{sub obs} decreased. However, the three metal ions (Cu{sup 2+}, Co{sup 2+}, and Ni{sup 2+}) enhanced the removal of PBDEs. The enhancement effect was followed the order Ni{sup 2+} > Cu{sup 2+} > Co{sup 2+}. As the concentration of metal ions increased, the promotion effect improved. The synergistic effect of HA and the metal ions was manifested in the combination of the inhibitory effect and the enhancement effect. The values of the first-order kinetic constants (k{sub obs}) under the combined effect were between the values of the rate constants under the individual components. The inhibitory mechanism was the chemisorption of HA, i.e., the benzene carboxylic and phenolic hydroxyl groups in HA occupied the surfactant reactive sites of nZVI, thus inhibiting the removal of BDE209. The promotion mechanism of Cu{sup 2+}, Co{sup 2+}, and Ni{sup 2+} can be explained by their reduction to zero valence on the nZVI surface; furthermore, Ni{sup 2+} strongly affects the debromination and dehydrogenation of BDE209, leading to a stronger promotability than Cu{sup 2+}or Co{sup 2+}.

  17. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Gomes, Ruth; Bhaumik, Asim [Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India); Dutta, Saikat [Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan (China)

    2014-11-01

    A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state {sup 13}C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N{sub 2} sorption, HR-TEM, and NH{sub 3} temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  18. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Ruth Gomes

    2014-11-01

    Full Text Available A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  19. Cholesterol efflux from THP-1 macrophages is impaired by the fatty acid component from lipoprotein hydrolysis by lipoprotein lipase

    Yang, Yanbo; Thyagarajan, Narmadaa; Coady, Breanne M.; Brown, Robert J., E-mail: rbrown@mun.ca

    2014-09-05

    Highlights: • Lipoprotein hydrolysis products were produced by lipoprotein lipase. • Hydrolysis products lowers expression of macrophage cholesterol transporters. • Hydrolysis products reduces expression of select nuclear receptors. • Fatty acid products lowers cholesterol transporters and select nuclear receptors. • Fatty acid products reduces cholesterol efflux from macrophages. - Abstract: Lipoprotein lipase (LPL) is an extracellular lipase that primarily hydrolyzes triglycerides within circulating lipoproteins. Macrophage LPL contributes to atherogenesis, but the mechanisms behind it are poorly understood. We hypothesized that the products of lipoprotein hydrolysis generated by LPL promote atherogenesis by inhibiting the cholesterol efflux ability by macrophages. To test this hypothesis, we treated human THP-1 macrophages with total lipoproteins that were hydrolyzed by LPL and we found significantly reduced transcript levels for the cholesterol transporters ATP binding cassette transporter A1 (ABCA1), ABCG1, and scavenger receptor BI. These decreases were likely due to significant reductions for the nuclear receptors liver-X-receptor-α, peroxisome proliferator activated receptor (PPAR)-α, and PPAR-γ. We prepared a mixture of free fatty acids (FFA) that represented the ratios of FFA species within lipoprotein hydrolysis products, and we found that the FFA mixture also significantly reduced cholesterol transporters and nuclear receptors. Finally, we tested the efflux of cholesterol from THP-1 macrophages to apolipoprotein A-I, and we found that the treatment of THP-1 macrophages with the FFA mixture significantly attenuated cholesterol efflux. Overall, these data show that the FFA component of lipoprotein hydrolysis products generated by LPL may promote atherogenesis by inhibiting cholesterol efflux, which partially explains the pro-atherogenic role of macrophage LPL.

  20. Cholesterol efflux from THP-1 macrophages is impaired by the fatty acid component from lipoprotein hydrolysis by lipoprotein lipase

    Highlights: • Lipoprotein hydrolysis products were produced by lipoprotein lipase. • Hydrolysis products lowers expression of macrophage cholesterol transporters. • Hydrolysis products reduces expression of select nuclear receptors. • Fatty acid products lowers cholesterol transporters and select nuclear receptors. • Fatty acid products reduces cholesterol efflux from macrophages. - Abstract: Lipoprotein lipase (LPL) is an extracellular lipase that primarily hydrolyzes triglycerides within circulating lipoproteins. Macrophage LPL contributes to atherogenesis, but the mechanisms behind it are poorly understood. We hypothesized that the products of lipoprotein hydrolysis generated by LPL promote atherogenesis by inhibiting the cholesterol efflux ability by macrophages. To test this hypothesis, we treated human THP-1 macrophages with total lipoproteins that were hydrolyzed by LPL and we found significantly reduced transcript levels for the cholesterol transporters ATP binding cassette transporter A1 (ABCA1), ABCG1, and scavenger receptor BI. These decreases were likely due to significant reductions for the nuclear receptors liver-X-receptor-α, peroxisome proliferator activated receptor (PPAR)-α, and PPAR-γ. We prepared a mixture of free fatty acids (FFA) that represented the ratios of FFA species within lipoprotein hydrolysis products, and we found that the FFA mixture also significantly reduced cholesterol transporters and nuclear receptors. Finally, we tested the efflux of cholesterol from THP-1 macrophages to apolipoprotein A-I, and we found that the treatment of THP-1 macrophages with the FFA mixture significantly attenuated cholesterol efflux. Overall, these data show that the FFA component of lipoprotein hydrolysis products generated by LPL may promote atherogenesis by inhibiting cholesterol efflux, which partially explains the pro-atherogenic role of macrophage LPL

  1. Kinetics and Mechanism of Oxidation of L-Cysteine by Bis-3-di-2-pyridylketone-2-thiophenylhydrazone-iron(III) Complex in Acidic Medium

    Ismail Warad; Mohammed Al-Nuri; Maher Abu Eid; Zeid Al-Othman; Saud Al-Resayes; Nizam Diab

    2010-01-01

    The kinetics of oxidation of L-cysteine by 3-di-2-pyridylketone-2-thiophenylhydrazone-iron(III), [Fe(DPKTH)2] 3+ complex in acidic medium was studied spectrophotometrically at 36 °C temperature. The molar ratios of DPKTH to iron(III) and iron(II) individually, were found to be [2:1] [DPKTH : iron(III)/(II)]. The reaction was stroked to be first-order with respect to iron(III) and L-cysteine, second-order with respected to DPKTH ligand and reversed second-order with respected to hydrogen ion c...

  2. Kinetic spectrophotometric determination of trace copper(II) ions by their catalytic effect on the reduction of brilliant cresyl blue by ascorbic acid

    ULUSOY, Halil İbrahim; GÜRKAN, Ramazan; AKÇAY, Mehmet

    2011-01-01

    In the present study, a novel catalytic-kinetic spectrophotometric method was developed for the determination of trace amounts of copper. It is based on the catalytic effect of Cu(II) on the reduction of brilliant cresyl blue (BCB) by ascorbic acid in pH 5.0 acetate buffer medium. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of BCB at 624 nm. The operating conditions regarding concentration of reagents, pH, time, and temperature were esta...

  3. Mathematical modeling of kinetics of volume condensation of water and sulfuric acid vapors during electron-beam purification of power plant flue gases

    The kinetic equations system, describing the volume condensation process of water and purification of power plant flue gases is developed. The role of water and sulfuric acid vapors nucleation, the drops growth on the account of H2O and H2SO4 molecule condensation thereon and drops coagulation due to their Brownian movement in the summary process is analyzed. It is shown that dissolution of other gaseous compounds (SO2, NH3, etc.) in the molecule drops may be considered in the approximation of the gas-liquid quasi-equilibrium

  4. Kinetics of iodomethylated hexadecanoic acid metabolism in the rat myocardium: influence of the number and the position of methyl radicals

    Fagret, D.; Bontemps, L.; Apparu, M.; Keriel, C.; Mathieu, J.P.; Pernin, C.; Vidal, M.; Comet, M.; Cuchet, P.

    1985-01-01

    The methyl-branched fatty acids, if radioiodine labelled in alpha position, are potentially adapted to a selective study of FA myocardial uptake. To determine the position and the number of methyl radicals that are necessary to obtain a maximal uptake and a minimal degradation, we measured time-activity evolution of isolated and perfused rat hearts after an injection of iodinated fatty acids which are mono- or dimethylated in alpha or beta position. Except for dimethyl fatty acid, the uptake is similar for all fatty acids studied to that of the straight chain analogue; beta mono- or dimethyl fatty acids seem best adapted to a study of the uptake because alpha monomethyl fatty acids undergo a metabolic degradation and alpha mono- and dimethyl fatty acids induce ventricular fibrillations.

  5. Relations between basic milk components and free fatty acid content in Holstein cow milk as lipolysis parameter

    Luděk Stádník

    2015-02-01

    Full Text Available The aim of this study was to evaluate in detail the relationship between the basic milk components (fat and protein percentage and the free fatty acids (FFA content, as indicators of spontaneous and/or induced lipolysis. The additional aim of the study was to compare the FFA content of milk with respect to spontaneous and induced lipolysis. Milking was carried out in herringbone parlour twice a day. In total, 540 milk samples were obtained for evaluation of spontaneous (n=240 and induced lipolysis (n=300. The milk samples for determination of basic milk components and FFA (li¬polysis levels were collected during four subsequent lactation weeks. Milk samples for spontaneous lipolysis detection were taken directly in parlour immediately after milking using the ICAR methodology and subsequently grouped. Induced lipolysis was observed from bulk milk in time 0, 1, 2, 3, and 4 hours after milking (T0-T4. The evaluation of basic components and FFA content was carried on MILKOSCAN F120 (Foss Electronic; Denmark. Statistical evaluation was carried out using SAS 9.3. (SAS/STAT® 9.3, 2011. An increase of one percentage of milk fat was equal to 0.318 mmol x 100 g-1 FFA decline (spontaneous lipolysis or from 0.232 to 0.370 mmol x 100 g-1 FFA decline (induced lipolysis T0-T4 respectively. One percentage increase of milk protein was equal to 1.219 mmol x 100 g-1 FFA increase (spontaneous lipolysis or 0.421 to 1.531 mmol x 100 g-1 FFA decrease (induced lipolysis T0 - T4 respectively. Significant differences (P<0.01 were detected among FFA content in relation to spontaneous and induced lipolysis evaluated during storage and cooling after milking. The minimal differences were detected between the FFA content during 4 hours cooling and storage of milk in the tank.

  6. Root-zone acidity and nitrogen source affects Typha latifolia L. growth and uptake kinetics of ammonium and nitrate.

    Brix, Hans; Dyhr-Jensen, Kirsten; Lorenzen, Bent

    2002-12-01

    The NH(4)(+) and NO(3)(-) uptake kinetics by Typha latifolia L. were studied after prolonged hydroponics growth at constant pH 3.5, 5.0, 6.5 or 7.0 and with NH(4)(+) or NO(3)(-) as the sole N-source. In addition, the effects of pH and N source on H(+) extrusion and adenine nucleotide content were examined. Typha latifolia was able to grow with both N sources at near neutral pH levels, but the plants had higher relative growth rates, higher tissue concentrations of the major nutrients, higher contents of adenine nucleotides, and higher affinity for uptake of inorganic nitrogen when grown on NH(4)(+). Growth almost completely stopped at pH 3.5, irrespective of N source, probably as a consequence of pH effects on plasma membrane integrity and H(+) influx into the root cells. Tissue concentrations of the major nutrients and adenine nucleotides were severely reduced at low pH, and the uptake capacity for inorganic nitrogen was low, and more so for NO(3)(-)-fed than for NH(4)(+)-fed plants. The maximum uptake rate, V(max), was highest for NH(4)(+) at pH 6.5 (30.9 micro mol h(-1) g(-1) root dry weight) and for NO(3)(-) at pH 5.0 (31.7 micro mol h(-1) g(-1) root dry weight), and less than 10% of these values at pH 3.5. The affinity for uptake as estimated by the half saturation constant, K((1/2)), was lowest at low pH for NH(4)(+) and at high pH for NO(3)(-). The changes in V(max) and K((1/2)) were thus consistent with the theory of increasing competition between cations and H(+) at low pH and between anions and OH(-) at high pH. C(min) was independent of pH, but slightly higher for NO(3)(-) than for NH(4)(+) (C(min)(NH(4)(+)) approximately 0.8 mmol m(-3); C(min)(NO(3)(-)) approximately 2.8 mmol m(-3)). The growth inhibition at low pH was probably due to a reduced nutrient uptake and a consequential limitation of growth by nutrient stress. Typha latifolia seems to be well adapted to growth in wetland soils where NH(4)(+) is the prevailing nitrogen compound, but very low p

  7. Quantitative amino acid profiling and stable isotopically labeled amino acid tracer enrichment used for in vivo human systemic and tissue kinetics measurements

    Bornø, Andreas; van Hall, Gerrit

    kinetics measurements. Moreover, citrulline, ornithine, π-methyl-histidine, τ-methyl-l-histidine, hydroxy-proline and carnitine were analysed but when similar precision and accuray are required an additional stable istopically labeled internal standard for these meatablites should be be added....

  8. Thermal decomposition mechanism and non-isothermal kinetics of the polyoxometalate of ciprofloxacin with 12-tungstoboric acid

    WANG Dunjia; FANG Zhengdong; HAN Deyan

    2005-01-01

    The polyoxometalate complex (CPFX·HCl)4H5BW12O40·12H2O was prepared in aqueous solution for the first time, and characterized by elemental analysis, IR spectrum, and TG-DTG. The TG-DTG curves showed that its thermal decomposition was a our-step process consisting of the simultaneous collapse of Keggin anion. The intermediate and residue of the decomposition were identified by mean of TG-DTG, IR, and XRD technique. The non-isothermal kinetic data were analyzed by the Achar method and Coats-Redfern method. The apparent activation energy (E) and the pre-exponential factor (ln A) of each decomposition were obtained. The most probable thermal decomposition reaction mechanisms were proposed by comparison of the kinetic parameters. The kinetic equation for both the second stage and the third stage can be expressed as dα/dt = Ae-EIRT·(1 - α)2, and the fourth stage dα/dt = Ae-EIRT·( 1 - α). And their athematic expressions of the kinetic compensation effects of thermal decomposition reaction were also determined.

  9. Bifunctional cyclam-based ligands with phosphorus acid pendant moieties for radiocopper separation: thermodynamic and kinetic studies

    Paúrová, M.; Havlíčková, J.; Pospíšilová, Aneta; Vetrík, Miroslav; Císařová, I.; Stephan, H.; Pietzsch, H.-J.; Hrubý, Martin; Hermann, P.; Kotek, J.

    2015-01-01

    Roč. 21, č. 12 (2015), s. 4671-4687. ISSN 0947-6539 R&D Projects: GA ČR GAP304/12/0950 Institutional support: RVO:61389013 Keywords : copper * ion-selective resins * kinetics Subject RIV: FB - Endocrinology, Diabetology, Metabolism, Nutrition Impact factor: 5.731, year: 2014

  10. Extraction kinetics of Uranium(VI) and Thorium(IV) with Tri-iso-amyl phosphate from nitric acid using a Lewis Cell

    The extraction kinetics of uranium(VI) and thorium(IV) with Tri-iso-amyl phosphate (TiAP) from nitric acid medium has been investigated using a Lewis Cell. Especially, dependences of the extraction rate on stirring speed, temperature, interfacial area were firstly measured to elucidate the extraction kinetics regimes. The experimental results demonstrated that extraction kinetic of U(VI) is governed by chemical reactions at interface with an activation energy, Ea, of 43.41 kJ/mol, while the rate of Th(IV) extraction is proved to be intermediate controlled, of which the Ea is 23.20 kJ/mol. Reaction orders with respect to the influencing parameters of the extraction rate are determined, and the rate equations of U(VI) and Th(IV) at 293 K have been proposed as r = -dcUO2(NO3)2/dt = 1.80×10-3[UO2(NO3)2]1.01 [TiAP]0.55, r = -dcTh (NO3)4/dt = 1.88×10-3[Th (NO3)4]1.04 [TiAP]1.77[HNO3]0.38, respectively. (author)

  11. n-3 Polyunsaturated Fatty Acid Supplementation Has No Effect on Postprandial Triglyceride-Rich Lipoprotein Kinetics in Men with Type 2 Diabetes

    André J. Tremblay

    2016-01-01

    Full Text Available Dietary n-3 polyunsaturated fatty acids (PUFAs have been proposed to modulate plasma lipids, lipoprotein metabolism, and inflammatory state and to reduce triglyceride (TG concentrations. The present double-blind, randomized, placebo-controlled, crossover study investigated the effects of n-3 PUFA supplementation at 3 g/d for 8 weeks on the intravascular kinetics of intestinally derived apolipoprotein (apo B-48-containing lipoproteins in 10 men with type 2 diabetes. In vivo kinetics of the TG-rich lipoprotein (TRL apoB-48 and VLDL apoB-100 were assessed using a primed-constant infusion of L-[5,5,5-D3] leucine for 12 hours in a fed state. Compared with the placebo, n-3 PUFA supplementation significantly reduced fasting TG concentrations by −9.7% (P=0.05 but also significantly increased plasma levels of cholesterol (C (+6.0%, P=0.05, LDL-C (+12.2%, P=0.04, and HDL-C (+8.4, P=0.007. n-3 PUFA supplementation had no significant impact on postprandial TRL apoB-48 and VLDL apoB-100 levels or on the production or catabolic rates of these lipoproteins. These data indicate that 8-week supplementation with n-3 PUFAs in men with type 2 diabetes has no beneficial effect on TRL apoB-48 and VLDL apoB-100 levels or kinetics.

  12. Kinetics of co-crystal formation with caffeine and citric acid via liquid-assisted grinding analyzed using the distinct element method.

    Shimono, Keisuke; Kadota, Kazunori; Tozuka, Yuichi; Shimosaka, Atsuko; Shirakawa, Yoshiyuki; Hidaka, Jusuke

    2015-08-30

    The kinetics of co-crystal formation of caffeine (CF) with citric acid (CTA) was evaluated. Ball milling of CF and CTA in molar ratios of 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, and 1:4 was performed by the liquid-assisted grinding (LAG) method. The samples were characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC). Two types of co-crystals (co-crystal-1, a 1:1 CF-CTA co-crystal; and co-crystal-2, a new co-crystal form) were obtained. The kinetic characteristics of this new co-crystal formation were assessed by calculating the ball impact energy and force using the distinct element method (DEM) simulations. The results indicated that co-crystal-2 creation occurred under a condition in which the ball impact force exceeded a certain threshold value. Moreover, the total ball impact energy was positively correlated with co-crystal formation, exhibiting a higher ball impact force than the threshold value. The kinetics of co-crystal-2 formation was almost consistent with the Jander equation. Consequently, co-crystal-2 formation could be explained according to a three-dimensional diffusion mechanism. PMID:25998562

  13. Kinetics study on the dissolution of UO2 particles by microwave and conventional heating in 4 mol/L nitric acid

    2008-01-01

    The dissolution of UO2 particles in 4 mol·L-1 nitric acid medium at temperatures of 90-110℃ by mi- crowave heating and conventional heating has been investigated, respectively. It is found that the dissolution ratios of UO2 particles by microwave heating were 10%-40% higher than that by conven- tional heating. Kinetics research shows that the dissolution of UO2 particles in 4 mol·L-1 nitric acid is controlled by the diffusion control model for microwave heating and by the surface reaction control model for conventional heating. The diffusion control model for the dissolution of UO2 particles by mi- crowave heating could be explained by the diffuseness on the surface of UO2 particles.

  14. 葡萄糖高温降解生产乙酰丙酸的动力学研究%Kinetics of Levulinic Acid Formation from Glucose Decomposition at High Temperature

    常春; 马晓建; 岑沛霖

    2006-01-01

    Levulinic acid is a kind of new green platform chemical with wide application. The kinetics of levulinic acid formation from glucose decomposition at high temperature was investigated. Glucose containing 1%, 3% or 5% H2SO4 was treated at 170℃ or 190℃. For the various experimental conditions assayed, the time-courses of glucose and glucose degradation products (including 5-hydroxymethylfurfural and levulinic acid) were established. These variables were correlated with the reaction time based on the equations derived from a pseudo-homogeneous, first-order kinetic model,which provided a satisfactory interpretation of the experimental results. The set of kinetic parameters from regression of experimental data provided useful information for understanding the levulinic acid formation mechanism.

  15. Esterification of Oleic Acid for Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation

    Abiney L. Cardoso; Soraia Cristina Gonzaga Neves; Marcio J. da Silva

    2008-01-01

    The production of biodiesel from low-cost raw materials which generally contain high amounts of free fatty acids (FFAs) is a valuable alternative that would make their production costs more competitive than petroleum-derived fuel. Currently, the production of biodiesel from this kind of raw materials comprises a two-stage process, which requires an initial acid-catalyzed esterification of the FFA, followed by a basecatalyzed transesterification of the triglycerides. Commonly, the acid H2SO4 i...

  16. 酸洗对RDF热解动力学影响及半焦表面结构变化%INFLUENCE OF ACID TREATMENTOF RDF ON PYROLYSIS KINETIC AND SURFACE STRUCTURE

    吴家正; 朱彤; 肖郴松; 谢洪; 汪雄平; 洪丽娟; 张鹤声

    2001-01-01

    以5 W/%稀HCl溶液对各类城市生活垃圾衍生燃料(RDF)及其组分进行处理,考察在不同温度下快速热 解生成半焦的动力学参数变化,并对半焦的比表面积和孔体积的变化和分形维数进行分析研究。试验结果发现酸 洗后RDF热解速率提高,活化能降低。酸洗后半焦的比表面积和孔体积均有所减小,并随热解温度先升高而后下 降,在450℃附近出现极大值。对半焦的分形维数分析表明,酸洗后表面变得光滑,形成欧氏平面。%Refuse derived fuel (RDF) and its components were treated by 5% HC1 and the changes of kinetic parameters for rapid pyrolysis under different temperature were discussed. The changes of the specific surface area (SSA), pore volume (PV) and fractal dimension for residue were also investigated and analyzed in this paper. The experiment results show that the pyrolysis rate increases and activate energy decreases for RDF after acid treatment. SSA and PV of RDF vary with the reaction temperature during rapid pyrolysis. With increasing temperature, the SSA and PV of acid treated RDF residue rise in the beginning and down in the end. The maximum value appears near 450℃. Further more, the fractal feature of acid treated RDF residue is also discussed. The surface of residue seems smoother and form Euclidean plane after acid treatment.

  17. ICH GUIDANCE IN PRACTICE: DEVELOPMENT OF A VALIDATED STABILITY-INDICATING HIGH-PERFORMANCE LIQUID CHROMATOGRAPHIC ASSAY METHOD FOR FEBUXOSTAT AND DEGRADATION KINETIC STUDY IN ACID HYDROLYTIC CONDITION

    Megha V. Sheth* and Jigar J. Pandya

    2013-02-01

    Full Text Available The degradation behavior of Febuxostat was investigated under different stress degradation (hydrolytic, oxidative, photolytic and thermal conditions recommended by International Conference on Harmonization (ICH using HPLC and LCMS. Febuxostat was found to degrade significantly in acidic and alkaline conditions as well as in neutral hydrolysis. The drug was stable to dry heat, photolytic degradation and under oxidative condition. Resolution of drug and the degradation products formed under different stress studies were successfully achieved on a C-18 column utilizing Methanol- water (with 0.02%v/v TFA in the ratio of 95:5 and at the detection wavelength of 315 nm. The method was validated with respect to linearity, precision, accuracy, selectivity and specificity. The degradation kinetic of Febuxostat in acidic condition at different temperature was studied. The reaction order for Febuxostat in aqueous solvent system followed pseudo first order degradation kinetic. The catalytic rate constant and half-life at particular condition were determined. The Arrhenius plot showed the temperature dependence of Febuxostat.

  18. Kinetic and mechanism of the oxidation of chromium(III) complex with anthranil- N, N-diacetic acid by periodate ion in acidic aqueous solutions

    Ali, Ismat H.

    2015-06-01

    The kinetics of oxidation of [CrIII(atda)(H2O)2] (atda = anthranil- N, N-diacetato) complex by IO{4/-} was studied spectrophotometrically in aqueous solutions with pH range 2.20-3.34, 0.30 M ionic strength and in 20.0-40.0°C temperature range. The rate law of the reaction exhibited saturation kinetics. Values of the rate constant for the electron transfer process, the equilibrium constant for dissociation of [CrIII (atda)(H2O)2] to [CrIII (atda) (H2O)OH]+ + H+ and the pre-equilibrium formation constant were calculated. The thermodynamic activation parameters are reported. It is proposed that electron transfer proceeds through an inner-sphere mechanism via coordination of the IVII to chromium(III).

  19. Additive regulation of adiponectin expression by the mediterranean diet olive oil components oleic Acid and hydroxytyrosol in human adipocytes.

    Egeria Scoditti

    Full Text Available Adiponectin, an adipocyte-derived insulin-sensitizing and anti-inflammatory hormone, is suppressed in obesity through mechanisms involving chronic inflammation and oxidative stress. Olive oil consumption is associated with beneficial cardiometabolic actions, with possible contributions from the antioxidant phenol hydroxytyrosol (HT and the monounsaturated fatty acid oleic acid (OA, 18:1n-9 cis, both possessing anti-inflammatory and vasculo-protective properties. We determined the effects of HT and OA, alone and in combination, on adiponectin expression in human and murine adipocytes under pro-inflammatory conditions induced by the cytokine tumor necrosis factor(TNF-α. We used human Simpson-Golabi-Behmel syndrome (SGBS adipocytes and murine 3T3-L1 adipocytes as cell model systems, and pretreated them with 1-100 μmol/L OA, 0.1-20 μmol/L HT or OA plus HT combination before stimulation with 10 ng/mL TNF-α. OA or HT significantly (P<0.05 prevented TNF-α-induced suppression of total adiponectin secretion (by 42% compared with TNF-α alone as well as mRNA levels (by 30% compared with TNF-α alone. HT and OA also prevented-by 35%-TNF-α-induced downregulation of peroxisome proliferator-activated receptor PPARγ. Co-treatment with HT and OA restored adiponectin and PPARγ expression in an additive manner compared with single treatments. Exploring the activation of JNK, which is crucial for both adiponectin and PPARγ suppression by TNF-α, we found that HT and OA additively attenuated TNF-α-stimulated JNK phosphorylation (up to 55% inhibition. In conclusion, the virgin olive oil components OA and HT, at nutritionally relevant concentrations, have additive effects in preventing adiponectin downregulation in inflamed adipocytes through an attenuation of JNK-mediated PPARγ suppression.

  20. Additive regulation of adiponectin expression by the mediterranean diet olive oil components oleic Acid and hydroxytyrosol in human adipocytes.

    Scoditti, Egeria; Massaro, Marika; Carluccio, Maria Annunziata; Pellegrino, Mariangela; Wabitsch, Martin; Calabriso, Nadia; Storelli, Carlo; De Caterina, Raffaele

    2015-01-01

    Adiponectin, an adipocyte-derived insulin-sensitizing and anti-inflammatory hormone, is suppressed in obesity through mechanisms involving chronic inflammation and oxidative stress. Olive oil consumption is associated with beneficial cardiometabolic actions, with possible contributions from the antioxidant phenol hydroxytyrosol (HT) and the monounsaturated fatty acid oleic acid (OA, 18:1n-9 cis), both possessing anti-inflammatory and vasculo-protective properties. We determined the effects of HT and OA, alone and in combination, on adiponectin expression in human and murine adipocytes under pro-inflammatory conditions induced by the cytokine tumor necrosis factor(TNF)-α. We used human Simpson-Golabi-Behmel syndrome (SGBS) adipocytes and murine 3T3-L1 adipocytes as cell model systems, and pretreated them with 1-100 μmol/L OA, 0.1-20 μmol/L HT or OA plus HT combination before stimulation with 10 ng/mL TNF-α. OA or HT significantly (Pwell as mRNA levels (by 30% compared with TNF-α alone). HT and OA also prevented-by 35%-TNF-α-induced downregulation of peroxisome proliferator-activated receptor PPARγ. Co-treatment with HT and OA restored adiponectin and PPARγ expression in an additive manner compared with single treatments. Exploring the activation of JNK, which is crucial for both adiponectin and PPARγ suppression by TNF-α, we found that HT and OA additively attenuated TNF-α-stimulated JNK phosphorylation (up to 55% inhibition). In conclusion, the virgin olive oil components OA and HT, at nutritionally relevant concentrations, have additive effects in preventing adiponectin downregulation in inflamed adipocytes through an attenuation of JNK-mediated PPARγ suppression. PMID:26030149