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Sample records for acid components kinetics

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

    DEFF Research Database (Denmark)

    Pattison, David I; Davies, Michael Jonathan

    2004-01-01

    in 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...... are 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. The hydrothermal reaction kinetics of aspartic acid

    Science.gov (United States)

    Cox, Jenny S.; Seward, Terry M.

    2007-02-01

    Experimental data on the hydrothermal reaction kinetics of aspartic acid were acquired using a custom-built spectrophotometric reaction cell which permits in situ observation under hydrothermal conditions. The results of this study indicate that the reaction kinetics of dilute aspartic acid solutions are significantly different depending on the presence or absence of catalytic surfaces such as standard metal alloys. The spectroscopic data presented here represent the first direct observations, in situ and in real time, of an amino acid reacting in a hydrothermal solution. Quantitative kinetic information, including rate constants, concentration versus time profiles, and calculations of the individual component spectra, was obtained from the data using a chemometric approach based on factor analysis/principle component analysis which treats the rate expressions simultaneously as a system of differential algebraic equations (DAE) of index 1. Identification of the products was confirmed where possible by high pressure anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD). The reaction kinetics of aspartic acid under hydrothermal conditions was observed to be highly complex, in contrast to previous studies which indicated almost exclusively deamination. At lower temperatures (120-170 °C), several different reaction pathways were observed, including decarboxylation and polymerization, and the catalytic effects of reactor surfaces on the aspartic acid system were clearly demonstrated. At higher temperatures (above 170 °C), aspartic acid exhibited highly complex behaviour, with evidence indicating that it can simultaneously dimerize and cyclize, deaminate (by up to two pathways), and decarboxylate (by up to two pathways). These higher temperature kinetics were not fully resolvable in a quantitative manner due to the complexity of the system and the constraints of UV spectroscopy. The results of this study provide strong evidence that the reaction

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

    Science.gov (United States)

    Zhang, Dongmei; Hou, Lei; Zhu, Dongqiang; Chen, Wei

    2014-01-01

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-11-01

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

  5. Kinetics of dodecanedioic acid triglyceride in rats.

    Science.gov (United States)

    de Gaetano, A; Mingrone, G; Castagneto, M; Benedetti, G; Greco, A V; Gasbarrini, G

    1999-03-01

    The kinetics of the triglyceride of dodecanedioic acid (TGDA) has been investigated in 30 male Wistar rats after a rapid intravenous bolus injection. TGDA and its product of hydrolysis, nonesterified dodecanedioic acid (NEDA), were measured in plasma samples taken at different times using an improved high-performance liquid chromatographic method. The 24-h urinary excretion of TGDA was 1.54 +/- 0.37 micromol, corresponding to approximately 0.67% of the administered amount. Several kinetics models were considered, including central and peripheral compartments for the triglyceride and the free forms and expressing transports between compartments with combinations of linear, carrier-limited, or time-varying mechanisms. The parameter estimates of the kinetics of TGDA and of NEDA were finally obtained using a three-compartment model in which the transfer of TGDA to NEDA was assumed to be linear, through a peripheral compartment, and the tissue uptake of NEDA was assumed to be carrier limited. TGDA had a large volume of distribution ( approximately 0.5 l/kg body wt) with a fast disappearance rate from plasma (0.42 min-1), whereas NEDA had a very small volume of distribution ( approximately 0.04 l/kg body wt) and a tissue uptake with maximal transport rate of 0.636 mM/min. In conclusion, this first study on the triglyceride form of dodecanedioic acid indicates that it is rapidly hydrolyzed and that both triglyceride and nonesterified forms are excreted in the urine to a very low extent. The tissue uptake rate of NEDA is consistent with the possibility of achieving substantial energy delivery, should it be added to parenteral nutrition formulations. Furthermore, the amount of sodium administered with the triglyceride form is one-half of that necessary with the free diacid.

  6. Modelling dimercaptosuccinic acid (DMSA) plasma kinetics in humans

    NARCIS (Netherlands)

    van Eijkeren, Jan C H; Olie, J Daniël N; Bradberry, Sally M; Vale, J Allister; de Vries, Irma; Meulenbelt, Jan; Hunault, Claudine C

    2016-01-01

    CONTEXT: No kinetic models presently exist which simulate the effect of chelation therapy on lead blood concentrations in lead poisoning. OBJECTIVE: Our aim was to develop a kinetic model that describes the kinetics of dimercaptosuccinic acid (DMSA; succimer), a commonly used chelating agent, that c

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

    Science.gov (United States)

    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

  8. A kinetic study on benzoic acid pungency and sensory attributes of benzoic acid.

    Science.gov (United States)

    Otero-Losada, M E

    1999-06-01

    Aqueous solutions of benzoic acid (BA) were evaluated by two methods: (i) sensory profile: a descriptive test of sensory attributes combined with semiquantitative analysis; and (ii) pungency intensity measures as a function of time: a computerized recording using specific software. Kinetic parameters evaluated were maximal intensity (I(MAX)), total time of pungency (Ttot), rates of increase (V1) and decrease (V2), half-life (T1/2), area under curve (AUC) and time to maximal intensity (T(IMAX)). Results were analyzed by ANOVA, LSD test, iterative calculations and adjustment to equations according to mathematical models, regression analysis, principal component analysis (PCA) and clusters analysis. Pungency was the main sensory attribute of BA (3-36 mM) in the tongue and epiglottis. The seven kinetic parameters showed concentration-dependency (P pungency intensity best correlated with both concentration and persistence among kinetic parameters. Prototypical prickling of BA was observed at 12 and 18 mM.

  9. Belousov-Zhabotinsky oscillatory reaction. Kinetics of malonic acid decomposition

    Directory of Open Access Journals (Sweden)

    LJILJANA KOLAR-ANIC

    2000-10-01

    Full Text Available The kinetics of the Belousov-Zhabotinsky (BZ oscillatory reaction was analyzed. With this aim, the time evolution of a reaction mixture composed of malonic acid, bromate, sulfuric acid and cerium(III was studied at 298 K. Pseudo-first order kinetics with respect to malonic acid as the species undergoing decomposition with a corresponding rate constant, k = 7.5×10-3 min-1, was found.

  10. Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

    Science.gov (United States)

    Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines

    2011-01-01

    A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

  11. Crystallization kinetics of poly(lactic acid)-talc composites

    OpenAIRE

    Battegazzore, Daniele; Bocchini, Sergio; Frache, Alberto

    2011-01-01

    The crystallization kinetics of Poly(lactic acid) / talc composites were determined over a range of 0 wt.% to 15 wt.% of talc. Talc was found to change the crystallization kinetics. The presence of talc increases the crystallization rate and this increase is related to talc concentration and to crystallization temperature. In order to understand the effect of talc and PLA crystallinity on mechanical properties, dynamic mechanical thermal analyses were performed on Poly(lactic acid) / talc com...

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

    Energy Technology Data Exchange (ETDEWEB)

    Shende, R.V.; Levec, J.

    1999-10-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-12-01

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

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

    Directory of Open Access Journals (Sweden)

    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

  15. Kinetic resolution of racemic carboxylic acids through asymmetric protolactonization promoted by chiral phosphonous acid diester.

    Science.gov (United States)

    Sakuma, Masayuki; Sakakura, Akira; Ishihara, Kazuaki

    2013-06-07

    Chiral phosphonium salts induce the kinetic resolution of racemic α-substituted unsaturated carboxylic acids through asymmetric protolactonization. Both the lactones and the recovered carboxylic acids are obtained with high enantioselectivities and high S (= kfast/kslow) values. Asymmetric protolactonization also leads to the desymmetrization of achiral carboxylic acids. Notably, chiral phosphonous acid diester not only induced the enantioselectivity but also promoted protolactonization.

  16. Abiotic Racemization Kinetics of Amino Acids in Marine Sediments

    OpenAIRE

    Steen, Andrew D.; Bo Barker Jørgensen; Bente Aa Lomstein

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth be...

  17. Methylene Blue-Ascorbic Acid: An Undergraduate Experiment in Kinetics.

    Science.gov (United States)

    Snehalatha, K. C.; And Others

    1997-01-01

    Describes a laboratory exercise involving methylene blue and L-ascorbic acid in a simple clock reaction technique to illustrate the basic concepts of chemical kinetics. If stock solutions are supplied and each type of experiment takes no more than half an hour, the entire investigation can be completed in three practical sessions of three hours…

  18. Kinetically-defined component actions in gene repression.

    Directory of Open Access Journals (Sweden)

    Carson C Chow

    2015-03-01

    Full Text Available Gene repression by transcription factors, and glucocorticoid receptors (GR in particular, is a critical, but poorly understood, physiological response. Among the many unresolved questions is the difference between GR regulated induction and repression, and whether transcription cofactor action is the same in both. Because activity classifications based on changes in gene product level are mechanistically uninformative, we present a theory for gene repression in which the mechanisms of factor action are defined kinetically and are consistent for both gene repression and induction. The theory is generally applicable and amenable to predictions if the dose-response curve for gene repression is non-cooperative with a unit Hill coefficient, which is observed for GR-regulated repression of AP1LUC reporter induction by phorbol myristate acetate. The theory predicts the mechanism of GR and cofactors, and where they act with respect to each other, based on how each cofactor alters the plots of various kinetic parameters vs. cofactor. We show that the kinetically-defined mechanism of action of each of four factors (reporter gene, p160 coactivator TIF2, and two pharmaceuticals [NU6027 and phenanthroline] is the same in GR-regulated repression and induction. What differs is the position of GR action. This insight should simplify clinical efforts to differentially modulate factor actions in gene induction vs. gene repression.

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

    Directory of Open Access Journals (Sweden)

    B.Syama Sundar

    2014-06-01

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

  20. Heterogeneity in limb fatty acid kinetics in type 2 diabetes

    DEFF Research Database (Denmark)

    Sacchetti, M; Olsen, D B; Saltin, B;

    2005-01-01

    control subjects (n=7) for 5 h under baseline conditions and during a 4-h hyperinsulinaemic-euglycaemic clamp. METHODS: Limb fatty acid kinetics was determined by means of continuous [U-(13)C]palmitate infusion and measurement of arteriovenous differences. RESULTS: The systemic palmitate rate......AIMS/HYPOTHESIS: In order to test the hypothesis that disturbances in skeletal muscle fatty acid metabolism with type 2 diabetes are not equally present in the upper and lower limbs, we studied fatty acid kinetics simultaneously across the arm and leg of type 2 diabetic patients (n=6) and matched...... of appearance was 3.6+/-0.4 and 2.7+/-0.3 micromol.kg lean body mass(-1).min(-1) and decreased during the clamp by 26% (p=0.04) and 43% (ppalmitate uptake across the arm was similar in the two groups, whereas leg palmitate...

  1. Kinetic Monte Carlo method applied to nucleic acid hairpin folding.

    Science.gov (United States)

    Sauerwine, Ben; Widom, Michael

    2011-12-01

    Kinetic Monte Carlo on coarse-grained systems, such as nucleic acid secondary structure, is advantageous for being able to access behavior at long time scales, even minutes or hours. Transition rates between coarse-grained states depend upon intermediate barriers, which are not directly simulated. We propose an Arrhenius rate model and an intermediate energy model that incorporates the effects of the barrier between simulated states without enlarging the state space itself. Applying our Arrhenius rate model to DNA hairpin folding, we demonstrate improved agreement with experiment compared to the usual kinetic Monte Carlo model. Further improvement results from including rigidity of single-stranded stacking.

  2. Abiotic racemization kinetics of amino acids in marine sediments.

    Science.gov (United States)

    Steen, Andrew D; Jørgensen, Bo Barker; Lomstein, Bente Aa

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth below seafloor. Extrapolation to a typical cold deep sea sediment temperature of 3°C suggests racemization rate constants of 0.50×10(-5)-11×10(-5) yr(-1). These results can be used in conjunction with measurements of sediment age to predict the ratio of d:l amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial populations.

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

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... have been compared to the experimental results of de Wilde and van Tiggelen (1968) who measured the laminar burning velocities for HOCHO flames over a range of stoichiometries and dilution ratios. The modeling predictions are generally satisfactory. The governing reaction mechanisms are outlined based...... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...

  4. Crystallization kinetics of poly(lactic acid-talc composites

    Directory of Open Access Journals (Sweden)

    2011-10-01

    Full Text Available The crystallization kinetics of poly(lactic acid / talc composites were determined over a range of 0 to 15 wt% of talc. Talc was found to change the crystallization kinetics. The presence of talc increases the crystallization rate and this increase is related to talc concentration and to crystallization temperature. In order to understand the effect of talc and PLA crystallinity on mechanical properties, dynamic mechanical thermal analyses were performed on poly(lactic acid / talc composites before and after an annealing process. It was demonstrated that the presence of crystals improves thermomechanical properties but in order to achieve good results at high temperatures the reinforcing effect of a filler such as talc is necessary.

  5. Kinetic study of free fatty acid esterification reaction catalyzed by recoverable and reusable hydrochloric acid.

    Science.gov (United States)

    Su, Chia-Hung

    2013-02-01

    The catalytic performance and recoverability of several homogeneous acid catalysts (hydrochloric, sulfuric, and nitric acids) for the esterification of enzyme-hydrolyzed free fatty acid (FFA) and methanol were studied. Although all tested catalysts drove the reaction to a high yield, hydrochloric acid was the only catalyst that could be considerably recovered and reused. The kinetics of the esterification reaction catalyzed by hydrochloric acid was investigated under varying catalyst loading (0.1-1M), reaction temperature (303-343K), and methanol/FFA molar ratio (1:1-20:1). In addition, a pseudo-homogeneous kinetic model incorporating the above factors was developed. A good agreement (r(2)=0.98) between the experimental and calculated data was obtained, thus proving the reliability of the model. Furthermore, the reusability of hydrochloric acid in FFA esterification can be predicted by the developed model. The recoverable hydrochloric acid achieved high yields of FFA esterification within five times of reuse.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1999-07-01

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

  7. Kinetics of saturated, monounsaturated, and polyunsaturated fatty acids in humans.

    Science.gov (United States)

    Nelson, Robert H; Mundi, Manpreet S; Vlazny, Danielle T; Smailovic, Almira; Muthusamy, Kalpana; Almandoz, Jaime P; Singh, Ekta; Jensen, Michael D; Miles, John M

    2013-03-01

    Plasma free fatty acid (FFA) kinetics in humans are often measured with only one tracer. In study 1, healthy volunteers received infusions of [U-¹³C]linoleate, [U-¹³C]oleate, and [U-¹³C]palmitate during continuous feeding with liquid meals low (n = 12) and high (n = 5) in palmitate and containing three labeled fatty acids to measure FFA appearance and fractional spillover of lipoprotein lipase-generated fatty acids. Study 2 used an intravenous lipid emulsion to increase FFA concentrations during infusion of linoleate and palmitate tracers. In study 1, there were no differences in spillover of the three fatty acids for the low-palmitate meal, but linoleate spillover was greater than oleate or palmitate for the high-palmitate meal. In studies 1 and 2, clearance was significantly greater for linoleate than for the other FFAs. There was a negative correlation between clearance and concentration for each fatty acid in the two studies. In study 1, concentration and spillover correlated positively for oleate and palmitate but negatively for linoleate. In conclusion, linoleate spillover is greater than that of other fatty acids under some circumstances. Linoleate clearance is greater than that of palmitate or oleate, indicating a need for caution when using a single FFA to infer the behavior of all fatty acids.

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

    Institute of Scientific and Technical Information of China (English)

    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.

  9. Sulfuric acid leaching kinetics of South African chromite

    Institute of Scientific and Technical Information of China (English)

    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.

  10. Kinetics of dodecanedioic acid and effect of its administration on glucose kinetics in rats.

    Science.gov (United States)

    Bertuzzi, A; Mingrone, G; De Gaetano, A; Gandolfi, A; Greco, A V; Salinari, S

    1997-07-01

    Dodecanedioic acid (C12), a saturated aliphatic dicarboxylic acid with twelve C atoms, was given as an intraperitoneal bolus to male Wistar rats, with the aim of evaluating C12 suitability as an energy substrate for parenteral nutrition. The 24 h urinary excretion of C12 was 3.9% of the administered dose. C12 kinetics were investigated by a one-compartment model with saturable tissue uptake and reversible binding to plasma albumin. The analysis of plasma concentration and urinary excretion data from different animals yielded the population means of the kinetic parameters: renal clearance was 0.72 ml/min per kg body weight (BW) (much smaller than inulin clearance in the rat), and maximal tissue uptake was 17.8 mumol/min per kg BW corresponding to 123.7 J/min per kg BW. These results encourage the consideration of C12 as a possible substrate for parenteral nutrition. To investigate the effect of C12 administration on glucose kinetics, two other groups of rats, one treated with an intraperitoneal bolus of C12 and the other with saline, were subsequently given an intravenous injection of D[-U-14C]glucose in a tracer amount. Radioactivity data of both control and C12-treated rats were analysed by means of a two-compartment kinetic model which takes into account glucose recycling. The estimates of glucose pool size (2.3 mmol/kg BW) and total-body rate of disappearance (82.1 mumol/min per kg BW) in control rats agreed with published values. In C12-treated rats, the rate of disappearance appeared to be reduced to 36.7 mumol/min per kg BW and the extent of recycling appeared to be negligible.

  11. Kinetics of xylose dehydration into furfural in acetic acid

    Institute of Scientific and Technical Information of China (English)

    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.

  12. Abiotic racemization kinetics of amino acids in marine sediments.

    Directory of Open Access Journals (Sweden)

    Andrew D Steen

    Full Text Available The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth below seafloor. Extrapolation to a typical cold deep sea sediment temperature of 3°C suggests racemization rate constants of 0.50×10(-5-11×10(-5 yr(-1. These results can be used in conjunction with measurements of sediment age to predict the ratio of d:l amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial populations.

  13. Butyric acid esterification kinetics over Amberlyst solid acid catalysts: the effect of alcohol carbon chain length.

    Science.gov (United States)

    Pappu, Venkata K S; Kanyi, Victor; Santhanakrishnan, Arati; Lira, Carl T; Miller, Dennis J

    2013-02-01

    The liquid phase esterification of butyric acid with a series of linear and branched alcohols is examined. Four strong cation exchange resins, Amberlyst™ 15, Amberlyst™ 36, Amberlyst™ BD 20, and Amberlyst™ 70, were used along with para-toluenesulfonic acid as a homogeneous catalyst. The effect of increasing alcohol carbon chain length and branching on esterification rate at 60°C is presented. For all catalysts, the decrease in turnover frequency (TOF) with increasing carbon chain length of the alcohol is described in terms of steric hindrance, alcohol polarity, and hydroxyl group concentration. The kinetics of butyric acid esterification with 2-ethylhexanol using Amberlyst™ 70 catalyst is described with an activity-based, pseudo-homogeneous kinetic model that includes autocatalysis by butyric acid.

  14. Thermal Decomposition Kinetics of Abietic Acid in Static Air

    Institute of Scientific and Technical Information of China (English)

    NONG Weijian; CHEN Xiaopeng; WANG Linlin; LIANG Jiezhen; ZHONG Lingping; TONG Zhangfa

    2013-01-01

    The thermal decomposition of abietic acid in air was investigated under non-isothermal condition using thermograv,imetric analysis-differential thermal analysis (TGA-DTA) technique with heating rates of 5,10,15 and 25 K·min 1.The non-isothermal kinetic parameters were obtained via the analysis of the therrnogravimetric and differential thermogravimetric (TG-DTG) curves by using Flynn-Wall-Ozawa method and Kissinger method.The thermal decomposition mechanism of abietic acid was studied with four integral methods (Satava-Sesták,MacCallum-Tanner,ordinary integral and Agrawal).The results show that the thermal decomposition mechanism is nucleation and growth,and the mechanism function is Avrami-Erofeev equation with n equates 1/2.The activation energy and the pre-exponential factor are 64.04 kJ·mol-and 5.89×10 s-1,respectively.

  15. Acid base catalyzed transesterification kinetics of waste cooking oil

    Energy Technology Data Exchange (ETDEWEB)

    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)

  16. Kinetics of acid base catalyzed transesterification of Jatropha curcas oil.

    Science.gov (United States)

    Jain, Siddharth; Sharma, M P

    2010-10-01

    Out of various non-edible oil resources, Jatropha curcas oil (JCO) is considered as future feedstock for biodiesel production in India. Limited work is reported on the kinetics of transesterification of high free fatty acids containing oil. The present study reports the results of kinetic study of two-step acid base catalyzed transesterification process carried out at an optimum temperature of 65 °C and 50 °C for esterification and transesterification respectively under the optimum methanol to oil ratio of 3:7 (v/v), catalyst concentration 1% (w/w) for H₂SO₄ and NaOH. The yield of methyl ester (ME) has been used to study the effect of different parameters. The results indicate that both esterification and transesterification reaction are of first order with reaction rate constant of 0.0031 min⁻¹ and 0.008 min⁻¹ respectively. The maximum yield of 21.2% of ME during esterification and 90.1% from transesterification of pretreated JCO has been obtained.

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

    Directory of Open Access Journals (Sweden)

    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.

  18. Kinetics of coffee industrial residue pyrolysis using distributed activation energy model and components separation of bio-oil by sequencing temperature-raising pyrolysis.

    Science.gov (United States)

    Chen, Nanwei; Ren, Jie; Ye, Ziwei; Xu, Qizhi; Liu, Jingyong; Sun, Shuiyu

    2016-12-01

    This study was carried out to investigate the kinetics of coffee industrial residue (CIR) pyrolysis, the effect of pyrolysis factors on yield of bio-oil component and components separation of bio-oil. The kinetics of CIR pyrolysis was analyzed using distributed activation energy model (DAEM), based on the experiments in thermogravimetric analyzer (TGA), and it indicated that the average of activation energy (E) is 187.86kJ·mol(-1). The bio-oils were prepared from CIR pyrolysis in vacuum tube furnace, and its components were determined by gas chromatography/mass spectrometry (GC-MS). Among pyrolysis factors, pyrolysis temperature is the most influential factor on components yield of bio-oil, directly concerned with the volatilization and yield of components (palmitic acid, linoleic acid, oleic acid, octadecanoic acid and caffeine). Furthermore, a new method (sequencing temperature-raising pyrolysis) was put forward and applied to the components separation of bio-oil. Based on experiments, a solution of components separation of bio-oil was come out.

  19. 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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. The kinetics of iodide oxidation by hydrogen peroxide in acid solution

    Science.gov (United States)

    Milenković, M. C.; Stanisavljev, D. R.

    2011-12-01

    The kinetics of the complex reaction between I- and H2O2 in acid media was investigated. The particular attention was focused on the determination of the rate constant of the reaction between HIO and H2O2 involved in the investigated complex process. The examination of the whole kinetics was performed by simultaneously monitoring the evolution of O2 pressure, I{3/-} and I- concentrations. We modeled the behavior of experimentally followed components based on Liebhafsky's research. Our preliminary results suggest a significantly higher rate constant (3.5 × 107 M-1 s-1) of the reaction between HIO and H2O2 as those proposed in the literature.

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

    Science.gov (United States)

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

    2016-10-01

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

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

    OpenAIRE

    2011-01-01

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

  3. Kinetic model of water disinfection using peracetic acid including synergistic effects.

    Science.gov (United States)

    Flores, Marina J; Brandi, Rodolfo J; Cassano, Alberto E; Labas, Marisol D

    2016-01-01

    The disinfection efficiencies of a commercial mixture of peracetic acid against Escherichia coli were studied in laboratory scale experiments. The joint and separate action of two disinfectant agents, hydrogen peroxide and peracetic acid, were evaluated in order to observe synergistic effects. A kinetic model for each component of the mixture and for the commercial mixture was proposed. Through simple mathematical equations, the model describes different stages of attack by disinfectants during the inactivation process. Based on the experiments and the kinetic parameters obtained, it could be established that the efficiency of hydrogen peroxide was much lower than that of peracetic acid alone. However, the contribution of hydrogen peroxide was very important in the commercial mixture. It should be noted that this improvement occurred only after peracetic acid had initiated the attack on the cell. This synergistic effect was successfully explained by the proposed scheme and was verified by experimental results. Besides providing a clearer mechanistic understanding of water disinfection, such models may improve our ability to design reactors.

  4. Effect of diet-induced obesity on kinetic parameters of amino acid uptake by rat erythrocytes.

    Science.gov (United States)

    Picó, C; Pons, A; Palou, A

    1992-11-01

    The effects of cafeteria diet-induced obesity upon in vitro uptake of L-Alanine, Glycine, L-Lysine, L-Glutamine, L-Glutamic acid, L-Phenylalanine and L-Leucine by isolated rat erythrocytes have been studied. The total Phe and Leu uptakes followed Michaelis-Menten kinetics. The Glu uptake was fitted to diffusion kinetics. The uptakes of Ala, Gly, Lys and Gln were best explained by a two-component transport: one saturable and one diffusion. Obesity increased the Km value for Ala, Gln and Leu, and the Vmax value for Ala, but decreased the Vmax for Lys. Kinetic parameters of Phe uptake were unaffected by obesity. In addition, the pseudo-first order rate constant (Vmax/Km) for Ala, Gly, Gln, Lys and Leu uptake decreased as a result of cafeteria diet-induced obesity. The Kd value for Ala, Gly, Gln and Glu decreased and that of Lys increased as result of obesity. These adaptations could, at least in part, explain alterations in amino acid distribution between blood cells and plasma related to overfeeding or obesity.

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

    Directory of Open Access Journals (Sweden)

    N. A. Mohamed Farook

    2004-01-01

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

  6. Kinetics and mechanism of the oxidation process of two-component Fe-Al alloys

    Science.gov (United States)

    Przewlocka, H.; Siedlecka, J.

    1982-01-01

    The oxidation process of two-component Fe-Al alloys containing up to 7.2% Al and from 18 to 30% Al was studied. Kinetic measurements were conducted using the isothermal gravimetric method in the range of 1073-1223 K and 1073-1373 K for 50 hours. The methods used in studies of the mechanism of oxidation included: X-ray microanalysis, X-ray structural analysis, metallographic analysis and marker tests.

  7. Kinetic Modeling of Gasoline Surrogate Components and Mixtures under Engine Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Mehl, M; Pitz, W J; Westbrook, C K; Curran, H J

    2010-01-11

    Real fuels are complex mixtures of thousands of hydrocarbon compounds including linear and branched paraffins, naphthenes, olefins and aromatics. It is generally agreed that their behavior can be effectively reproduced by simpler fuel surrogates containing a limited number of components. In this work, an improved version of the kinetic model by the authors is used to analyze the combustion behavior of several components relevant to gasoline surrogate formulation. Particular attention is devoted to linear and branched saturated hydrocarbons (PRF mixtures), olefins (1-hexene) and aromatics (toluene). Model predictions for pure components, binary mixtures and multicomponent gasoline surrogates are compared with recent experimental information collected in rapid compression machine, shock tube and jet stirred reactors covering a wide range of conditions pertinent to internal combustion engines (3-50 atm, 650-1200K, stoichiometric fuel/air mixtures). Simulation results are discussed focusing attention on the mixing effects of the fuel components.

  8. Synthesis of L-2-amino-8-oxodecanoic acid: an amino acid component of apicidins

    OpenAIRE

    Linares de la Morena, María Lourdes; Agejas Chicharro, Francisco Javier; Alajarín Ferrández, Ramón; Vaquero López, Juan José; Álvarez-Builla Gómez, Julio

    2001-01-01

    The synthesis Of L-2-amino-8-oxodecanoic acid (Aoda) is described. This is a rare amino acid component of apicidins, a family of new cyclic tetrapeptides, inhibitors of histone deacetylase. Aoda was synthesised in seven steps from L-glutamic acid along with some derivatives. Universidad de Alcalá Fundación General de la Universidad de Alcalá FEDER

  9. Kinetics and reaction pathways of total acid number reduction of cyclopentane carboxylic acid using subcritical methanol

    Directory of Open Access Journals (Sweden)

    Mandal Pradip C.

    2016-09-01

    Full Text Available Cyclopentane carboxylic acid (CPCA is a model compound of Naphthenic acids (NAs. This objective of this paper is to discover total acid number (TAN reduction kinetics and pathways of the reaction between CAPA and subcritical methanol (SubC-MeOH. The experiments were carried out in an autoclave reactor at temperatures of 180-220°C, a methanol partial pressure (MPP of 3 MPa, reaction times of 0-30 min and CPCA initial gas phase concentrations of 0.016-0.04 g/mL. TAN content of the samples were analyzed using ASTM D 974 techniques. The reaction products were identified and quantified with the help of GC/MS and GC-FID respectively. Experimental results reveal that TAN removal kinetics followed first order kinetics with an activation energy of 13.97 kcal/mol and a pre-exponential factor of 174.21 s-1. Subcritical methanol is able to reduce TAN of CPCA decomposing CPCA into new compounds such as cyclopentane, formaldehyde, methyl acetate and 3-pentanol.

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

    Directory of Open Access Journals (Sweden)

    N. A. Mohamed Farook

    2011-01-01

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

  11. A kinetic study on the conversion of glucose to levulinic acid

    NARCIS (Netherlands)

    Girisuta, B; Janssen, LPBM; Heeres, HJ

    2006-01-01

    Levulinic acid has been identified as a promising green. biomass derived platform chemical. A kinetic study oil 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

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

    NARCIS (Netherlands)

    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

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

    Indian Academy of Sciences (India)

    Puttaswamy; Nirmala Vaz

    2001-08-01

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

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

    Science.gov (United States)

    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.

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

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; Kalyan K Banerji

    2004-03-01

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

  16. Kinetic theory of time correlation functions for a dense one-component plasma in a magnetic field

    NARCIS (Netherlands)

    Schoolderman, A.J.; Suttorp, L.G.

    1988-01-01

    The time-dependent correlations of a one-component plasma in a uniform magnetic field are studied with the help of kinetic theory. The time correlation functions of the particle density, the momentum density, and the kinetic energy density are evaluated for large time intervals. In the collision-dom

  17. Polymer materials and component evaluation in acidic-radiation environments

    Science.gov (United States)

    Celina, M.; Gillen, K. T.; Malone, G. M.; Clough, R. L.; Nelson, W. H.

    2001-07-01

    Polymeric materials used for cable/wire insulation, electrical connectors, O-rings, seals, and in critical components such as motors, level switches and resistive thermo-devices were evaluated under accelerated degradation conditions in combined radiation-oxidative elevated-temperature acidic-vapor (nitric/oxalic) environments relevant to conditions in isotope processing facilities. Experiments included the assessment of individual materials such as PEEK, polyimides, polyolefin based cable insulation, EPDM rubbers, various epoxy systems, commercial caulking materials as well as some functional testing of components. We discuss how to conduct laboratory experiments to simulate such complex hostile environments, describe some degradation effects encountered, and evaluate the impact on appropriate material and component selection.

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

    Science.gov (United States)

    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…

  19. Insulin dose response analysis of free fatty acid kinetics.

    Science.gov (United States)

    Jensen, Michael D; Nielsen, Søren

    2007-01-01

    Insulin regulation of free fatty acid (FFA) release is an important aspect of metabolic function; however, FFA release is exquisitely sensitive to insulin, which complicates the design and analysis of dose response experiments. We measured FFA ([(3)H]palmitate) and glucose ([(3)H]glucose) kinetics in 7 nonobese men, 7 nonobese women, 7 obese men, and 7 obese women by using a two-step insulin clamp (0.25 and 2.5 mU/kg fat-free mass per minute). Obese men and women were characterized as having a BMI of 28 or greater and body fat of 28% and 40% or greater for men and for women, respectively. Nonobese men and women had 22% and 35% or less body fat, respectively. All volunteers were Caucasian. Glucose disposal increased in a linear fashion with plasma insulin concentrations. The nonlinear suppression of plasma palmitate flux and concentrations could be linearized by logarithmically transforming both the insulin concentration and palmitate axes, except in nonobese men. We repeated the studies in 7 nonobese and 7 obese men, using 1.0 mU/kg fat-free mass per minute as the second insulin dose, which linearized the log-transformed lipolysis measures. The indices of insulin regulation of lipolysis predicted using 2 points (basal and second insulin dose) vs 3 points (basal, low, and high dose) were not different provided the proper second dose was selected. The EC(50) for insulin suppression of lipolysis correlated linearly with plasma triglycerides (r = 0.52, P < .001) and exponentially with insulin sensitivity(glucose) (r = 0.70, P < .001). We conclude that log transformation of insulin dose response data for FFA permits straightforward data analysis and simplifies the estimation of metabolically relevant parameters.

  20. Acid hydrolysis of corn stover using hydrochloric acid: Kinetic modeling and statistical optimization

    Directory of Open Access Journals (Sweden)

    Sun Yong

    2014-01-01

    Full Text Available The hydrolysis of corn stover using hydrochloric acid was studied. The kinetic parameters of the mathematical models for predicting the yields of xylose, glucose, furfural and acetic acid were obtained, and the corresponding xylose generation activation energy of 100 kJ/mol was determined. The characterization of corn stover using with different techniques during hydrolysis indicated an effective removal of xylan and the slightly alteration on the structures of cellulose and lignin. A 23five levels Central Composite Design (CCD was used to develop a statistical model for the optimization of process variables including acid concentration, pretreatment temperature and time. The optimum conditions determined by this model were found to be 108ºC for 80 minutes with acid concentration of 5.8%. Under these conditions, the maximised results are the following: xylose 19.93 g/L, glucose 1.2 g/L, furfural 1.5 g/L, acetic acid 1.3 g/L. The validation of the model indicates a good agreement between the experimental results and the predicted values.

  1. Effect of temperature on the nucleation kinetics of α L-glutamic acid

    Science.gov (United States)

    Lindenberg, Christian; Mazzotti, Marco

    2009-02-01

    In this work, the nucleation kinetics of α L-glutamic acid is determined on the basis of induction time measurements. L-Glutamic acid is precipitated by pH-shift in a stirred batch reactor. The induction times are measured at different supersaturations using ATR-FTIR spectroscopy and focused beam reflectance measurement (FBRM), and applying a previously developed method [J. Schöll, L. Vicum, M. Müller, M. Mazzotti, Precipitation of L-glutamic acid: Determination of nucleation kinetics. Chemical Engineering & Technology 29(2) (2006) 257-264]. Moreover, the effect of temperature on the induction time is studied. Together with independently measured growth kinetics, the nucleation rates are determined. Finally, the nucleation kinetics is used to calculate the interfacial energies. The analysis of the estimated kinetics parameters and of the calculated interfacial energies indicates a heterogeneous nucleation mechanism.

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

    Institute of Scientific and Technical Information of China (English)

    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.

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

    Institute of Scientific and Technical Information of China (English)

    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

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

    Indian Academy of Sciences (India)

    Madhu Khurana; Pradeep K Sharma; Kalyan K Banerji

    2000-04-01

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

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

    Directory of Open Access Journals (Sweden)

    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.

  6. KINETIC STUDIES ON THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY METALLIC MAGNESIUM-NITRIC ACID SYSTEM

    Institute of Scientific and Technical Information of China (English)

    WU Chinyung

    1983-01-01

    This article reports the polymerization kinetics of acrylonitrile initiated by metallic magnesiumnitric acid system. The rate of polymerization is independent of the amount of magnesium used; when the concentration of nitric acid is higher than acrylonitrile, the equation of polymerization kinetics may be expressed as Rp=1.91 × 105e-15000/RT[Mg]0 [AN]2·2 [HNO3]0·46 The result of copolymerization of acyrlonitrile and methyl acrylate supports a free-radical mechanism.

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

    Directory of Open Access Journals (Sweden)

    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.

  8. Leaching of spent lead acid battery paste components by sodium citrate and acetic acid.

    Science.gov (United States)

    Zhu, Xinfeng; He, Xiong; Yang, Jiakuan; Gao, Linxia; Liu, Jianwen; Yang, Danni; Sun, Xiaojuan; Zhang, Wei; Wang, Qin; Kumar, R Vasant

    2013-04-15

    A sustainable method, with minimal pollution and low energy cost in comparison with the conventional smelting methods, is proposed for treating components of spent lead-acid battery pastes in aqueous organic acid(s). In this study, PbO, PbO2, and PbSO4, the three major components in a spent lead paste, were individually reacted with a mixture of aqueous sodium citrate and acetic acid solution. Pure lead citrate precursor of Pb3(C6H5O7)2 · 3H2O is the only product crystallized in each leaching experiment. Conditions were optimized for individual lead compounds which were then used as the basis for leaching real industrial spent paste. In this work, efficient leaching process is achieved and raw material cost is reduced by using aqueous sodium citrate and acetic acid, instead of aqueous sodium citrate and citric acid as reported in a pioneering hydrometallurgical method earlier. Acetic acid is not only cheaper than citric acid but is also more effective in aiding dissolution of the lead compounds thus speeding up the leaching process in comparison with citric acid. Lead citrate is readily crystallized from the aqueous solution due to its low solubility and can be combusted to directly produce leady oxide as a precursor for making new battery pastes.

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

    Indian Academy of Sciences (India)

    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.

  10. Mechanism and Kinetics Study for Photocatalytic Oxidation Degradation: A Case Study for Phenoxyacetic Acid Organic Pollutant

    Directory of Open Access Journals (Sweden)

    Kian Mun Lee

    2015-01-01

    Full Text Available Photocatalysis is a rapidly expanding technology for wastewater treatment, including a wide range of organic pollutants. Thus, understanding the kinetics and mechanism of the photocatalytic oxidation (PCO for degradation of phenoxyacetic acid (PAA is an indispensable component of risk assessment. In this study, we demonstrated that the central composite design (CCD coupled with response surface methodology (RSM was successfully employed to probe the kinetics and mechanism of PCO degradation for PAA using an efficient zinc oxide (ZnO photocatalyst. In our current case study, four independent factors such as ZnO dosage, initial concentration of PAA, solution pH, and reaction time on the PCO degradation for PAA were examined in detail. Based on our results obtained from RSM analyses, an efficient pathway leading to the high degradation rate (>90% was applying 0.4 g/L of ZnO dosage with 16 mg/L of concentration of PAA at pH 6.73 for 40 minutes. The experimental results were fitted well with the derived response model with R2 = 0.9922. This study offers a cost-effective way for probing our global environmental water pollution issue.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  12. Dissociation kinetics of the thyrotropin-receptor complex. Characterization of a slowly dissociable component.

    Science.gov (United States)

    Powell-Jones, C H; Saltiel, A R; Thomas, C G; Nayfeh, S N

    1981-11-01

    The kinetics of the dissociation of thyrotropin (TSH) from human thyroid plasma membranes were studied in an attempt to further understand the molecular dynamics of the TSH--receptor interaction. Dissociation of bound [125I]TSH from thyroid plasma membranes was a biphasic process consisting of rapidly and slowly dissociable components, RDC and SDC, respectively. The dilution induced dissociation of bound [125I]TSH was enhanced by the addition of excess TSH (DEC). DEC was proportional to the dose of unlabeled TSH and its magnitude increased linearly with temperature. These results are in contrast to those reported for the kinetics of [125I]insulin dissociation. The functional significance of DEC remains largely unexplained. It was found that the fraction of SDC was dependent upon time of association in a temperature-dependent and apparently saturable process. It could not be attributed to alterations in the electrophoretic, immunologic or binding properties of [125I]TSH. Furthermore, no correlation was observed between generation of SDC and change in the Scatchard profile of TSH binding, in contrast to studies on growth hormone. These data suggest that, like some other polypeptide hormones, binding of TSH to its receptor does not proceed according to laws describing simple, rapidly reversible, bimolecular reactions. Furthermore, bound TSH undergoes a receptor-mediated conversion from a rapidly to a slowly dissociable state with time of incubation.

  13. The estimate of kinetic powers of jets in FRII radio galaxies: existence of invisible components?

    CERN Document Server

    Ito, H; Kawakatu, N; Isobe, N; Yamada, S

    2008-01-01

    We investigate the total kinetic powers (L_j) and ages (t_age) of powerful jets in FR II radio galaxies by comparison of the dynamical model of expanding cocoons with observations. We select four FR II radio sources (Cygnus A, 3C 223, 3C 284, and 3C 219), for which the mass-density profiles of intracluster medium (ICM) are known in the literature. It is found that large fractions > 0.02 - 0.7 of the Eddington luminosity (L_Edd) are carried away as a kinetic power of jet. The upper limit of estimated 2 L_j / L_Edd are larger than unity (< 10) for some sources, suggesting a possibility of super-Eddington mass accretions. As a consequence of the large powers, we also find that the total energy stored in the cocoon (E_c) exceeds the energy derived from the minimum energy condition for the energy of radiating non-thermal electrons and magnetic fields (E_min): 4< E_c /E_min <310. This implies that most of the energy in cocoon is carried by invisible components such as thermal leptons (electron and positron...

  14. The Estimate of Kinetic Power of Jets in FR II Radio Galaxies: Existence of Invisible Components?

    Science.gov (United States)

    Ito, Hirotaka; Kino, Motoki; Kawakatu, Nozomu; Isobe, Naoki; Yamada, Shoichi

    2008-10-01

    We investigate the total kinetic power (Lj) and age (tage) of powerful jets in FR II radio galaxies by comparison of the dynamical model of expanding cocoons with observations. We select four FR II radio sources (Cygnus A, 3C 223, 3C 284, and 3C 219), for which the mass-density profiles of the intracluster medium (ICM) are known in the literature. It is found that large fractions gtrsim0.02-0.7 of the Eddington luminosity (LEdd) are carried away as kinetic power of jets. The upper limit of estimated 2Lj/LEdd is larger than unity (lesssim10) for some sources, suggesting the possibility of super-Eddington mass accretions. As a consequence of the large powers, we also find that the total energy stored in the cocoon (Ec) exceeds the energy derived from the minimum energy condition for the energy of radiating nonthermal electrons and magnetic fields (Emin): 4 < Ec/Emin < 310. This implies that most of the energy in the cocoon is carried by invisible components such as thermal leptons (electron and positron) and/or protons.

  15. Kinetic and potential components of the exact time-dependent correlation potential

    CERN Document Server

    Luo, Kai; Sandoval, Ernesto D; Elliott, Peter; Maitra, Neepa T

    2013-01-01

    The exact exchange-correlation (xc) potential of time-dependent density functional theory has been shown to have striking features. For example, step and peak features are generically found when the system is far from its ground-state, and these depend nonlocally on the density in space and time. We analyze the xc potential by decomposing it into kinetic and interaction potential components, and comparing each with their exact-adiabatic counterparts, for a range of dynamical situations in model one-dimensional (1D) two-electron systems. We find that often, but not always, the kinetic contri- bution is mostly responsible for these features, that are missed by the adiabatic approximation. The adiabatic approximation often makes a smaller error for the potential contribution, which we write in two parts, one being the Coulomb potential due to the time-dependent xc hole. These observations also held in non-equilibrium cases we studied where there are large features in the correlation po- tential although no step ...

  16. Kinetics of photoelectrocatalytic degradation of humic acid using B2 O3·TiO2/Ti photoelectrode

    Institute of Scientific and Technical Information of China (English)

    JIANG Yan-li; LIU Hui-ling; LU Chun-mei

    2005-01-01

    An innovative photoelectrode, B2O3·TiO2/Ti electrode, was prepared by galvanostaticanodisation. The morphology and crystalline examination results indicated that the anatase was the dominant component. The kinetics of photoelectrocatalytic(PEC) degradation of humic acid(HA) was investigated; the results demonstrated that effects from strongness to weakness on the photoelectrocatalytic degraded rate of humic acid: power of UV-lamp, area of TiO2 film, bias, original concentration of humic acid solution. The optimum conditions were power of UV-lamp 125 W, area of TiO2 film 42.0 cm2 , bias 1.4 V, original concentration of humic acid solution 5 mg/L in this PEC reaction system.

  17. Adsorption and desorption kinetics of carbofuran in acid soils.

    Science.gov (United States)

    Bermúdez-Couso, Alipio; Fernández-Calviño, David; Pateiro-Moure, Miriam; Nóvoa-Muñoz, Juan Carlos; Simal-Gándara, Jesús; Arias-Estévez, Manuel

    2011-06-15

    Carbofuran adsorption and desorption were investigated in batch and stirred flow chamber (SFC) tests. The carbofuran adsorption capacity of the soils was found to be low and strongly dependent on their clay and organic carbon contents. Carbofuran sorption was due mainly (>80%) to fast adsorption processes governed by intraparticle diffusion. The adsorption kinetic constant for the pesticide ranged from 0.047 to 0.195 min(-1) and was highly correlated with constant n in the Freundlich equation (r=0.965, Pcarbofuran desorption to be highly variable and negatively correlated with eCEC and the clay content. The SFC tests showed that soil organic carbon (C) plays a key role in the irreversibility of carbofuran adsorption. Carbofuran desorption increased rapidly at C contents below 4%. The desorption kinetic constant for the compound (0.086-0.195 min(-1)) was generally higher than its adsorption kinetic constant; therefore, carbofuran is more rapidly desorbed than it is adsorbed in soil.

  18. Kinetics of levulinic acid and furfural production from Miscanthus × giganteus.

    Science.gov (United States)

    Dussan, K; Girisuta, B; Haverty, D; Leahy, J J; Hayes, M H B

    2013-12-01

    This study investigated the kinetics of acid hydrolysis of the cellulose and hemicellulose in Miscanthus to produce levulinic acid and furfural under mild temperature and high acid concentration. Experiments were carried out in an 8L-batch reactor with 9%-wt. biomass loading, acid concentrations between 0.10 and 0.53 M H2SO4, and at temperatures between 150 and 200°C. The concentrations of xylose, glucose, furfural, 5-hydroxymethylfurfural and levulinic acid were used in two mechanistic kinetic models for the prediction of the performance of ideal continuous reactors for the optimisation of levulinic acid and the concurrent production of furfural. A two-stage arrangement was found to maximise furfural in the first reactor (PFR - 185°C, 0.5M H2SO4, 27.3%-mol). A second stage leads to levulinic acid yields between 58% and 72%-mol at temperatures between 160 and 200°C.

  19. Kinetic study of oxalic acid inhibition on enzymatic browning.

    Science.gov (United States)

    Son, S M; Moon, K D; Lee, C Y

    2000-06-01

    Oxalic acid has a strong antibrowning activity. The inhibitory pattern on catechol-PPO model system appeared to be competitive, with a K(i) value of 2.0 mM. When the PPO was incubated with oxalic acid, the activity was not recovered via dialysis, but the inactivated enzyme partially recovered its activity when cupric ion was added. Comparing the relative antibrowning effectiveness of oxalic acid with other common antibrowning agents, oxalic acid with I(50) value of 1.1 mM is as effective as kojic acid and more potent than cysteine and glutathione.

  20. Transmission electron microscopic examination of phosphoric acid fuel cell components

    Science.gov (United States)

    Pebler, A.

    1986-01-01

    Transmission electron microscopy (TEM) was used to physically characterize tested and untested phosphoric acid fuel cell (PAFC) components. Those examined included carbon-supported platinum catalysts, carbon backing paper, and Teflon-bonded catalyst layers at various stages of fabrication and after testing in pressurized PAFC's. Applicability of electron diffraction and electron energy loss spectroscopy for identifying the various phases was explored. The discussion focuses on the morphology and size distribution of platinum, the morphology and structural aspects of Teflon in catalyst layers, and the structural evidence of carbon corrosion. Reference is made to other physical characterization techniques where appropriate. A qualitative model of the catalyst layer that emerged from the TEM studies is presented.

  1. Approximate linear confidence and curvature of a kinetic model of dodecanedioic acid in humans.

    Science.gov (United States)

    Panunzi, Simona; De Gaetano, Andrea; Mingrone, Geltrude

    2005-11-01

    Dicarboxylic acids with an even number of carbon atoms have been proposed as an alternate energy substrate for enteral or parenteral nutrition in the acutely ill patient, due to their water solubility and their yielding TCA cycle intermediates upon beta-oxidation. In the present work, a nonlinear compartmental model of the kinetics of dodecanedioic acid is developed, and its parameters are estimated from time concentration experimental observations obtained from six healthy volunteers undergoing a per os administration of 3 g of the substance. Although the model is linear in the transfer of the free substance from plasma to the tissues, the exchange between gut and plasma compartments is represented as a saturable function. Albumin binding is then incorporated to obtain the final model in terms of the measured total concentrations. Estimates of the model's structural parameters were computed for each experimental subject, and the usual single-subject approximate confidence regions for the parameters were derived by inversion of the Hessian at the optimum. To verify the applicability of this approximation, the nonlinearity of the expectation surface at the optimum was measured by computing the normal (intrinsic) component of curvature. Because the model curvature was excessive in all subjects, the usual approximation could not be trusted to provide acceptable approximations to the parameter confidence regions. A suitable Monte Carlo simulation yielded empirical joint parameter distributions from which the approximate parameter variances could finally be obtained.

  2. Disproportionation Kinetics of Hypoiodous Acid As Catalyzed and Suppressed by Acetic Acid-Acetate Buffer.

    Science.gov (United States)

    Urbansky, Edward T.; Cooper, Brian T.; Margerum, Dale W.

    1997-03-26

    The kinetics of the disproportionation of hypoiodous acid to give iodine and iodate ion (5HOI right harpoon over left harpoon 2I(2) + IO(3)(-) + H(+) + 2H(2)O) are investigated in aqueous acetic acid-sodium acetate buffer. The rate of iodine formation is followed photometrically at -log [H(+)] = 3.50, 4.00, 4.50, and 5.00, &mgr; = 0.50 M (NaClO(4)), and 25.0 degrees C. Both catalytic and inhibitory buffer effects are observed. The first process is proposed to be a disproportionation of iodine(I) to give HOIO and I(-); the iodide then reacts with HOI to give I(2). The reactive species (acetato-O)iodine(I), CH(3)CO(2)I, is postulated to increase the rate by assisting in the formation of I(2)O, a steady-state species that hydrolyzes to give HOIO and I(2). Inhibition is postulated to result from the formation of the stable ion bis(acetato-O)iodate(I), (CH(3)CO(2))(2)I(-), as buffer concentration is increased. This species is observed spectrophotometrically with a UV absorption shoulder (lambda = 266 nm; epsilon = 530 M(-)(1) cm(-)(1)). The second process is proposed to be a disproportionation of HOIO to give IO(3)(-) and I(2). Above 1 M total buffer, the reaction becomes reversible with less than 90% I(2) formation. Rate and equilibrium constants are resolved and reported for the proposed mechanism.

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

    Institute of Scientific and Technical Information of China (English)

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

  5. Abiotic racemization kinetics of amino acids in marine sediments

    DEFF Research Database (Denmark)

    Steen, Andrew; Jørgensen, Bo Barker; Lomstein, Bente Aagaard

    2013-01-01

    Enantiomeric ratios of amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic racemize abiotically. Based on a heating experiment, we report Arrhenius parameters...... between different amino acids or depths. These results can be used in conjunction with measurements of sediment age to predict the ratio of D:L amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial...

  6. Effects of L-Aspartic acid on the step retreat kinetics of calcite

    Science.gov (United States)

    Yoshino, Toru; Kagi, Hiroyuki

    2012-01-01

    Effects of L-Aspartic acid (L-Asp) on step retreat kinetics in the dissolution of calcite were investigated. The step retreat velocities under surface-controlled kinetics were determined from in-situ atomic force microscopic observations using an improved flow-through system. Comparison of the present results with those obtained under a mixed kinetics condition revealed that the addition of L-Asp promotes the transport process in the calcite dissolution through acid-base and/or complex forming reactions in the diffusion boundary layer. Additionally, promotion of the acute and obtuse step retreats by the L-Asp additive was observed under surface-controlled kinetics. This report is the first to clarify that L-Asp promotes surface processes in the dissolution of calcite.

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

    Indian Academy of Sciences (India)

    Poonam Gupta; Seema Kothari

    2001-04-01

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

  8. Kinetics of acid-catalyzed cleavage of cumene hydroperoxide.

    Science.gov (United States)

    Levin, M E; Gonzales, N O; Zimmerman, L W; Yang, J

    2006-03-17

    The cleavage of cumene hydroperoxide, in the presence of sulfuric acid, to form phenol and acetone has been examined by adiabatic calorimetry. As expected, acid can catalyze cumene hydroperoxide reaction at temperatures below that of thermally-induced decomposition. At elevated acid concentrations, reactivity is also observed at or below room temperature. The exhibited reactivity behavior is complex and is significantly affected by the presence of other species (including the products). Several reaction models have been explored to explain the behavior and these are discussed.

  9. Energetics and kinetics of anaerobic aromatic and fatty acid degradation

    Energy Technology Data Exchange (ETDEWEB)

    McInerney, M.J.

    1992-11-16

    The kinetics of benzoate degradation by the anaerobic syntrophic bacterium, Syntrophus buswellii, was studied in coculture with Desulfovibrio strain G11. The threshold value for benzoate degradation was dependent on the acetate concentration with benzoate threshold values ranging from 2.4 [mu]M at 20 mM acetate to 30.0 [mu]M at 65 mM acetate. Increasing acetate concentrations also inhibited the rate of benzoate degradation with a apparent K[sub i] for acetate inhibition of 7.0 mM. Lower threshold values were obtained when nitrate rather than sulfate was the terminal electron acceptor. These data are consistent with a thermodynamic explanation for the threshold, and suggest that there is a minimum Gibbs free energy value required for the degradation of benzoate. An acetoacetyl-CoA thiolase has been isolated from Syntrophomonas wolfei; it is apparently a key enzyme controlling the synthesis of poly-B-hydroxyalkanoate from acetyl-CoA in this organism. Kinetic characterization of the acetoacetyl-CoA thiolase from S. wolfei showed that it is similar in its structural, kinetic, and apparent regulatory properties to other biosynthetic acetoacetyl-CoA thiolases from phylogenetically distinct bacteria that synthesize PHA. Intracellular concentrations of CoA and acetyl-CoA are believed to be critical factors regulating the activity of the acetoacetyl-CoA thiolase in S. wolfei. We have also isolated and characterized several new halophilic anaerobic fermentative anaerobes. Phylogenetic analysis indicates that one of these bacteria is a new species in the genus, Haloanaerobium. Two other species appear to be members of the genus, Halobacteroides. Several halophilic acetoclastic methanogenic bacteria have also been isolated and their physiological properties are currently under investigation. We have also isolated an acetate-using dissimilatory iron-reducing bacterium.

  10. A study on degradation kinetics of ascorbic acid in amla (Phyllanthus emblica L.) during cooking.

    Science.gov (United States)

    Nisha, P; Singhal, Rekha S; Pandit, Aniruddha B

    2004-08-01

    The kinetics of ascorbic acid degradation in amla (Phyllanthus emblica L.) as well as in pure ascorbic acid solutions at initial concentrations present in amla over a temperature range of 50-120 degrees C (steady-state temperature) has been studied. The ascorbic acid degradation followed first-order reaction kinetics where the rate constant increased with an increase in temperature. The temperature dependence of degradation was adequately modeled by the Arrhenius equation. The activation energies were found to be 4.09 kcal/mole for amla and 4.49 kcal/mole for pure vitamin solution. The degradation kinetics of ascorbic acid was also evaluated in normal open pan cooking, pressure-cooking and a newly developed and patented fuel-efficient EcoCooker (unsteady state heating process). A mathematical model was developed using the steady-state kinetic parameters obtained to predict the losses of ascorbic acid from the time-temperature data of the unsteady state heating processing method. The results obtained indicate the ascorbic acid degradation is of a similar order of magnitude in all the methods of cooking.

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

    Institute of Scientific and Technical Information of China (English)

    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.

  12. Reaction Kinetics Between Acetic Acid and Ag2+

    Institute of Scientific and Technical Information of China (English)

    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

  13. Age-Related Differences in Gait Kinematics, Kinetics, and Muscle Function: A Principal Component Analysis.

    Science.gov (United States)

    Schloemer, Sarah A; Thompson, Julie A; Silder, Amy; Thelen, Darryl G; Siston, Robert A

    2017-03-01

    Age-related increased hip extensor recruitment during gait is a proposed compensation strategy for reduced ankle power generation and may indicate a distal-to-proximal shift in muscle function with age. Extending beyond joint level analyses, identifying age-related changes at the muscle level could capture more closely the underlying mechanisms responsible for movement. The purpose of this study was to characterize and compare muscle forces and induced accelerations during gait in healthy older adults with those of young adults. Simulations of one gait cycle for ten older (73.9 ± 5.3 years) and six young (21.0 ± 2.1 years) adults walking at their self-selected speed were analyzed. Muscle force and induced acceleration waveforms, along with kinematic, kinetic, and muscle activation waveforms, were compared between age-groups using principal component analysis. Simulations of healthy older adults had greater gluteus maximus force and vertical support contribution, but smaller iliacus force, psoas force, and psoas vertical support contribution. There were no age-group differences in distal muscle force, contribution, or ankle torque magnitudes. Later peak dorsiflexion and peak ankle angular velocity in older adults may have contributed to their greater ankle power absorption during stance. These findings reveal the complex interplay between age-related changes in neuromuscular control, kinematics, and muscle function during gait.

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

    Indian Academy of Sciences (India)

    Dimple Garg; Seema Kothari

    2004-11-01

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

  15. The kinetics of chemical processes affecting acidity in the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Pienaar, J.J.; Helas, G. [Potchefstroom University of Christian Higher Education, Potchefstroom (South Africa). Atmospheric Chemistry Research Group

    1996-03-01

    The dominant chemical reactions affecting atmospheric pollution chemistry and in particular, those leading to the formation of acid rain are outlined. The factors controlling the oxidation rate of atmospheric pollutants as well as the rate laws describing these processes are discussed in the light of our latest results and the current literature.

  16. Evaporation kinetics of acetic acid-water solutions

    Science.gov (United States)

    Duffey, K.; Wong, N.; Saykally, R.; Cohen, R. C.

    2012-12-01

    The transport of water molecules across vapor-liquid interfaces in the atmosphere is a crucial step in the formation and evolution of cloud droplets. Despite decades of study, the effects of solutes on the mechanism and rate of evaporation and condensation remain poorly characterized. The present work aims to determine the effect of atmospherically-relevant solutes on the evaporation rate of water. In our experiments, we create a train of micron-sized droplets and measure their temperature via Raman thermometry as they undergo evaporation without condensation. Analysis of the cooling rate yields the evaporation coefficient (γ). Previous work has shown that inorganic salts have little effect on γ, with surface-adsorbing anions causing a slight reduction in the coefficient from that measured for pure water. Organic acids are ubiquitous in aqueous aerosol and have been shown to disrupt the surface structure of water. Here we describe measurements of the evaporation rate of acetic acid solutions, showing that acetic acid reduces γ to a larger extent than inorganic ions, and that γ decreases with increasing acetic acid concentration.

  17. Kinetic characteristics of acidic and alkaline ceramidase in human epidermis

    NARCIS (Netherlands)

    Houben, E.; Uchida, Y.; Nieuwenhuizen, W.F.; Paepe, K. de; Vanhaecke, T.; Holleran, W.M.; Rogiers, V.

    2007-01-01

    It has recently become evident that at least five ceramidase (CDase) isoforms are present in human epidermis, and that specifically acidic CDase (aCDase) and alkaline CDase (alkCDase) activities increase during keratinocyte differentiation, and thus might play a pivotal role(s) in permeability barri

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

    Institute of Scientific and Technical Information of China (English)

    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.

  19. Spectrophotometric method for determination and kinetics of amino acids through their reaction with syringaldehyde

    Science.gov (United States)

    Medien, H. A. A.

    1998-02-01

    A spectrophotometric method is described for the determination of amino acids. The method is based on the reaction between amino acids and syringaldehyde at pH 9.0, by which a color is developed with maximum absorption at 420 nm in aqueous methyl alcohol. The absorption of the product obeys Beer's law within the concentration range of 0.025-0.5 mM of original amino acid. The kinetics of the reaction follows overall second order kinetics, first order in each of the reactants. The rates of the reaction were investigated as a function of pH of the reaction medium and structure of the amino compounds. Logarithms of the second-order rate constants increased with amino acid anion concentration as the pH was increased. The mechanisms of the reaction have been discussed.

  20. Crystallization kinetics of poly-(lactic acid) with and without talc: Optical microscopy and calorimetric analysis

    Science.gov (United States)

    Refaa, Z.; Boutaous, M.; Rousset, F.; Fulchiron, R.; Zinet, M.; Xin, S.; Bourgin, P.

    2014-05-01

    Poly-(lactic acid) or PLA is a biodegradable polymer synthesized from renewable resources. Recently, the discovery of new polymerization routes has allowed increasing the produced volumes. As a consequence, PLA is becoming of great interest for reducing the dependence on petroleum-based plastics. Because of its interesting mechanical properties, PLA is seen as a potential substitute for some usual polymers. However, its relatively slow crystallization kinetics can be a disadvantage with regard to industrial applications. The crystallization kinetics of PLA can be enhanced by adding nucleating agents, which also influences on crystalline morphology and rheological behavior. In the present work, the isothermal quiescent crystallization kinetics of both neat PLA and PLA/talc composite (5 wt% talc) are investigated. The effects of talc on the overall crystallization kinetics and on the crystalline morphology are analyzed using both optical microscopy measurements and thermal analysis by differential scanning calorimetry.

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

    Science.gov (United States)

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

    2016-05-01

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

  2. Changes of lymphocyte kinetics in the normal rat, induced by the lymphocyte mobilizing agent polymethacrylic acid

    NARCIS (Netherlands)

    Ormai, S.; Hagenbeek, A.; Palkovits, M.; Bekkum, D.W. van

    1973-01-01

    The changes in lymphocyte kinetics induced by the lymphocyte mobilizing agent polymethacrylic acid (PMAA) were studied in the normal rat. Quantitative data are presented concerning the degree of lymphocyte mobilization in the spleen and in various lymph nodes at different times after PMAA administra

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

    Science.gov (United States)

    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. ...

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

    NARCIS (Netherlands)

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

    2002-01-01

    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) sy

  5. Degradation kinetic modelling of ascorbic acid and colour intensity in pasteurised blood orange juice during storage.

    Science.gov (United States)

    Remini, Hocine; Mertz, Christian; Belbahi, Amine; Achir, Nawel; Dornier, Manuel; Madani, Khodir

    2015-04-15

    The stability of ascorbic acid and colour intensity in pasteurised blood orange juice (Citrus sinensis [L.] Osbeck) during one month of storage was investigated at 4-37 °C. The effects of ascorbic acid fortification (at 100, 200 mg L(-1)) and deaeration, temperature/time storage on the kinetic behaviour were determined. Ascorbic acid was monitored by HPLC-DAD and colour intensity by spectrophotometric measurements. Degradation kinetics were best fitted by first-order reaction models for both ascorbic acid and colour intensity. Three models (Arrhenius, Eyring and Ball) were used to assess the temperature-dependent degradation. Following the Arrhenius model, activation energies were ranged from 51 to 135 kJ mol(-1) for ascorbic acid and from 49 to 99 kJ mol(-1) for colour intensity. The effect of storage temperature and deaeration are the most influent factors on kinetics degradation, while the fortification revealed no significant effect on ascorbic acid content and colour intensity.

  6. Chromium(VI) reduction kinetics by zero-valent iron in moderately hard water with humic acid: iron dissolution and humic acid adsorption.

    Science.gov (United States)

    Liu, Tongzhou; Tsang, Daniel C W; Lo, Irene M C

    2008-03-15

    In zerovalent iron treatment systems, the presence of multiple solution components may impose combined effects that differ from corresponding individual effects. The copresence of humic acid and hardness (Ca2+/Mg2+) was found to influence Cr(VI) reduction by Feo and iron dissolution in a way different from their respective presence in batch kinetics experiments with synthetic groundwater at initial pH 6 and 9.5. Cr(VI) reduction rate constants (k(obs)) were slightly inhibited by humic acid adsorption on iron filings (decreases of 7-9% and 10-12% in the presence of humic acid alone and together with hardness, respectively). The total amount of dissolved Fe steadily increased to 25 mg L(-1) in the presence of humic acid alone because the formation of soluble Fe-humate complexes appeared to suppress iron precipitation. Substantial amounts of soluble and colloidal Fe-humate complexes in groundwater may arouse aesthetic and safety concerns in groundwater use. In contrast, the coexistence of humic acid and Ca2+/Mg2+ significantly promoted aggregation of humic acid and metal hydrolyzed species, as indicated by XPS and TEM analyses, which remained nondissolved (>0.45 microm) in solution. These metal-humate aggregates may impose long-term impacts on PRBs in subsurface settings.

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

    Institute of Scientific and Technical Information of China (English)

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Science.gov (United States)

    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.

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

    DEFF Research Database (Denmark)

    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 0...

  11. The influence of temperature on the decomposition kinetics of peracetic acid in solutions

    OpenAIRE

    Kunigk L.; Gomes D.R.; Forte F.; Vidal K.P.; Gomes L.F.; Sousa P.F.

    2001-01-01

    Peracetic acid is a powerful sanitizer that has only recently been introduced in the Brazilian food industry. The main disadvantage of this sanitizer is its decomposition rate. The main purpose of this paper is to present results obtained in experiments carried out to study the decomposition kinetics of peracetic acid in aqueous solutions at 25, 35, 40 and 45 °C. The decompositon of peracetic acid is a first-order reaction. The decomposition rate constants are between 1.71x10-3 h -1 for 25 °C...

  12. Adsorption kinetics of organophosphonic acids on plasma-modified oxide-covered aluminum surfaces.

    Science.gov (United States)

    Giza, M; Thissen, P; Grundmeier, G

    2008-08-19

    Tailoring of oxide chemistry on aluminum by means of low-pressure water and argon plasma surface modification was performed to influence the kinetics of the self-assembly process of octadecylphosphonic acid monolayers. The plasma-induced surface chemistry was studied by in situ FTIR reflection-absorption spectroscopy (IRRAS). Ex situ IRRAS and X-ray photoelectron spectroscopy were applied for the analysis of the adsorbed self-assembled monolayers. The plasma-induced variation of the hydroxide to oxide ratio led to different adsorption kinetics of the phosphonic acid from dilute ethanol solutions as measured by means of a quartz crystal microbalance. Water plasma treatment caused a significant increase in the density of surface hydroxyl groups in comparison to that of the argon-plasma-treated surface. The hydroxyl-rich surface led to significantly accelerated adsorption kinetics of the phosphonic acid with a time of monolayer formation of less than 1 min. On the contrary, decreasing the surface hydroxyl density slowed the adsorption kinetics.

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

    Directory of Open Access Journals (Sweden)

    B.L. Hiran

    2016-11-01

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

  14. Kinetic study of the complexation of gallic acid with Fe(II)

    Science.gov (United States)

    Lu, Li-li; Li, Ying-hua; Lu, Xiu-yang

    2009-10-01

    Kinetic study on the complexation of gallic acid with ferrous sulfate was performed using UV-Vis absorption spectroscopy. Under the experimental conditions, the stoichiometric composition of the formed complex is 1:1. The complexation reaction was found to be a second-order one. The influences of temperature, ionic strength and solvents on the complexation reaction were investigated. According to the Arrhenius equation, the apparent activation energy of the complexation reaction was evaluated to be 71.64 kJ × mol -1. A three-step reaction mechanism was proposed, which can well explain the kinetic results obtained.

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

    Science.gov (United States)

    Hu, Ruikang; Zhang, Lifeng; Hu, Jiangyong

    2016-06-01

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

  16. Essential fatty acids as functional components of foods- a review.

    Science.gov (United States)

    Kaur, Narinder; Chugh, Vishal; Gupta, Anil K

    2014-10-01

    During the recent decades, awareness towards the role of essential fatty acids in human health and disease prevention has been unremittingly increasing among people. Fish, fish oils and some vegetable oils are rich sources of essential fatty acids. Many studies have positively correlated essential fatty acids with reduction of cardiovascular morbidity and mortality, infant development, cancer prevention, optimal brain and vision functioning, arthritis, hypertension, diabetes mellitus and neurological/neuropsychiatric disorders. Beneficial effects may be mediated through several different mechanisms, including alteration in cell membrane composition, gene expression or eicosanoid production. However, the mechanisms whereby essential fatty acids affect gene expression are complex and involve multiple processes. Further understanding of the molecular aspects of essential fatty acids will be the key to devising novel approaches to the treatment and prevention of many diseases.

  17. Conversion of syngas to liquid hydrocarbons over a two-component (Cr{sub 2}O{sub 3}-ZnO and ZSM-5 zeolite) catalyst: kinetic modelling and catalyst deactivation

    Energy Technology Data Exchange (ETDEWEB)

    Erena, J.; Arandes, J.M.; Bilbao, J.; Gayubo, A.G. [Universidad del Pais Vasco, Bilbao (Spain). Dept. de Ingeneria Quimica; De Lasa, H.I. [University of Western Ontario, London, ONT (Canada). Chemical Reactor Engineering Centre

    2000-05-01

    The present study describes the kinetics of syngas transformation into liquid hydrocarbons (boiling point in the gasoline range) using as catalyst a mixture of a metallic component, Cr{sub 2}O{sub 3}-ZnO, and of an acidic component, ZSM-5 zeolite. Experimental results were obtained in an isothermal fixed-bed integral reactor. The validity of several kinetic models, available for methanol synthesis, is analysed and modifications are proposed. These changes involve a rate equation with a CO{sub 2} concentration-dependent term. Catalyst deactivation is also evaluated and the effect of the operating conditions on coke deposition is established. Moreover, the rate of CO conversion and the change of catalytic activity with time-on-stream were described using a kinetic model showing a weak influence of temperature. (Author)

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

    Science.gov (United States)

    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.

  19. Crystallization kinetics of calcium carbonate at a stoichiometric ratio of components

    Science.gov (United States)

    Pochitalkina, I. A.; Kekin, P. A.; Morozov, A. N.; Petropavlovskii, I. A.; Kondakov, D. F.

    2016-12-01

    The formal kinetics of calcium carbonate crystallization in aqueous solutions is studied at a stoichiometric ratio of Ca2+ and CO3 2- ions. The kinetics of the process was monitored by convenient and reliable methods (complexometric analysis for calcium in an aqueous solution and energy dispersive and microscopic measurement of solid particle sizes). The effect the temperature and degree of supersaturation have on the periods of induction and mass crystallization and the equilibrium concentration of calcium ions in solution is estimated at continuously controlled pH and solution ionic strength. The kinetic parameters ( n, k, τ1/2, E a) of calcium carbonate crystallization are calculated. It is shown that calcium carbonate with a calcite structure formed at a stoichiometric ratio of reagents, and changes in the temperature (25-45°C) and the solution's degree of supersaturation (2-6) within the considered range had no effect on the characteristics of the solid phase.

  20. Kinetic study of empty fruit bunch using hot liquid water and dilute acid.

    Science.gov (United States)

    Kim, Jun Seok; Choi, Won Il; Kang, Minsu; Park, Ji Yeon; Lee, Jin-Suk

    2012-07-01

    Empty fruit bunch (EFB), a residual product of the palm plantation, is an attractive biomass for biorefinery. As xylan is susceptible to high temperature pretreatment, it is important to setup a proper pretreatment condition to maximize the sugar recovery from EFB. Kinetic parameters of mathematical models were obtained in order to predict the concentration of xylose, glucose, furfural, and acetic acid in the hydrolysate and to find production conditions of xylose. We investigated the kinetics of hot liquid water and dilute sulfuric acid hydrolysis over a 40-min period using a self-designed setup by measuring the concentrations of released sugars (xylose, glucose) and degradation products (acetic acid and furfural). The reaction was performed within the range 160∼180 °C, under reaction conditions of various concentration of sulfuric acid (0.1∼0.2%) and 1:7 solid-liquid ratio in a batch reactor. The kinetic constants can be expressed by the Arrhenius equation with the activation energy for the hydrolysis of sugar and decomposition of sugar. The activation energy of xylose was determined to be 136.2187 kJ mol(-1).

  1. Catalytic Kinetic Resolution of Saturated N-Heterocycles by Enantioselective Amidation with Chiral Hydroxamic Acids.

    Science.gov (United States)

    Kreituss, Imants; Bode, Jeffrey W

    2016-12-20

    The preparation of enantioenriched chiral compounds by kinetic resolution dates back to the laboratories of Louis Pasteur in the middle of the 19th century. Unlike asymmetric synthesis, this process can always deliver enantiopure material (ee > 99%) if the reactions are allowed to proceed to sufficient conversion and the selectivity of the process is not unity (s > 1). One of the most appealing and practical variants is acylative kinetic resolution, which affords easily separable reaction products, and several highly efficient enzymatic and small molecule catalysts are available. Unfortunately, this method is applicable to limited substrate classes such as alcohols and primary benzylamines. This Account focuses on our work in catalytic acylative kinetic resolution of saturated N-heterocycles, a class of molecules that has been notoriously difficult to access via asymmetric synthesis. We document the development of hydroxamic acids as suitable catalysts for enantioselective acylation of amines through relay catalysis. Alongside catalyst optimization and reaction development, we present mechanistic studies and theoretical calculation accounting for the origins of selectivity and revealing the concerted nature of many amide-bond forming reactions. Immobilization of the hydroxamic acid to form a polymer supported reagent allows simplification of the experimental setup, improvement in product purification, and extension of the substrate scope. The kinetic resolutions are operationally straight forward: reactions proceed at room temperature and open to air conditions, without generation of difficult-to-remove side products. This was utilized to achieve decagram scale resolution of antimalarial drug mefloquine to prepare more than 50 g of (+)-erythro-meflqouine (er > 99:1) from the racemate. The immobilized quasienantiomeric acyl hydroxamic acid reagents were also exploited for a rare practical implementation of parallel kinetic resolution that affords both enantiomers of

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

    Science.gov (United States)

    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

    2015-09-02

    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.

  3. Microcalorimetric Investigation on the Kinetics of the Oxidation of Ascorbic Acid with Hydrogen Peroxide

    Institute of Scientific and Technical Information of China (English)

    MENG,Xiang-Guang(孟祥光); KOU,Xing-Ming(寇兴明); XIE,Jia-Qing(谢家庆); DU,Juan(杜娟); ZENG,Xian-Cheng(曾宪诚)

    2004-01-01

    Based on the thermokinetic theory, a novel thermokinetic research method-self-function regression method,which could be used to determine the kinetic parameters k1, k2 and k 1 of the complex reaction:B+C(k1 k-1)Ik2→ P, was proposed in this paper. The kinetics of the reaction of ascorbic acid (H2A) with hydrogen peroxide was investigated at pH=5-7 and T=298.15 K, and the kinetic parameters k1, k 2 and k-1 were obtained with this method. The kinetics of the reaction was investigated in detail. The kinetic parameters of the oxidation of ascorbic monoanion (HA) and ascorbic dianion (A2-) with hydrogen peroxide were 3.33 × 10-3 s-1 and 25.48 s-1 at 298.15 K, respectively. The molar enthalpy change for the reaction was -554.64 kJ · mol-1 in phosphate buffer solution at pH 7 and at 298.15 K.

  4. Study of kinetics of degradation of cyclohexane carboxylic acid by acclimated activated sludge.

    Science.gov (United States)

    Wang, Chunhua; Shi, Shuian; Chen, Hongyan

    2016-01-01

    Activated sludge contains complex microorganisms, which are highly effective biodegrading agents. In this study, the kinetics of biodegradation of cyclohexane carboxylic acid (CHCA) by an acclimated aerobic activated sludge were investigated. The results showed that after 180 days of acclimation, the activated sludge could steadily degrade >90% of the CHCA in 120 h. The degradation of CHCA by the acclimated activated sludge could be modeled using a first-order kinetics equation. The equations for the degradation kinetics for different initial CHCA concentrations were also obtained. The kinetics constant, kd, decreased with an increase in the CHCA concentration, indicating that, at high concentrations, CHCA had an inhibiting effect on the microorganisms in the activated sludge. The effects of pH on the degradation kinetics of CHCA were also investigated. The results showed that a pH of 10 afforded the highest degradation rate, indicating that basic conditions significantly promoted the degradation of CHCA. Moreover, it was found that the degradation efficiency for CHCA increased with an increase in temperature and concentration of dissolved oxygen under the experimental conditions.

  5. Mechanistic and Kinetic Insight into Spontaneous Cocrystallization of Isoniazid and Benzoic Acid.

    Science.gov (United States)

    Sarceviča, Inese; Orola, Liana; Nartowski, Karol P; Khimyak, Yaroslav Z; Round, Andrew N; Fábián, László

    2015-08-03

    Solid-state cocrystallization is of contemporary interest because it offers an easy and efficient way to produce cocrystals, which are recognized as prospective pharmaceutical materials. Research explaining solid-state cocrystallization mechanisms is important but still too scarce to give a broad understanding of factors governing and limiting these reactions. Here we report an investigation of the mechanism and kinetics of isoniazid cocrystallization with benzoic acid. This reaction is spontaneous; however, its rate is greatly influenced by environmental conditions (humidity and temperature) and pretreatment (milling) of the sample. The acceleration of cocrystallization in the presence of moisture is demonstrated by kinetic studies at elevated humidity. The rate dependence on humidity stems from moisture facilitated rearrangements on the surface of isoniazid crystallites, which lead to cocrystallization in the presence of benzoic acid vapor. Furthermore, premilling the mixture of the cocrystal ingredients eliminated the induction time of the reaction and considerably increased its rate.

  6. Revisiting the Kinetics and Mechanism of the Tetrathionate-Hypochlorous Acid Reaction in Nearly Neutral Medium

    Science.gov (United States)

    Varga, Dénes; Horváth, Attila K.

    2009-11-01

    The tetrathionate-hypochlorous acid reaction has been investigated in nearly neutral medium at I = 0.5 M ionic strength and T = 25.0 ± 0.1 °C in dihydrogen-phosphate-hydrogen-phosphate buffer by UV-vis spectrophotometry. In excess of hypochlorous acid, the stoichiometry was found to be S4O62- + 7HOCl + 3H2O → 4SO42- + 7Cl- + 13H+, but in excess of tetrathionate colloidal sulfur precipitates. On the basis of the simultaneous evaluation of the kinetic curves, a nine-step kinetic model with four fitted and five fixed rate coefficients is proposed. Analogous oxidation reactions of tetrathionate are also compared and discussed.

  7. Technology and kinetics of free fatty acids esterification in tung oil

    Institute of Scientific and Technical Information of China (English)

    GAN Meng-yu; PAN Deng; LI Xiao-mei; HE Ling; CHEN Qi

    2009-01-01

    We studied the esterificatien of free fatty acids (FFA) in tung oil with methanol by using activated carbon treated with sulfuric acid as a catalyst, and investigated the effect of different temperatures, methanol/oil mole ratio and catalyst amount on the conversion of FFA. Results show that the optimal reaction condition is when the reaction time is 2 h, the mass fraction of the catalyst to total material is 5%, the molar ratio of menthol to FFA is 15 : 1, and the reaction temperature is 368.15 K. We also investigated the kinetics of esterification at various temperatures. Results indicate that the rate-control step could be attributed to the surface reaction, and within the range of the experimental conditions, the as-calculated kinetics formula can depict the esterification processes well.

  8. A novel kinetic model for polysaccharide dissolution during atmospheric acetic acid pretreatment of sugarcane bagasse.

    Science.gov (United States)

    Zhao, Xuebing; Morikawa, Yuichi; Qi, Feng; Zeng, Jing; Liu, Dehua

    2014-01-01

    Acetic acid (AcH) pretreatment of sugarcane bagasse with the catalysis of sulfuric acid (SA) could greatly enhance the enzymatic digestibility of cellulose. However, polysaccharide dissolution happened inevitably during the pretreatment. It was found that the simplest model, which assumes that the total polysaccharides were reactive to be dissolved, could not well describe the kinetic behavior of polysaccharide dissolution. A novel pseudo-homogenous kinetic model was thus developed by introducing a parameter termed as "potential dissolution degree" (δ(d)) based on the multilayered structure of cell wall. It was found that solid xylan and glucan dissolutions were a first-order reaction with respect to the dissolvable fraction. Due to the delignification action of AcH, polysaccharide dissolutions were enhanced in AcH media compared with those in aqueous system. Acetylizations of cellulose and sugars were also observed, and AcH concentration showed a significant influence on the degree of acetylization.

  9. The influence of naphthaleneacetic acid (NAA) and coumarin on flavonoid production by fungus Phellinus sp.: modeling of production kinetic profiles.

    Science.gov (United States)

    Ma, Xiao-Kui; Li, Le; Peterson, Eric Charles; Ruan, Tingting; Duan, Xiaoyi

    2015-11-01

    For the purpose of improving the fungal production of flavonoids, the influence of naphthaleneacetic acid (NAA) and coumarin on flavonoid production by fungus Phellinus sp. P0988 was investigated by developing the corresponding kinetics of flavonoid production in a 7-L bioreactor. Phellinus sp. was confirmed to form flavonoids in pellets and broth when cultivated in basic medium, and the optimum concentration of NAA and coumarin in medium for flavonoid production were determined to be 0.03 and 0.02 g/L, respectively. The developed unstructured mathematical models were in good agreement with the experimental results with respect to flavonoid production kinetic profiles with NAA and coumarin supplementation at optimum levels and revealed significant accuracy in terms of statistical consistency and robustness. Analysis of these kinetic processes indicated that NAA and coumarin supplementations imposed a stronger positive influence on flavonoid production and substrate consumption compared to their effects on cell growth. The separate addition of NAA and coumarin resulted in enhancements in final product accumulation and productivity, achieving final flavonoid concentrations of 3.60 and 2.75 g/L, respectively, and glucose consumption showed a significant decrease compared to the non-supplemented control as well. Also, the separate presence of NAA and coumarin respectively decreased maintenance coefficients (M s) from 2.48 in the control to 1.39 and 0.22, representing decreases of 43.9 and 91.1 %, respectively. The current study is the first known application of mathematical kinetic models to explore the influence of medium components adding on flavonoid production by fungi.

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

    Institute of Scientific and Technical Information of China (English)

    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.

  11. Kinetic studies on vapor phase carbonylation of methanol to acetic acid over Rh/Ys catalyst

    Institute of Scientific and Technical Information of China (English)

    柳忠阳; 潘平来; 朱长城; 袁国卿

    1997-01-01

    A novel catalyst Rh/Ys for the carbonylation of methanol to acetic acid with CH3I as the promoter shows excellent activity and selectivity.The reaction is kinetically controlled.The reaction rate is in proportion to the concentration of Rh and CH3I but has nothing to do with those of CH3OHH and CO.The surface active energy is Ea ~51.02 kJ/mol.A mechanism is also proposed.

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

    Indian Academy of Sciences (India)

    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.

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

    Institute of Scientific and Technical Information of China (English)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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)

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

    Science.gov (United States)

    Bari, S.; Alvarado, F.; Postma, J.; Sobocinski, P.; Hoekstra, R.; Schlathölter, T.

    2009-01-01

    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.

  16. Suitability of Isotope Kinetic Approach to Assess Phos—phorus Status and Bioavailability of Major Acidic Soils in Subtropical China

    Institute of Scientific and Technical Information of China (English)

    XIONGLIMING; J.C.FARDEAU

    1997-01-01

    A 32P isotope kinetic approach was used to describe the chemical status and bioavailability of phosphorus in 32 acidic soils from subtropical China.By determining the residual radoactivity,rt,in soil solution at different time,t,after introduction of the isotope in an amount of R into the steady soil-water system,a well-defined isotope kinetic model was established,and upon this model the decrease rate ,n,of log(rt/R) with respect to logt,the mean sojourn time of phosphate ions in solution,the mean exchange rate and the mean flux of phosphate ions between soil solid and solution phases were calculated.Other parameters,such as the exchangeable P within the first minute of isotope exchange(E1),and P in various compartments that could be exchanged with solution phosphte ions at different perods of time,were also obtained.For these acidic soils,the r1/R had a significant correlation with the contents of clay and free Al2O3 where r1 is the radioactivity in solution 1 minute after introduction of the isotope into the system.Parameter n also had a significant correlation with clay content and a neagtive correlation with soil pH,E1 values and Cp,the P concentration in soil solution,also Significantly correlated with clay and sesquioxide contents of the soils.these indicated that these isotope kinetic parameters were largely influenced by P-fixing components of the soils.For the soils with strong P-fixing ability,the E1 values overestimated labile P pools and hence their correlations with A values and plant P uptake were not significant .The other iostope kinetic parameters also had no significant correlation with plant P uptak.On the other hand,the convetional chemical-extracted p correlated better with plant P uptake .It was concluded that the iostope kinetic method could assess the p chemical status yet it would inappropriate in predicting plant available P for soils with a high P-fixing ability as the problem of an overestimation of soil lable P in these soils was

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

    Directory of Open Access Journals (Sweden)

    J. E. N. Brainer

    2014-12-01

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

  18. The influence of temperature on the decomposition kinetics of peracetic acid in solutions

    Directory of Open Access Journals (Sweden)

    L. Kunigk

    2001-06-01

    Full Text Available Peracetic acid is a powerful sanitizer that has only recently been introduced in the Brazilian food industry. The main disadvantage of this sanitizer is its decomposition rate. The main purpose of this paper is to present results obtained in experiments carried out to study the decomposition kinetics of peracetic acid in aqueous solutions at 25, 35, 40 and 45 °C. The decompositon of peracetic acid is a first-order reaction. The decomposition rate constants are between 1.71x10-3 h -1 for 25 °C and 9.64x10-3 h-1 for 45 °C. The decomposition rate constant is affected by temperature according to the Arrhenius equation, and the activation energy for the decomposition of peracetic acid in aqueous solutions prepared from the commercial formulation used in this work is 66.20 kJ/mol.

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

    Science.gov (United States)

    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.

  20. Stochastic kinetic model of two component system signalling reveals all-or-none, graded and mixed mode stochastic switching responses.

    Science.gov (United States)

    Kierzek, Andrzej M; Zhou, Lu; Wanner, Barry L

    2010-03-01

    Two-component systems (TCSs) are prevalent signal transduction systems in bacteria that control innumerable adaptive responses to environmental cues and host-pathogen interactions. We constructed a detailed stochastic kinetic model of two component signalling based on published data. Our model has been validated with flow cytometry data and used to examine reporter gene expression in response to extracellular signal strength. The model shows that, depending on the actual kinetic parameters, TCSs exhibit all-or-none, graded or mixed mode responses. In accordance with other studies, positively autoregulated TCSs exhibit all-or-none responses. Unexpectedly, our model revealed that TCSs lacking a positive feedback loop exhibit not only graded but also mixed mode responses, in which variation of the signal strength alters the level of gene expression in induced cells while the regulated gene continues to be expressed at the basal level in a substantial fraction of cells. The graded response of the TCS changes to mixed mode response by an increase of the translation initiation rate of the histidine kinase. Thus, a TCS is an evolvable design pattern capable of implementing deterministic regulation and stochastic switches associated with both graded and threshold responses. This has implications for understanding the emergence of population diversity in pathogenic bacteria and the design of genetic circuits in synthetic biology applications. The model is available in systems biology markup language (SBML) and systems biology graphical notation (SBGN) formats and can be used as a component of large-scale biochemical reaction network models.

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

    DEFF Research Database (Denmark)

    Jones, Andrew M; Grassi, Bruno; Christensen, Peter Møller

    2011-01-01

    state of knowledge concerning the mechanistic bases of the V¿O2 slow component and describes practical interventions which can attenuate the slow componentand thus enhance exercise tolerance. There is strong evidence that, during CWR exercise, the development of the V¿O2 slow component is associated...

  2. Kinetic studies on the Rhizomucor miehei lipase catalyzed esterification reaction of oleic acid with 1-butanol in a biphasic system

    NARCIS (Netherlands)

    Kraai, G.N.; Winkelman, J.G.M.; de Vries, Johannes; Heeres, H.J.

    2008-01-01

    The kinetics of the esterification of oleic acid with 1 -butanol catalyzed by free Rhizomucor miehei lipase in a biphasic system was studied in a batch reactor. The reaction appeared to proceed via a Ping Pong bi-bi mechanism with I -butanol inhibition. The kinetic constants of the model were determ

  3. Palladium Catalysts for Fatty Acid Deoxygenation: Influence of the Support and Fatty Acid Chain Length on Decarboxylation Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Ford, JP; Immer, JG; Lamb, HH

    2012-03-29

    Supported metal catalysts containing 5 wt% Pd on silica, alumina, and activated carbon were evaluated for liquid-phase deoxygenation of stearic (octadecanoic), lauric (dodecanoic), and capric (decanoic) acids under 5 % H-2 at 300 A degrees C and 15 atm. On-line quadrupole mass spectrometry (QMS) was used to measure CO + CO2 yield, CO2 selectivity, H-2 consumption, and initial decarboxylation rate. Post-reaction analysis of liquid products by gas chromatography was used to determine n-alkane yields. The Pd/C catalyst was highly active and selective for stearic acid (SA) decarboxylation under these conditions. In contrast, SA deoxygenation over Pd/SiO2 occurred primarily via decarbonylation and at a much slower rate. Pd/Al2O3 exhibited high initial SA decarboxylation activity but deactivated under the test conditions. Similar CO2 selectivity patterns among the catalysts were observed for deoxygenation of lauric and capric acids; however, the initial decarboxylation rates tended to be lower for these substrates. The influence of alkyl chain length on deoxygenation kinetics was investigated for a homologous series of C-10-C-18 fatty acids using the Pd/C catalyst. As fatty acid carbon number decreases, reaction time and H-2 consumption increase, and CO2 selectivity and initial decarboxylation rate decrease. The increase in initial decarboxylation rates for longer chain fatty acids is attributed to their greater propensity for adsorption on the activated carbon support.

  4. Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Stout, R B

    2001-04-01

    A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface

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

    Institute of Scientific and Technical Information of China (English)

    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

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

    Science.gov (United States)

    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.

  7. Kinetic analysis of lauric acid hydroxylation by human cytochrome P450 4A11.

    Science.gov (United States)

    Kim, Donghak; Cha, Gun-Su; Nagy, Leslie D; Yun, Chul-Ho; Guengerich, F Peter

    2014-10-07

    Cytochrome P450 (P450) 4A11 is the only functionally active subfamily 4A P450 in humans. P450 4A11 catalyzes mainly ω-hydroxylation of fatty acids in liver and kidney; this process is not a major degradative pathway, but at least one product, 20-hydroxyeicosatetraenoic acid, has important signaling properties. We studied catalysis by P450 4A11 and the issue of rate-limiting steps using lauric acid ω-hydroxylation, a prototypic substrate for this enzyme. Some individual reaction steps were studied using pre-steady-state kinetic approaches. Substrate and product binding and release were much faster than overall rates of catalysis. Reduction of ferric P450 4A11 (to ferrous) was rapid and not rate-limiting. Deuterium kinetic isotope effect (KIE) experiments yielded low but reproducible values (1.2-2) for 12-hydroxylation with 12-(2)H-substituted lauric acid. However, considerable "metabolic switching" to 11-hydroxylation was observed with [12-(2)H3]lauric acid. Analysis of switching results [Jones, J. P., et al. (1986) J. Am. Chem. Soc. 108, 7074-7078] and the use of tritium KIE analysis with [12-(3)H]lauric acid [Northrop, D. B. (1987) Methods Enzymol. 87, 607-625] both indicated a high intrinsic KIE (>10). Cytochrome b5 (b5) stimulated steady-state lauric acid ω-hydroxylation ∼2-fold; the apoprotein was ineffective, indicating that electron transfer is involved in the b5 enhancement. The rate of b5 reoxidation was increased in the presence of ferrous P450 mixed with O2. Collectively, the results indicate that both the transfer of an electron to the ferrous·O2 complex and C-H bond-breaking limit the rate of P450 4A11 ω-oxidation.

  8. Biodegradation kinetics of 4-fluorocinnamic acid by a consortium of Arthrobacter and Ralstonia strains.

    Science.gov (United States)

    Hasan, Syed A; Wietzes, Piet; Janssen, Dick B

    2012-02-01

    Arthrobacter sp. strain G1 is able to grow on 4-fluorocinnamic acid (4-FCA) as sole carbon source. The organism converts 4-FCA into 4-fluorobenzoic acid (4-FBA) and utilizes the two-carbon side-chain for growth with some formation of 4-fluoroacetophenone as a dead-end side product. We also have isolated Ralstonia sp. strain H1, an organism that degrades 4-FBA. A consortium of strains G1 and H1 degraded 4-FCA with Monod kinetics during growth in batch and continuous cultures. Specific growth rates of strain G1 and specific degradation rates of 4-FCA were observed to follow substrate inhibition kinetics, which could be modeled using the kinetic models of Haldane-Andrew and Luong-Levenspiel. The mixed culture showed complete mineralization of 4-FCA with quantitative release of fluoride, both in batch and continuous cultures. Steady-state chemostat cultures that were exposed to shock loadings of substrate responded with rapid degradation and returned to steady-state in 10-15 h, indicating that the mixed culture provided a robust system for continuous 4-FCA degradation.

  9. Kinetics of color development in glucose/Amino Acid model systems at different temperatures

    Directory of Open Access Journals (Sweden)

    Ana Paola Echavarría

    2016-01-01

    Full Text Available This study investigated the influence of temperature on the color development of melanoidins formed from a single combination of glucose with amino acid. The selected amino acid, commonly found in apple juice and highly reactive in the Maillard reaction, were asparagine (Asn, aspartic acid (Asp and glutamic acid (Glu. For this, the color development was evaluated by measuring browning at 420 nm and color measurements by spectrophotometry and colorimetry methods. The effect of temperature on the color intensity, the absorption of melanoidins were also measured at different wavelengths (280, 325, 405. The value of melanoidins formed from all model systems was located on a dominant wavelength of 325 nm, the ultra violet zone of the diagram. A first-order kinetic model was applied to L* and the evolution of color difference ΔE*. In addition, a*, b* values, significantly differences were found in the glucose/aspartic acid model system in the brown-red zone. Therefore, the color development of the melanoidins was influenced by the type of amino acid and temperature, and it is thought that the a* and b* values can be used to explain the differences among the amino acid in the color development of melanoidins.

  10. Kinetics of canine dental calculus crystallization: an in vitro study on the influence of inorganic components of canine saliva.

    Science.gov (United States)

    Borah, Ballav M; Halter, Timothy J; Xie, Baoquan; Henneman, Zachary J; Siudzinski, Thomas R; Harris, Stephen; Elliott, Matthew; Nancollas, George H

    2014-07-01

    This work identifies carbonated hydroxyapatite (CAP) as the primary component of canine dental calculus, and corrects the long held belief that canine dental calculus is primarily CaCO3 (calcite). CAP is known to be the principal crystalline component of human dental calculus, suggesting that there are previously unknown similarities in the calcification that occurs in these two unique oral environments. In vitro kinetic experiments mimicking the inorganic components of canine saliva have examined the mechanisms of dental calculus formation. The solutions were prepared so as to mimic the inorganic components of canine saliva; phosphate, carbonate, and magnesium ion concentrations were varied individually to investigate the roll of these ions in controlling the nature of the phases that is nucleated. To date, the inorganic components of the canine oral systems have not been investigated at concentrations that mimic those in vivo. The mineral composition of the synthetic calculi grown under these conditions closely resembled samples excised from canines. This finding adds new information about calculus formation in humans and canines, and their sensitivity to chemicals used to treat these conditions.

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

    DEFF Research Database (Denmark)

    Kaasgaard, Thomas; Leidy, Chad; Crowe, J.H.

    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...... was heated from the ripple phase and into the ripple-phase/fluid-phase coexistence temperature region, the AFM images revealed that several dynamic properties of the ripple phase are important for the melting behavior of the lipid mixture. Onset of melting is observed at grain boundaries between different......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...

  12. Reaction of a sterically hindered iron(III porphyrin with peroxyacetic acid: degradation kinetics

    Directory of Open Access Journals (Sweden)

    P. PRAKASH

    2005-09-01

    Full Text Available A kinetic analysis of the reaction between peracetic acid (AcOOH, and tetrakis (pentafluorophenyl - 21H, 23H-porphine iron(III chloride, Fe(F20TPPCl, in acetonitrile showed that the peracetic acid oxidatively destroys Fe(F20TPPCl. This is in contrast to an assumption that the oxidative degradation of metalloporphyrins can be prevented by the introduction of electron-withdrawing substituents into the phenyl groups of the porphyrin ligand. A UV-visible spectroscopic study showed a degree of macro cycle destruction of the tetrapyrrole conjucation of the metalloporphyrin. The degradation takes place via oxoperferryl species. The first step of the reaction mechanism is the reversible formation of an adduct ’X’(k1/k-1 between Fe(F20TPPCl and peracetic acid, followed by an irreversible step (k2 for the formation of oxoperferryl species.

  13. Kinetics of salivary pH after acidic beverage intake by patients undergoing orthodontic treatment.

    Science.gov (United States)

    Turssi, Cecilia P; Silva, Carolina S; Bridi, Enrico C; Amaral, Flavia Lb; Franca, Fabiana Mg; Basting, Roberta T

    2015-01-01

    The saliva of patients undergoing orthodontic treatment with fixed appliances can potentially present a delay in the diluting, clearing, and buffering of dietary acids due to an increased number of retention areas. The aim of this clinical trial was to compare salivary pH kinetics of patients with and without orthodontic treatment, following the intake of an acidic beverage. Twenty participants undergoing orthodontic treatment and 20 control counterparts had their saliva assessed for flow rate, pH, and buffering capacity. There was no significant difference between salivary parameters in participants with or without an orthodontic appliance. Salivary pH recovery following acidic beverage intake was slower in the orthodontic subjects compared to controls. Patients with fixed orthodontic appliances, therefore, seem to be at higher risk of dental erosion, suggesting that dietary advice and preventive care need to be implemented during orthodontic treatment.

  14. A kinetic study on the Novozyme 435-catalyzed esterification of free fatty acids with octanol to produce octyl esters.

    Science.gov (United States)

    Chowdhury, Avisha; Mitra, Debarati

    2015-01-01

    Octyl esters can serve as an important class of biolubricant components replacing their mineral oil counterparts. The purpose of the current work was to investigate the enzymatic esterification reaction of free fatty acids (FFA, from waste cooking oil) with octanol in a solvent-free system using a commercial lipase Novozyme 435. It was found that the esterificaton reaction followed the Ping-pong bi-bi kinetics with no inhibition by substrates or products within the studied concentration range. The maximum reaction rate was estimated to be 0.041 mol L(-1) g(-1) h(-1) . Additionally, the stability of Novozyme 435 in the current reaction system was studied by determining its activity and final conversion of FFA to esters after 12 successive utilizations. Novozyme 435 exhibited almost 100% enzyme activity up to 7 cycles of reaction and gradually decreased (by 5%) thereafter. The kinetic parameters evaluated from the study shall assist in the design of reactors for large-scale production of octyl esters from a cheap biomass source. The enzyme reusability data can further facilitate mass production by curtailing the cost of expensive enzyme consumption.

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    Polyethylene glycols (PEGs) are attractive as excipients in the manufacture of drug products because they are water soluble and poorly immunogenic. They are used in various pharmaceutical preparations. However, because of their terminal hydroxyl groups, PEGs can participate in esterification...... 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......, it is important to be aware of this drug-excipient interaction, as it can reduce the shelf-life of a low-average molecular weight PEG formulation considerably. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 103:2424-2433, 2014....

  16. Kinetics and Mechanism of the Oxidation of Menthol by Potassium Bromate in Acidic Solution

    Directory of Open Access Journals (Sweden)

    Ravikant na

    2014-06-01

    Full Text Available No suitable method is available for the estimation of menthol, hence in all kinetic results reported in this chapter, menthol was in excess over potassium bromate and the stoichiometry was also determined under the experimental conditions where menthol (substrate was in excess over potassium bromate (oxidant. Present study was focused on the analysis of kinetics and mechanism of oxidation of neomenthol by potassium bromate in acidic medium. For oxidizing neomenthol, potassium bromate stock solution (5.0×10─2 mol. dm─3 was prepared by dissolving exactly weighed quantity of potassium bromate in doubly distilled water. The suitable reaction mixtures were prepared and left at 313 K for over 24 hours to ensure complete oxidation of neomenthol. The unreacted potassium bromate was determined iodometrically and the results indicate that one mole of potassium bromate is consumed for every three moles of neomenthol and leads to the formation of menthone (ketone.

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

    Science.gov (United States)

    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.

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

    Institute of Scientific and Technical Information of China (English)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-02-15

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

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

    DEFF Research Database (Denmark)

    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......‐fat content (SFC) measurements for a given oil at different cooling rates and degrees of dilution. The developed model can accommodate more polymorphs simultaneously and performs well with respect to predicting crystallization onset, rate of crystallization and final SFC value. It can also qualitatively...

  1. Kinetic modeling of lactic acid production from batch submerged fermentation of cheese whey

    Energy Technology Data Exchange (ETDEWEB)

    Tango, M.S.A.; Ghaly, A.E.

    1999-12-01

    A kinetic model for the production of lactic acid through batch submerged fermentation of cheese whey using Lactobacillus helveticus was developed. The model accounts for the effect of substrate limitation, substrate inhibition, lactic acid inhibition, maintenance energy and cell death on the cell growth, substrate utilization, and lactic acid production during the fermentation process. The model was evaluated using experimental data from Tango and Ghaly (1999). The predicted results obtained from the model compared well with experimental (R{sup 2} = 0.92--0.98). The model was also used to investigate the effect of the initial substrate concentration on the lag period, fermentation time, specific growth rate, and cell productivity during batch fermentation. The maximum specific growth rate ({micro}{sub m}), the saturation constant (K{sub S}), the substrate inhibition constant (K{sub IS}), and the lactic acid inhibition constant (K{sub IP}) were found to be 0.25h{sup {minus}1}, 0.9 g/L, 250.0 g/L, and 60.0 g/L, respectively. High initial lactose concentration in cheese whey reduced both the specific growth rate and substrate utilization rate due to the substrate inhibition phenomenon. The maximum lactic acid production occurred at about 100 g/L initial lactose concentration after 40 h of fermentation. The maximum lactic acid concentration above which Lactobacillus helveticus did not grow was found to be 80.0 g/L.

  2. Kinetics and thermodynamics of the attack of a phosphate ore by acid solutions at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Antar, K. [Faculty of Science of Tunis, Chemistry Department, Applied Thermodynamics Laboratory, 2092 Tunis El Manar (Tunisia); Jemal, M. [Faculty of Science of Tunis, Chemistry Department, Applied Thermodynamics Laboratory, 2092 Tunis El Manar (Tunisia)], E-mail: jemal@planet.tn

    2008-08-15

    A calorimetric study of the kinetics and thermodynamics of the attack of a phosphate ore from Gafsa region (Tunisia) by phosphoric acid and by a mixture of phosphoric acid and sulfuric acids is undertaken at different temperatures. Two samples of the same ore having different grain size have been used. At 25 deg. C, the dissolution enthalpy in phosphoric acid solution equals -233.6 {+-} 2.2 J/g for both of the samples. Attack by the mixture of acids is strongly dependent on the solid granulometry. Interpretation of the calorimetric results by Avrami model shows the existence of three domains attributed to phosphate ore dissolution/H{sub 2}PO{sub 4}{sup -} neutralisation, hemihydrate (HH) precipitation and hemihydrate/dihydrate (DH) transformation. The attack by the acid mixture was performed at higher temperatures and showed in addition the transitional formation of the anhydrous sulfate (AH) at T {>=} 55 deg. C, which transforms into dihydrate after the HH/DH transformation.

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

    DEFF Research Database (Denmark)

    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...

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    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  

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

    Science.gov (United States)

    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.

  7. Incorporating Geochemical And Microbial Kinetics In Reactive Transport Models For Generation Of Acid Rock Drainage

    Science.gov (United States)

    Andre, B. J.; Rajaram, H.; Silverstein, J.

    2010-12-01

    Acid mine drainage, AMD, results from the oxidation of metal sulfide minerals (e.g. pyrite), producing ferrous iron and sulfuric acid. Acidophilic autotrophic bacteria such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans obtain energy by oxidizing ferrous iron back to ferric iron, using oxygen as the electron acceptor. Most existing models of AMD do not account for microbial kinetics or iron geochemistry rigorously. Instead they assume that oxygen limitation controls pyrite oxidation and thus focus on oxygen transport. These models have been successfully used for simulating conditions where oxygen availability is a limiting factor (e.g. source prevention by capping), but have not been shown to effectively model acid generation and effluent chemistry under a wider range of conditions. The key reactions, oxidation of pyrite and oxidation of ferrous iron, are both slow kinetic processes. Despite being extensively studied for the last thirty years, there is still not a consensus in the literature about the basic mechanisms, limiting factors or rate expressions for microbially enhanced oxidation of metal sulfides. An indirect leaching mechanism (chemical oxidation of pyrite by ferric iron to produce ferrous iron, with regeneration of ferric iron by microbial oxidation of ferrous iron) is used as the foundation of a conceptual model for microbially enhanced oxidation of pyrite. Using literature data, a rate expression for microbial consumption of ferrous iron is developed that accounts for oxygen, ferrous iron and pH limitation. Reaction rate expressions for oxidation of pyrite and chemical oxidation of ferrous iron are selected from the literature. A completely mixed stirred tank reactor (CSTR) model is implemented coupling the kinetic rate expressions, speciation calculations and flow. The model simulates generation of AMD and effluent chemistry that qualitatively agrees with column reactor and single rock experiments. A one dimensional reaction

  8. Kinetic study of the prehydrolysis of bagasse pith with hydrochloric acid in an agitated system

    Energy Technology Data Exchange (ETDEWEB)

    Villan Guerra, J.; Iglesias, R.G.; Lopez Planes, R.

    1981-01-01

    The hydrolysis of bagasse pith at 90-100 degrees with 0.25 N HCl gave sugar in 22% yield after 120 min. With 0.5 N HCl, the yield was 28% after 240 min. The specific constants of pentosan decomposition and of sugar formation were calculated, and the kinetic parameters (frequency factor, activation energy, and order of acid concentration) were determined. The pentosan decomposition constants were higher and the activation energies lower than literature values for hydrolysis with H/sub 2/SO/sub 4/.

  9. Origin of Kinetic Resolution of Hydroxy Esters through Catalytic Enantioselective Lactonization by Chiral Phosphoric Acids.

    Science.gov (United States)

    Changotra, Avtar; Sunoj, Raghavan B

    2016-08-05

    Kinetic resolution is a widely used strategy for separation and enrichment of enantiomers. Using density functional theory computations, the origin of how a chiral BINOL-phosphoric acid catalyzes the selective lactonization of one of the enantiomers of α-methyl γ-hydroxy ester is identified. In a stepwise mechanism, the stereocontrolling transition state for the addition of the hydroxyl group to the si face of the ester carbonyl in the case of the S isomer exhibits a network of more effective noncovalent interactions between the substrate and the chiral catalyst.

  10. Extraction Kinetics of Rare Earth Elements with sec-Octylphenoxy Acetic Acid

    Institute of Scientific and Technical Information of China (English)

    YUE,Shan-Tang(乐善堂); LIAO,Wu-Ping(廖伍平); LI,De-Qian(李德谦); SU,Qiang(苏锵)

    2002-01-01

    The kinetics of RE (La, Gd, Er, Yb and Y)extraction with sec-octylphenoxy acetic acid was investigated using a constant interfacial area cell with laminar flow at 303 K. The natures of the extracted complexes have some effect on the extraction rate which is controlled by the reaction rate of M(Ⅲ) and extractant molecules at two-phase interface for Er(Ⅲ), Yb(Ⅲ) and Y(Ⅲ), by a mixed chemical reaction-diffusion for Gd(Ⅲ) and a diffusion for La(Ⅲ). The extractant molecules tend to adsorb at the interface. So an interfacial extraction reaction model was derived.

  11. Syringic acid, a novel natural phenolic acid, normalizes hyperglycemia with special reference to glycoprotein components in experimental diabetic rats

    Institute of Scientific and Technical Information of China (English)

    Jayachandran Muthukumaran; Subramani Srinivasan; Vinayagam Ramachandran; Udaiyar Muruganathan

    2013-01-01

    Objective:To evaluate the antidiabetic effect of syringic acid, a natural phenolic compound on the levels of glycoprotein components in plasma and tissues of alloxan induced diabetic rats. Methods:Diabetes was induced in maleWistar rats by a single intraperitoneal injection of alloxan(150 mg/kg b.w).Syringic acid(50 mg/kg b.w) was administered orally for30 d.The effects of syringic acid on plasma glucose, insulin,C-peptide, plasma and tissue glycoproteins were studied.Results:Oral administration of syringic acid(50 mg/kg b.w) for30 d positively modulates the glycemic status in alloxan induced diabetic rats.The levels of plasma glucose were decreased with significant increase of plasma insulin andC-peptide level.The altered levels of plasma and tissue glycoprotein components were restored to near normal.No significant changes were noticed in normal rats treated with syringic acid.Conclusions:The present findings suggest that syringic acid can potentially ameliorate glycoprotein components abnormalities in addition to its antidiabetic effect in experimental diabetes, further clinical studies are required to evaluate the use of syringic acid as an effective therapeutic agent for the treatment of diabetes mellitus.

  12. Chemical Kinetics Mechanism Reduction Based on Principal Component Analysis: Development and Testing of Some New Implementations

    Science.gov (United States)

    2013-05-01

    developed at the U.S. Army Aviation and Missile Research, Development, and Engineering Center (AMRDEC). Referred to as the impinging stream vortex... engine (ISVE), the concept was fueled at the time with monomethylhydrazine (MMH) and inhibited red fuming nitric acid (IRFNA). Even though MMH and IRFNA...reactions targeted, 190 reaction sets were constructed. (This number included nonunique assemblages.) The smallest mechanism that produced a

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

    Institute of Scientific and Technical Information of China (English)

    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

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

    Science.gov (United States)

    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 water. The results indicate that HNO3 was only weakly dissociated in the 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.

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

    Directory of Open Access Journals (Sweden)

    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.

  16. Active food packaging based on molecularly imprinted polymers: study of the release kinetics of ferulic acid.

    Science.gov (United States)

    Otero-Pazos, Pablo; Rodríguez-Bernaldo de Quirós, Ana; Sendón, Raquel; Benito-Peña, Elena; González-Vallejo, Victoria; Moreno-Bondi, M Cruz; Angulo, Immaculada; Paseiro-Losada, Perfecto

    2014-11-19

    A novel active packaging based on molecularly imprinted polymer (MIP) was developed for the controlled release of ferulic acid. The release kinetics of ferulic acid from the active system to food simulants (10, 20, and 50% ethanol (v/v), 3% acetic acid (w/v), and vegetable oil), substitutes (95% ethanol (v/v) and isooctane), and real food samples at different temperatures were studied. The key parameters of the diffusion process were calculated by using a mathematical modeling based on Fick's second law. The ferulic acid release was affected by the temperature as well as the percentage of ethanol of the simulant. The fastest release occurred in 95% ethanol (v/v) at 20 °C. The diffusion coefficients (D) obtained ranged between 1.8 × 10(-11) and 4.2 × 10(-9) cm(2)/s. A very good correlation between experimental and estimated data was obtained, and consequently the model could be used to predict the release of ferulic acid into food simulants and real food samples.

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

    Directory of Open Access Journals (Sweden)

    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

  18. Volatile fatty acid degradation kinetics in anaerobic process; Cinetica de la degradacion de acidos grasos volatiles en procesos anaerobios

    Energy Technology Data Exchange (ETDEWEB)

    Riscado, S.; Osuna, B.; Iza, J.; Ruiz, E. [Universidad del Pais Vasco. Bilbao (Spain)

    1998-10-01

    While searching for the optimal substrate load for anaerobic toxicity assays, the inhibition caused by the propionic acid has been addressed. Lab scale experiments have been carried out to assess the effects of different loads and acid ratios. Results bad been subjected to kinetic analysis and show the degradation follows a first order kinetic, and acetic is easier to degrade than propionic acid. The optimal load for a 100 ml vial assay is composed of 158 mg COD of the 3:1:1 HAc:HPr:HBu mixture. (Author) 9 refs.

  19. Kinetic and Mechanistic Investigation of Pyrano[2,3-d]pyrimidine Formation in the Presence of Catalyst under Novel One-Pot Three-Component Reaction

    Directory of Open Access Journals (Sweden)

    Sayyed Mostafa Habibi-Khorassani

    2014-01-01

    Full Text Available Sodium acetate was applied as an efficient catalyst for the one-pot, three-component condensation reactions consisting of 4-nitrobenzaldehyde 2, malononitrile 3, and thiobarbituric acid 1. Use of nontoxic reaction components, short reaction times, environmental, easy work-up, and high yields are some remarkable advantages of this method. Kinetics and mechanism of the reaction were spectrally studied and the second order rate constant (kovr = k1 was automatically calculated by the standard equations contained within the program. The second order rate constant [Ln(kovr = k1, Ln(kovr = k1/T] that depended on reciprocal temperature was in good agreement with the Arrhenius and Eyring equations, respectively. This data provided the suitable plots for calculating the activation energy and parameters (Ea, ΔG‡, ΔS‡, and ΔH‡ of the reaction. Furthermore, from studying the effects of solvent, concentration, and catalyst on the reaction rate, useful information was obtained regarding the mechanism. The results showed that the first step of the reaction mechanism is a rate determining step (RDS. The proposed mechanism was confirmed in accordance with the experimental data and also the steady state approximation.

  20. Kinetics of ascorbic acid loss during hot water blanching of fluted pumpkin (Telfairia occidentalis) leaves.

    Science.gov (United States)

    Ariahu, Charles C; Abashi, Diana K; Chinma, Chiemela Enyinnaya

    2011-08-01

    The kinetics of thermal degradation of ascorbic acid in fluted pumpkin leaves were investigated from 60 to 90°C (pH 5.0 to 6.5). Ascorbic acid degradation was modeled as a first order rate reaction with the rate constants increasing with increase in pH of the medium. The pH and temperature dependence of the rates of destruction gave highly significant correlations when analyzed by the thermal resistance and activated complex reaction rate methods. Activation energy (Ea) ranged from 41.2 to 18.2 kJ/mol while D-values ranged from 103.3 to 22.4 min. The changes in activation energy affected Ko values which ranged from 5.98 × 10(4) to 41.7 min(-1).

  1. Kinetic and Mechanistic Study of the Reduction of Chromium(VI by Lactic Acid

    Directory of Open Access Journals (Sweden)

    Jinhuan Shan

    2008-01-01

    Full Text Available The kinetics and mechanism of the reduction of chromium(VI by lactic acid (Lac in aqueous acidic medium was studied with spectrophotometry in a temperature range of 298.15 K~313.15 K. Under the conditions of the pseudo-first order ([Lac]0≫[Cr(VI]0, the observed rate constant (obs increased with the increase in [Lac] and [H+]. There is no salt effect. Based on the experimental results, a probable reaction mechanism of oxidation was proposed. The rate equation derived from the mechanism could explain all the experimental phenomena. Activation parameters along with rate constant of the rate-determining step have been evaluated.

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

    Institute of Scientific and Technical Information of China (English)

    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.

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

    Institute of Scientific and Technical Information of China (English)

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

    2003-01-01

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

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

    Directory of Open Access Journals (Sweden)

    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.

  5. Amino acid supplementation does not alter whole-body phenylalanine kinetics in Arabian geldings.

    Science.gov (United States)

    Urschel, Kristine L; Geor, Raymond J; Hanigan, Mark D; Harris, Pat A

    2012-03-01

    Stable isotope infusion methods have not been extensively used in horses to study protein metabolism. The objectives were to develop infusion and sampling methodologies for [1-(13)C] phenylalanine and apply these methods to determine whether the addition of supplemental amino acids to a control diet affected whole-body phenylalanine kinetics in mature horses. Arabian geldings were studied using a 6-h primed (9 μmol/kg), constant (6 μmol · kg(-1) · h(-1)) i.v. infusion of L-[1-(13)C] phenylalanine, with blood and breath sampled every 30 min, to measure whole-body phenylalanine kinetics in response to receiving the control diet (n = 12) or the control diet supplemented with equimolar amounts of glutamate (+Glu; 55 mg · kg(-1) · d(-1); n = 5), leucine (+Leu; 49 mg · kg(-1) · d(-1); n = 5), lysine (+Lys; 55 mg · kg(-1) · d(-1); n = 5), or phenylalanine (+Phe; 62 mg · kg(-1) · d(-1); n = 6). The plasma concentrations of the supplemented amino acid in horses receiving the +Leu, +Lys, and +Phe diets were 58, 53, and 36% greater, respectively, than for the control treatment (P phenylalanine and breath (13)CO(2) enrichments by 60 and 270 min, respectively. Phenylalanine flux (+20%) and oxidation (+110%) were greater (P phenylalanine disposal or phenylalanine release from protein breakdown. The developed methods are a valuable way to study protein metabolism and assess dietary amino acid adequacy in horses and will provide a useful tool for studying amino acid requirements in the future.

  6. Kinetics and mechanism of the oxidation of bromide by periodate in aqueous acidic solution.

    Science.gov (United States)

    Szél, Viktor; Csekő, György; Horváth, Attila K

    2014-11-13

    The periodate–bromide reaction has been studied spectrophotometrically mainly in excess of bromide ion, monitoring the formation of the total amount of bromine at 450 nm at acidic buffered conditions and at a constant ionic strength in the presence of a phosphoric acid/dihydrogen phosphate buffer. The stoichiometry of the reaction was established to be strictly IO4(–) + 2Br(–) + 2H(+) → Br2 + IO3(–) + H2O. The formal kinetic order of the reactants was found to be perfectly one and two in the cases of periodate and bromide, respectively, but that of the hydrogen ion lies between one and two. We have also provided experimental evidence that dihydrogen phosphate accelerates the formation of bromine, suggesting the appearance of strong buffer assistance. On the basis of the experiments, a simple two-step kinetic model is proposed involving BrIO3 as a key intermediate that perfectly explains all of the experimental findings. Furthermore, we have also shown that in huge excess of bromide, the apparent rate coefficient obtained from the individual curve fitting method of the absorbance–time series is necessarily independent of the initial periodate concentration that may falsely be interpreted as the rate of bromine formation is also independent of the concentration of periodate.

  7. Kinetics of Acid Blue 1 Adsorption from Aqueous Solution by Carbonaceous Substrate Produced from Biotic Precursor

    Institute of Scientific and Technical Information of China (English)

    FAZLULLAH,Khan Bangash; SULTAN,Alam; IRSHAD,Ahmad

    2007-01-01

    Adsorption of acid blue 1 from aqueous solution onto carbonaceous substrate produced from the wood of Paulownia tomentosa was investigated. The samples characterized by FTIR, SEM, EDS and XRD techniques, indicated that the surface functional groups like carboxyl, lactones or phenols and ethers have disappeared at high activation temperature (800 ℃) and as a result porous structure was developed that has a positive effect on the adsorption capacity. Bangham and parabolic diffusion models were applied to the kinetic adsorption data, which show that the adsorption of acid blue 1 was a diffusion controlled process. The reaction rate increased with the increase in temperatures of both the adsorption and activation. Thermodynamic parameters like △E≠, △H≠, △S≠ and △G≠ were calculated from the kinetic data. The negative values of △S≠ reflected the decrease in the disorder of the system at the solid-solution interface during adsorption. Gibbs free energy (△G≠), representing the driving force for the affinity of dye for the carbon surface, increased with the increase in sample activation and the adsorption temperatures.

  8. Kinetics of dissociative adsorption of formic acid on electrodes of tetrahexahedral platinum nanocrystals

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    In the present paper we study the kinetics of dissociative adsorption of formic acid on the electrode of tetrahexahedral platinum nanocrystals (THH Pt NCs). In situ FTIR spectroscopic results demonstrate that HCOOH can be oxidized to CO2 at a low potential (-0.2 V(SCE)) on the THH Pt NCs electrode, and the chemical bonds inside formic acid molecule are broken to form adsorbed COL species. The kinetics of the dissociative adsorption of HCOOH was quantitatively investigated by employing programmed potential step technique. It has been determined that, in 5 × 10-3 mol·L-1 HCOOH + 0.1 mol·L-1 H2SO4 solution, the maximal value of the average rate (υamax) of dissociative adsorption of HCOOH on a commercial Pt/C catalyst electrode is 8.58 × 10-10 mol·cm-2·s-1, while on the THH Pt NCs the υamax is 1.5 times larger than the υamax measured on Pt/C and reaches 13.19 × 10-10 mol·cm-2·s-1. The results have revealed that the reactivity of the THH Pt NCs is much higher than that of the Pt/C catalysts.

  9. Kinetics and mechanism of the oxidation of pentathionate ion by chlorine dioxide in a slightly acidic medium.

    Science.gov (United States)

    Xu, Li; Csekő, György; Petz, Andrea; Horváth, Attila K

    2014-02-27

    The chlorine dioxide-pentathionate reaction has been studied at a slightly acidic medium by conventional UV-vis spectroscopy monitoring the absorbance at 430 nm. We have shown that pentathionate was oxidized to sulfate, but chlorate is also a marginal product of the reaction besides the chloride ion. The stoichiometry of the reaction can be established as a linear combination of two limiting stoichiometries under our experimental conditions. Kinetics of the reaction was found to be also complex because initial rate studies revealed that formal kinetic orders of both the hydrogen ion and chlorine dioxide is far from unity. Moreover, log-log plot of the initial rate against pentathionate concentration indicated a nonconstant formal kinetic order. We also observed a significant catalytic effect of chloride ion. Based on our observations and simultaneous evaluation of the kinetic curves, an 11-step kinetic model is obtained with 6 fitted rate coefficients. A relatively simple rate equation has also been derived and discussed.

  10. Pyrolysis Kinetics of Physical Components of Wood and Wood-Polymers Using Isoconversion Method

    Directory of Open Access Journals (Sweden)

    John Zondlo

    2013-01-01

    Full Text Available Two hardwood species, namely red oak and yellow-poplar, were separated into their bark, sapwood and heartwood components. The samples were tested for calorific value, specific gravity, proximate analysis, mineral composition, chemical composition, ultimate analysis, and thermo-chemical decomposition behavior. In addition, the thermo-chemical decomposition behaviors of cellulose, xylan, and lignin polymers were also tested. Thermo-chemical decomposition behavior was assessed using a thermo-gravimetric (TGA system by heating the sample from 50 °C to 700 °C at the heating rates of 10, 30 and 50 °C/min under nitrogen. The activation energy was calculated for various fractional conversion values using the isoconversion method. The results showed that char yields of lignin, cellulose and xylan were 41.43%, 4.45% and 1.89%, respectively, at the end of pyrolysis. Furthermore, cellulose, xylan and lignin decomposed dramatically in the temperature range of 320 °C to 360 °C, 150 °C to 230 °C and 100 °C to 410 °C, respectively, with decomposition peaks occurring at 340 °C, 200 °C and 340 °C, respectively. In addition, the maximum activation energy for cellulose was 381 kJ/mol at 360 °C and for xylan it was 348 kJ/mol at 210 °C.

  11. Component

    Directory of Open Access Journals (Sweden)

    Tibor Tot

    2011-01-01

    Full Text Available A unique case of metaplastic breast carcinoma with an epithelial component showing tumoral necrosis and neuroectodermal stromal component is described. The tumor grew rapidly and measured 9 cm at the time of diagnosis. No lymph node metastases were present. The disease progressed rapidly and the patient died two years after the diagnosis from a hemorrhage caused by brain metastases. The morphology and phenotype of the tumor are described in detail and the differential diagnostic options are discussed.

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

    Indian Academy of Sciences (India)

    G P Panigrahi; Jagannath Panda

    2000-12-01

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

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Institute of Scientific and Technical Information of China (English)

    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. Amino acid metabolism in the human fetus at term: leucine, valine, and methionine kinetics.

    Science.gov (United States)

    van den Akker, Chris H P; Schierbeek, Henk; Minderman, Gardi; Vermes, Andras; Schoonderwaldt, Ernst M; Duvekot, Johannes J; Steegers, Eric A P; van Goudoever, Johannes B

    2011-12-01

    Human fetal metabolism is largely unexplored. Understanding how a healthy fetus achieves its fast growth rates could eventually play a pivotal role in improving future nutritional strategies for premature infants. To quantify specific fetal amino acid kinetics, eight healthy pregnant women received before elective cesarean section at term, continuous stable isotope infusions of the essential amino acids [1-13C,15N]leucine, [U-13C5]valine, and [1-13C]methionine. Umbilical blood was collected after birth and analyzed for enrichments and concentrations using mass spectrometry techniques. Fetuses showed considerable leucine, valine, and methionine uptake and high turnover rates. α-Ketoisocaproate, but not α-ketoisovalerate (the leucine and valine ketoacids, respectively), was transported at net rate from the fetus to the placenta. Especially, leucine and valine data suggested high oxidation rates, up to half of net uptake. This was supported by relatively low α-ketoisocaproate reamination rates to leucine. Our data suggest high protein breakdown and synthesis rates, comparable with, or even slightly higher than in premature infants. The relatively large uptakes of total leucine and valine carbon also suggest high fetal oxidation rates of these essential branched chain amino acids.

  16. Kinetics and mechanism of the reaction of gold(III chloride complexes with formic acid

    Directory of Open Access Journals (Sweden)

    Pacławski K.

    2015-01-01

    Full Text Available In this work, the results of kinetic studies of the redox reaction of gold(III chloride complexes ([AuCl4]- with formic acid, are presented. Obtained data suggest the complex character of the reaction which leads to the [AuCl2]- and [AuCl3(COOH]- ions formation as intermediates. In the pH range over 2.5, the final product of the reaction is metallic gold. From the analysis of kinetic data, the rate limiting step is found to be the gold metallic phase formation. The stage of Au(III reduction is relatively fast with the second-order rate constant equal to 61.8 M-1s-1 at temperature 50ºC. The rate of the studied reaction depends on the temperature, reactants concentration and chloride ions concentration. As a result of the data analysis, the scheme of the reaction path has been suggested. Also, the values of enthalpy and entropy of activation for the reaction have been determined.

  17. Reaction kinetics for synthesis of sec-butyl alcohol catalyzed by acid-functionalized ionic liquid

    Institute of Scientific and Technical Information of China (English)

    Ting Qiu; Wenli Tang; Chenggang Li; Chengming Wu; Ling Li

    2015-01-01

    The acid-functionalized ionic liquid ([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) show that the synthesis method is feasible and high purity of ionic liquid can be obtained. Using [HSO3Pmim]HSO4 as the catalyst, we studied the reaction kinetics of synthesizing sec-butyl alcohol from sec-butyl acetate and methanol by transesterification in a high-pressure batch reactor. The effects of temperature, initial molar ratio of methanol to ester, and catalyst concentration on the conversion of sec-butyl acetate were studied. Based on its possible reaction mechanism, a ho-mogeneous kinetic model was established. The results show that the reaction heatΔH is 10.94 × 103 J·mol−1, so the reaction is an endothermic reaction. The activation energies Ea+and Ea−are 60.38 × 103 and 49.44 × 103 J·mol−1, respectively.

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

    Directory of Open Access Journals (Sweden)

    Y. I. Hassan

    2012-01-01

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

  19. Kinetic study on reactive extraction for chiral separation of phenylsuccinic acid enantiomers

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    The kinetics of the extraction of phenylsuccinic acid(PSA) enantiomers by hydroxypropyl-β-cyclodextrin(HP-β-CD) in a modified Lewis cell was studied,in which HP-β-CD dissolved in 0.1 mol L-1 NaH2PO4/H3PO4 buffer solution(pH = 2.5) was selected as the chiral extractant.PSA enantiomers were extracted from organic phase to aqueous phase in the extraction module.The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of this extraction module.The different parameters affecting the extraction rate such as agitation speed,interfacial area,initial concentration of PSA enantiomers in organic phase as well as HP-β-CD concentration in aqueous phase were separately studied.The experimental results demonstrate that the extraction reactions are fast.The reactions were found to be first order with respect to PSA and second order with respect to HP-β-CD with forward rate constants of 3.4 × 10-2 m6 mol-2 s-1 for R-PSA and 9.96 × 10?3 m6 mol-2 s-1 for S-PSA.These data will be useful in the design of extraction processes.

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

    Directory of Open Access Journals (Sweden)

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

    Science.gov (United States)

    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.

  2. Study of the Extraction Kinetics of Lithium by Leaching β-Spodumene with Hydrofluoric Acid

    Directory of Open Access Journals (Sweden)

    Gustavo D. Rosales

    2016-09-01

    Full Text Available Parameters affecting the kinetics of the dissolution of β-spodumene with hydrofluoric acid have been investigated. The experimental tests were carried out in a closed vessel. The influence of several parameters, such as stirring speed, temperature, and reaction time were studied in order to deduce the kinetics of the dissolution reaction. The other parameters, particle size −45 μm; HF concentration 4% v/v, and the solid–liquid ratio 0.95% w/v were kept constant. The results indicate that the stirring speed does not have an important effect on the dissolution of the mineral above 330 rpm. The extent of the leaching of β-spodumene increases with temperature and reaction time augmentations. Scanning electron microscope (SEM analyses of some residues in which the conversion was lower than 30% indicated a selective attack on certain zones of the particle. The treatment of the experimental data was carried out using the Modelado software. The model that best represents the dissolution of the mineral is the following: ln(1 − X = −b1 [ln(1 + b2t − b2t/(1 + b2t]. This model is based on “nucleation and growth of nuclei” theory, and describes the style of attack physically observed by SEM on the residues.

  3. Isotherm and kinetics study for acrylic acid removal using powdered activated carbon.

    Science.gov (United States)

    Kumar, Arvind; Prasad, B; Mishra, I M

    2010-04-15

    The potential of powdered activated carbon (PAC) for the adsorption of acrylic acid (AA) from aqueous solution was studied at the initial concentration (C(0)) in the range of 50-500 mg/l over the temperature range of 303-348 K. The equilibrium adsorption studies were carried out to evaluate the effect of adsorbent dosage and contact time, change in pH by adding adsorbents and the initial concentration. Langmuir, Freundlich and Redlich-Peterson (R-P) equilibrium isotherm models were tested to represent the data. Error functions were used to test their validity to fit of the adsorption data with the isotherm and kinetic models. The Freundlich isotherm equation is found to best represent the equilibrium separation data in the temperature range of 303-348 K. The maximum adsorption capacity of AA onto PAC was obtained as q(m)=36.23 mg/g with an optimum PAC dosage w=20 g/l at 303 K for C(0)=100 mg/l. The pseudo-second-order kinetics is found to represent the experimental AA-PAC data. The negative value of DeltaG(ad)(o) (-16.60 to -18.18 kJ/mol K) indicate the feasibility and spontaneity of the adsorption process.

  4. A high-resolution study of surfactant partitioning and kinetic limitations for two-component internally mixed aerosols

    Science.gov (United States)

    Suda, S. R.; Petters, M. D.

    2013-12-01

    Atmospheric aerosols serve as cloud condensation nuclei (CCN), altering cloud properties and ultimately affecting climate through their effect on the radiative balance. Aerosol CCN activity depends in part on aerosol composition and surfactant compounds are of particular interest because surfactants are enriched at the water/air interface, resulting in a radial concentration gradient within the aqueous droplet. Accurate treatment of the surfactant concentration gradient complicates the otherwise straightforward predictions of CCN activity for aerosols of known composition. To accurately evaluate predictions made by theory, laboratory studies investigating the relationship between critical supersaturation and dry diameter of particles that include surfactants require significant reduction in measurement uncertainty for both water-uptake and CCN measurements. Furthermore, uncertainties remain regarding kinetic limitations to surfactant partitioning that could result in deviation from predictions based on equilibrium thermodynamics. This study attempts to address some of these issues through high-resolution analysis of CCN activity of two-component mixed surfactant/non-surfactant aerosols at different internal mixing ratios performed with and without a water-uptake time delay to ascertain whether or not the observed effects are kinetically limited. We present new data for the aerosols consisting of 1) the ionic surfactant sodium dodecyl sulfate (SDS) with ammonium sulfate, 2) SDS with sodium chloride and 3) the strong non-ionic fluorosurfactant Zonyl with an organic proxy glucose. As a point of reference we also evaluated the mixture of ammonium sulfate with glucose. Aerosol activation diameters were determined using CCN analysis in conjunction with scanning mobility size classification and high sheath-to-aerosol flow ratios. This resulted in CCN-derived kappa values that could be determined within +/-5% relative error. To test whether dynamic surfactant partitioning

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

    Institute of Scientific and Technical Information of China (English)

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

    2009-01-01

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

  6. Adsorption kinetics and thermodynamics of acid Bordeaux B from aqueous solution by graphene oxide/PAMAMs.

    Science.gov (United States)

    Zhang, Fan; He, Shengfu; Zhang, Chen; Peng, Zhiyuan

    2015-01-01

    Graphene oxide/polyamidoamines dendrimers (GO/PAMAMs) composites were synthesized via modifying GO with 2.0 G PAMAM. The adsorption behavior of the GO/PAMAMs for acid Bordeaux B (ABB) was studied and the effects of media pH, adsorption time and initial ABB concentration on adsorption capacity of the adsorbent were investigated. The optimum pH value of the adsorption of ABB onto GO/PAMAMs was 2.5. The maximum adsorption capacity increased from 325.78 to 520.83 mg/g with the increase in temperature from 298 to 328 K. The equilibrium data followed the Langmuir isotherm model better than the Freundlich model. The kinetic study illustrated that the adsorption of ABB onto GO/PAMAMs fit the pseudo-second-order model. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process.

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

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Qingwei; Ren, Jing [Department of Environmental Science and Engineering, Fudan University, Shanghai 200433 (China); Huang, Honghui [Key Laboratory of Fisheries Ecology Environment, Ministry of Agriculture, Guangzhou 510300 (China); Wang, Shoubing [Department of Environmental Science and Engineering, Fudan University, Shanghai 200433 (China); Wang, Xiangrong, E-mail: xrxrwang@vip.sina.com [Department of Environmental Science and Engineering, Fudan University, Shanghai 200433 (China); Fan, Zhengqiu, E-mail: zhqfan@fudan.edu.cn [Department of Environmental Science and Engineering, Fudan University, Shanghai 200433 (China)

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer For the first time, degradation of MC-LR by nitrous acid under UV 365 nm was discovered. Black-Right-Pointing-Pointer The effects of factors on MC-LR degradation were analyzed based on kinetic study. Black-Right-Pointing-Pointer Mass spectrometry was applied for identification of intermediates and products. Black-Right-Pointing-Pointer Special intermediates involved in this study were identified. Black-Right-Pointing-Pointer Degradation mechanisms were proposed according to the results of LC-MS analysis. - Abstract: Degradation of microcystin-LR (MC-LR) in the presence of nitrous acid (HNO{sub 2}) under irradiation of 365 nm ultraviolet (UV) was studied for the first time. The influence of initial conditions including pH value, NaNO{sub 2} concentration, MC-LR concentration and UV intensity were studied. MC-LR was degraded in the presence of HNO{sub 2}; enhanced degradation of MC-LR was observed with 365 nm UV irradiation, caused by the generation of hydroxyl radicals through the photolysis of HNO{sub 2}. The degradation processes of MC-LR could well fit the pseudo-first-order kinetics. Mass spectrometry was applied for identification of the byproducts and the analysis of degradation mechanisms. Major degradation pathways were proposed according to the results of LC-MS analysis. The degradation of MC-LR was initiated via three major pathways: attack of hydroxyl radicals on the conjugated carbon double bonds of Adda, attack of hydroxyl radicals on the benzene ring of Adda, and attack of nitrosonium ion on the benzene ring of Adda.

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

    Science.gov (United States)

    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. Kinetic investigation of a solvent-free, chemoenzymatic reaction sequence towards enantioselective synthesis of a β-amino acid ester.

    Science.gov (United States)

    Strompen, Simon; Weiss, Markus; Ingram, Thomas; Smirnova, Irina; Gröger, Harald; Hilterhaus, Lutz; Liese, Andreas

    2012-06-01

    A solvent-free, chemoenzymatic reaction sequence for the enantioselective synthesis of β-amino acid esters has been kinetically and thermodynamically characterized. The coupled sequence comprises a thermal aza-Michael addition of cheap starting materials and a lipase catalyzed aminolysis for the kinetic resolution of the racemic ester. Excellent ee values of >99% were obtained for the β-amino acid ester at 60% conversion. Kinetic constants for the aza-Michael addition were obtained by straightforward numerical integration of second-order rate equations and nonlinear fitting of the progress curves. A different strategy had to be devised for the biocatalytic reaction. Initially, a simplified Michaelis-Menten model including product inhibition was developed for the reaction running in THF as an organic solvent. Activity based parameters were used instead of concentrations in order to facilitate the transfer of the kinetic model to the solvent-free system. Observed solvent effects not accounted for by the use of thermodynamic activities were incorporated into the kinetic model. Enzyme deactivation was observed to depend on the ratio of the applied substrates and also included in the kinetic model. The developed simple model is in very good agreement with the experimental data and allows the simulation and optimization of the solvent-free process.

  11. Quantitative milk genomics: estimation of variance components and prediction of fatty acids in bovine milk

    DEFF Research Database (Denmark)

    Krag, Kristian

    The composition of bovine milk fat, used for human consumption, is far from the recommendations for human fat nutrition. The aim of this PhD was to describe the variance components and prediction probabilities of individual fatty acids (FA) in bovine milk, and to evaluate the possibilities...

  12. Peroxynitrous acid induces structural and functional modifications to basement membranes and its key component, laminin

    DEFF Research Database (Denmark)

    Degendorfer, Georg; Chuang, Christine Y.; Hammer, Astrid;

    2015-01-01

    Basement membranes (BM) are specialized extracellular matrices underlying endothelial cells in the artery wall. Laminin, the most abundant BM glycoprotein, is a structural and biologically active component. Peroxynitrous acid (ONOOH), a potent oxidizing and nitrating agent, is formed in vivo at s...

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

    Directory of Open Access Journals (Sweden)

    Zhaksyntay Kairbekov

    2012-12-01

    Full Text Available It was established that in 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. 

  14. Gallic acid is the major component of grape seed extract that inhibits amyloid fibril formation.

    Science.gov (United States)

    Liu, Yanqin; Pukala, Tara L; Musgrave, Ian F; Williams, Danielle M; Dehle, Francis C; Carver, John A

    2013-12-01

    Many protein misfolding diseases, for example, Alzheimer's, Parkinson's and Huntington's, are characterised by the accumulation of protein aggregates in an amyloid fibrillar form. Natural products which inhibit fibril formation are a promising avenue to explore as therapeutics for the treatment of these diseases. In this study we have shown, using in vitro thioflavin T assays and transmission electron microscopy, that grape seed extract inhibits fibril formation of kappa-casein (κ-CN), a milk protein which forms amyloid fibrils spontaneously under physiological conditions. Among the components of grape seed extract, gallic acid was the most active component at inhibiting κ-CN fibril formation, by stabilizing κ-CN to prevent its aggregation. Concomitantly, gallic acid significantly reduced the toxicity of κ-CN to pheochromocytoma12 cells. Furthermore, gallic acid effectively inhibited fibril formation by the amyloid-beta peptide, the putative causative agent in Alzheimer's disease. It is concluded that the gallate moiety has the fibril-inhibitory activity.

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

    Directory of Open Access Journals (Sweden)

    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.

  16. SU-E-T-751: Three-Component Kinetic Model of Tumor Growth and Radiation Response for Stereotactic Radiosurgery

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Y; Dahlman, E; Leder, K; Hui, S [University of Minnesota, Minneapolis, MN (United States)

    2015-06-15

    Purpose: To develop and study a kinetic model of tumor growth and its response to stereotactic radiosurgery (SRS) by assuming that the cells in irradiated tumor volume were made of three types. Methods: A set of ordinary differential equations (ODEs) were derived for three types of cells and a tumor growth rate. It is assumed that the cells were composed of actively proliferating cells, lethally damaged-dividing cells, and non-dividing cells. We modeled the tumor volume growth with a time-dependent growth rate to simulate the saturation of growth. After SRS, the proliferating cells were permanently damaged and converted to the lethally damaged cells. The amount of damaged cells were estimated by the LQ-model. The damaged cells gradually stopped dividing/proliferating and died with a constant rate. The dead cells were cleared from their original location with a constant rate. The total tumor volume was the sum of the three components. The ODEs were numerically solved with appropriate initial conditions for a given dosage. The proposed model was used to model an animal experiment, for which the temporal change of a rhabdomyosarcoma tumor volume grown in a rat was measured with time resolution sufficient to test the model. Results: To fit the model to the experimental data, the following characteristics were needed with the model parameters. The α-value in the LQ-model was smaller than the commonly used value; furthermore, it decreased with increasing dose. At the same time, the tumor growth rate after SRS had to increase. Conclusions: The new 3-component model of tumor could simulate the experimental data very well. The current study suggested that the radiation sensitivity and the growth rate of the proliferating tumor cells may change after irradiation and it depended on the dosage used for SRS. These preliminary observations must be confirmed by future animal experiments.

  17. ADSORPTION OF 1,2,4-ACID BY WEAKLY BASIC RESIN:ISOTHERMS,THERMODYNAMICS AND KINETICS

    Institute of Scientific and Technical Information of China (English)

    Fu-qiang Liu; Jin-long Chen; Chao Long; Ai-min Li; Guan-dao Gao; Quan-xing Zhang

    2004-01-01

    The adsorption properties, including the adsorption isotherms, thermodynamics and kinetics, of 1-arnino-2-naphthol-4-sulfonic acid (1,2,4-acid) onto weakly basic resin ND900 are investigated. Both the Langmuir and Freundlich equations can give a good fit to the adsorption isotherms, which indicates an endothermic and a favorable adsorption in our study range. A high yield in elimination of about 45.21%-97.28% is obtained for the tested adsorption systems. The capacity and affinity of the adsorption increase with temperature, due to the phenomena of "solvent-motivated" effects. The value of △H is 51.59 kJ/mol, which indicates a chemical adsorption and then expects the poor desorption property of ND900. The negative value of AG indicates the spontaneous nature of the adsorption process, and the positive value of △S shows the increased randomness at the solid/solution interface during the adsorption process. The value of the adsorption rate constant lower than 0.013 min-1 is indicative of a slow adsorption rate. The intra-particle diffusion must be one of the rate limiting steps.

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Directory of Open Access Journals (Sweden)

    Rajesh N. Singru

    2009-01-01

    Full Text Available 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 technique in which sample is subjected to condition of continuous increase in temperature at linear rate. Thermal study of the resins was carried out to determine their mode of decomposition and relative thermal stabilities. Thermal decomposition curves were studied carefully with minute details. The Freeman-Carroll and Sharp-Wentworth methods have been used in the present investigation to calculate thermal activation energy and different kinetic parameter of the terpolymer resins. Thermal activation energy (Ea calculated with above two mentioned methods are in close agreement. The advantage of Freeman-Carroll method is to calculate both the order of reaction (n and energy of activation in one single stage by keeping heating rate constant. By using data of thermogravimetric analysis, various thermodynamic parameters like frequency factor (Z, entropy change (Δ S, free energy change (Δ F and apparent entropy (S* have been determined using Freeman-Carroll method.

  20. Relationship between body fat mass and free fatty acid kinetics in men and women.

    Science.gov (United States)

    Mittendorfer, Bettina; Magkos, Faidon; Fabbrini, Elisa; Mohammed, B Selma; Klein, Samuel

    2009-10-01

    An increased release of free fatty acids (FFAs) into plasma likely contributes to the metabolic complications associated with obesity. However, the relationship between body fat and FFA metabolism is unclear because of conflicting results from different studies. The goal of our study was to determine the inter-relationships between body fat, sex, and plasma FFA kinetics. We determined FFA rate of appearance (Ra) in plasma, by using stable isotopically labeled tracer techniques, during basal conditions in 106 lean, overweight, and obese, nondiabetic subjects (43 men and 63 women who had 7.0-56.0% body fat). Correlation analyses demonstrated: (i) no differences between men and women in the relationship between fat mass (FM) and total FFA Ra (micromol/min); (ii) total FFA Ra increased linearly with increasing FM (r=0.652, Pfashion with increasing FM (r=-0.806; Pmen; and (v) abdominal fat itself was not an important determinant of total FFA Ra. We conclude that total body fat, not regional fat distribution or sex, is an important modulator of the rate of FFA release into plasma. Although increased adiposity is associated with a decrease in fatty acid release in relationship to FM, this downregulation is unable to completely compensate for the increase in FM, so total FFA Ra and FFA Ra with respect to FFM are greater in women than in men and in obese than in lean subjects.

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

    Directory of Open Access Journals (Sweden)

    Jayachamarajapura Pranesh Shubha

    2014-01-01

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

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

    Science.gov (United States)

    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.

  3. Oxidation of ferrous nitrilotriacetic acid with oxygen : A model for oxygen mass transfer parallel to reaction kinetics

    NARCIS (Netherlands)

    Demmink, JF; Beenackers, AACM

    1997-01-01

    The kinetics of the reaction of ferrous chelate of nitrilotriacetic acid (NTA) and gaseous oxygen were studied in a stirred-cell reactor. The initial concentration of ferrous chelate was 0.100 kmol/m(3). Other reaction conditions include 293

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

    Science.gov (United States)

    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. Study of reaction parameters and kinetics of esterification of lauric acid with butanol by immobilized Candida antarctica lipase.

    Science.gov (United States)

    Shankar, Sini; Agarwal, Madhu; Chaurasia, S P

    2013-12-01

    Esterification of lauric acid with n-butanol, catalyzed by immobilized Candida antarctica lipase (CAL) in aqueous-organic biphasic solvent system was studied. Effects of various reaction parameters on esterification were investigated, such as type and amount of solvent, amount of buffer, pH, temperature, speed of agitation, amount of enzyme, butanol and lauric acid. The most suitable reaction conditions for esterification were observed at 50 degrees C and pH 7.0 using 5000 micromoles of lauric acid, 7000 pmoles of butanol, 0.25 ml phosphate buffer, 1 ml of isooctane as the solvent and 50 mg of immobilized enzyme in the reaction medium at agitation speed of 150 rpm. Maximum esterification of 96.36% was acheived in 600 min of reaction time at n-butanol to lauric acid molar ratio of 1: 0.7. Kinetic study for the esterification of lauric acid with n-butanol using immobilized CAL was carried out and the kinetic constants were estimated by using non-linear regression method. The estimated value of Michaelis kinetic constants for butanol (KmBt) and acid (KmAc) were 451.56 (M) and 4.7 x 10(-7)(M), respectively and the value of dissociation constant (KBt) of the butanol-lipase complex was 9.41 x 10(7)(M). The estimated constants agreed fairly well with literature data.

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

    Directory of Open Access Journals (Sweden)

    A. W. Birdsall

    2014-08-01

    Full Text Available 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. 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 a similar magnitude, 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.

  7. Synthesis of protected (2S,4R)-2-amino-4-methyldecanoic acid, a proposed component of culicinins

    Institute of Scientific and Technical Information of China (English)

    Wei Zhang; Tian Tian Sun; Duo Mei; Jun Fei Wang; Ying Xia Li

    2008-01-01

    The protected (2S,4R)-2-amino-4-methyldecanoic acid, a proposed component of culicinins has been synthesized over 10 steps and in total 28% yields using Wittig reaction and Schollkopf amino acid synthesis as key steps.

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

    Science.gov (United States)

    Kara, Ali; Demirbel, Emel; Tekin, Nalan; Osman, Bilgen; Beşirli, Necati

    2015-04-09

    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 parameters (free energy change, ΔG(0) enthalpy change, ΔH(0); and entropy change, ΔS(0)) for the adsorption have been evaluated.

  9. Plasma free amino acid kinetics in rainbow trout (Oncorhynchus mykiss) using a bolus injection of 15N-labeled amino acids.

    Science.gov (United States)

    Robinson, Jacob William; Yanke, Dan; Mirza, Jeff; Ballantyne, James Stuart

    2011-02-01

    To gain insight into the metabolic design of the amino acid carrier systems in fish, we injected a bolus of (15)N amino acids into the dorsal aorta in mature rainbow trout (Oncorhynchus mykiss). The plasma kinetic parameters including concentration, pool size, rate of disappearance (R(d)), half-life and turnover rate were determined for 15 amino acids. When corrected for metabolic rate, the R(d) values obtained for trout for most amino acids were largely comparable to human values, with the exception of glutamine (which was lower) and threonine (which was higher). R(d) values ranged from 0.9 μmol 100 g(-1) h(-1) (lysine) to 22.1 μmol 100 g(-1) h(-1) (threonine) with most values falling between 2 and 6 μmol 100 g(-1) h(-1). There was a significant correlation between R(d) and the molar proportion of amino acids in rainbow trout whole body protein hydrolysate. Other kinetic parameters did not correlate significantly with whole body amino acid composition. This indicates that an important design feature of the plasma-free amino acids system involves proportional delivery of amino acids to tissues for protein synthesis.

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

    Institute of Scientific and Technical Information of China (English)

    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.

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

    Directory of Open Access Journals (Sweden)

    Zhaksyntay Kairbekov

    2012-12-01

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

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

    Directory of Open Access Journals (Sweden)

    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.

  13. The novel kinetics expression of Cadmium (II) removal using green adsorbent horse dung humic acid (Hd-Ha)

    Science.gov (United States)

    Basuki, Rahmat; Santosa, Sri Juari; Rusdiarso, Bambang

    2017-03-01

    Humic acid from dry horse dung powder has been prepared and this horse dung humic acid (HD-HA) was then applied as a sorbent to adsorb Cadmium(II) from a solution. Characterization of HD-HA was conducted by detection of its functional group, UV-Vis spectra, ash level, and total acidity. Result of the work showed that HD-HA had similar character compared with peat soil humic acid (PS-HA) and previous researchers. The adsorption study of this work was investigated by batch experiment in pH 5. The thermodynamics parameters in this work were determined by the Langmuir isotherm model for monolayer sorption and Freundlich isotherm model multilayer sorption. Monolayer sorption capacity (b) for HD-HA was 1.329 × 10-3 mol g-1, equilibrium constant (K) was 5.651 (mol/L)-1, and multilayer sorption capacity was 2.646 × 10-2 mol g-1. The kinetics parameters investigated in this work were determined by the novel kinetics expression resulted from the mathematical derivation the availability of binding sites of sorbent. Adsorption rate constant (ka) from this novel expression was 43.178 min-1 (mol/L)-1 and desorption rate constant (kd) was 1.250 × 10-2 min-1. Application of the kinetics model on sorption Cd(II) onto HD-HA showed the nearly all of models gave a good linearity. However, only this proposed kinetics expression has good relation with Langmuir model. The novel kinetics expression proposed in this paper seems to be more realistic and reasonable and close to the experimental real condition because the value of ka/kd (3452 (mol/L)-1) was fairly close with K from Langmuir isotherm model (5651 (mol/L)-1). Comparison of this novel kinetics expression with well-known Lagergren pseudo-first order kinetics and Ho pseudo-second order kinetics was also critically discussed in this paper.

  14. Kinetic study on the enzymatic esterification of octanoic acid and hexanol by immobilized Candida antarctica lipase B

    DEFF Research Database (Denmark)

    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...... a Ping-Pong bi-bi mechanism with dead-end inhibition by both substrates and, based on the proposed model, the kinetic constants of the esterification reaction are estimated. These parameters are verified to be intrinsic – neither external nor internal mass transfer resistances are significant...

  15. Effects of some components of acid-mine drainage and acid deposition on the spermatozoa of longear sunfish, Lepomis megalotis

    Energy Technology Data Exchange (ETDEWEB)

    Pearson, B.J.

    1983-01-01

    The effects of low pH and the metals aluminum, zinc, and cadmium, components of acid-mine effluents and acid deposition, on spermatozoa of longear sunfish, Lepomis megalotis, were investigated. Sperm were exposed to solutions of 400 ppm aluminum chloride, 50 ppm zinc chloride, 2 ppm cadmium chloride, separately and in combination, at pH values of 6.9, 4.8, and 3.8. Sperm were additionally exposed to test solutions in which the metal salt concentration was reduced by one-half and observed for changes in motility and in the ability to exclude stain. All test solutions at a low pH were deleterious, the greatest damage occurring in solutions of a combination of all 3 metal chlorides and of aluminum chloride separately. Motility tests showed that both full and reduced metal concentrations had significant effects on motility. Staining tests were supportive of motility test results and indicated that in most cases shorter exposure times did not significantly improve survival rates. It was generally found that a decrease in pH increased the effects of each metal separately and when combined. Aluminum, zinc, and cadmium chlorides appeared to act antagonistically when tested in combination. It was concluded that the components of acid waters which were tested have deleterious effects on longer spermatozoa, reducing their viability and thereby reducing reproductive success of the species.

  16. Fundamental study of the mechanism and kinetics of cellulose hydrolysis by acids and enzymes. Progress report, June 1, 1975--December 31, 1975

    Energy Technology Data Exchange (ETDEWEB)

    Tsao, G T

    1976-02-01

    This project deals with acidic and enzymatic hydrolysis of cellulosic materials. Highlights of the first eight months of out project are as follows. (1) Essentially homogeneous C/sub 1/, C/sub x/, and Cellobiase enzyme have been isolated from Cellulase-Onozuka of Trichodeima viride origin. Besides the 3 major components, one protein of a molecular weight of 10,000 was purified, which has strong C/sub x/ activity and also another (M.W. 23,000) with strong C/sub 1/ activity. (2) Kinetics of Cellobiase has been investigated and its kinetics constant accurately determined. Immobilization of this enzyme on porous glass was successful. (3) Absorption of SO/sub 2/ at atmospheric pressure increased digestibility of delignated cellulose but not the natural materials such as corn stalk. A pressurizable absorption unit is being built. (4) Kinetics models for purified C/sub 1/ and C/sub x/ are postulated and equations derived. Experimental tests will be made when sufficient quantities of purified C/sub 1/ and C/sub x/ enzyme are prepared. (5) A lignin digesting, white-rot fungus, Pleurotus ostreatus, has cultivated in our laboratory. It has grown well and heavy. (6) A number of electron micrographs were made with untreated cellulosic materials, which showed that the method of drying the specimens for electromicroscopy is important. Ordinary drying procedures will alter their physical structures. A technique, critical point drying, is being practiced, which will not change the structure. (auth)

  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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kara, Ali, E-mail: akara@uludag.edu.tr [Uludag University, Faculty of Arts and Science, Department of Chemistry, 16059 Bursa (Turkey); Demirbel, Emel [Uludag University, Faculty of Arts and Science, Department of Chemistry, 16059 Bursa (Turkey); Tekin, Nalan [Kocaeli University, Faculty of Arts and Science, Department of Chemistry, 41380 Kocaeli (Turkey); Osman, Bilgen; Beşirli, Necati [Uludag University, Faculty of Arts and Science, Department of Chemistry, 16059 Bursa (Turkey)

    2015-04-09

    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 N{sub 2} 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

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

    Institute of Scientific and Technical Information of China (English)

    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.

  20. Vapour and acid components separation from gases by membranes principles and engineering approach to membranes development

    Science.gov (United States)

    Kagramanov, G. G.; Storojuk, I. P.; Farnosova, E. N.

    2016-09-01

    The modern commercially available polymer membranes and membrane modules for purification of gases, containing acid components, simultaneously with dehumidification of treated gas streams, were developed and commercialized in the very end of XXth century. The membranes basic properties - selectivity (separation factor) and permeation flow rates - are relatively far from satisfying the growing and modern-scale industrial need in purification technologies and corresponding equipments. The attempt to formulate the basic principles, scientific and engineering approaches to the development of prospective membranes for the purification of gases, especially such as natural and oil gases, from acid components, simultaneously with drying them, was being made. For this purpose the influence of various factors - polymer nature, membrane type, structure, geometrical and mass-transfer characteristics, etc. - were studied and analyzed in order to formulate the basic principles and demands for development of membranes, capable to withstand successfully the sever conditions of exploitation.

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

    Energy Technology Data Exchange (ETDEWEB)

    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)

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

    Science.gov (United States)

    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...

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

    Science.gov (United States)

    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).

  4. PRINCIPAL COMPONENT ANALYSIS OF FACTORS DETERMINING PHOSPHATE ROCK DISSOLUTION ON ACID SOILS

    Directory of Open Access Journals (Sweden)

    Yusdar Hilman

    2016-10-01

    Full Text Available Many of the agricultural soils in Indonesia are acidic and low in both total and available phosphorus which severely limits their potential for crops production. These problems can be corrected by application of chemical fertilizers. However, these fertilizers are expensive, and cheaper alternatives such as phosphate rock (PR have been considered. Several soil factors may influence the dissolution of PR in soils, including both chemical and physical properties. The study aimed to identify PR dissolution factors and evaluate their relative magnitude. The experiment was conducted in Soil Chemical Laboratory, Universiti Putra Malaysia and Indonesian Center for Agricultural Land Resources Research and Development from January to April 2002. The principal component analysis (PCA was used to characterize acid soils in an incubation system into a number of factors that may affect PR dissolution. Three major factors selected were soil texture, soil acidity, and fertilization. Using the scores of individual factors as independent variables, stepwise regression analysis was performed to derive a PR dissolution function. The factors influencing PR dissolution in order of importance were soil texture, soil acidity, then fertilization. Soil texture factors including clay content and organic C, and soil acidity factor such as P retention capacity interacted positively with P dissolution and promoted PR dissolution effectively. Soil texture factors, such as sand and silt content, soil acidity factors such as pH, and exchangeable Ca decreased PR dissolution.

  5. A two component system is involved in acid adaptation of Lactobacillus delbrueckii subsp. bulgaricus.

    Science.gov (United States)

    Cui, Yanhua; Liu, Wei; Qu, Xiaojun; Chen, Zhangting; Zhang, Xu; Liu, Tong; Zhang, Lanwei

    2012-05-20

    The Gram-positive bacterium Lactobacillus delbrueckii subsp. bulgaricus is of vital importance to the food industry, especially to the dairy industry. Two component systems (TCSs) are one of the most important mechanisms for environmental sensing and signal transduction in the majority of Gram-positive and Gram-negative bacteria. A typical TCS consists of a histidine protein kinase (HPK) and a cytoplasmic response regulator (RR). To investigate the functions of TCSs during acid adaptation in L. bulgaricus, we used quantitative PCR to reveal how TCSs expression changes during acid adaptation. Two TCSs (JN675228/JN675229 and JN675230/JN675231) and two HPKs (JN675236 and JN675240) were induced during acid adaptation. These TCSs were speculated to be related with the acid adaptation ability of L. bulgaricus. The mutants of JN675228/JN675229 were constructed in order to investigate the functions of JN675228/JN675229. The mutants showed reduced acid adaptation compared to that of wild type, and the complemented strains were similar to the wild-type strain. These observations suggested that JN675228 and JN675229 were involved in acid adaptation in L. bulgaricus. The interaction between JN675228 and JN675229 was identified by means of yeast two-hybrid system. The results indicated there is interaction between JN675228 and JN675229.

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

    Science.gov (United States)

    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.

  7. KINETICS STUDY ON MELT GRAFTING ACRYLIC ACID ONTO LLDPE USING REACTIVE EXTRUSION

    Institute of Scientific and Technical Information of China (English)

    Qiang Shi; Lian-chao Zhu; Chuan-lun Cai; Jing-hua Yin

    2005-01-01

    The kinetics of melt grafting acrylic acid (AA) onto linear low density polyethylene (LLDPE) by using reactive extrusion was investigated. The polymeric peroxides (POOP and POOH) generated by electron beam irradiation were used to initiate the graft reaction. The samples taken out from the barrel at five ports along screw axis were analyzed by FTIR. The spectra show that both the graft copolymerization and homopolymerization proceed in two stages: the graft degree (or mass of homopolymer) increases linearly with the reaction time in the initial stage, and then gradually in the second stage. The rate of graft copolymerization Rg is always faster than that of homopolymerization Rh in the present system and the activation interpreted in terms of solubility and diffusion of monomer, as well as the reactivity and the concentration of reactive species.The relationships between reaction rate and monomer concentration and peroxide concentration were found to be. Rg ∝ [M]1.46[POOP+POOH]0.53 and Rh ∝ [M]1.08[POOH]0.51, which indicate that the addition of monomer to polymeric radicals is a slow step for the graft copolymerization.

  8. Kinetics of Photocatalytic Degradation of Formic Acid over Silica Composite Films Based on Polyoxometalates

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The composite films, XW11O39n-/SiO2, (X refers to Si, Ge or P, respectively) were prepared by tetraethoxysilane (TEOS) hydrolysis sol-gel method via spin-coating technique. Formation of the composite films is due to strong chemical reaction of organic silanol group with the surface oxygen atoms of XW11O39n-, resulted in the saturation of the surface of the lacunary polyoxometalates (POMs). Therefore, the coordination structural model of the films was proposed. As for the films, retention of the primary Keggin structure was confirmed by UV-vis, FT-IR spectra and MAS NMR. The surface morphology of the films was characterized by SEM, indicating that the film surface is relatively uniform, and the layer thickness is in the range of 250~350 nm. Aqueous formic acid (FA) (0-20 mmol/L) was degraded into CO2 and H2O by irradiating the films in the near-UV area. The results show that all the films have photocatalytic activities and the degradation reaction follows Langmuir-Hinshelwood first order kinetics.

  9. The Viability of a Nonenzymatic Reductive Citric Acid Cycle Kinetics and Thermochemistry

    Science.gov (United States)

    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.

  10. Stability of HAMLET--a kinetically trapped alpha-lactalbumin oleic acid complex.

    Science.gov (United States)

    Fast, Jonas; Mossberg, Ann-Kristin; Svanborg, Catharina; Linse, Sara

    2005-02-01

    The stability toward thermal and urea denaturation was measured for HAMLET (human alpha-lactalbumin made lethal to tumor cells) and alpha-lactalbumin, using circular dichroism and fluorescence spectroscopy as well as differential scanning calorimetry. Under all conditions examined, HAMLET appears to have the same or lower stability than alpha-lactalbumin. The largest difference is seen for thermal denaturation of the calcium free (apo) forms, where the temperature at the transition midpoint is 15 degrees C lower for apo HAMLET than for apo alpha-lactalbumin. The difference becomes progressively smaller as the calcium concentration increases. Denaturation of HAMLET was found to be irreversible. Samples of HAMLET that have been renatured after denaturation have lost the specific biological activity toward tumor cells. Three lines of evidence indicate that HAMLET is a kinetic trap: (1) It has lower stability than alpha-lactalbumin, although it is a complex of alpha-lactalbumin and oleic acid; (2) its denaturation is irreversible and HAMLET is lost after denaturation; (3) formation of HAMLET requires a specific conversion protocol.

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

    Science.gov (United States)

    Ross, D.S.

    2007-01-01

    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. ?? 2006 Springer Science + Business Media B.V.

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

    Science.gov (United States)

    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.

  13. Kinetic Study of the Acid Degradation of Lignin Model Compound Intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Sturgeon, M.; Kim, S.; Chmely, S. C.; Foust, T. D.; Beckham, G. T.

    2012-01-01

    Lignin is a major constituent of biomass, which remains underutilized in selective biomass conversion strategies to renewable fuels and chemicals. Here we are interested in understanding the mechanisms related to the acid deconstruction of lignin with a combined theoretical and experimental approach. Two model dimers with a b-O-4 aryl ether linkage (2-phenoxy-1-phenethanol and 2-phenoxy-1-phenyl-1,3 propanediol) were synthesized and deconstructed in H2SO4. The major products of the acidolysis of the b-O-4 compounds consisted of phenol and two aldehydes, phenylacetaldehyde and benzaldehyde. Quantum mechanical calculations were employed to elucidate possible deconstruction mechanisms with transition state theory. To confirm the proposed mechanisms a kentic study of several possible intermediates was done under similar acidolysis conditions. Epoxystyrene and 1-phenyl-1,2-ethandiol were used as intermediates. 2-phenoxyvinylbenzene was synthesized and subsequently deconstructed in H2SO4. The kinetics and product distribution of these intermediates were then used in confirming our proposed mechanisms.

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  16. Solid components and acid buffering capacity of soils in South China

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    The effects of soil solid components on soil sensitivityto acid deposition were studied in this paper by sequentialextraction method. A multiple regression equation of soilsensitivity was set up on the basis of stepwise regressionanalysis. The results showed that organic matter expressed dualeffects that were decided by soil original pH value andexchangeable cation composition on acid buffering reactions. Thehydrolysis of activated oxides was a very important protonbuffering reaction when in low pH situation. The crystalline oxidesalso played a role in the buffering reactions, but the role wasrestricted by the rate of activation of oxides. Meanwhile, theresults by stepwise analysis showed that factors that hadsignificant effect on soil acid buffering capacity were content ofmontmorillite, soil original pH value, Alo, Mno and CEC indecreasing order. Finally, sixteen soils were classified into fourtypes of sensitive with single index cluster and multiple fuzzy cluster analysis respectively.

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

    Science.gov (United States)

    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.

  18. Whole body creatine and protein kinetics in healthy men and women: effects of creatine and amino acid supplementation.

    Science.gov (United States)

    Kalhan, Satish C; Gruca, Lourdes; Marczewski, Susan; Bennett, Carole; Kummitha, China

    2016-03-01

    Creatine kinetics were measured in young healthy subjects, eight males and seven females, age 20-30 years, after an overnight fast on creatine-free diet. Whole body turnover of glycine and its appearance in creatine was quantified using [1-(13)C] glycine and the rate of protein turnover was quantified using L-ring [(2)H5] phenylalanine. The creatine pool size was estimated by the dilution of a bolus [C(2)H3] creatine. Studies were repeated following a five days supplement creatine 21 g.day(-1) and following supplement amino acids 14.3 g day(-1). Creatine caused a ten-fold increase in the plasma concentration of creatine and a 50 % decrease in the concentration of guanidinoacetic acid. Plasma amino acids profile showed a significant decrease in glycine, glutamine, and taurine and a significant increase in citrulline, valine, lysine, and cysteine. There was a significant decrease in the rate of appearance of glycine, suggesting a decrease in de-novo synthesis (p = 0.006). The fractional and absolute rate of synthesis of creatine was significantly decreased by supplemental creatine. Amino acid supplement had no impact on any of the parameters. This is the first detailed analysis of creatine kinetics and the effects of creatine supplement in healthy young men and women. These methods can be applied for the analysis of creatine kinetics in different physiological states.

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

    Directory of Open Access Journals (Sweden)

    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.

  20. Kinetically controlled synthesis of monoglyceryl esters from chiral and prochiral acids methyl esters catalyzed by immobilized Rhizomucor miehei lipase.

    Science.gov (United States)

    Acosta, Andreina; Filice, Marco; Fernandez-Lorente, Gloria; Palomo, Jose M; Guisan, Jose M

    2011-01-01

    Partial acylation of only one primary hydroxyl group of glycerol generates a chiral center at position 2. Rhizomucor miehei lipase (RML) catalyzes the kinetically controlled transesterification of different aromatic carboxylic acids methyl esters with glycerol. High synthetic yields of glyceryl esters (around 70-80%) were obtained even in the presence of significant concentrations of water (from 5% to 20%). After a long incubation of the reaction mixture in the presence of the biocatalyst only pure free acid was obtained. Other lipases (from Geobacillus thermocatenulatus and from Thermomyces lanuginose) also catalyzed similar kinetically controlled transesterifications although less efficiently. RML immobilized on Sepharose-Q showed a high activity and specificity, compared to the immobilization by other techniques, only producing monoglyceryl esters with all substrates. In particular, monoglyceryl-phenylmalonate product was synthesized in 82% overall yield and >99% diastereomeric excess at pH 7.0 and 37°C and 90% glycerol.

  1. Leaching kinetics of molybdenum from Ni-Mo ore in sulfuric acid solution with sodium peroxodisulfate as oxidant

    Institute of Scientific and Technical Information of China (English)

    刘志雄; 尹周澜; 陈义光; 熊利芝

    2015-01-01

    The leaching kinetics of molybdenum from Ni-Mo ore in sulfuric acid solution with sodium peroxodisulfate was studied. The effects including leaching temperature, reaction time, particle size, stirring speed, and concentrations of sulfuric acid and sodium peroxodisulfate were investigated. The leaching process of molybdenum from Ni-Mo ore is controlled by the chemical reaction through the solid layer across the unreacted shrinking core. The apparent activation energy of the leaching of molybdenum is calculated to be 41.0 kJ/mol and the leaching kinetics equation of molybdenum from Ni-Mo ore is expressed as 1−(1−a)1/3=3405.7exp[−41030.0/(RT)]t.

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

    Indian Academy of Sciences (India)

    Puttaswamy; S Dakshayani

    2014-11-01

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

  3. Fatty acid and drug binding to a low-affinity component of human serum albumin, purified by affinity chromatography

    DEFF Research Database (Denmark)

    Vorum, H; Pedersen, A O; Honoré, B

    1992-01-01

    of two albumin components about 40% of the albumin having high affinity and about 60% having low affinity. By affinity chromatography we succeeded in purifying the low-affinity component from the mixture. The high-affinity component, however, could not be isolated. We further analyzed the fatty acid...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-15

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

  5. Isotherm, kinetic and thermodynamics study of humic acid removal process from aquatic environment by chitosan nano particle

    Directory of Open Access Journals (Sweden)

    Maryam Ghafoori

    2016-09-01

    Full Text Available Background and Aim: Humic substances include natural organic polyelectrolyte materials that formed most of the dissolved organic carbon in aquatic environments. Reaction between humic substances and chlorine leading to formation of disinfection byproducts (DBPs those are toxic, carcinogenic and mutagenic. The aim of this study was investigation of isotherms, kinetics and thermodynamics of humic acid removal process by nano chitosan from aquatic environment. Materials and Methods: This practical research was an experimental study that performed in a batch system. The effect of various parameters such as pH, humic acid concentration, contact time, adsorbent dosage, isotherms, thermodynamics and Kinetics of humic acid adsorption process were investigated. Humic acid concentration measured using spectrophotometer at wave length of 254 nm. Results: The results of this research showed that maximum adsorption capacity of nanochitosan that fall out in concentration of 50 mg/l and contact time of 90 minutes was 52.34 mg/g. Also, the maximum adsorption was observed in pH = 4 and adsorbent dosage 0.02 g. Laboratory data show that adsorption of humic acid by nanochitosan follow the Langmuir isotherm model. According to result of thermodynamic study, entropy changes (ΔS was equal to 2.24 J/mol°k, enthalpy changes (ΔH was equal to 870 kJ/mol and Gibbs free energy (ΔG was negative that represent the adsorption process is spontaneous and endothermic. The kinetics of adsorption has a good compliant with pseudo second order model. Conclusion: Regarding to results of this study, nano chitosan can be suggested as a good adsorbent for the removal of humic acids from aqueous solutions.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Novel kinetic and background current selectivity in the even harmonic components of fourier transformed square-wave voltammograms of surface-confined azurin.

    Science.gov (United States)

    Zhang, Jie; Guo, Si-Xuan; Bond, Alan M; Honeychurch, Michael J; Oldham, Keith B

    2005-05-12

    Fourier transform analysis of ramped square-wave voltammograms indicates the availability of a novel form of kinetic selectivity for surface-confined electron-transfer processes. Thus, for all the even harmonic components, quasi-reversible processes are sensitive to the surface coverage, the reversible potential, the electron-transfer rate constant (k(0')), and the electron-transfer coefficient (alpha), as well as to the amplitude (DeltaE) and frequency (f) of the square wave and dc scan rate. Additionally, it is insensitive to background capacitance current. In contrast, reversible processes and background currents are predicted to be absent from the even harmonics and only detectable in the odd harmonic components. The square-wave voltammetry of the surface-confined quasi-reversible azurin process azurin[Cu(II)] + e(-) right arrow over left arrow azurin[Cu(I)] at a paraffin-impregnated graphite electrode has been employed as a model system to test theoretical predictions. Most voltammetric characteristics of the even harmonic components obtained from the Fourier analysis are consistent with electrode kinetic values of k(0') = 90 s(-1) and alpha = 0.48, although some nonideality possibly due to kinetic dispersion also is apparent. Conditions also have been determined under which a readily generated waveform constructed from the Fourier series of sine waves produces voltammograms that are essentially indistinguishable from those predicted when an ideal square wave is employed.

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

    Science.gov (United States)

    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.

  9. Application of Modified Red Mud for Adsorption of Acid Orange 7 (AO7 Dye from Aqueous Solution: Isotherms, Kinetics Studies

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Zazouli

    2015-09-01

    Full Text Available Application of modified red mud for adsorption of Acid Orang 7 (AO7 dye from aqueous solution: Isotherms, Kinetics studies Abstract: Backgroud: Existence of color is one of the problems of industrial effluent such as textile industries. The dyes can be removed by various methods. Therefore, the aim of this study is evaluation of adsorption rate of acid orange (AO7 from aqueous solution by activated red mud. Material and method: This is an empirical lab study. Red mud was used as an absorbent to remove of acid orange 7 dye. The effect of various parameters on performance of absorbent was investigated and the isotherms and kinetics of adsorption was determined. The dye concentration was measured in wavelength of 452 nm by spectrophotometer. Results: The results showed that red mud surface area is 30 m2/g. The results showed that dye removal was highest at a solution pH 3 and a powder dose of 12 g/L. The AO7 removal percentage decreased from %98 to %55 at 60 min contact time when the concentration of dye was increased from 10 mg/L to 100 mg/L. The equilibrium data is best fitted on Langmuir isotherm and the adsorption kinetic model follows pseudo-second model. conclusion: The results of this study showed that red mud is able to adsorption of dye and can be used as effective and inexpensive absorbent to treat of textile effluent.

  10. The Kinetic Aspects of the Interaction of Nitrite Ions with Sulfanilic Acid and 1-Naphthylamine in Aqueous and Micellar Media

    Science.gov (United States)

    Korneeva, O. I.; Chernova, R. K.; Doronin, S. Yu.

    2008-04-01

    The kinetics of the reaction of nitrite ions with sulfanilic acid and 1-naphthylamine in aqueous and micellar (sodium dodecyl sulfate) media was studied step-by-step. The diazotization of sulfanilic acid with the nitrite ion was found to occur virtually instantaneously. Anionic surfactant micelles did not influence the rate of this reaction. The calculated effective rate constants and activation energies of the azo coupling reaction between synthesized sulfophenyldiazonium and 1-naphthylamine showed that the passage from water into the micellar medium decelerated the reaction. It was found that sodium dodecyl sulfate micelles played the role of a reagent separator.

  11. Effect of Temperature and pH on Formulating the Kinetic Growth Parameters and Lactic Acid Production of Lactobacillus bulgaricus

    Directory of Open Access Journals (Sweden)

    Marzieh Aghababaie

    2014-09-01

    Results: Second order model for Xmax, μmax, P and K was significant but product formation parameters were almost constant. The optimum values of temperature and pH for attaining maximum biomass, maximum specific growth rate, and maximum acid production were obtained at 44 °C and 5.7, respectively. Conclusions: The attained empirical mathematical correlations of RSM alongside the kinetic equations could be used to determine growth conditions under predefined temperature and pH in the fermentation process. Keywords: Lactobacillus bulgaricus, Richards model, Response surface methodology, Lactic acid production, Luedeking-Piret model

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

    Institute of Scientific and Technical Information of China (English)

    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 .

  13. Kinetic parameters of oscillating reaction of amino acid-BrO-3-Mn2+-H2SO4-acetone system

    Institute of Scientific and Technical Information of China (English)

    LI Zongxiao; YUAN Chunlan; NIE Fei

    2005-01-01

    The oscillating behavior of thirteen amino acids [leucine (Leu), threonine (Thr), arginine (Arg), lysine (Lys), histidine (His), alanine (Ala), glutamine (Glu), glycine (Gly), methionine (Met), cystine (Cys), tryptophan (Trp), serine (Ser) and tyrosine (Tyr)] in amino acid--Mn2+-H2SO4-acetone system is studied by using a potentiometric determination. With the help of the oscillatory induction period and oscillation period obtained by the oscillating wave, and Arrhenius equation, the kinetic parameters [the apparent activation energy (E) and pre-exponential constant (A)] and rate constant (k) of the above-mentioned oscillating reaction are estimated.

  14. Reaction kinetics and critical phenomena: iodination of acetone in isobutyric acid + water near the consolute point.

    Science.gov (United States)

    Hu, Baichuan; Baird, James K

    2010-01-14

    The rate of iodination of acetone has been measured as a function of temperature in the binary solvent isobutyric acid (IBA) + water near the upper consolute point. The reaction mixture was prepared by the addition of acetone, iodine, and potassium iodide to IBA + water at its critical composition of 38.8 mass % IBA. The value of the critical temperature determined immediately after mixing was 25.43 degrees C. Aliquots were extracted from the mixture at regular intervals in order to follow the time course of the reaction. After dilution of the aliquot with water to quench the reaction, the concentration of triiodide ion was determined by the measurement of the optical density at a wavelength of 565 nm. These measurements showed that the kinetics were zeroth order. When at the end of 24 h the reaction had come to equilibrium, the critical temperature was determined again and found to be 24.83 degrees C. An Arrhenius plot of the temperature dependence of the observed rate constant, k(obs), was linear over the temperature range 27.00-38.00 degrees C, but between 25.43 and 27.00 degrees C, the values of k(obs) fell below the extrapolation of the Arrhenius line. This behavior is evidence in support of critical slowing down. Our experimental method and results are significant in three ways: (1) In contrast to in situ measurements of optical density, the determination of the optical density of diluted aliquots avoided any interference from critical opalescence. (2) The measured reaction rate exhibited critical slowing down. (3) The rate law was pseudo zeroth order both inside and outside the critical region, indicating that the reaction mechanism was unaffected by the presence of the critical point.

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

    Institute of Scientific and Technical Information of China (English)

    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.

  16. ω-Amino Acid:Pyruvate Transaminase from Alcaligenes denitrificans Y2k-2: a New Catalyst for Kinetic Resolution of β-Amino Acids and Amines

    OpenAIRE

    Yun, Hyungdon; Lim, Seongyop; Cho, Byung-Kwan; Kim, Byung-Gee

    2004-01-01

    Alcaligenes denitrificans Y2k-2 was obtained by selective enrichment followed by screening from soil samples, which showed ω-amino acid:pyruvate transaminase activity, to kinetically resolve aliphatic β-amino acid, and the corresponding structural gene (aptA) was cloned. The gene was functionally expressed in Escherichia coli BL21 by using an isopropyl-β-d-thiogalactopyranoside (IPTG)-inducible pET expression system (9.6 U/mg), and the recombinant AptA was purified to show a specific activity...

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

    NARCIS (Netherlands)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Hlawiczka, Stanislaw [Institute for Ecology of Industrial Areas, Katowice (Poland); Department of Environmental Protection and Engineering, Technical University of Czestochowa, Czestochowa (Poland); Korszun, Katarzyna [Institute for Ecology of Industrial Areas, Katowice (Poland)

    2012-07-15

    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{sup +}, K{sup +}, Mg{sup 2+}, Ca{sup 2+}, SO{sub 4}{sup 2-}, NO{sub 3}{sup -}, Cl{sup -}, and NH{sub 4}{sup +} 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)

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

    Science.gov (United States)

    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.

  20. Quinic acid is a biologically active component of the Uncaria tomentosa extract C-Med 100.

    Science.gov (United States)

    Akesson, Christina; Lindgren, Hanna; Pero, Ronald W; Leanderson, Tomas; Ivars, Fredrik

    2005-01-01

    We have previously reported that the C-Med 100 extract of the plant Uncaria tomentosa induces prolonged lymphocyte half life and hence increased spleen cell number in mice receiving the extract in their drinking water. Further, the extract induces cell proliferation arrest and inhibits activation of the transcriptional regulator nuclear factor kappaB (NF-kappaB) in vitro. We now report that mice exposed to quinic acid (QA), a component of this extract, had significantly increased number of spleen cells, thus recapitulating the in vivo biological effect of C-Med 100 exposure. Commercially supplied QA (H(+) form) did not, however, inhibit cell proliferation in vitro, while the ammonia-treated QA (QAA) was a potent inhibitor. Both QA and QAA inhibited NF-kappaB activity in exposed cells at similar concentrations. Thus, our present data identify QA as a candidate component for both in vivo and in vitro biological effects of the C-Med 100 extract.

  1. Effects of intravenous solutions on acid-base equilibrium: from crystalloids to colloids and blood components.

    Science.gov (United States)

    Langer, Thomas; Ferrari, Michele; Zazzeron, Luca; Gattinoni, Luciano; Caironi, Pietro

    2014-01-01

    Intravenous fluid administration is a medical intervention performed worldwide on a daily basis. Nevertheless, only a few physicians are aware of the characteristics of intravenous fluids and their possible effects on plasma acid-base equilibrium. According to Stewart's theory, pH is independently regulated by three variables: partial pressure of carbon dioxide, strong ion difference (SID), and total amount of weak acids (ATOT). When fluids are infused, plasma SID and ATOT tend toward the SID and ATOT of the administered fluid. Depending on their composition, fluids can therefore lower, increase, or leave pH unchanged. As a general rule, crystalloids having a SID greater than plasma bicarbonate concentration (HCO₃-) cause an increase in plasma pH (alkalosis), those having a SID lower than HCO₃- cause a decrease in plasma pH (acidosis), while crystalloids with a SID equal to HCO₃- leave pH unchanged, regardless of the extent of the dilution. Colloids and blood components are composed of a crystalloid solution as solvent, and the abovementioned rules partially hold true also for these fluids. The scenario is however complicated by the possible presence of weak anions (albumin, phosphates and gelatins) and their effect on plasma pH. The present manuscript summarises the characteristics of crystalloids, colloids, buffer solutions and blood components and reviews their effect on acid-base equilibrium. Understanding the composition of intravenous fluids, along with the application of simple physicochemical rules best described by Stewart's approach, are pivotal steps to fully elucidate and predict alterations of plasma acid-base equilibrium induced by fluid therapy.

  2. Decoupling the contribution of dispersive and acid-base components of surface energy on the cohesion of pharmaceutical powders.

    Science.gov (United States)

    Shah, Umang V; Olusanmi, Dolapo; Narang, Ajit S; Hussain, Munir A; Tobyn, Michael J; Heng, Jerry Y Y

    2014-11-20

    This study reports an experimental approach to determine the contribution from two different components of surface energy on cohesion. A method to tailor the surface chemistry of mefenamic acid via silanization is established and the role of surface energy on cohesion is investigated. Silanization was used as a method to functionalize mefenamic acid surfaces with four different functional end groups resulting in an ascending order of the dispersive component of surface energy. Furthermore, four haloalkane functional end groups were grafted on to the surface of mefenamic acid, resulting in varying levels of acid-base component of surface energy, while maintaining constant dispersive component of surface energy. A proportional increase in cohesion was observed with increases in both dispersive as well as acid-base components of surface energy. Contributions from dispersive and acid-base surface energy on cohesion were determined using an iterative approach. Due to the contribution from acid-base surface energy, cohesion was found to increase ∼11.7× compared to the contribution from dispersive surface energy. Here, we provide an approach to deconvolute the contribution from two different components of surface energy on cohesion, which has the potential of predicting powder flow behavior and ultimately controlling powder cohesion.

  3. The kinetics of photocatalytic degradation of aliphatic carboxylic acids in an UV/TiO2 suspension system.

    Science.gov (United States)

    Chen, Q; Song, J M; Pan, F; Xia, F L; Yuan, J Y

    2009-10-01

    Kinetic studies on the photocatalytic degradation of aliphatic carboxylic acids were carried out in a slurry photoreactor with in-situ monitoring, employing artificial UV light as the source of energy and nano-TiO2 powder as the catalyst. The influences on the photocatalytic degradation such as the initial concentration of reactant (C0), catalyst dosage (CTiO2), UV intensity (Ia) and pH value have been investigated. Good agreement has been obtained between the value calculated by Langmuir-Freundlich-Hinshelwood (L-F-H) model and experimental data, with coefficient of multiple determination (R2) varying from 0.880 to 0.999. The L-F-H model has been proven to be feasible in describing the kinetic characteristic of the photocatalytic degradation of aliphatic carboxylic acids. Moreover, the apparent reaction rate constant (k) of the photocatalytic degradation of dicarboxylic acids is higher than that of monocarboxylic acids with the same carbon atoms. This shows that the photocatalytic degradation rate is favoured by different chemical structure.

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Borowiak-Resterna, Aleksandra [Institute of Chemical Technology and Engineering, Poznan University of Technology, Pl. Marii Sklodowskiej-Curie 2, 60-965 Poznan (Poland); Cierpiszewski, Ryszard [Poznan University of Economics, Faculty of Commodity Science, al. Niepodleglosci 10, 61-875 Poznan (Poland); Prochaska, Krystyna, E-mail: Krystyna.Prochaska@put.poznan.pl [Institute of Chemical Technology and Engineering, Poznan University of Technology, Pl. Marii Sklodowskiej-Curie 2, 60-965 Poznan (Poland)

    2010-07-15

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

  7. Discrimination and evaluation of the effects of uncompensated resistance and slow electrode kinetics from the higher harmonic components of a fourier transformed large-amplitude alternating current voltammogram.

    Science.gov (United States)

    Zhang, Jie; Guo, Si-Xuan; Bond, Alan M

    2007-03-15

    The influence of uncompensated resistance (also called the IRu effect, where I is current and Ru is uncompensated resistance) and slow electrode kinetics have been assessed for the dc and first five ac harmonics derived from Fourier transformed large-amplitude ac voltammetry. Resistance and rate constant conditions emphasized correspond to those where separation of effects attributable to either parameter is essentially impossible under conditions of dc cyclic voltammetry. Results derived from simulations and experiments demonstrate that it is relatively easy to discriminate and quantify contributions from these two effects over a wide range of values using the fourth and fifth harmonic ac components derived from single large-amplitude ac voltammetric measurement. Furthermore, these ac components also are essentially devoid of background charging current. Concepts developed initially from simulations are confirmed by experimental studies on the following: (a) the oxidation of ferrocene, in moderately resistive CH3CN and highly resistive CH2Cl2 (represents examples of IRu effect on a reversible electron-transfer process); (b) the reduction of a low 0.2 mM concentration of [Fe(CN)6]3- in the highly conductive 3 M KCl electrolyte media (case of slow kinetics with negligible IRu effect); (c) and reduction of a high 10 mM concentration of [Fe(CN)6]3- in less conductive aqueous 0.5 M KCl electrolyte media (example where the simultaneous effects of both IRu and slow kinetics need to be resolved).

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

    Science.gov (United States)

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

    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.

  9. Kinetics of extracting phosphoric acid and sulfuric acid in composite system%复合体系下磷酸和硫酸的萃取动力学

    Institute of Scientific and Technical Information of China (English)

    张莉; 丁瑶; 刘玉娟

    2012-01-01

    In order to deeply understand the mechanism and dynamic characteristics under the extraction process, the extraction kinetics of phosphoric acid and sulfuric acid was investigated by using constant-interface cell in the composite system. The effects of specific interfacial area, the concentration of phosphoric acid in the optimum extraction conditions and the concentration of sulfuric acid in the optimum extraction conditions on the extraction rate of phosphoric acid and sulfuric acid were reviewed. The kinetic equation of the extraction of phosphoric acid and sulfuric acid was put forward in the sulfuric acid-phosphoric acid system at 60 ℃. The results show that the extraction rate of phosphoric acid and sulfuric acid decreases with the increase of specific interfacial area, and increases with the increase of the initial concentration of phosphate in the aqueous phase gradually. With increasing the initial concentration of sulfuric acid in the aqueous phase, the extraction rate of phosphate is improved. The raw industrial phosphoric acid was used to verify the acid extraction kinetics. The result reveals that the extraction rates of the calculated values agree with the measured values of sulfuric acid and phosphoric acid.%为了深入了解萃取过程的机理和动力学特征,采用了恒界面池法研究了复合体系下磷酸和硫酸的萃取动力学,分别考察了比界面积、初始水相中磷酸浓度、初始水相中硫酸浓度对磷酸、硫酸萃取速率的影响,并提出了60℃下硫酸-磷酸复合体系中萃取磷酸和硫酸的动力学方程.实验结果表明:磷酸和硫酸的萃取速率随着比界面积增大而减小,随着初始水相中磷酸浓度的升高而逐步增加;初始水相中硫酸浓度的增大也有利于提高磷酸和硫酸的萃取速率.并研究了在60℃硫酸-磷酸复合体系中,磷酸和硫酸的萃取动力学方程,并用工业原料磷酸对萃取动力学进行了验证,

  10. Photocatalytic degradation kinetics of naphthenic acids in oil sands process-affected water: Multifactorial determination of significant factors.

    Science.gov (United States)

    Leshuk, Tim; de Oliveira Livera, Diogo; Peru, Kerry M; Headley, John V; Vijayaraghavan, Sucharita; Wong, Timothy; Gu, Frank

    2016-12-01

    Oil sands process-affected water (OSPW) is generated as a byproduct of bitumen extraction in Canada's oil sands. Due to the water's toxicity, associated with dissolved acid extractable organics (AEO), especially naphthenic acids (NAs), along with base-neutral organics, OSPW may require treatment to enable safe discharge to the environment. Heterogeneous photocatalysis is a promising advanced oxidation process (AOP) for OSPW remediation, however, predicting treatment efficacy can be challenging due to the unique water chemistry of OSPW from different tailings ponds. The objective of this work was to study various factors affecting the kinetics of photocatalytic AEO degradation in OSPW. The rate of photocatalytic treatment varied significantly in two different OSPW sources, which could not be accounted for by differences in AEO composition, as studied by high resolution mass spectrometry (HRMS). The effects of inorganic water constituents were investigated using factorial and response surface experiments, which revealed that hydroxyl (HO) radical scavenging by iron (Fe(3+)) and bicarbonate (HCO3(-)) inhibited the NA degradation rate. The effects of NA concentration and temperature on the treatment kinetics were also evaluated in terms of Langmuir-Hinshelwood and Arrhenius models; pH and temperature were identified as weak factors, while dissolved oxygen (DO) was critical to the photo-oxidation reaction. Accounting for all of these variables, a general empirical kinetic expression is proposed, enabling prediction of photocatalytic treatment performance in diverse sources of OSPW.

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

    NARCIS (Netherlands)

    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.

  12. Effects of acetic acid on the kinetics of xylose fermentation by an engineered, xylose-isomerase-based Saccharomyces cerevisiae strain.

    Science.gov (United States)

    Bellissimi, Eleonora; van Dijken, Johannes P; Pronk, Jack T; van Maris, Antonius J A

    2009-05-01

    Acetic acid, an inhibitor released during hydrolysis of lignocellulosic feedstocks, has previously been shown to negatively affect the kinetics and stoichiometry of sugar fermentation by (engineered) Saccharomyces cerevisiae strains. This study investigates the effects of acetic acid on S. cerevisiae RWB 218, an engineered xylose-fermenting strain based on the Piromyces XylA (xylose isomerase) gene. Anaerobic batch cultures on synthetic medium supplemented with glucose-xylose mixtures were grown at pH 5 and 3.5, with and without addition of 3 g L(-1) acetic acid. In these cultures, consumption of the sugar mixtures followed a diauxic pattern. At pH 5, acetic acid addition caused increased glucose consumption rates, whereas specific xylose consumption rates were not significantly affected. In contrast, at pH 3.5 acetic acid had a strong and specific negative impact on xylose consumption rates, which, after glucose depletion, slowed down dramatically, leaving 50% of the xylose unused after 48 h of fermentation. Xylitol production was absent (fermentation in acetic -acid-stressed cultures at pH 3.5 could be restored by applying a continuous, limiting glucose feed, consistent with a key role of ATP regeneration in acetic acid tolerance.

  13. Nutritional value of protein hydrolysis products (oligopeptides and free amino acids) as a consequence of absorption and metabolism kinetics

    Science.gov (United States)

    Rerat, A.

    1995-01-01

    When pigs were submitted to duodenal infusion of solutions containing a large percentage of small peptides (PEP) or free amino acids with the same pattern (AAL) amino acids appear in the portal blood more rapidly and more uniformly after infusion of PEP then after infusion of AAL, with the notable exception of methionine for which the opposite was true. These differences were lowered when a carbohydrate (maltose dextrin) was present in the solution, but nevertheless remained significant for the first hour after the infusion. The long-term (8-hour) uptake of free amino acids into the liver and the peripheral tissues differed in profile according to the nature of the duodenal infusion. Peripheral uptake was appreciably less well balanced after infusion of free amino acids (deficiency of threonine and phenylalanine) than after infusion of small peptides (deficiency of methionine). Accordingly, in the rat, under conditions of discontinuous enteral nutrition the mixture of small peptides was of greater nutritive value than the mixture of free amino acids. It thus appears that the absorption kinetics which results in important variations in the temporal distribution of free amino acids in the tissues may be at the origin of transitory imbalances in tissue amino acid uptake, and as a result of a lower nutritive value.

  14. Kinetic analysis of strains of lactic acid bacteria and acetic acid bacteria in cocoa pulp simulation media toward development of a starter culture for cocoa bean fermentation.

    Science.gov (United States)

    Lefeber, Timothy; Janssens, Maarten; Camu, Nicholas; De Vuyst, Luc

    2010-12-01

    The composition of cocoa pulp simulation media (PSM) was optimized with species-specific strains of lactic acid bacteria (PSM-LAB) and acetic acid bacteria (PSM-AAB). Also, laboratory fermentations were carried out in PSM to investigate growth and metabolite production of strains of Lactobacillus plantarum and Lactobacillus fermentum and of Acetobacter pasteurianus isolated from Ghanaian cocoa bean heap fermentations, in view of the development of a defined starter culture. In a first step, a selection of strains was made out of a pool of strains of these LAB and AAB species, obtained from previous studies, based on their fermentation kinetics in PSM. Also, various concentrations of citric acid in the presence of glucose and/or fructose (PSM-LAB) and of lactic acid in the presence of ethanol (PSM-AAB) were tested. These data could explain the competitiveness of particular cocoa-specific strains, namely, L. plantarum 80 (homolactic and acid tolerant), L. fermentum 222 (heterolactic, citric acid fermenting, mannitol producing, and less acid tolerant), and A. pasteurianus 386B (ethanol and lactic acid oxidizing, acetic acid overoxidizing, acid tolerant, and moderately heat tolerant), during the natural cocoa bean fermentation process. For instance, it turned out that the capacity to use citric acid, which was exhibited by L. fermentum 222, is of the utmost importance. Also, the formation of mannitol was dependent not only on the LAB strain but also on environmental conditions. A mixture of L. plantarum 80, L. fermentum 222, and A. pasteurianus 386B can now be considered a mixed-strain starter culture for better controlled and more reliable cocoa bean fermentation processes.

  15. Synthesis, molecular docking and kinetic properties of β-hydroxy-β-phenylpropionyl-hydroxamic acids as Helicobacter pylori urease inhibitors.

    Science.gov (United States)

    Xiao, Zhu-Ping; Peng, Zhi-Yun; Dong, Jing-Jun; Deng, Rui-Cheng; Wang, Xu-Dong; Ouyang, Hui; Yang, Pan; He, Juan; Wang, Yuan-Feng; Zhu, Man; Peng, Xiao-Chun; Peng, Wan-Xi; Zhu, Hai-Liang

    2013-10-01

    Inhibition of urease results in Helicobacter pylori growth arrest in the stomach, promoting urease as promising targets for gastrointestinal ulcer therapy. Twenty hybrid derivatives of flavonoid scaffold and hydroxamic acid, β-hydroxy-β-phenylpropionylhydroxamic acids, were therefore synthesized and evaluated against H. pylori urease. Biological evaluation of these compounds showed improved urease inhibition exhibiting micromolar to mid-nanomolar IC50 values. Most importantly, 3-(3-chlorophenyl)-3-hydroxypropionyl-hydroxamic acid (6g) exhibited high potency with IC50 of 0.083±0.004 μM and Ki of 0.014±0.003 μM, indicating that 6g is an excellent candidate to develop novel antiulcer agent. A mixture of competitive and uncompetitive mechanism was putatively proposed to understand the inconsistency between the crystallographic and kinetic studies for the first time, which is supported by our molecular docking studies.

  16. Nitrogen removal of ramie stalk treated by acid wastewater combined with Clostridium thermocellum and the kinetic study of pyrolysis.

    Science.gov (United States)

    Wang, Buyun; Li, Ting; Zhu, Ning; Xiao, Bo

    2013-02-01

    A pretreatment was developed to remove nitrogen from ramie residue and cotton stalk to eliminate potential nitrogen pollutants in biomass energy production. In the pretreatment, straw was treated with acid wastewater from bioleaching for 3 h followed by Clostridium thermocellum incubation for 2 h. Most nitrogen was removed from biomass waste and the major was that in protein. Pyrolysis process revealed most hemicellulose was removed and the kinetics fitted the first-order equation well. Apparent activation energy of ramie residue increased a little and mass loss became concentrated. Ultimate analysis and pyrolysis analysis revealed the treatment did not weaken the application value of biomass in energy production. Replacing acid wastewater with sulphuric acid, a higher nitrogen removal could be achieved; however, activation energy increased sharply.

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

    Science.gov (United States)

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

    2016-05-05

    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.

  18. Oleic acid is a key cytotoxic component of HAMLET-like complexes.

    Science.gov (United States)

    Permyakov, Sergei E; Knyazeva, Ekaterina L; Khasanova, Leysan M; Fadeev, Roman S; Zhadan, Andrei P; Roche-Hakansson, Hazeline; Håkansson, Anders P; Akatov, Vladimir S; Permyakov, Eugene A

    2012-01-01

    HAMLET is a complex of α-lactalbumin (α-LA) with oleic acid (OA) that selectively kills tumor cells and Streptococcus pneumoniae. To assess the contribution of the proteinaceous component to cytotoxicity of HAMLET, OA complexes with proteins structurally and functionally distinct from α-LA were prepared. Similar to HAMLET, the OA complexes with bovine β-lactoglobulin (bLG) and pike parvalbumin (pPA) (bLG-OA-45 and pPA-OA-45, respectively) induced S. pneumoniae D39 cell death. The activation mechanisms of S. pneumoniae death for these complexes were analogous to those for HAMLET, and the cytotoxicity of the complexes increased with OA content in the preparations. The half-maximal inhibitory concentration for HEp-2 cells linearly decreased with rise in OA content in the preparations, and OA concentration in the preparations causing HEp-2 cell death was close to the cytotoxicity of OA alone. Hence, the cytotoxic action of these complexes against HEp-2 cells is induced mostly by OA. Thermal stabilization of bLG upon association with OA implies that cytotoxicity of bLG-OA-45 complex cannot be ascribed to molten globule-like conformation of the protein component. Overall, the proteinaceous component of HAMLET-like complexes studied is not a prerequisite for their activity; the cytotoxicity of these complexes is mostly due to the action of OA.

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

    Institute of Scientific and Technical Information of China (English)

    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.

  20. Kinetics and Mechanism of the Oxidation of Naphthol Green B by Peroxydisulphate Ion in Aqueous Acidic Medium

    Directory of Open Access Journals (Sweden)

    B. Myek

    2014-01-01

    Full Text Available The kinetics of the oxidation of naphthol green B (NGB3− by peroxydisulphate ion has been carried out in aqueous acidic medium at λmax of 700 nm, T=23±1°C, and I=0.50 mol dm−3 (NaCl. The reaction shows a first-order dependence on oxidant and reductant concentration, respectively. The stoichiometry of the NGB—S2O82- reaction is 1 : 2. Change in hydrogen ions concentration of the reaction medium has no effect on the rate of the reaction. Added cations and anions decreased the rate of the reaction. The results of spectroscopic and kinetic investigation indicate that no intermediate complex is probably formed in the course of this reaction.

  1. Kinetic studies on the formation of nitrosamines I. Formation of dimethylnitrosamine in aqeous solution of perchloric acid.

    Science.gov (United States)

    Cachaza, J M; Casado, J; Castro, A; López Quintela, M A

    1978-01-01

    The kinetics of nitrosation of dimethylamine (DMA) in aqueous perchloric acid solution have been studied using a differential spectrophotometric technique. The rate law is Initial rate = e[DMA]0 [nitrite]2 0 [H+]/(f + [H+])2 where [DMA]0 and [nitrite]0 represent initial stoichiometric concentrations. At 310.0 K and mu = 2.0 M, e = (2.2 +/- 0.2) X 10(-5) M-1 s-1 and f = (1.28 +/- 0.02) X 10(-3) M. The associated activation energy is 56 +/- 3 kJ mol-1. A clear inhibition of the nitrosation rate by ionic strength has been observed in which only the kinetic parameter (f) has an effective change. It is concluded that under the experimental conditions of this work only the dinitrogen trioxid is the effective carrier for the nitrosation.

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Science.gov (United States)

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

    2014-04-07

    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.

  4. Quantitative amino acid profiling and stable isotopically labeled amino acid tracer enrichment used for in vivo human systemic and tissue kinetics measurements.

    Science.gov (United States)

    Bornø, Andreas; van Hall, Gerrit

    2014-03-01

    An important area within clinical functional metabolomics is in vivo amino acid metabolism and protein turnover measurements for which accurate amino acid concentrations and stable isotopically labeled amino acid enrichments are mandatory not the least when tissue metabolomics is determined. The present study describes a new sensitive liquid chromatography tandem mass-spectrometry method quantifying 20 amino acids and their tracer(s) ([ring-(13)C6]/D5Phenylalanine) in human plasma and skeletal muscle specimens. Before analysis amino acids were extracted and purified via deprotonization/ion exchange, derivatized using a phenylisothiocyanate reagent and each amino acid was quantitated with its own stable isotopically labeled internal standard (uniformly labeled-(13)C/(15)N). The method was validated according to general recommendations for chromatographic analytical methods. The calibration curve correlations for amino acids were on average; r(2)=0.998. Interday accuracy for amino acids determined in spiked plasma was on average 97.3% and the coefficient of variation (CV) was 2.6%. The ([ring-(13)C6]/D5Phenylalanine) enrichment CV's for machine reproducibility in muscle tissue fluid and plasma were 4.4 and 0.8%, and the interday variability was 3.4% and the recovery was 90.5%, respectively. In conclusion, we have developed and validated a method for quantitative amino acid profiling that meets the requirements for systemic and tissue human in vivo amino acid and protein turnover 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.

  5. Breakdown kinetics of C-hydroxymethyl beta-dicarbonyl derivatives of carbon acids: implications in the bioconversion rate of C-phosphoryloxymethyl prodrugs of carbon acids.

    Science.gov (United States)

    Dhareshwar, Sundeep S; Stella, Valentino J

    2009-05-01

    The kinetics of conversion of C-hydroxymethyl derivatives of pharmaceutically relevant beta-dicarbonyl carbon acids of two series, pyrazolidin-3,5-diones and inden-1,3-diones, and a model carbon acid back to the respective carbon acids were studied as a function of pH at 25 degrees C and an ionic strength of 0.15 M. This is a somewhat surprising reaction since it involves the facile breakdown of a carbon-carbon bond. The slopes of the pH-rate profiles for the dehydroxymethylation were approximately unity, which along with the lack of buffer catalysis, indicates a specific-base mechanism involving spontaneous breakdown of the oxymethyl anion. This breakdown generates the conjugate base of the respective carbon acids. Thus within a series, there exists a correlation between the second-order rate constant for dehydroxymethylation and the pK(a) of the corresponding carbon acid with a shorter conversion/dehydroxymethylation half-life (at all given pH values) with decreasing pK(a) of the parent carbon acid. The increasing acidity of the carbon acid affords an increase in the leaving group ability of the carbanion, and therefore facilitation of the rate-determining unimolecular carbon-carbon bond cleavage. Since the hydroxymethyl derivative is an intermediate in the bioconversion of C-phosphoryloxymethyl prodrugs of carbon acids, also under study, the relationship allows one to reasonably predict how facile the dehydroxymethylation would be for any new beta-dicarbonyl carbon acid.

  6. 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

    Energy Technology Data Exchange (ETDEWEB)

    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.

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

    Science.gov (United States)

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

    2015-02-01

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

  8. Antimicrobial activity against Xanthomonas albilineans and fermentation kinetics of a lactic acid bacterium isolated from the sugar cane crop

    Directory of Open Access Journals (Sweden)

    Liliana Serna-Cock

    2013-09-01

    Full Text Available Xanthomonas albilineans is a pathogen that causes leaf scald disease in sugarcane (Saccharum officinarum L. This disease causes the death of seedlings and consequently results in economic losses for sugarcane growers. The objective of this work was to isolate a lactic acid bacterium with antimicrobial activity against X. albilineans from sugarcane crops and to evaluate its antimicrobial activity and its lactic acid production kinetics, biomass yield, and substrate consumption in three different fermentation substrates. To isolate the lactic acid bacterium, samples were collected from different parts of infected and non-infected sugarcane plants of var. CC85-92. Lactococcus lactis ssp. lactis was isolated from the leaves of healthy crops, and showed in vitro antimicrobial activity against the pathogen. Batch fermentations of this isolate (at 32 °C, agitation of 100 rpm, and pH 6 were performed using a commercial substrate (MRS, a commercial substrate supplemented with glucose (MRSG, and a substrate produced from agricultural crop residues (ACR. The highest antimicrobial activity was 5.83 mm in the ACR substrate after 6 h of fermentation. The maximum biomass production of 3.37 g L-1 and the maximum lactic acid production of 12.1 g L-1 were obtained in the MRSG substrate. The lactic acid production did not show any significant differences between the substrates. This lactic acid bacterium showed antimicrobial activity against X. albilineans and is thus a biological alternative for the control of leaf scald disease in sugarcane.

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

    Institute of Scientific and Technical Information of China (English)

    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%.

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

    Indian Academy of Sciences (India)

    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.

  11. Kinetics of 12-Hydroxyoctadecanoic Acid SAFiN Crystallization Rationalized Using Hansen Solubility Parameters.

    Science.gov (United States)

    Rogers, Michael A; Marangoni, Alejandro G

    2016-12-06

    Changes in solvent chemistry influenced kinetics of both nucleation and crystallization of 12-hydroxyoctadecenoic, as determined using differential scanning calorimetry and applying a modified Avrami model to the calorimetric data. Altering solvent properties influenced solvent-gelator compatibility, which in turn altered the chemical potential of the system at the onset of crystallization, the kinetics of gelation, and the resulting 12HOA crystal fiber length. The chemical potential at the onset of crystallization was linearly correlated to both the hydrogen-bonding Hansen solubility parameter and the solvent-gelator vectorial distance in Hansen space, Ra. Our work suggests that solvent properties can be modulated to affect the solubility of 12HOA, which in turn influences the kinetics of crystallization and the self-assembly of this organogelator into supramolecular crystalline structures. Therefore, modulation of solvent properties during organogelation can be used to control fiber length and thus engineer the physical properties of the gel.

  12. Enzymatic saccharification of acid pretreated corn stover: Empirical and fractal kinetic modelling.

    Science.gov (United States)

    Wojtusik, Mateusz; Zurita, Mauricio; Villar, Juan C; Ladero, Miguel; Garcia-Ochoa, Felix

    2016-11-01

    Enzymatic hydrolysis of corn stover was studied at agitation speeds from 50 to 500rpm in a stirred tank bioreactor, at high solid concentrations (20% w/w dry solid/suspension), 50°C and 15.5mgprotein·gglucane(-1). Two empirical kinetic models have been fitted to empirical data, namely: a potential model and a fractal one. For the former case, the global order dramatically decreases from 13 to 2 as agitation speed increases, suggesting an increment in the access of enzymes to cellulose in terms of chemisorption followed by hydrolysis. For its part, the fractal kinetic model fits better to data, showing its kinetic constant a constant augmentation with increasing agitation speed up to a constant value at 250rpm and above, when mass transfer limitations are overcome. In contrast, the fractal exponent decreases with rising agitation speed till circa 0.19, suggesting higher accessibility of enzymes to the substrate.

  13. Enzymatic dynamic kinetic resolution of racemic N-formyl- and N-carbamoyl-amino acids using immobilized L-N-carbamoylase and N-succinyl-amino acid racemase.

    Science.gov (United States)

    Soriano-Maldonado, Pablo; Las Heras-Vazquez, Francisco Javier; Clemente-Jimenez, Josefa María; Rodriguez-Vico, Felipe; Martínez-Rodríguez, Sergio

    2015-01-01

    Taking advantage of the catalytic promiscuity of L-carbamoylase from Geobacillus stearothermophilus CECT43 (BsLcar) and N-succinyl-amino acid racemase from Geobacillus kaustophilus CECT4264 (GkNSAAR), we have evaluated the production of different optically pure L-α-amino acids starting from different racemic N-formyl- and N-carbamoyl-amino acids using a dynamic kinetic resolution approach. The enzymes were immobilized on two different solid supports, resulting in improved stability of the enzymes in terms of thermostability and storage when compared to the enzymes in solution. The bienzymatic system retained up to 80% conversion efficiency after 20 weeks at 4 °C and up to 90% after 1 week at 45 °C. The immobilization process also resulted in a great enhancement of the activity of BsLcar toward N-formyl-tryptophan, showing for the first time that substrate specificity of L-carbamoylases can be influenced by this approach. The system was effective for the biosynthesis of natural and unnatural L-amino acids (enantiomeric excess (e.e.) >99.5%), such as L-methionine, L-alanine, L-tryptophan, L-homophenylalanine, L-aminobutyric acid, and L-norleucine, with a higher performance toward N-formyl-α-amino acid substrates. Biocatalyst reuse was studied, and after 10 reaction cycles, over 75% activity remained.

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

    Indian Academy of Sciences (India)

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

    2005-07-01

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

  15. Investigation Of The Hydrolysis Of Isocyanic Acid In Urea SCR: Catalyst Screening And Low-Temperature Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Piazzesi, G.; Elsener, M.; Kroecher, O.; Wokaun, A.

    2005-03-01

    Several oxide catalysts were tested for the hydrolysis of isocyanic acid under typical diesel exhaust conditions. Among the tested catalysts, TiO{sub 2} and ZrO{sub 2} have been shown to be the most active catalysts. The kinetics of the HNCO hydrolysis over TiO{sub 2} at low temperatures was studied and reaction orders and the activation energy were determined. The effect of NO{sub 2} on the catalytic activity of TiO{sub 2} was also investigated, revealing that, at low temperatures, the formation of ammonium nitrate inhibits the reaction. (author)

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

    Science.gov (United States)

    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.

  17. Enduracididine, a rare amino acid component of peptide antibiotics: Natural products and synthesis

    Science.gov (United States)

    Atkinson, Darcy J; Naysmith, Briar J; Furkert, Daniel P

    2016-01-01

    Rising resistance to current clinical antibacterial agents is an imminent threat to global public health and highlights the demand for new lead compounds for drug discovery. One such potential lead compound, the peptide antibiotic teixobactin, was recently isolated from an uncultured bacterial source, and demonstrates remarkably high potency against a wide range of resistant pathogens without apparent development of resistance. A rare amino acid residue component of teixobactin, enduracididine, is only known to occur in a small number of natural products that also possess promising antibiotic activity. This review highlights the presence of enduracididine in natural products, its biosynthesis together with a review of analogues of enduracididine. Reported synthetic approaches to the cyclic guanidine structure of enduracididine are discussed, illustrating the challenges encountered to date in the development of efficient synthetic routes to facilitate drug discovery efforts inspired by the discovery of teixobactin. PMID:28144300

  18. Enduracididine, a rare amino acid component of peptide antibiotics: Natural products and synthesis

    Directory of Open Access Journals (Sweden)

    Darcy J. Atkinson

    2016-11-01

    Full Text Available Rising resistance to current clinical antibacterial agents is an imminent threat to global public health and highlights the demand for new lead compounds for drug discovery. One such potential lead compound, the peptide antibiotic teixobactin, was recently isolated from an uncultured bacterial source, and demonstrates remarkably high potency against a wide range of resistant pathogens without apparent development of resistance. A rare amino acid residue component of teixobactin, enduracididine, is only known to occur in a small number of natural products that also possess promising antibiotic activity. This review highlights the presence of enduracididine in natural products, its biosynthesis together with a review of analogues of enduracididine. Reported synthetic approaches to the cyclic guanidine structure of enduracididine are discussed, illustrating the challenges encountered to date in the development of efficient synthetic routes to facilitate drug discovery efforts inspired by the discovery of teixobactin.

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

    NARCIS (Netherlands)

    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. Poly(amic acid)s and their poly(amide imide) counterparts containing azobenzene moieties: Characterization, imidization kinetics and photochromic properties

    Energy Technology Data Exchange (ETDEWEB)

    Konieczkowska, Jolanta [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland); Institute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice (Poland); Janeczek, Henryk [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland); Kozanecka-Szmigiel, Anna, E-mail: annak@if.pw.edu.pl [Faculty of Physics, Warsaw University of Technology, 75 Koszykowa Str., 00-662 Warszawa (Poland); Schab-Balcerzak, Ewa, E-mail: eschab-balcerzak@cmpw-pan.edu.pl [Centre of Polymer and Carbon Materials, Polish Academy of Sciences, 34 M. Curie-Sklodowska Str., 41-819 Zabrze (Poland)

    2016-09-01

    We report on a series of novel photochromic poly(amide imide)s and their poly(amic acid) precursors bearing azobenzene chromophores as the side groups. The chemical structures of the polymers were designed so that they exhibited an enhanced thermal stability combined with a large and stable birefringence photogenerated by light of the wavelengths belonging to a wide spectral range. The polymers possessed rigidly attached azochromophores in the content of either one or two per a repeating unit, which in the latter case differed in their structures. The imidization kinetics of the poly(amic acid)s was investigated by differential scanning calorimetry and the kinetic parameters were estimated using Ozawa and Kissinger methods. Measurements of the selected physical properties of the polymers, such as solubility, supramolecular structure, linear absorption, thermal stability, glass transition and photochromic response were performed and used for determination of the structure-property relations. The measurements of photochromic properties showed a very efficient generation of optical anisotropy upon blue and violet irradiation, for both the poly(amide imide)s containing two different chromophores in the repeating unit and for their precursors. For these poly(amide imide)s and for their precursors an exceptionally slow decrease in the photoinduced optical anisotropy in the dark was also observed. - Highlights: • Three azopoly(amide imide)s were obtained from azopoly(amic acid)s. • Chosen physicochemical properties and photochromic responses were measured. • Desired optical response was found for polymers with two azo-dyes in repeating unit. • Structure-property relations were shown.

  1. Kinematic viscosity of biodiesel components (fatty acid alkyl esters) and related compounds at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Gerhard Knothe; Kevin R. Steidley [US Department of Agriculture, Peoria, IL (United States). National Center for Agricultural Utilization Research

    2007-11-15

    Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats is, has undergone rapid development and acceptance as an alternative diesel fuel. Kinematic viscosity is one of the fuel properties specified in biodiesel standards, with 40{sup o}C being the temperature at which this property is to be determined and ranges of acceptable kinematic viscosity given. While data on kinematic viscosity of biodiesel and related materials at higher temperatures are available in the literature, this work reports on the kinematic viscosity of biodiesel and a variety of fatty acid alkyl esters at temperatures from 40{sup o}C down to -10{sup o}C in increments of 5{sup o}C using the appropriately modified standard reference method ASTM D445. Investigating the low-temperature properties of biodiesel, including viscosity, of biodiesel and its components is important because of the problems associated with the use of biodiesel under these conditions. Such data may aid in developing biodiesel fuels optimized for fatty ester composition. An index termed here the low-temperature viscosity ratio (LTVR) using data at 0{sup o}C and 40{sup o}C (divide viscosity value at 0{sup o}C by viscosity value at 40{sup o}C) was used to evaluate individual compounds but also mixtures by their low-temperature viscosity behavior. Compounds tested included a variety of saturated, monounsaturated, diunsaturated and triunsaturated fatty esters, methyl ricinoleate, in which the OH group leads to a significant increase in viscosity as well as triolein, as well as some fatty alcohols and alkanes. Esters of oleic acid have the highest viscosity of all biodiesel components that are liquids at low temperatures. The behavior of blends of biodiesel and some fatty esters with a low-sulfur diesel fuel was also investigated. 28 refs., 3 figs., 10 tabs.

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

    DEFF Research Database (Denmark)

    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...

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

    Science.gov (United States)

    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...

  4. Nitro-fatty acid reaction with glutathione and cysteine. Kinetic analysis of thiol alkylation by a Michael addition reaction.

    Science.gov (United States)

    Baker, Laura M S; Baker, Paul R S; Golin-Bisello, Franca; Schopfer, Francisco J; Fink, Mitchell; Woodcock, Steven R; Branchaud, Bruce P; Radi, Rafael; Freeman, Bruce A

    2007-10-19

    Fatty acid nitration by nitric oxide-derived species yields electrophilic products that adduct protein thiols, inducing changes in protein function and distribution. Nitro-fatty acid adducts of protein and reduced glutathione (GSH) are detected in healthy human blood. Kinetic and mass spectrometric analyses reveal that nitroalkene derivatives of oleic acid (OA-NO2) and linoleic acid (LNO2) rapidly react with GSH and Cys via Michael addition reaction. Rates of OA-NO2 and LNO2 reaction with GSH, determined via stopped flow spectrophotometry, displayed second-order rate constants of 183 M(-1)S(-1) and 355 M(-1)S(-1), respectively, at pH 7.4 and 37 degrees C. These reaction rates are significantly greater than those for GSH reaction with hydrogen peroxide and non-nitrated electrophilic fatty acids including 8-iso-prostaglandin A2 and 15-deoxy-Delta(12,14)-prostaglandin J2. Increasing reaction pH from 7.4 to 8.9 enhanced apparent second-order rate constants for the thiol reaction with OA-NO2 and LNO2, showing dependence on the thiolate anion of GSH for reactivity. Rates of nitroalkene reaction with thiols decreased as the pKa of target thiols increased. Increasing concentrations of the detergent octyl-beta-d-glucopyranoside decreased rates of nitroalkene reaction with GSH, indicating that the organization of nitro-fatty acids into micellar or membrane structures can limit Michael reactivity with more polar nucleophilic targets. In aggregate, these results reveal that the reversible adduction of thiols by nitro-fatty acids is a mechanism for reversible post-translational regulation of protein function by nitro-fatty acids.

  5. Modification of the cellulosic component of hemp fibers using sulfonic acid derivatives: Surface and thermal characterization.

    Science.gov (United States)

    George, Michael; Mussone, Paolo G; Bressler, David C

    2015-12-10

    The aim of this study was to characterize the surface, morphological, and thermal properties of hemp fibers treated with two commercially available, inexpensive, and water soluble sulfonic acid derivatives. Specifically, the cellulosic component of the fibers were targeted, because cellulose is not easily removed during chemical treatment. These acids have the potential to selectively transform the surfaces of natural fibers for composite applications. The proposed method proceeds in the absence of conventional organic solvents and high reaction temperatures. Surface chemical composition and signature were measured using gravimetric analysis, X-ray photoelectron spectroscopy (XPS) and Fourier transform infra-red spectroscopy (FTIR). XPS data from the treated hemp fibers were characterized by measuring the reduction in O/C ratio and an increase in abundance of the C-C-O signature. FTIR confirmed the reaction with the emergence of peaks characteristic of disubstituted benzene and amino groups. Grafting of the sulfonic derivatives resulted in lower surface polarity. Thermogravimetric analysis revealed that treated fibers were characterized by lower percent degradation between 200 and 300 °C, and a higher initial degradation temperature.

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

    Institute of Scientific and Technical Information of China (English)

    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.

  7. Adsorption Kinetics of Acid Orange 7 on Nano-CeO2-TiO2 in Water.

    Science.gov (United States)

    Song, Xiaozhen; Zhao, Bin; Gu, Mingjie; Li, Ruixing

    2015-09-01

    To investigate the application of nano-CeO2-TiO2 as a sorbent in wastewater treatment, CeO2-TiO2 powder was prepared by the solvothermal method and then characterized. The adsorption kinetics of the adsorption of acid orange 7 (AO7) on CeO2-TiO2 were investigated under various conditions, such as initial concentration, temperature, and pH of the AO7 solution. Kinetic analyses were conducted with both Lagergren pseudo-first and pseudo-second order models. The results showed that the CeO2-TiO2 powder was composed of cubic CeO2 and anatase TiO2 with a specific surface area of 140.42 m2 x g(-1). The adsorption capacity of AO7 on CeO2-TiO2 increased with increasing starting concentration of AO7, but decreased with increasing temperature. The most favorable pH range of the A07 solution was 3-8 for the adsorption of AO7 on CeO2-TiO2. The results revealed that the adsorption kinetics of AO7 on CeO2-TiO2 matched the pseudo-second order model very well. The results indicate that CeO2-TiO2 has a potential application in the removal of AO7 from wastewater.

  8. Kinetics of the esterification of active pharmaceutical ingredients containing carboxylic acid functionality in polyethylene glycol: formulation implications.

    Science.gov (United States)

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

    2014-08-01

    Polyethylene glycols (PEGs) are attractive as excipients in the manufacture of drug products because they are water soluble and poorly immunogenic. They are used in various pharmaceutical preparations. However, because of their terminal hydroxyl groups, PEGs can participate in esterification 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, whereas HPLC-MS was used to identify reaction products. The esterification reactions were observed to be reversible. A second-order reversible kinetic model was applied and rate constants were determined. The rate constants demonstrated that cetirizine was esterified about 240 times faster than indomethacin at 80 °C. The shelf-life for cetirizine in a PEG 400 formulation at 25 °C expressed as t(95%) was predicted to be only 30 h. Further, rate constants for esterification of cetirizine in PEG 1000 in relation to PEG 400 decreased by a factor of 10, probably related to increased viscosity. However, it is important to be aware of this drug-excipient interaction, as it can reduce the shelf-life of a low-average molecular weight PEG formulation considerably.

  9. Science Letters:Evaluation of a kinetic uricase method for serum uric acid assay by predicting background absorbance of uricase reaction solution with an integrated method

    Institute of Scientific and Technical Information of China (English)

    LIAO Fei; ZHAO Yun-sheng; ZHAO Li-na; TAO Jia; ZHU Xiao-yun; LIU Lan

    2006-01-01

    A patented kinetic uricase method was evaluated for serum uric acid assay. Initial absorbance of the reaction mixture before uricase action (A0) was obtained by correcting the absorbance at 293 nm measured before the addition of uricase solution,and background absorbance (Ab) was predicted by an integrated method. Uric acid concentration in reaction solution was calculated from △A, the difference between A0 and Ab, using the absorptivity preset for uric acid. This kinetic uricase method exhibited CV<4.3% and recovery of 100%. Lipids, bilirubin, hemoglobin, ascorbic acid, reduced glutathione and xanthine <0.32 mmol/L in serum had no significant effects. △A linearly responded to 1.2 to 37.5 μmol/L uric acid in reaction solution containing 15 μl serum.The slope of linear response was consistent with the absorptivity preset for uric acid while the intercept was consistent with that for serum alone. Uric acid concentrations in clinic sera by different uricase methods positively correlated to each other. By Bland-Altman analysis, this kinetic uricase method accorded with that by quantifying the total change of UV absorbance on the completion of uricase reaction. These results demonstrated that this kinetic uricase method is reliable for serum uric acid assay with enhanced resistance to both xanthine and other common errors, wider range of linear response and much lower cost.

  10. Effect of micella interesterification on fatty acids composition and volatile components of soybean and rapeseed oils

    Directory of Open Access Journals (Sweden)

    Afifi, Sherine M.

    2000-10-01

    Full Text Available Micella interesterification of soybean and rapeseed oils was carried out using 0.2, 0.4 and 0.6 percentages of nickel catalyst, each at different temperatures of 60, 90 and 120ºC for 2, 4, and 6 hours. The proposed interesterification reaction conditions to obtain an oil with low linoleic acid level were 0.2 % nickel catalyst at 120ºC for 4 hours, 0.4% nickel catalyst at 90ºC for 4 hours and 0.6% at 60ºC for 4 hours. Fatty acid composition and chemical analysis of the interesterified and non-esterified oils were estimated. Selected samples undergo heating at 180ºC for 4 hours determining the volatile components. The appearance of some components supported the interesterification process for modification of fatty acid constituents of the oils.Se ha llevado a cabo la interesterificación en fase miscelar de aceites de soja y de colza usando un 0.2%, 0.4% y 0.6% de níquel como catalizador, a diferentes temperaturas (60, 90 y 120ºC durante 2, 4 y 6 horas. Las condiciones de reacción de interesterificación propuestas para obtener un aceite con niveles de ácidos linolénicos bajos fueron 0.2 % de níquel a 120ºC durante 4 horas, 0.4 % de níquel a 90ºC durante 4 horas y 0.6 % a 60ºC durante 4 horas. Se han estimado la composición en ácidos grasos y el análisis químico de los aceites interesterificados y no-esterificados. Las muestras seleccionadas se sometieron a calentamiento a 180ºC durante 4 horas determinando los componentes volátiles. La aparición de algunos componentes apoyó el proceso de interesterificación por modificación de los ácidos grasos constituyentes de los aceites.

  11. [Study on compatibility of Salviae Miltiorrhizae Radix et Rhizoma and Chuanxiong Rhizoma based on pharmacokinetics of effective components salvianolic acid B and ferulic acid in rat plasma].

    Science.gov (United States)

    Zhang, Cui-ying; Zhang, Hong; Dong, Yu; Ren, Wei-guang; Chen, Heng-wen

    2015-04-01

    A study was made on the pharmacokinetic regularity of effective components salvianolic acid B and ferulic acid in Salviae Miltiorrhizae Radix et Rhizoma (SMRR) and Chuanxiong Rhizoma(CR) in rats, so as to discuss the compatibility mechanism of Salviae Miltiorrhizae Radix et Rhizoma and Chuanxiong Rhizoma. Rats were randomly divided into three groups and intravenously injected with 50 mg x kg(-1) salvianolic acid B for the single SMRR extracts group, 0.5 mg x kg(-1) ferulic acid for the single CR extracts group and 50 mg x kg(-1) salvianolic acid B + 0.5 mg x kg(-1) ferulic acid for the SMRR and CR combination group. The blood samples were collected at different time points and purified by liquid-liquid extraction with ethyl acetate. With chloramphenicol as internal standard (IS), UPLC was adopted to determine concentrations of salvianolic acid B and ferulic acid. The pharmacokinetic parameters of salvianolic acid B and ferulic acid were calculated with WinNonlin 6.2 software and analyzed by SPSS 19.0 statistical software. The UPLC analysis method was adopted to determine salvianolic acid B and ferulic acid in rat plasma, including linear equation, stability, repeatability, precision and recovery. The established sample processing and analysis methods were stable and reliable, with significant differences in major pharmacokinetic parameters, e.g., area under the curve (AUC), mean residence time (MRT) and terminal half-life (t(1/2)). According to the experimental results, the combined application of SMRR and CR can significantly impact the pharmacokinetic process of their effective components in rats and promote the wide distribution, shorten the action time and prolong the in vivo action time of salvianolic acid B and increase the blood drug concentration and accelerate the clearance of ferulic acid in vivo.

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

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

    Institute of Scientific and Technical Information of China (English)

    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.

  15. Bioremoval of Basic Violet 3 and Acid Blue 93 by Pseudomonas putida and its adsorption isotherms and kinetics.

    Science.gov (United States)

    Arunarani, A; Chandran, Preethy; Ranganathan, B V; Vasanthi, N S; Sudheer Khan, S

    2013-02-01

    Basic Violet 3 and Acid Blue 93 are the most important group of synthetic colourants extensively used in textile industries for dyeing cotton, wool, silk and nylon. Release of these dye pollutants in to the environment adversely affects the human health and aquatic organisms. The present study we used Pseudomonas putida MTCC 4910 for the adsorptive removal of Basic Violet 3 and Acid Blue 93 from the aqueous solutions. The pH (4-9) and NaCl concentrations (1mM-1M) did not influence the adsorption process. The equilibrium adsorption process fitted well to Freundlich model than Langmuir model. The kinetics of adsorption fitted well by pseudo-second-order. Thus in the present study an attempt has been made to exploit the dye removal capability of P. putida MTCC 4910, and it was found to be an efficient microbe that could be used for bio removal of dyes from textile effluents.

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

    Directory of Open Access Journals (Sweden)

    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

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

    Science.gov (United States)

    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.

  18. Performance, kinetic, and biodegradation pathway evaluation of anaerobic fixed film fixed bed reactor in removing phthalic acid esters from wastewater

    Science.gov (United States)

    Ahmadi, Ehsan; Yousefzadeh, Samira; Ansari, Mohsen; Ghaffari, Hamid Reza; Azari, Ali; Miri, Mohammad; Mesdaghinia, Alireza; Nabizadeh, Ramin; Kakavandi, Babak; Ahmadi, Peyman; Badi, Mojtaba Yegane; Gholami, Mitra; Sharafi, Kiomars; Karimaei, Mostafa; Ghoochani, Mahboobeh; Brahmand, Masoud Binesh; Mohseni, Seyed Mohsen; Sarkhosh, Maryam; Rezaei, Soheila; Asgharnia, Hosseinali; Dehghanifard, Emad; Jafari, Behdad; Mortezapour, Alireza; Moghaddam, Vahid Kazemi; Mahmoudi, Mohammad Molla; Taghipour, Nader

    2017-01-01

    Emerging and hazardous environmental pollutants like phthalic acid esters (PAEs) are one of the recent concerns worldwide. PAEs are considered to have diverse endocrine disrupting effects on human health. Industrial wastewater has been reported as an important environment with high concentrations of PAEs. In the present study, four short-chain PAEs including diallyl phthalate (DAP), diethyl phthalate (DEP), dimethyl phthalate (DMP), and phthalic acid (PA) were selected as a substrate for anaerobic fixed film fixed bed reactor (AnFFFBR). The process performances of AnFFFBR, and also its kinetic behavior, were evaluated to find the best eco-friendly phthalate from the biodegradability point of view. According to the results and kinetic coefficients, removing and mineralizing of DMP occurred at a higher rate than other phthalates. In optimum conditions 92.5, 84.41, and 80.39% of DMP, COD, and TOC were removed. DAP was found as the most bio-refractory phthalate. The second-order (Grau) model was selected as the best model for describing phthalates removal. PMID:28216654

  19. Macroscopic, thermodynamic, kinetic and microscopic study of nitric acid pickling of Elektron 21 (EV31A magnesium alloy

    Directory of Open Access Journals (Sweden)

    Benjamin Mouls

    2014-12-01

    Full Text Available The study of pickling of the EL21T6 substrate in a nitric acid bath firstly provided knowledge of the influence of the different experimental parameters (concentration of acid, temperature and stirring of the solution in relation to the etching rate. This experimental part led to the choice of standard pickling (Tbath = 25 °C, moderate stirring (250 rpm, [HNO3] = 1.20 mol/L, duration of 2 min so as to obtain constant removal of material, even after several uses of the pickling bath. SEM observations also confirmed that in these operating conditions, pickling concerns both the grains of the matrix and the precipitates of type Mg3(Nd, Gd, leading to uniform removal of material from the surface. Working from a number of assumptions, thermodynamic and chemical kinetic studies then allowed a pickling mechanism to be proposed and led to obtaining values for the corresponding kinetic parameters (order of reaction, constant of mean rate, activation energy to be obtained.

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

    Science.gov (United States)

    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.

  1. Kinetics and Mechanisms of the Acid-base Reaction Between NH3 and HCOOH in Interstellar Ice Analogs

    Science.gov (United States)

    Bergner, Jennifer B.; Öberg, Karin I.; Rajappan, Mahesh; Fayolle, Edith C.

    2016-10-01

    Interstellar complex organic molecules 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 the kinetics and mechanisms of a potential ion-generating, acid-base reaction between NH3 and HCOOH to form the salt NH{}4+HCOO-. We observe salt growth at temperatures as low as 15 K, 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 ± 30 K with a pre-exponential factor 1.4 ± 0.4 × 10-3 s-1. The pre-reaction rate varies under different experimental conditions and likely represents a combination of diffusion and orientation of reactant molecules. For a diffusion-limited case, the pre-reaction barrier is 770 ± 110 K with a pre-exponential factor of ˜7.6 × 10-3 s-1. Acid-base chemistry of common ice constituents is thus a potential cold pathway to generating ions in interstellar ices.

  2. Kinetics of eicosapentaenoic acid in brain, heart and liver of conscious rats fed a high n-3 PUFA containing diet.

    Science.gov (United States)

    Igarashi, Miki; Chang, Lisa; Ma, Kaizong; Rapoport, Stanley I

    2013-01-01

    Eicosapentaenoic acid (EPA, 20:5n-3), a precursor of docosahexaenoic acid (DHA), may benefit cardiovascular and brain health. Quantifying EPA's in vivo kinetics might elucidate these effects. [1-(14)C]EPA was infused i.v. for 5min in unanesthetized male rats fed a standard EPA-DHA diet. Plasma and microwaved tissue were analyzed. Kinetic parameters were calculated using our compartmental model. At 5min, 31-48% of labeled EPA in brain and heart was oxidized, 7% in liver. EPA incorporation rates from brain and liver precursor EPA-CoA pools into lipids, mainly phospholipids, were 36 and 2529nmol/s/g×10(-4), insignificant for heart. Deacylation-reacylation half-lives were 22h and 38-128min. Conversion rates to DHA equaled 0.65 and 25.1nmol/s/g×10(-4), respectively. The low brain concentration and incorporation rate and high oxidation of EPA suggest that, if EPA has a beneficial effect in brain, it might result from its suppression of peripheral inflammation and hepatic conversion to bioactive DHA.

  3. Performance, kinetic, and biodegradation pathway evaluation of anaerobic fixed film fixed bed reactor in removing phthalic acid esters from wastewater

    Science.gov (United States)

    Ahmadi, Ehsan; Yousefzadeh, Samira; Ansari, Mohsen; Ghaffari, Hamid Reza; Azari, Ali; Miri, Mohammad; Mesdaghinia, Alireza; Nabizadeh, Ramin; Kakavandi, Babak; Ahmadi, Peyman; Badi, Mojtaba Yegane; Gholami, Mitra; Sharafi, Kiomars; Karimaei, Mostafa; Ghoochani, Mahboobeh; Brahmand, Masoud Binesh; Mohseni, Seyed Mohsen; Sarkhosh, Maryam; Rezaei, Soheila; Asgharnia, Hosseinali; Dehghanifard, Emad; Jafari, Behdad; Mortezapour, Alireza; Moghaddam, Vahid Kazemi; Mahmoudi, Mohammad Molla; Taghipour, Nader

    2017-02-01

    Emerging and hazardous environmental pollutants like phthalic acid esters (PAEs) are one of the recent concerns worldwide. PAEs are considered to have diverse endocrine disrupting effects on human health. Industrial wastewater has been reported as an important environment with high concentrations of PAEs. In the present study, four short-chain PAEs including diallyl phthalate (DAP), diethyl phthalate (DEP), dimethyl phthalate (DMP), and phthalic acid (PA) were selected as a substrate for anaerobic fixed film fixed bed reactor (AnFFFBR). The process performances of AnFFFBR, and also its kinetic behavior, were evaluated to find the best eco-friendly phthalate from the biodegradability point of view. According to the results and kinetic coefficients, removing and mineralizing of DMP occurred at a higher rate than other phthalates. In optimum conditions 92.5, 84.41, and 80.39% of DMP, COD, and TOC were removed. DAP was found as the most bio-refractory phthalate. The second-order (Grau) model was selected as the best model for describing phthalates removal.

  4. Protein homeostasis disorders of key enzymes of amino acids metabolism: mutation-induced protein kinetic destabilization and new therapeutic strategies.

    Science.gov (United States)

    Pey, Angel L

    2013-12-01

    Many inborn errors of amino acids metabolism are caused by single point mutations affecting the ability of proteins to fold properly (i.e., protein homeostasis), thus leading to enzyme loss-of-function. Mutations may affect protein homeostasis by altering intrinsic physical properties of the polypeptide (folding thermodynamics, and rates of folding/unfolding/misfolding) as well as the interaction of partially folded states with elements of the protein homeostasis network (such as molecular chaperones and proteolytic machineries). Understanding these mutational effects on protein homeostasis is required to develop new therapeutic strategies aimed to target specific features of the mutant polypeptide. Here, I review recent work in three different diseases of protein homeostasis associated to inborn errors of amino acids metabolism: phenylketonuria, inherited homocystinuria and primary hyperoxaluria type I. These three different genetic disorders involve proteins operating in different cell organelles and displaying different structural complexities. Mutations often decrease protein kinetic stability of the native state (i.e., its half-life for irreversible denaturation), which can be studied using simple kinetic models amenable to biophysical and biochemical characterization. Natural ligands and pharmacological chaperones are shown to stabilize mutant enzymes, thus supporting their therapeutic application to overcome protein kinetic destabilization. The role of molecular chaperones in protein folding and misfolding is also discussed as well as their potential pharmacological modulation as promising new therapeutic approaches. Since current available treatments for these diseases are either burdening or only successful in a fraction of patients, alternative treatments must be considered covering studies from protein structure and biophysics to studies in animal models and patients.

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

    Science.gov (United States)

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

    2012-07-01

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

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

    Indian Academy of Sciences (India)

    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.

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

    Science.gov (United States)

    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.

  8. Biodegradation kinetics of 4-fluorocinnamic acid by a consortium of Arthrobacter and Ralstonia strains

    NARCIS (Netherlands)

    Hasan, Syed A.; Wietzes, Piet; Janssen, Dick B.

    2012-01-01

    Arthrobacter sp. strain G1 is able to grow on 4-fluorocinnamic acid (4-FCA) as sole carbon source. The organism converts 4-FCA into 4-fluorobenzoic acid (4-FBA) and utilizes the two-carbon side-chain for growth with some formation of 4-fluoroacetophenone as a dead-end side product. We also have isol

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

    Directory of Open Access Journals (Sweden)

    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 

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

    Science.gov (United States)

    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

  11. Kinetics and Mechanism of Bioactivation via S-Oxygenation of Anti-Tubercular Agent Ethionamide by Peracetic Acid.

    Science.gov (United States)

    Chipiso, Kudzanai; Logan, Isabelle E; Eskew, Matthew W; Omondi, Benard; Simoyi, Reuben H

    2016-10-11

    The kinetics and mechanism of the oxidation of the important antitubercular agent, ethionamide, ETA (2-ethylthioisonicotinamide), by peracetic acid (PAA) have been studied. It is effectively a biphasic reaction with an initial rapid first phase of the reaction which is over in about 5 s and a second slower phase of the reaction which can run up to an hour. The first phase involves the addition of a single oxygen atom to ethionamide to form the S-oxide. The second phase involves further oxidation of the S-oxide to desulfurization of ETA to give 2-ethylisonicotinamide. In contrast to the stability of most organosulfur compounds, the S-oxide of ETA is relatively stable and can be isolated. In conditions of excess ETA, the stoichiometry of the reaction was strictly 1:1: CH3CO3H + Et(C5H4)C(═S)NH2 → CH3CO2H + Et(C5H4)C(═NH)SOH. In this oxidation, it was apparent that only the sulfur center was the reactive site. Though ETA was ultimately desulfurized, only the S-oxide was stable. Electrospray ionization (ESI) spectral analysis did not detect any substantial formation of the sulfinic and sulfonic acids. This suggests that cleavage of the carbon-sulfur bond occurs at the sulfenic acid stage, resulting in the formation of an unstable sulfur species that can react further to form more stable sulfur species. In this oxidation, no sulfate formation was observed. ESI spectral analysis data showed a final sulfur species in the form of a dimeric sulfur monoxide species, H3S2O2. We derived a bimolecular rate constant for the formation of the S-oxide of (3.08 ± 0.72) × 10(2) M(-1) s(-1). Oxidation of the S-oxide further to give 2-ethylisonicotinamide gave zero order kinetics.

  12. Kinetic analysis of bifidobacterial metabolism reveals a minor role for succinic acid in the regeneration of NAD+ through its growth-associated production.

    Science.gov (United States)

    Van der Meulen, Roel; Adriany, Tom; Verbrugghe, Kristof; De Vuyst, Luc

    2006-08-01

    Several strains belonging to the genus Bifidobacterium were tested to determine their abilities to produce succinic acid. Bifidobacterium longum strain BB536 and Bifidobacterium animalis subsp. lactis strain Bb 12 were kinetically analyzed in detail using in vitro fermentations to obtain more insight into the metabolism and production of succinic acid by bifidobacteria. Changes in end product formation in strains of Bifidobacterium could be related to the specific rate of sugar consumption. When the specific sugar consumption rate increased, relatively more lactic acid and less acetic acid, formic acid, and ethanol were produced, and vice versa. All Bifidobacterium strains tested produced small amounts of succinic acid; the concentrations were not more than a few millimolar. Succinic acid production was found to be associated with growth and stopped when the energy source was depleted. The production of succinic acid contributed to regeneration of a small part of the NAD+, in addition to the regeneration through the production of lactic acid and ethanol.

  13. Energetics and kinetics of anaerobic aromatic and fatty acid degradation. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Michael J. McInerney

    1996-06-24

    The factors that affect the rate and extent of a model aromatic compound, benzoate, in methanogenic environments was studied. Benzoate is degraded to a threshold concentration below which no further substrate degradation occurs. The threshold concentration depended on the substrate concentration and the amount of acetate present. The threshold value was not a function of the kinetic ability of the organism or toxicity of the end products. Rather a minimal Gibb's free energy value may exist where thermodynamic constraints preclude further benzoate degradation. In addition, new bacterial species were isolated and described, that degrade benzoate or reduce iron, cobalt and other metals.

  14. THE KINETICS OF SAPONIFICATION OF IODOACETIC ACID BY SODIUM HYDROXIDE AND BY CERTAIN ALKALINE BUFFER SOLUTIONS.

    Science.gov (United States)

    Brdicka, R

    1936-07-20

    1. The rate of the saponification of iodoacetic acid in sodium hydroxide and alkaline buffer solutions yielding glycollic acid was measured by means of Heyrovský's polarographic method. 2. From the bimolecular velocity constants, increasing with the ionic strength of the solution, the Brönsted factor, F, which characterizes the primary salt effect, was calculated. 3. In the borate buffer solutions the monomolecular constants of the saponification were determined which, at values above the pH of neutralization of boric acid, show a proportionality to the concentration of hydroxyl anions. Below the pH of neutralization of boric acid, they are proportional to the concentration of borate anions.

  15. The complete amino acid sequence of the major component myoglobin of Amazon river dolphin (Inia geoffrensis).

    Science.gov (United States)

    Dwulet, F E; Bogardt, R A; Jones, B N; Lehman, L D; Gurd, F R

    1975-12-02

    The complete amino acid sequence of the major component myoglobin from Amazon River dolphin, Inia geoffrensis, was determined by specific cleavage of the protein to obtain large peptides which are readily degraded by the automatic sequencer. Three easily separable peptides were obtained by cleaving the protein with cyanogen bromide at the methionine residues and four peptides were obtained by cleaving the methyl-acetimidated protein with trypsin at the arginine residues. From these peptides over 85% of the sequence was completed. The remainder of the sequence was obtained by fragmentation of the large cyanogen bromide peptide with trypsin. This protein differs from that of the common porpoise, Phocoena phocoena, at seven positions, from that of the common dolphin, Delphinus delphis, at 11 positions, and from that of the sperm whale, Physeter catodon, at 15 positions. By comparison of this sequence with the three-dimensional structure of sperm whale myoglobin it appears that those residues close to the heme group are most conserved followed by those in nonhelical regions and lastly by those in the helical segments. All of the substitutions observed in this sequence fit easily into the three-dimensional structure of the sperm whale myoglobin.

  16. Is Lactate an undervalued functional component of lactic acid bacteria-fermented food products?

    Directory of Open Access Journals (Sweden)

    Graciela eGarrote

    2015-06-01

    Full Text Available Although it has been traditionally regarded as an intermediate of carbon metabolism and major component of fermented dairy products contributing to organoleptic and antimicrobial properties of food, there is evidence gathered in recent years that lactate has bioactive properties that may be responsible of broader properties of functional foods. Lactate can regulate critical functions of several key players of the immune system such as macrophages and dendritic cells, being able to modulate inflammatory activation of epithelial cells as well. Intraluminal levels of lactate derived from fermentative metabolism of lactobacilli have been shown to modulate inflammatory environment in intestinal mucosa. The molecular mechanisms responsible to these functions, including histone deacetylase dependent-modulation of gene expression and signalling through G-protein coupled receptors have started to be described. Since lactate is a major fermentation product of several bacterial families with probiotic properties, we here propose that it may contribute to some of the properties attributed to these microorganisms and in a larger view, to the properties of food products fermented by lactic acid bacteria.

  17. The effect of oxygen supply on the dual growth kinetics of Acidithiobacillus thiooxidans under acidic conditions for biogas desulfurization.

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

  19. Theoretical analysis of kinetic isotope effects on proton transfer reactions between substituted alpha-methoxystyrenes and substituted acetic acids.

    Science.gov (United States)

    Wong, Kin-Yiu; Richard, John P; Gao, Jiali

    2009-10-01

    Primary kinetic isotope effects (KIEs) on a series of carboxylic acid-catalyzed protonation reactions of aryl-substituted alpha-methoxystyrenes (X-1) to form oxocarbenium ions have been computed using the second-order Kleinert variational perturbation theory (KP2) in the framework of Feynman path integrals (PI) along with the potential energy surface obtained at the B3LYP/6-31+G(d,p) level. Good agreement with the experimental data was obtained, demonstrating that this novel computational approach for computing KIEs of organic reactions is a viable alternative to the traditional method employing Bigeleisen equation and harmonic vibrational frequencies. Although tunneling makes relatively small contributions to the lowering of the free energy barriers for the carboxylic acid catalyzed protonation reaction, it is necessary to include tunneling contributions to obtain quantitative estimates of the KIEs. Consideration of anharmonicity can further improve the calculated KIEs for the protonation of substituted alpha-methoxystyrenes by chloroacetic acid, but for the reactions of the parent and 4-NO(2) substituted alpha-methoxystyrene with substituted carboxylic acids, the correction of anharmonicity overestimates the computed KIEs for strong acid catalysts. In agreement with experimental findings, the largest KIEs are found in nearly ergoneutral reactions, DeltaG(o) approximately 0, where the transition structures are nearly symmetric and the reaction barriers are relatively low. Furthermore, the optimized transition structures are strongly dependent on the free energy for the formation of the carbocation intermediate, that is, the driving force DeltaG(o), along with a good correlation of Hammond shift in the transition state structure.

  20. Relative contribution of combined kinetic and exchange energy terms vs the electronic component of molecular electrostatic potential in hardness potential derivatives.

    Science.gov (United States)

    Bhattacharjee, Rituparna; Roy, Ram Kinkar

    2013-11-14

    The relative contribution of the sum of kinetic [(10/9)CFρ(r)2/3] and exchange energy [(4/9)CXρ(r)1/3] terms to that of the electronic part of the molecular electrostatic potential [Vel(r)] in the variants of hardness potential is investigated to assess the proposed definition of Δ+h(k) = −[VelN+1(k) – VelN(k)] and Δ–h(k) = −[VelN(k) – VelN–1(k)] (Saha; et al. J. Comput. Chem. 2013, 34, 662). Some substituted benzenes and polycyclic aromatic hydrocarbons (PAHs) (undergoing electrophilic aromatic substitution), carboxylic acids, and their derivatives are chosen to carry out the theoretical investigation as stated above. Intra- and intermolecular reactivity trends generated by Δ+h(k) and Δ–h(k) are found to be satisfactory and are correlated reasonably well with experimental results.

  1. Time-dependent extraction kinetics of infused components of different Indian black tea types using UV spectroscopy

    Directory of Open Access Journals (Sweden)

    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.

  2. Adsorption kinetics,isotherm,and thermodynamic studies of adsorption of pollutant from aqueous solutions onto humic acid

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    In the present study,humic acid was used as an adsorbent for the investigation of the adsorption kinetics,isotherms,and thermo-dynamic parameters of hexavalent chromium from aqueous solution at varying pH,temperatures,and concentrations.Adsorption isotherms and equilibrium adsorption capacities were determined by the fittings of the experimental data to three well-known iso-therm models:Langmuir,Freundlich,and Redlich-Peterson.The results showed that the Langmuir and Redlich-Peterson models appear to fit the adsorption better than did the Freundlich adsorption model for the adsorption of chromium onto humic acid.The equilibrium constants were used to calculate thermodynamic parameters such as the change of free energy,enthalpy,and entropy.The derived adsorption constants (logaL) and their temperature dependencies from Langmuir isotherm have been used to calculate the corresponding thermodynamic quantities such as the free energy of adsorption,heat,and entropy of adsorption.The thermo-dynamic data indicate that Cr (VI) adsorption onto humic acid is entropically driven and characterized by physical adsorption.

  3. Normal solution and transport coefficients to the Enskog-Landau kinetic equation for a two-component system of charged hard spheres The Chapman-Enskog method

    CERN Document Server

    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.

  4. Detection of methylglyoxal as a degradation product of DNA and nucleic acid components treated with strong acid.

    Science.gov (United States)

    Chaplen, F W; Fahl, W E; Cameron, D C

    1996-05-01

    The 1,2-diaminobenzene derivation assay for methylglyoxal in biological systems involves the use of perchloric acid, both as a deproteinizing agent and to prevent the spontaneous formation of methylglyoxal from glycolytic pathway intermediates. However, while using a modification of the standard literature assay to measure methylglyoxal in Chinese hamster ovary cells, we found that oxidation of nucleic acids and related compounds by perchloric or trichloroacetic acid results in the formation of methylglyoxal. Compounds containing 2-deoxyribose gave higher levels of methylglyoxal than those containing ribose; purine nucleotides and deoxynucleotides gave more methylglyoxal than did the pyrimidines. Nucleic acids were the most susceptible to degradation, with 12-fold more methylglyoxal being formed from DNA than RNA. Oxidation of nucleic acids increased with higher temperatures and with decreasing nucleic acid fragment size. Another product of nucleic acid oxidation was 2,3-butanedione, the 1,2-diaminobenzene derivative of which is sometimes used as an internal standard during methylglyoxal measurement. Unless accounted for during the assay procedure, the generation of methylglyoxal and 2,3-butanedione due to the oxidation of nucleic acids may lead to substantial errors in the determination of methylglyoxal concentrations in biological systems.

  5. Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

    Institute of Scientific and Technical Information of China (English)

    ZHAI Yong-qing; LIU Hong-mei; YANG Lin; YANG Guo-zhong; SONG Wen-yu; LIU Yu-kai

    2007-01-01

    In this study, the kinetics and mechanism of the iridium(Ⅲ)-catalyzed oxidation of ethanol amine(EAN) by cerium(Ⅳ) in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298-313 K. It was found that the reaction is of first order with respect to Ce(Ⅳ) and Ir(Ⅲ), and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order([EAN](》)[Ce(Ⅳ)]) rate constant kobs decreases with the increase of [H+] and [HSO-4]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of kobs on the concentration of hydrogen sulfate, Ce(SO4)2 was found to be the kinetically active species. The rate constants of the rate-determining step together with the activation parameters were evaluated.

  6. Kinetics and mechanisms of the acid-base reaction between NH$_3$ and HCOOH in interstellar ice analogs

    CERN Document Server

    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...

  7. Kinetics and microbial ecology of batch sulfidogenic bioreactors for co-treatment of municipal wastewater and acid mine drainage.

    Science.gov (United States)

    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.

  8. Kinetic analysis of acid orange 7 degradation by pulsed discharge plasma combined with activated carbon and the synergistic mechanism exploration.

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    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.

  10. Kinetic Aspects of Leaching Zinc from Waste Galvanizing Zinc by Using Hydrochloric Acid Solutions

    Science.gov (United States)

    Sminčáková, Emília; Trpčevská, Jarmila; Pirošková, Jana

    2016-10-01

    In this work, the results of acid leaching of flux skimmings coming from two plants are presented. Sample A contained two phases, Zn(OH)Cl and NH4Cl. In sample B, the presence of three phases, Zn5(OH)8Cl2·H2O, (NH4)2(ZnCl4) and ZnCl2(NH3)2, was proved. The aqueous solution of hydrochloric acid and distilled water was used as the leaching medium. The effects of the leaching time, temperature and concentration of the leaching medium on the zinc extraction were investigated. The apparent activation energy, E a = 4.61 kJ mol-1, and apparent reaction order n = 0.18 for sample A, and the values E a = 6.28 kJ mol-1 and n = 0.33 for sample B were experimentally determined. Zinc leaching in acid medium is a diffusion-controlled process.

  11. Kinetics and thermodynamics of interaction between sulfonamide antibiotics and humic acids: Surface plasmon resonance and isothermal titration microcalorimetry analysis.

    Science.gov (United States)

    Xu, Juan; Yu, Han-Qing; Sheng, Guo-Ping

    2016-01-25

    The presence of sulfonamide antibiotics in the environments has been recognized as a crucial issue. Their migration and transformation in the environment is determined by natural organic matters that widely exist in natural water and soil. In this study, the kinetics and thermodynamics of interactions between humic acids (HA) and sulfamethazine (SMZ) were investigated by employing surface plasmon resonance (SPR) combined with isothermal titration microcalorimetry (ITC) technologies. Results show that SMZ could be effectively bound with HA. The binding strength could be enhanced by increasing ionic strength and decreasing temperature. High pH was not favorable for the interaction. Hydrogen bond and electrostatic interaction may play important roles in driving the binding process, with auxiliary contribution from hydrophobic interaction. The results implied that HA existed in the environment may have a significant influence on the migration and transformation of organic pollutants through the binding process.

  12. Synthesis and Kinetics of a Novel Mimic with Glutathione Peroxidase Activity-Tellurium-containing Hyaluronic Acid (TeHA)

    Institute of Scientific and Technical Information of China (English)

    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.

  13. Equilibrium and kinetics study on the adsorption of perfluorooctanoic acid from aqueous solution onto powdered activated carbon.

    Science.gov (United States)

    Qu, Yan; Zhang, Chaojie; Li, Fei; Bo, Xiaowen; Liu, Guangfu; Zhou, Qi

    2009-09-30

    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 1h 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.

  14. Post-mortem kinetics of meat tenderness and the components of the calpain system in bull skeletal muscle.

    Science.gov (United States)

    Thomson, B C; Dobbie, P M; Singh, K; Speck, P A

    1996-11-01

    Eight strip loins (M. longissimus dorsi) from pasture fed Friesian bulls were aged at 15 °C for a range of times from 1 to 120 h. pH declined from 6.29 (SE 0.119) one hour post slaughter to an ultimate pH of 5.48 (SE 0.013). The activities of the components of the calpain system (μ-calpain, m-calpain and calpastatin) were determined after separation on a DEAE-sephacel column. There was a dramatic decline in μ-calpain activity post slaughter with a complete disappearance within 48 h. The rates of decline in m-calpain and calpastatin activity were slower with 30% and 50% remaining 120 h post slaughter, respectively. The rapid decline in μ-calpain activity relative to the calpastatin activity is likely to reduce the degree of tenderisation and ultimate tenderness of the meat.

  15. Sugar-assisted kinetic resolution of amino acids and amplification of enantiomeric excess of organic molecules.

    Science.gov (United States)

    Córdova, Armando; Sundén, Henrik; Xu, Yongmei; Ibrahem, Ismail; Zou, Weibiao; Engqvist, Magnus

    2006-07-17

    The origins of biological homochirality have intrigued researchers since Pasteur's discovery of the optical activity of biomolecules. Herein, we propose and demonstrate a novel alternative for the evolution of homochirality that is not based on autocatalysis and forges a direct relationship between the chirality of sugars and amino acids. This process provides a mechanism in which a racemic mixture of an amino acid can catalyze the formation of an optically active organic molecule in the presence of a sugar product of low enantiomeric excess.

  16. Unique honey bee (Apis mellifera hive component-based communities as detected by a hybrid of phospholipid fatty-acid and fatty-acid methyl ester analyses.

    Directory of Open Access Journals (Sweden)

    Kirk J Grubbs

    Full Text Available Microbial communities (microbiomes are associated with almost all metazoans, including the honey bee Apis mellifera. Honey bees are social insects, maintaining complex hive systems composed of a variety of integral components including bees, comb, propolis, honey, and stored pollen. Given that the different components within hives can be physically separated and are nutritionally variable, we hypothesize that unique microbial communities may occur within the different microenvironments of honey bee colonies. To explore this hypothesis and to provide further insights into the microbiome of honey bees, we use a hybrid of fatty acid methyl ester (FAME and phospholipid-derived fatty acid (PLFA analysis to produce broad, lipid-based microbial community profiles of stored pollen, adults, pupae, honey, empty comb, and propolis for 11 honey bee hives. Averaging component lipid profiles by hive, we show that, in decreasing order, lipid markers representing fungi, Gram-negative bacteria, and Gram-positive bacteria have the highest relative abundances within honey bee colonies. Our lipid profiles reveal the presence of viable microbial communities in each of the six hive components sampled, with overall microbial community richness varying from lowest to highest in honey, comb, pupae, pollen, adults and propolis, respectively. Finally, microbial community lipid profiles were more similar when compared by component than by hive, location, or sampling year. Specifically, we found that individual hive components typically exhibited several dominant lipids and that these dominant lipids differ between components. Principal component and two-way clustering analyses both support significant grouping of lipids by hive component. Our findings indicate that in addition to the microbial communities present in individual workers, honey bee hives have resident microbial communities associated with different colony components.

  17. Effect of hydrodynamics on kinetics of gluconic acid enzymatic production in bubble column reactor

    Directory of Open Access Journals (Sweden)

    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.

  18. Biodegradation of Acid Anthraquinone Dye in a Facultative-aerobic Process: Kinetics and Products

    Institute of Scientific and Technical Information of China (English)

    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.

  19. Energetics and kinetics of anaerobic aromatic and fatty acid degradation. Progress report, November 1993--November 1994

    Energy Technology Data Exchange (ETDEWEB)

    McInerney, M.J.

    1994-12-06

    Factors influencing the rate and extent of benzoate degradation by the anaerobic syntrophic consortia were studied. Nonlinear regression analysis showed that the cause of the benzoate threshold was not a diminished benzoate degradation capacity. Analysis of cocultures with hydrogen users that differed in their hydrogen utilization capacities showed that the threshold did not depend on the kinetic properties of the syntrophic partner. These data support a thermodynamic explanation for the threshold, and exclude the possibility that a change in the affinity of the enzyme system due to acetate inhibition caused the threshold. Modeling studies showed that the threshold value could be predicted from the concentrations of the end products, assuming a critical Gibb`s free energy value. This work shows that interspecies acetate transfer is important in controlling the extent of metabolism by syntrophic organisms.

  20. Energetics and kinetics of anaerobic aromatic and fatty acid degradation. Progress report, November 1992--November 1993

    Energy Technology Data Exchange (ETDEWEB)

    McInerney, M.J.

    1993-11-12

    The kinetics of benzoate degradation by the anaerobic syntrophic bacterium, Syntrophus buswellii, in coculture with different sulfate reducers was studied with sulfate or nitrate as the electron acceptor. A threshold value for benzoate degradation dependent on the acetate concentration was observed with sulfate, but not nitrate, as the electron acceptor. No threshold was observed in tricultures containing an acetate-using sulfate reducer. The addition of the acetate-using sulfate reducer to cocultures that had degraded benzoate to its threshold value resulted in further degradation of benzoate to levels below the analytical detection limit (ca. 200 nM). These data are consistent with a thermodynamic explanation for the threshold, and exclude the possibility that the threshold was the result of the inhibitory action of the undissociated form of acetate.

  1. Invariant Aspartic Acid in Muscle Nicotinic Receptor Contributes Selectively to the Kinetics of Agonist Binding

    Science.gov (United States)

    Lee, Won Yong; Sine, Steven M.

    2004-01-01

    We examined functional contributions of interdomain contacts within the nicotinic receptor ligand binding site using single channel kinetic analyses, site-directed mutagenesis, and a homology model of the major extracellular region. At the principal face of the binding site, the invariant αD89 forms a highly conserved interdomain contact near αT148, αW149, and αT150. Patch-clamp recordings show that the mutation αD89N markedly slows acetylcholine (ACh) binding to receptors in the resting closed state, but does not affect rates of channel opening and closing. Neither αT148L, αT150A, nor mutations at both positions substantially affects the kinetics of receptor activation, showing that hydroxyl side chains at these positions are not hydrogen bond donors for the strong acceptor αD89. However substituting a negative charge at αT148, but not at αT150, counteracts the effect of αD89N, demonstrating that a negative charge in the region of interdomain contact confers rapid association of ACh. Interpreted within the structural framework of ACh binding protein and a homology model of the receptor ligand binding site, these results implicate main chain amide groups in the domain harboring αW149 as principal hydrogen bond donors for αD89. The specific effect of αD89N on ACh association suggests that interdomain hydrogen bonding positions αW149 for optimal interaction with ACh. PMID:15504901

  2. Association of adiponectin,free fatty acids,and insulin resistance with metabolic syndrome and its components in Uygur Xinjiang

    Institute of Scientific and Technical Information of China (English)

    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

  3. Multiple amino acid sequence alignment nitrogenase component 1: insights into phylogenetics and structure-function relationships.

    Directory of Open Access Journals (Sweden)

    James B Howard

    Full Text Available Amino acid residues critical for a protein's structure-function are retained by natural selection and these residues are identified by the level of variance in co-aligned homologous protein sequences. The relevant residues in the nitrogen fixation Component 1 α- and β-subunits were identified by the alignment of 95 protein sequences. Proteins were included from species encompassing multiple microbial phyla and diverse ecological niches as well as the nitrogen fixation genotypes, anf, nif, and vnf, which encode proteins associated with cofactors differing at one metal site. After adjusting for differences in sequence length, insertions, and deletions, the remaining >85% of the sequence co-aligned the subunits from the three genotypes. Six Groups, designated Anf, Vnf , and Nif I-IV, were assigned based upon genetic origin, sequence adjustments, and conserved residues. Both subunits subdivided into the same groups. Invariant and single variant residues were identified and were defined as "core" for nitrogenase function. Three species in Group Nif-III, Candidatus Desulforudis audaxviator, Desulfotomaculum kuznetsovii, and Thermodesulfatator indicus, were found to have a seleno-cysteine that replaces one cysteinyl ligand of the 8Fe:7S, P-cluster. Subsets of invariant residues, limited to individual groups, were identified; these unique residues help identify the gene of origin (anf, nif, or vnf yet should not be considered diagnostic of the metal content of associated cofactors. Fourteen of the 19 residues that compose the cofactor pocket are invariant or single variant; the other five residues are highly variable but do not correlate with the putative metal content of the cofactor. The variable residues are clustered on one side of the cofactor, away from other functional centers in the three dimensional structure. Many of the invariant and single variant residues were not previously recognized as potentially critical and their identification

  4. Multiple amino acid sequence alignment nitrogenase component 1: insights into phylogenetics and structure-function relationships.

    Science.gov (United States)

    Howard, James B; Kechris, Katerina J; Rees, Douglas C; Glazer, Alexander N

    2013-01-01

    Amino acid residues critical for a protein's structure-function are retained by natural selection and these residues are identified by the level of variance in co-aligned homologous protein sequences. The relevant residues in the nitrogen fixation Component 1 α- and β-subunits were identified by the alignment of 95 protein sequences. Proteins were included from species encompassing multiple microbial phyla and diverse ecological niches as well as the nitrogen fixation genotypes, anf, nif, and vnf, which encode proteins associated with cofactors differing at one metal site. After adjusting for differences in sequence length, insertions, and deletions, the remaining >85% of the sequence co-aligned the subunits from the three genotypes. Six Groups, designated Anf, Vnf , and Nif I-IV, were assigned based upon genetic origin, sequence adjustments, and conserved residues. Both subunits subdivided into the same groups. Invariant and single variant residues were identified and were defined as "core" for nitrogenase function. Three species in Group Nif-III, Candidatus Desulforudis audaxviator, Desulfotomaculum kuznetsovii, and Thermodesulfatator indicus, were found to have a seleno-cysteine that replaces one cysteinyl ligand of the 8Fe:7S, P-cluster. Subsets of invariant residues, limited to individual groups, were identified; these unique residues help identify the gene of origin (anf, nif, or vnf) yet should not be considered diagnostic of the metal content of associated cofactors. Fourteen of the 19 residues that compose the cofactor pocket are invariant or single variant; the other five residues are highly variable but do not correlate with the putative metal content of the cofactor. The variable residues are clustered on one side of the cofactor, away from other functional centers in the three dimensional structure. Many of the invariant and single variant residues were not previously recognized as potentially critical and their identification provides the bases for

  5. Kinetic characteristics of polygalacturonase enzymes hydrolyzing galacturonic acid oligomers using isothermal titration calorimetry

    Science.gov (United States)

    Polygalacturonase enzymes hydrolyze the polygalacturonic acid chains found in pectin. Interest in polygalacturonase enzymes continues as they are useful in a number of industrial processes and conversely, detrimental, as they are involved in maceration of economically important crops. While a good...

  6. Kinetic Spectrophotometric Method for Determination of Oxalic Acid and Its application in Lathyrus sativus

    Institute of Scientific and Technical Information of China (English)

    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

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

    NARCIS (Netherlands)

    Bari, S.; Alvarado, F.; Postma, J.; Sobocinski, P.; Hoekstra, R.; Schlatholter, T.

    2009-01-01

    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 radiatio

  8. Nucleation kinetics of urea succinic acid –ferroelectric single crystal

    Energy Technology Data Exchange (ETDEWEB)

    Dhivya, R. [Crystal growth and Crystallography Division, School of Advanced Sciences, VIT University, Vellore-632014, Tamilnadu (India); Voohrees College, Vellore-632014, Tamilnadu (India); Vizhi, R. Ezhil, E-mail: rezhilvizhi@vit.ac.in, E-mail: revizhi@gmail.com; Babu, D. Rajan [Crystal growth and Crystallography Division, School of Advanced Sciences, VIT University, Vellore-632014, Tamilnadu (India)

    2015-06-24

    Single crystals of Urea Succinic Acid (USA) were grown by slow cooling technique. The crystalline system was confirmed by powder X-ray diffraction. The metastable zonewidth were carried out for various temperatures i.e., 35°, 40°, 45° and 50°C. The induction period is experimentally determined and various nucleation parameters have been estimated.

  9. Determination of an ageing factor for lead/acid batteries. 1. Kinetic aspects

    Science.gov (United States)

    Armenta-Deu, C.; Donaire, T.

    The capacity of lead/acid batteries decreases with the number of cycles. This process is known as ageing. The reduction of capacity affects not only the operation time but also the performance of the accumulator and of the system attached to the battery. One of the main procedures affected by the battery ageing is the determination of the state-of-charge. In this paper, a parameter called 'ageing factor', fa, which represents the reduction of the available energy in lead/acid batteries, is introduced. A method to calculate this factory and its incidence on battery performance has also been developed. The method is intended to predict 'ageing' effects on lead/acid batteries as a non-destructive method, as well as on-line battery operation. The method is based on the effective reduction in electrolyte specific gravity in a fully charged lead/acid battery computed from the change of the slope of the electrolyte density during charge with the number of cycles, and the subsequent reduction in discharge time. A correlation process between the reduction of the energy delivered by the electrochemical cell, the reduction of the discharge time, and the apparent change of the slope of electrolyte density has been developed, resulting in an analytical expression that may be used to compute the effective reduction in available energy in lead/acid batteries. The results of the experiments have proven the merit of the proposed system: the predicted values are in good agreement with experimental data, the associated error in the a estimation being lower than 9%, a result which has been considered acceptable to validate the proposed method.

  10. Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and products identification

    Directory of Open Access Journals (Sweden)

    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.

  11. Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and product identification

    Science.gov (United States)

    Mendez, M.; Ciuraru, R.; Gosselin, S.; Batut, S.; Visez, N.; Petitprez, D.

    2013-12-01

    The heterogeneous reaction of Cl• radicals with submicron 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 vapours and introduced into the reactor, where chlorine atoms were 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 gas chromatography-mass spectrometer (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 analysis has 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 were identified by GC/MS. The formation of alcohols and monocarboxylic acids is also suspected. A reaction pathway for the main products and more functionalized species is proposed. 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. They help to understand the aging of primary tropospheric aerosol containing fatty acids.

  12. Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and products identification

    Science.gov (United States)

    Mendez, M.; Ciuraru, R.; Gosselin, S.; Batut, S.; Visez, N.; Petitprez, D.

    2013-06-01

    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.

  13. Cr(VI) reduction capability of humic acid extracted from the organic component of municipal solid waste

    Institute of Scientific and Technical Information of China (English)

    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.

  14. Role of specific components from commercial inactive dry yeast winemaking preparations on the growth of wine lactic acid bacteria.

    Science.gov (United States)

    Andújar-Ortiz, Inmaculada; Pozo-Bayón, Maria Angeles; García-Ruiz, Almudena; Moreno-Arribas, M Victoria

    2010-07-28

    The role of specific components from inactive dry yeast preparations widely used in winemaking on the growth of three representative wine lactic acid bacteria (Oenococcus oeni, Lactobacillus hilgardii and Pediococcus pentosaceus) has been studied. A pressure liquid extraction technique using solvents of different polarity was employed to obtain extracts with different chemical composition from the inactive dry yeast preparations. Each of the extracts was assayed against the three lactic acid bacteria. Important differences in the effect of the extracts on the growth of the bacteria were observed, which depended on the solvent employed during the extraction, on the type of commercial preparations and on the lactic acid bacteria species. The extracts that exhibited the most different activity were chemically characterized in amino acids, free monosaccharides, monosaccharides from polysaccharides, fatty acids and volatile compounds. In general, specific amino acids and monosaccharides were related to a stimulating effect whereas fatty acid composition and likely some volatile compounds seemed to show an inhibitory effect on the growth of the lactic acid bacteria. These results may provide novel and useful information in trying to obtain better and more specific formulations of winemaking inactive dry yeast preparations.

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

    DEFF Research Database (Denmark)

    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 ......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...

  16. Energetics and kinetics of anaerobic aromatic and fatty acid degradation. Progress report, March 1992--June 1995

    Energy Technology Data Exchange (ETDEWEB)

    McInerney M.J.

    1995-06-23

    Factors affecting the rate and extent of benzoate degradation by anaerobic syntrophic consortia were studied. Cocultures of a syntrophic benzoate degrader, strain SB, with a hydrogen/formate-using sulfate reducer degraded benzoate to a threshold that depended on the amount of substrate and acetate present. The benzoate threshold was not a function of the inhibition of benzoate degradation capacity by acetate or the toxicity of the undissociated form of acetate. Rather, a critical or minimal Gibb`s free energy value may exist where thermodynamic constraints preclude further benzoate degradation. A sensitive assay to detect low formate concentrations was developed to measure the formate levels when the benzoate threshold was reached. We showed that increased acetate concentrations, even when hydrogen and formate levels are low, affects the extent of benzoate degradation, implicating the importance of interspecies acetate transfer. In addition to benzoate, various saturated and unsaturated fatty acids, 2-methylbutyrate, and methyl esters of fatty acids supported growth in coculture with a hydrogen-using partner. SB is the only syntrophic bacterium known to use both benzoate and fatty acids. Phylogenetic analysis showed that SB clustered with sulfate reducers in the delta subclass of the Proteobacteria. SB grew well in coculture with Desulfoarculus baarsii, a sulfate reducer that uses formate but not hydrogen. This unequivocally shows that SB can grow by interspecies formate transfer.

  17. Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways.

    Science.gov (United States)

    Perez-Benito, Joaquin F

    2011-09-08

    The reactions of permanganate ion with seven α-amino acids in aqueous KH(2)PO(4)/K(2)HPO(4) buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO(4)(-)) and 418 nm (formation of colloidal MnO(2)). All of the reactions studied were autocatalyzed by colloidal MnO(2), with the contribution of the autocatalytic reaction pathway decreasing in the order glycine > l-threonine > l-alanine > l-glutamic acid > l-leucine > l-isoleucine > l-valine. The rate constants corresponding to the nonautocatalytic and autocatalytic pathways were obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways were determined and analyzed to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the nonautocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the α-amino acid. Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (nonautocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.

  18. Mechanism and kinetics of aluminum dissolution during copper sorption by acidity paddy soil in South China.

    Science.gov (United States)

    Liu, Peiya; Li, Yujiao; Wen, Qinliang; Dong, Changxun; Pan, Genxing

    2015-08-01

    Soil aggregates were prepared from a bulk soil collected from paddy soil in the Taihu Lake region and aluminum (Al) dissolution, solution pH changes during copper (Cu(2+)) sorption were investigated with static sorption and magnetic stirring. Kinetics of Cu(2+) sorption and Al dissolution were also studied by magnetic stirring method. No Al dissolution was observed until Cu(2+) sorption was greater than a certain value, which was 632, 450, 601 and 674 mg/kg for sand, clay, silt, and coarse silt fractions, respectively. Aluminum dissolution increased with increasing Cu(2+) sorption and decreasing solution pH. An amount of dissolved Al showed a significant positive correlation with non-specific sorption of Cu(2+) (R(2)>0.97), and it was still good under different pH values (R(2)>0.95). Copper sorption significantly decreased solution pH. The magnitude of solution pH decline increased as Cu(2+) sorption and Al dissolution increased. The sand and clay fraction had a less Al dissolution and pH drop due to the higher ferric oxide, Al oxide and organic matter contents. After sorption reaction for half an hour, the Cu(2+) sorption progress reached more than 90% while the Al dissolution progress was only 40%, and lagged behind the Cu(2+) sorption. It indicated that aluminum dissolution is associated with non-specific sorption.

  19. 炭基固体酸催化废油脂合成生物柴油动力学研究%Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

    Institute of Scientific and Technical Information of China (English)

    舒庆; 高继贤; 廖玉会; 王金福

    2011-01-01

    The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied. Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt. These catalysts were characterized on the basis of elemental analysis, acidity site concentration, the Brunauer-Emmett-Teller (BET) surface area and pore size. The kinetic parameters with the two catalysts were determined, and the reaction system can be described as a pseudo homogeneous catalyzed reaction. All the forward and reverse reactions follow second order kinetics. The calculated concentration values from the kinetic equations are in good agreement with experimental values.

  20. Microencapsulation of H. pluvialis oleoresins with different fatty acid composition: Kinetic stability of astaxanthin and alpha-tocopherol.

    Science.gov (United States)

    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.

  1. Electrolytic deposition of calcium phosphate/chitosan coating on titanium alloy: Growth kinetics and influence of current density, acetic acid, and chitosan

    NARCIS (Netherlands)

    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

  2. Lactobacilli reduce cell cytotoxicity caused by Streptococcus pyogenes by producing lactic acid that degrades the toxic component lipoteichoic acid.

    Science.gov (United States)

    Maudsdotter, Lisa; Jonsson, Hans; Roos, Stefan; Jonsson, Ann-Beth

    2011-04-01

    Lactobacilli are known to prevent colonization by many pathogens; nevertheless, the mechanisms of their protective effect are largely unknown. In this work, we investigated the role of lactobacilli during infection of epithelial cells with group A streptococci (GAS). GAS cause a variety of illnesses ranging from noninvasive disease to more severe invasive infections, such as necrotizing fasciitis and toxic shock-like syndrome. Invasion of deeper tissues is facilitated by GAS-induced apoptosis and cell death. We found that lactobacilli inhibit GAS-induced host cell cytotoxicity and shedding of the complement regulator CD46. Further, survival assays demonstrated that lactic acid secreted by lactobacilli is highly bactericidal toward GAS. In addition, lactic acid treatment of GAS, but not heat killing, prior to infection abolishes the cytotoxic effects against human cells. Since lipoteichoic acid (LTA) of GAS is heat resistant and cytotoxic, we explored the effects of lactic acid on LTA. By applying such an approach, we demonstrate that lactic acid reduces epithelial cell damage caused by GAS by degrading both secreted and cell-bound LTA. Taken together, our experiments reveal a mechanism by which lactobacilli prevent pathogen-induced host cell damage.

  3. Effect of nitroxin and humic acid on yield and yield components of faba bean

    Directory of Open Access Journals (Sweden)

    Kholdi Abolfazl

    2015-01-01

    Full Text Available Quality and quantity improvement of crops using organic matter and low-cost method in the field is very important. Bio-fertilizer nitroxin and humic acid can increase root and shoot biomass through improved intake of nutrition and they can lead to quality and quantity improvement of product. An experiment was carried out as a completely randomized block design with 4 treatments to study the effect of nitroxin and humic acid on faba bean (Vicia faba L. traits. Trial treatments included control, nitroxin, humic acid and nitroxin + humic acid. Analysis of variance showed that the effect of combination of nitroxin + humic acid was significant (p< 1% on some traits such as stem height and yield of faba bean. The highest yield (2,315 kg ha-1 was obtained under nitroxin + humic acid treatment.

  4. Effect of extra virgin olive oil components on the arachidonic acid cascade, colorectal cancer and colon cancer cell proliferation

    Directory of Open Access Journals (Sweden)

    C. E. Storniolo

    2016-12-01

    Full Text Available The mediterranean diet (MD reduced the risk of colorectal cancer (CRC, and olive oil, the primary source of fat in the MD, has also been found to have a protective effect. However, animals fed with oleic acid present a high number of intestinal tumours, suggesting that oleic acid and olive oil consumption can exert different effects on CRC. Considering that extra virgin olive oil (EVOO is a complex mix of fatty acids and minor compounds such as polyphenols, hydrocarbons, phytosterols and triterpenes; and that these compounds have antioxidant activity and consequently they can modulate the arachidonic acid (AA cascade and eicosanoid synthesis. This review analyzes the state of the art of olive oil components on the AA cascade and cellular mechanism involved in CRC such as intestinal epithelial cell growth/apoptosis, to understand the fact that the consumption of seed oils with high oleic content or EVOO will probably have different effects on CRC development.

  5. Physico-chemical quality and homogeneity of folic acid and iron in enriched flour using principal component analysis.

    Science.gov (United States)

    Soeiro, Bruno T; Boen, Thaís R; Wagner, Roger; Lima-Pallone, Juliana A

    2009-01-01

    The aim of the present work was to determine parameters of the corn and wheat flour matrix, such as protein, lipid, moisture, ash and carbohydrates, folic acid and iron contents. Three principal components explained 91% of the total variance. Wheat flours were characterized by high protein and moisture content. On the other hand, the corn flours had the greater carbohydrates, lipids and folic acid levels. The concentrations of folic acid were lower than the issued value for wheat flours. Nevertheless, corn flours presented extremely high values. The iron concentration was higher than that recommended in Brazilian legislation. Poor homogenization of folic acid and iron was observed in enriched flours. This study could be useful to help the governmental authorities in the enriched food programs evaluation.

  6. Mechanism and kinetics of electrochemical degradation of uric acid using conductive-diamond anodes.

    Science.gov (United States)

    Dbira, Sondos; Bensalah, Nasr; Bedoui, Ahmed

    2016-12-01

    Uric acid (UA) is one of the principal effluents of urine wastewaters, widely used in agriculture as fertilizer, which is potentially dangerous and biorefractory. Hence, the degradation of UA (2,6,8-trihydroxy purine) in aqueous solution of pH 3.0 has been studied by conductive-diamond electrochemical oxidation. Hydroxyl radicals formed from water oxidation at the surface of boron-doped diamond anodes were the main oxidizing agents. Effects of current density and supporting electrolyte on the degradation rate and process efficiency are assessed. Results show that the increase of current density from 20 to 60 mA cm(-2) leads to a decrease in the efficiency of the electrochemical process. In addition, the best degradation occurred in the presence of NaCl as conductive electrolyte. Interestingly, an almost total mineralization of 50 ppm UA was obtained when anodic oxidation was performed at low current densities (20 mA cm(-2)) and in the presence of NaCl. This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of UA. The identification of UA transformation products was performed by high-performance liquid chromatography (HPLC). HPLC analysis of treated solutions revealed that oxalic acid and urea were the two intermediates found. Oxalic acid was the most persistent product. Based on detected intermediates and bibliographic research, a mechanism of UA mineralization by anodic oxidation has been proposed. Ionic chromatography analysis confirmed the release of [Formula: see text] and [Formula: see text] ions during UA mineralization.

  7. Preparation and release kinetics of betulinic acid/ CS drug-loaded microspheres

    Directory of Open Access Journals (Sweden)

    Zhou Hao Ran

    2016-01-01

    Full Text Available Chitosan(CS is the unique alkaline polysaccharide in nature, because of its perfect biocompatibility and degradability, it is widely used in medicine, soft release and control release. The betulinic acid is the derivative of betulin, it has many pharmacological activities, such as anti- inflammatory, antitumor, anti-malaria and anti-HIV. In this paper, the Span-80 was used as emulsifiers, the glutaraldehyde was used as crosslinker. With the method of orthogonal experiment, the preparation technology was optimized. The microspheres were characterized by SEM and its degree of crosslinking, drug-loading rate and encapsulation efficiency were tested at the same time.

  8. Kinetics of Amino Acid racemization (epimerisation) in the dentine of fossil and modern bear teeth

    OpenAIRE

    Torres Pérez-Hidalgo, Trinidad José de

    2003-01-01

    The present study examines the question of whether heating experiments on modern bear teeth dentine model the pattern of D/L racemization in fossil teeth. Using samples of modern bear teeth dentine heated at 65°C, 85°C (up to 53 days), and 105°C (up to 71 days), and three independently dated fossil bear teeth, we have compared the modes of racemization induced by temperature in the modern samples and by time on the fossil samples. We have studied seven amino acids (aspartic and...

  9. Functional properties of whey, whey components, and essential amino acids: mechanisms underlying health benefits for active people (review).

    Science.gov (United States)

    Ha, Ewan; Zemel, Michael B

    2003-05-01

    Whey proteins and amino acid supplements have a strong position in the sports nutrition market based on the purported quality of proteins and amino acids they provide. Recent studies employing stable isotope methodology demonstrate the ability of whey proteins or amino acid mixtures of similar composition to promote whole body and muscle protein synthesis. Other developing avenues of research explore health benefits of whey that extend beyond protein and basic nutrition. Many bioactive components derived from whey are under study for their ability to offer specific health benefits. These functions are being investigated predominantly in tissue culture systems and animal models. The capacity of these compounds to modulate adiposity, and to enhance immune function and anti-oxidant activity presents new applications potentially suited to the needs of those individuals with active lifestyles. This paper will review the recent literature that describes functional properties of essential amino acids, whey proteins, whey-derived minerals and other compounds and the mechanisms by which they may confer benefits to active people in the context that exercise is a form of metabolic stress. The response to this stress can be positive, as with the accretion of more muscle and improved functionality or greater strength. However, overall benefits may be compromised if immune function or general health is challenged in response to the stress. From a mechanistic standpoint, whey proteins, their composite amino acids, and/or associated compounds may be able to provide substrate and bioactive components to extend the overall benefits of physical activity.

  10. Kinetic modeling of tricarboxylic acid cycle and glyoxylate bypass in Mycobacterium tuberculosis, and its application to assessment of drug targets

    Directory of Open Access Journals (Sweden)

    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

  11. Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

    Science.gov (United States)

    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

  12. A reproducible analytical system based on the multi-component analysis of triterpene acids in Ganoderma lucidum.

    Science.gov (United States)

    Da, Juan; Cheng, Chun-Ru; Yao, Shuai; Long, Hua-Li; Wang, Yan-Hong; Khan, Ikhlas A; Li, Yi-Feng; Wang, Qiu-Rong; Cai, Lu-Ying; Jiang, Bao-Hong; Liu, Xuan; Wu, Wan-Ying; Guo, De-An

    2015-06-01

    Ultra-performance liquid chromatography (UPLC) and Single Standard for Determination of Multi-Components (SSDMC) are becoming increasingly important for quality control of medicinal herbs; this approach was developed for Ganoderma lucidum. Special attention was necessary for the appropriate selection of markers, for determining the reproducibility of the relative retention times (RRT), and for the accuracy of conversion factors (F). Finally, ten components were determined, with ganoderic acid A serving as single standard. Stable system parameters were established, and with successful resolution of those issues, this analytical method could be used more broadly.

  13. Mechanism and kinetics in reactions of caffeic acid with radicals by pulse radiolysis and calculation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xifeng; Cai, Zhongli; Katsumura, Yosuke [Tokyo Univ., Tokai, Ibaraki (Japan). Nuclear Engineering Research Lab

    2000-03-01

    The interaction of caffeic acid with e{sub aq}{sup -}, (CH{sub 3}){sub 2}(OH) CCH{sub 2}{sup {center_dot}}, CO{sub 2}{sup {center_dot}}{sup -}, H{sup {center_dot}}, {center_dot}OH and N{sub 3}{sup {center_dot}} radicals were studied by {gamma}-, pulse radiolysis and molecular orbital calculation. UV-visible spectra of electron/{center_dot}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)

  14. Kinetics study of aqueous sorption of phenanthrene to humic acids and sediments

    Institute of Scientific and Technical Information of China (English)

    LIU Rui-xia; TANG Hong-xiao

    2004-01-01

    The sorption behavior was determined for a model polycyclic aromatic hydrocarbon(PAH), i.e., phenanthrene(PHN), from water to three humic acids(HAs) and three sediments in different reacting time. The chemical compositions of HA samples were measured using cross polarization magic angle spinning carbon-13(CPMAS 13C) NMR along with elemental analysis. The dissolved humic substances dissociating from solid HAs and sediments were characterized by 1H NMR. The experiments indicated that the sorption modes and mechanisms of natural sorbents for PHN varied significantly between short(<7 d) and long contact time and the reaction time should be taken into consideration in studying the overall sorption process. The sorption capacity() and exponent() might be relative to the properties of dissolved humic materials in initial stage but the solid aromatic organic matter after long time reaction. According to the experiments performed in this investigation and the previous researches, a conceptive sorption model was established.

  15. The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

    Directory of Open Access Journals (Sweden)

    J. Zahardis

    2007-01-01

    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 commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal is described. 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 oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN. 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, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids 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

  16. Recycling of metal-organic chemical vapor deposition waste of GaN based power device and LED industry by acidic leaching: Process optimization and kinetics study

    Science.gov (United States)

    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.

  17. One-pot five-component synthesis of highly functionalized piperidines using oxalic acid dihydrate as a homogenous catalyst

    Institute of Scientific and Technical Information of China (English)

    Seyed Sajad Sajadikhah; Malek Taher Maghsoodlou; Nourallah Hazeri; Sayyed Mostafa Habibi-Khorassani; Anthony C. Willis

    2012-01-01

    An efficient green protocol is described for the preparation of highly functionalized piperidines via a one-pot five-component reaction between aromatic aldehydes,anilines and β-ketoesters in the presence of oxalic acid dihydrate as catalyst in ethanol at ambient temperature.The structure as well as the relative stereochemistry of these compounds was confirmed by single X-ray crystallographic analysis.

  18. Orthogonal translation components for the in vivo incorporation of unnatural amino acids

    Science.gov (United States)

    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.

  19. Orthogonal translation components for the in vivo incorporation of unnatural amino acids

    Energy Technology Data Exchange (ETDEWEB)

    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.

  20. Orthogonal translation components for the in vivo incorporation of unnatural amino acids

    Energy Technology Data Exchange (ETDEWEB)

    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.

  1. Determination of sugars, organic acids, aroma components, and carotenoids in grapefruit pulps.

    Science.gov (United States)

    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.

  2. Acarbose Isolation with Gel Type Strong Acid Cation Exchange Resin:Equilibrium, Kinetic and Thermodynamic Studies

    Institute of Scientific and Technical Information of China (English)

    王亚军; 于蕾; 郑裕国; 王远山; 沈寅初

    2013-01-01

    Acarbose, a potentα-glucosidase inhibitor, is widely used as an oral anti-diabetic drug for the treatment of the type 2, non-insulin-dependent diabetes. In this work, a gel type strong acid cation exchange resin 001×4 was applied to isolate acarbose from fermentation broth. It was demonstrated that cation exchanger 001×4 displayed a large adsorption capacity and quick exchange rate for acarbose. The static adsorption equilibrium data were well fitted to the Langmuir equation. Column adsorption experiments demonstrated that high dynamic adsorption capacity was reached at bed height of 104.4 mm, feed flow rate of 1.0 ml·min-1 and acarbose concentration of 4.0 mg·ml-1. Under the optimized conditions, the column chromatography packed with cation exchanger 001×4 recovered 74.3%(by mass) of acarbose from Actinoplanes utahensis ZJB-08196 fermentation broth with purity of 80.1%(by mass), demonstrating great potential in the practical applications in acarbose separation.

  3. Reactions between Criegee Intermediates and the Inorganic Acids HCl and HNO3 : Kinetics and Atmospheric Implications.

    Science.gov (United States)

    Foreman, Elizabeth S; Kapnas, Kara M; Murray, Craig

    2016-08-22

    Criegee intermediates (CIs) are a class of reactive radicals that are thought to play a key role in atmospheric chemistry through reactions with trace species that can lead to aerosol particle formation. Recent work has suggested that water vapor is likely to be the dominant sink for some CIs, although reactions with trace species that are sufficiently rapid can be locally competitive. Herein, we use broadband transient absorption spectroscopy to measure rate constants for the reactions of the simplest CI, CH2 OO, with two inorganic acids, HCl and HNO3 , both of which are present in polluted urban atmospheres. Both reactions are fast; at 295 K, the reactions of CH2 OO with HCl and HNO3 have rate constants of 4.6×10(-11)  cm(3)  s(-1) and 5.4×10(-10)  cm(3)  s(-1) , respectively. Complementary quantum-chemical calculations show that these reactions form substituted hydroperoxides with no energy barrier. The results suggest that reactions of CIs with HNO3 in particular are likely to be competitive with those with water vapor in polluted urban areas under conditions of modest relative humidity.

  4. Release Kinetic in Yogurt from Gallic Acid Microparticles with Chemically Modified Inulin.

    Science.gov (United States)

    García, Paula; Vergara, Cristina; Robert, Paz

    2015-10-01

    Gallic acid (GA) was encapsulated with native (NIn), cross-linked (CIn) and acetylated (AIn) inulin by spray-drying. Inulin microparticles were characterized by encapsulation efficiency (EE) and their release profile in yogurt. The EE was significantly higher for GA-CIn (98%) compared with GA-NIn (81%) and GA-AIn (77%) microparticles, showing the effect of the modification of inulin on interaction of GA-polymer. GA release profile data in yogurt for GA-CIn, GA-NIn and GA-AIn were fitted to Peppas and Higuchi models in order to obtain the GA release rate constant. Although the GA release rate constants were significantly different among systems, these differences were slight and the GA release was fast (80% inulin-systems did not control GA release in yogurt. The mechanism of GA release followed a Fickian diffusion and relaxation of chains for all microparticles. According to the release profile, these microparticles would be best suited for use in instant foods.

  5. Isothermal crystallization kinetics of Poly (lactic acid) studied by ultrafast chip calorimeter

    Science.gov (United States)

    Jiang, Jing; Jiang, Wei; Huang, Zijie; Zhou, Dongshan; Xue, Gi

    2012-02-01

    Poly (lactic acid) (PLA) is a biocompatible, biodegradable polymer which has attracted much attention. The crystallization ability, as one of the most factors influencing the physical properties of the biomaterials such as thermal, mechanical, and biodegradable properties, has been widely studied mainly by differential scanning calorimeters. However, although the crystallization of PLA is relatively slow, it's difficult to avoid the crystallization from the nuclei or the structure reorganization of the metastable crystalline formed during the annealing process when we use the normal DSC with the heating rate on the level of tens of K/min. With the chip calorimeter whose scanning rate can go up to 1000 K/s, we can avoid the structure reorganization of metastable crystalline during the heating. In this case we annealed the PLA sample in the 80-120^oC temperature range and found the relationship between the onset the melting temperature Tm and crystallization temperature Tc is Tm= 0.53Tc+ 213.5 and the equilibrium melting temperature is Tm,f =179.6^oC.

  6. Kinetics of amino acid and glucose absorption following pancreatic diversion in the pig

    Science.gov (United States)

    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 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.

  7. Kinetics and mechanism of catalytic hydroprocessing of components of coal-derived liquids. Twentieth quarterly report, February 16, 1984-May 15, 1984

    Energy Technology Data Exchange (ETDEWEB)

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

    1984-06-26

    Kinetics data have been determined for the catalytic hydroprocessing of the acidic fractions of a heavy distillate of a liquid derived from Powhatan No. 5 coal. A commercial, sulfided Ni-Mo/..gamma..-Al/sub 2/O/sub 3/ catalyst was used in the experiments, carried out at 350/sup 0/C and 120 atm with the coal liquid fractions dissolved in cyclohexane. The feed and hydrotreated products were analyzed by gas chromatography/mass spectrometry. The data were analyzed with group-type methods for compound classes, and results were also obtained for some individual organooxygen compounds. Catalytic hydroprocessing leads to a large increase in the number of compounds and a shift to lower boiling ranges. The data are broadly consistent with reaction networks determined with pure compounds; the most important reactions include aromatic ring hydrogenation, hydrodeoxygenation, and hydrodemethylation. Pseudo first-order rate constants for conversion of the predominant organooxygen compounds are on the order of 10/sup -4/ L/(g of catalyst.s); the reactivity decreases in the order cyclohexylphenol > dimethylhydroxyindane > tetrahydronaphthol > phenylphenol > 1-naphthol. 12 references, 15 figures, 5 tables.

  8. The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

    Directory of Open Access Journals (Sweden)

    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

  9. Kinetic evaluation and process performance of an upflow anaerobic filter reactor degrading terephthalic acid.

    Science.gov (United States)

    Davutluoglu, Orkun I; Seckin, Galip

    2014-01-01

    The anaerobic degradation of terephthalic acid (TA) as the sole organic carbon source was studied in an upflow anaerobic filter (UAF) reactor. The reactor was seeded with biomass obtained from a full-scale upflow anaerobic sludge bed (UASB) reactor and was used to treat wastewater from a petrochemical facility producing dimethyl terephthalate. The UAF reactor was operated for 252 d with a constant hydraulic retention time of 24 h, and the organic loading rate (OLR) was gradually increased from 1 to 10 g-chemical oxygen demand (COD)/L d. After a lag period of approximately 40 d, the COD removal efficiency increased exponentially and high removal rate values (≈90%) were obtained, except for at highest OLR (10 g-COD/L d). The high removal rates and the robustness of the reactor performance could be attributed to the formation of biofilm as well as granular sludge. The methane production rates (0.22 to 2.15 L/d) correlated well with the removed OLRs (0.3 to 6.8 g-COD/L d) during the various phases of treatment, indicating that the main mechanism of TA degradation occurs via methanogenic reactions. The average methane content of the produced biogas was 70.3%. The modified Stover-Kincannon model was found to be applicable for the anaerobic degradation of TA in UAFs (Umax = 64.5, KB = 69.1 g-COD/L d and Ymax = 0.27 L-CH4/g-CODremoved). These results suggest that UAF reactors are among the most effective reactor configurations for the anaerobic degradation of TA.

  10. Acetic Acid, the active component of vinegar, is an effective tuberculocidal disinfectant.

    Science.gov (United States)

    Cortesia, Claudia; Vilchèze, Catherine; Bernut, Audrey; Contreras, Whendy; Gómez, Keyla; de Waard, Jacobus; Jacobs, William R; Kremer, Laurent; Takiff, Howard

    2014-02-25

    Effective and economical mycobactericidal disinfectants are needed to kill both Mycobacterium tuberculosis and non-M. tuberculosis mycobacteria. We found that acetic acid (vinegar) efficiently kills M. tuberculosis after 30 min of exposure to a 6% acetic acid solution. The activity is not due to pH alone, and propionic acid also appears to be bactericidal. M. bolletii and M. massiliense nontuberculous mycobacteria were more resistant, although a 30-min exposure to 10% acetic acid resulted in at least a 6-log10 reduction of viable bacteria. Acetic acid (vinegar) is an effective mycobactericidal disinfectant that should also be active against most other bacteria. These findings are consistent with and extend the results of studies performed in the early and mid-20th century on the disinfectant capacity of organic acids. IMPORTANCE Mycobacteria are best known for causing tuberculosis and leprosy, but infections with nontuberculous mycobacteria are an increasing problem after surgical or cosmetic procedures or in the lungs of cystic fibrosis and immunosuppressed patients. Killing mycobacteria is important because Mycobacterium tuberculosis strains can be multidrug resistant and therefore potentially fatal biohazards, and environmental mycobacteria must be thoroughly eliminated from surgical implements and respiratory equipment. Currently used mycobactericidal disinfectants can be toxic, unstable, and expensive. We fortuitously found that acetic acid kills mycobacteria and then showed that it is an effective mycobactericidal agent, even against the very resistant, clinically important Mycobacterium abscessus complex. Vinegar has been used for thousands of years as a common disinfectant, and if it can kill mycobacteria, the most disinfectant-resistant bacteria, it may prove to be a broadly effective, economical biocide with potential usefulness in health care settings and laboratories, especially in resource-poor countries.

  11. Kinetics study of heterogeneous reactions of ozone with erucic acid using an ATR-IR flow reactor.

    Science.gov (United States)

    Leng, Chunbo; Hiltner, Joseph; Pham, Hai; Kelley, Judas; Mach, Mindy; Zhang, Yunhong; Liu, Yong

    2014-03-01

    The ozone initiated heterogeneous oxidation of erucic acid (EA) thin film was investigated using a flow system combined with attenuated total reflection infrared spectroscopy (ATR-IR) over wide ranges of ozone concentrations (0.25-60 ppm), thin film thickness (0.1-1.0 μm), temperatures (263-298 K), and relative humidities (0-80% RH) for the first time. Pseudo-first-order rate constants, kapp, and overall reactive uptake coefficients, γ, were obtained through changes in the absorbance of C[double bond, length as m-dash]O stretching bands at 1695 cm(-1), which is assigned to the carbonyl group in carboxylic acid. Results showed that the reaction followed the Langmuir-Hinshelwood mechanism and kapp was largely dominated by surface reaction over bulk phase reaction. In addition, both the kapp and the γ values showed very strong temperature dependences (∼two orders of magnitude) over the temperature range; in contrast, they only slightly increased with increasing RH values from 0-80%. According to the kapp values as a function of temperature, the activation energy for the heterogeneous reaction was estimated to be 80.6 kJ mol(-1). Our results have suggested that heterogeneous reactions between ozone and unsaturated solid surfaces likely have a substantially greater temperature dependence than liquid ones. Moreover, the hygroscopic properties of EA thin films before and after exposure to ozone were also studied by measurement of water uptake. Based on the hygroscopicity data, the insignificant RH effect on reaction kinetics was probably due to the relatively weak water uptake by the unreacted and reacted EA thin films.

  12. Novel insights in transport mechanisms and kinetics of phenylacetic acid and penicillin-G in Penicillium chrysogenum.

    Science.gov (United States)

    Douma, Rutger D; Deshmukh, Amit T; de Jonge, Lodewijk P; de Jong, Bouke W; Seifar, Reza M; Heijnen, Joseph J; van Gulik, Walter M

    2012-01-01

    Although penicillin-G (PenG) production by the fungus Penicillium chrysogenum is a well-studied process, little is known about the mechanisms of transport of the precursor phenylacetic acid (PAA) and the product PenG over the cell membrane. To obtain more insight in the nature of these mechanisms, in vivo stimulus response experiments were performed with PAA and PenG in chemostat cultures of P. chrysogenum at time scales of seconds to minutes. The results indicated that PAA is able to enter the cell by passive diffusion of the undissociated acid at a high rate, but is at the same time actively excreted, possibly by an ATP-binding cassette transporter. This results in a futile cycle, dissipating a significant amount of metabolic energy, which was confirmed by increased rates of substrate and oxygen consumption, and carbon dioxide production. To estimate the kinetic properties of passive import and active export of PAA over the cell membrane, a dynamic mathematical model was constructed. With this model, a good description of the dynamic data could be obtained. Also, PenG was found to be rapidly taken up by the cells upon extracellular addition, indicating that PenG transport is reversible. The measured concentration gradient of PenG over the cell membrane corresponded well with facilitated transport. Also, for PenG transport, a dynamic model was constructed and validated with experimental data. The outcome of the model simulations was in agreement with the presence of a facilitated transport system for PenG.

  13. Kinetic and equilibrium constants of phytic acid and ferric and ferrous phytate derived from nuclear magnetic resonance spectroscopy.

    Science.gov (United States)

    Heighton, Lynne; Schmidt, Walter F; Siefert, Ronald L

    2008-10-22

    Inositol phosphates are metabolically derived organic phosphates (P) that increasingly appear to be an important sink and source of P in the environment. Salts of myo-inositol hexakisdihydrogen phosphate (IHP) or more commonly phytate are the most common inositol phosphates in the environment. IHP resists acidic dephosphorylation and enzymatic dephosphorylation as ferric or ferrous IHP. Mobility of IHP iron complexes is potentially pH and redox responsive, making the time scale and environmental fate and transport of the P associated with the IHP of interest to the mass balance of phosphorus. Ferric and ferrous complexes of IHP were investigated by proton nuclear magnetic resonance spectroscopy ( (1)H NMR) and enzymatic dephosphorylation. Ferrous IHP was found to form quickly and persist for a longer period then ferric IHP. Dissociation constants derived from (1)H NMR experiments of chemically exchanging systems at equilibrium were 1.11 and 1.19 and formation constants were 0.90 and 0.84 for ferric and ferrous IHP, respectively. The recovery of P from enzymatic dephosphorylation of ferric and ferrous IHP was consistent with the magnitude of the kinetic and equilibrium rate constants.

  14. Kinetics and Mechanism of Electron Transfer to Heptavalent Manganese by DL-Aspartic Acid in Alkaline Aqueous and Micellar Media

    Directory of Open Access Journals (Sweden)

    M. Sanjana

    2013-01-01

    Full Text Available The kinetics and mechanism of the electron transfer of dl-Aspartic acid (Asp by Mn (VII in alkaline medium has been studied spectrophotometrically over the range 2.0≤103[Asp] ≤5.0 mol dm−3; 0.01≤[OH-]≤0.05 mol dm−3; 298≤T≤318 K and I=0.05 mol dm−3 (KNO3. The reaction exhibits first-order dependence in [MnO4-]T but shows fractional-order dependence in both [Asp]T and [OH−]T. The reaction was studied in the presence of sodium dodecyl sulfate (SDS; an increase in the rate with the increase in the micellar concentration was observed. The products were characterized by spectral analysis. A mechanism involving free radicals is proposed. Asp binds MnO4- to form a complex that subsequently decomposes to products. Activation parameters ΔH° (kJ mol−1 and ΔS° (JK−1 mol−1 for the reaction are 5.62 ± 0.35 and −227.65 ± 1.1, respectively. The negative value of ΔS° indicates that oxidation occurs via inner sphere mechanism.

  15. Characterization of hydroxybenzoic acid chelating resins: equilibrium, kinetics, and isotherm profiles for Cd(II and Pb(II uptake

    Directory of Open Access Journals (Sweden)

    BHAVNA A. SHAH

    2011-06-01

    Full Text Available Chelating ion-exchange resins were synthesized by polycondensation of ortho/para hydroxybenzoic acid with resorcinol/catechol employing formaldehyde as cross-linking agent at 80±5 °C in DMF. The resins were characterized by FTIR and XRD. The uptake behaviour of synthesized resins for Cd(II and Pb(II ions have been studied depending on contact time, pH, metal ion concentration and temperature. The sorption data obtained at optimized conditions were analyzed by the Langmuir and Freundlich isotherms. Experimental data of all metal–resin system were best represented by the Freundlich isotherm. The maximum obtained sorption capacity for cadmium was 69.53 mg g-1 and 169.32 mg g-1 for Lead. The adsorption process follows first order kinetics and the specific rate constant Kr was obtained by the application of the Lagergan equation. Thermodynamic parameters ∆Gads, ∆Sads and ∆Hads were calculated for the metal–resin systems. The external diffusion rate constant (KS and the intra-particle diffusion rate constant (Kid were calculated by the Spahn–Schlunder and Weber–Morris models, respectively. The sorption process was found to follow an intra-particle diffusion phenomenon.

  16. Acid Blue 25 adsorption on base treated Shorea dasyphylla sawdust: Kinetic,isotherm, thermodynamic and spectroscopic analysis

    Institute of Scientific and Technical Information of China (English)

    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.

  17. Anodically generated manganese(III) sulphate for the oxidation of dipeptides in aqueous sulphuric acid medium: A kinetic study

    Indian Academy of Sciences (India)

    M N Kumara; D Channe Gowda; A Thimme Gowda; K S Rangappa

    2004-01-01

    The kinetic of oxidation of dipeptides (DP) namely valyl-glycine (Val-Gly), alanyl-glycine (Ala-Gly) and glycyl-glycine (Gly-Gly), by Mn(III) have been studied in the presence of sulphate ions in acid medium at 26°C. The reaction was followed spectrophotometrically at max = 500 nm. A firstorder dependence of the rate on both [Mn(III)]$_o$ and [DP]o was observed. The rate is independent of the concentration of reduction product, Mn(II) and hydrogen ions. The effects of varying the dielectric constant of the medium and addition of anions such as sulphate, chloride and perchlorate were studied. The activation parameters have been evaluated using Arrhenius and Eyring plots. The oxidation products were isolated and characterized. A mechanism involving the reaction of DP with Mn(III) in the ratelimiting step is suggested. An apparent correlation was noted between the rate of oxidation and the hydrophobicity of these dimers, where increased hyphobicity results in increased rate of oxidation.

  18. Omega 3 fatty acids increase spontaneous release of cytosolic components from tumor cells

    Energy Technology Data Exchange (ETDEWEB)

    Jenski, L.J.; Sturdevant, L.K.; Ehringer, W.D.; Stillwell, W. (Department of Biology, Indiana University-Purdue University, Indianapolis (United States))

    1991-05-01

    Mice fed menhaden (fish) oil or coconut oil-rich diets were inoculated intraperitoneally with a rapidly growing leukemia, T27A. After one week, the tumor cells were harvested, and 51Cr was used to label intracellular molecules. Spontaneous release of 51Cr was used as a measure of plasma membrane permeability. Compared to cells from mice fed coconut oil (rich in saturated fatty acids), tumor cells from mice fed menhaden oil (rich in long chain polyunsaturated omega 3 fatty acids) showed an increased level of spontaneous 51Cr release, which was exacerbated by increased temperature and reduced by extracellular protein. At physiological salt concentrations, the released 51Cr was detected in particles of approximately 2700 daltons. Enhanced permeability correlated with the incorporation of dietary (fish oil) omega 3 polyunsaturated fatty acids docosahexaenoic and eicosapentaenoic acid into the tumor cells. The results demonstrate that omega 3 fatty acids are incorporated into cellular constituents of tumor cells and change properties associated with the plasma membrane. This result suggests that dietary manipulation may be used to enhance tumor cell permeability and contribute to tumor eradication.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-05-01

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

  20. 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

    Science.gov (United States)

    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

  1. Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

    Science.gov (United States)

    Fawzy, Ahmed

    2016-03-15

    The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated.

  2. Parvalbumins from coelacanth muscle. III. Amino acid sequence of the major component.

    Science.gov (United States)

    Jauregui-Adell, J; Pechere, J F

    1978-09-26

    The primary structure of the major parvalbumin (pI = 4.52) from coelacanth muscle (Latimeria chalumnae) has been determined. Sequence analysis of the tryptic peptides, in some cases obtained with beta-trypsin, accounts for the total amino acid content of the protein. Chymotryptic peptides provide appropriate sequence overlaps, to complete the localization of the tryptic peptides. Examination of the amino acid sequence of this protein shows the typical structure of a beta-parvalbumin. Its position in the dendrogram of related calcium-binding proteins corresponds to that usually accepted for crossopterygians.

  3. Production of lactobionic acid and sorbitol from lactose/fructose substrate using GFOR/GL enzymes from Zymomonas mobilis cells: a kinetic study.

    Science.gov (United States)

    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.

  4. Lipid metabolism during bacterial growth, sporulation, and germination: kinetics of fatty acid and macromolecular synthesis during spore germination and outgrowth of Bacillus thuringiensis.

    Science.gov (United States)

    Nickerson, K W; De Pinto, J; Bulla, L A

    1975-01-01

    The timing and kinetics of fatty acid synthesis are delineated for Bacillus thuringiensis spore germination and outgrowth by analyzing [U-14C]acetate and [2-3H]glycerol incorporation into chloroform-methanol-extractable and trichloroacetic acid-precipitable lipids. In addition to measurement of pulsed and continuous labeling of fatty acids, monitoring the incorporation of radioactive phenylalanine, thymidine, and uridine from the onset of germination through first cell division provides a profile of biochemical activities related to membrane differentiation and cellular development. Upon germination, ribonucleic acid synthesis is initiated, immediately followed by rapid and extensive fatty acid synthesis that in turn precedes protein, deoxyribonucleic acid and triglyceride synthesis. Significantly, formation of fatty acids from acetate exhibits further developmental periodicity in which a large transient increase in fatty acid synthetic activity coincides with the approach of cell division. Radiorespirometric analyses indicates only slight oxidative decarboxylation of acetate and corroborates the extreme involvement of acetate in specific fatty acid biosynthetic reactions throughout cellular modification. These findings graphically demonstrate an intimate association of fatty acid metabolism with commitment to spore outgrowth and subsequent cell division.

  5. 菊粉酸降解动力学研究%Kinetic Studies on Acid Catalyzed Hydrolysis of Inulin

    Institute of Scientific and Technical Information of China (English)

    许威; 罗登林; 陈瑞红; 刘建学

    2012-01-01

    通过考察温度、溶液pH值及水分含量对菊粉酸降解的影响,探索菊粉酸水解规律。结果表明:菊粉水溶液在pH 5.0~7.0、温度低于100℃时具有良好的稳定性;但当pH值低于4.0时,菊粉出现明显的水解反应。菊粉溶液在不同温度和pH值下的酸降解动力学表明,其水解反应遵循一级反应动力学方程。利用菊粉凝胶特性考察水分含量与菊粉酸降解的关系,发现相同pH值(pH=3)条件下,水分含量越高,菊粉降解速率越快,凝胶中菊粉降解速率低于菊粉水溶液降解速率。%The effects of temperature,pH and water content on inulin hydrolysis were studied to understand the acid catalyzed hydrolysis process of inulin for industrial production of high-fructose syrup.The results showed that inulin solution had a good thermal stability at a pH value in the range of 5.0-7.0 and a temperature below 100 ℃,while inulin degradation started to occur when the pH was lower than 4.0.The acid catalyzed hydrolysis dynamics of inulin at different levels of temperature and pH showed that the reaction followed the first-order kinetics well.The relation between inulin gel degradation induced by acid and water content was also investigated.At the same pH,the higher water content,the faster inulin hydrolysis,and the degradation rate of inulin was lower in gel than in aqueous solution.

  6. Oxalic Acid Catalyzed Three Component One Pot Synthesis of 3,4-Dihydroquinazolin-4-ones

    Institute of Scientific and Technical Information of China (English)

    SANGSHETTI Jaiprakash-N.; KOKARE Nagnnath-D.; SHINDE Devanand-B.

    2008-01-01

    An efficient one-pot method for synthesis of an array of 3,4-dihydroquinazolin-4-ones from anthranilicacid, triethyl orthoformate, and anilines using oxalic acid as a catalyst was described. The present protocol offers im-provements for the synthesis of 3,4-dihydroquinazolin-4-ones with regard to short reaction time, high yields of products, and simplicity in operation.

  7. Multi-Component synthesis and computational studies of three novel thio-barbituric acid carbohydrate derivatives

    Science.gov (United States)

    Gupta, Stuti; Khare, Naveen K.

    2017-01-01

    The thio-barbituric acid is convenient starting compound for the preparation of fused heterocycles and its 5-substituted derivatives which are pharmacologically one of the most important classes of compounds. The fused compounds of thio-barbituric acid, 4-(1R,2S,3S,4S)-1,2,3,4,5-tetrahydroxy pentyl-10-phenyl-1,3,6,8,9,10 hexahydro-2,7-dithiooxopyrido [2,3-d; 6,5'] dipyrimidine-4,5 diones (1), 4-(1S,2S,3S,4S)-1,2,3,4,5-tetrahydroxy pentyl-10-phenyl-1,3,6,8,9,10 hexahydro-2,7-dithiooxopyrido [2,3-d; 6,5'] dipyrimidine-4,5 diones (2), 3-(1R,2S,3S)-1,2,3,4-tetrahydroxy butyl-10-phenyl-1,3,6,8,9,10 hexahydro-2,7-dithiooxopyrido [2,3-d; 6,5'] dipyrimidine-4,5 diones (3) have been synthesized in single step by the condensation of thio-barbituric acid with sugars (L-rhamnose, L-fucose and L-arabinose) & aniline using para-toluene sulfonic acid (p-TSA) as an effective acid catalyst under refluxing conditions. The molecular structure and detailed spectroscopic analysis of all three novel synthesized thiones derivatives have been performed using experimental techniques like 1H, 13C NMR, 2D (COSY, HSQC, DEPT-135 and DEPT-90) as well as theoretical calculations by density functional theory (DFT) using B3LYP and 6-311G + (d, p) basis set. The strength and nature of weak intramolecular interactions have been studied by atom in molecule (AIM) approach. Global reactivity descriptors have been computed to predict reactivity and reactive sites in the molecule.

  8. Leaching potential and changes in components of metals in two acidic ferrisols

    Institute of Scientific and Technical Information of China (English)

    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.

  9. Spatial distribution of soil acidity components in natural area field in the region Humaitá, Amazonas

    Directory of Open Access Journals (Sweden)

    Bruno Campos Mantovanelli

    2016-08-01

    Full Text Available Amazonian are highly weathered soils and characterized by high acidity, high aluminum saturation and low nutrient concentration, due to the high leach rates. The objective of this study was to evaluate the spatial distribution of acidity components in natural field environment in the region of Humaita, Amazonas. The study area is located in the region of Humaitá, south of Amazonas state, being situated in the geographical coordinates of (7 30 '24 "S and 63º 04' 56" W, the soil is classified as Cambissolo Háplico Alítico plíntico (CXalf. Soil samplings were conducted between March and October 2012 respectively in the natural field area, collected in sampling grid layout with dimensions of 70 mx 70 m and regular spacing between sampling points 10 m, sampled at two depths: 0 , 0 to 0.020 me 0.40-0.60 m. The following chemical analyzes were performed: pH in water potentiometrically determined by the ratio 1: 2.5, the exchangeable aluminum was determined from extraction solution KCl 1 mol / L-1 and the potential acidity extracted with buffered solution of calcium acetate pH 7.0. The results were subjected to analysis of descriptive statistics and geostatistics. From the mean values obtained for the soil acidity components to the natural field area, these results demonstrate the acidic nature of the soil environment and the possible correlation of a low concentration of bases due to the greater complexation of Al3+.

  10. COLLAPSE KINETIC OF COMPOSITES BASED ON COPOLYMERS OF ACRYLIC ACID AND ACRYLAMIDE FILLED WITH BENTONITE IN AQUEOUS SOLUTIONS OF POLYVALENT METALS

    Directory of Open Access Journals (Sweden)

    V. E. Sitnikova

    2017-01-01

    Full Text Available Polymer polyelectrolyte hydrogel composites of acrylic acid and acrylamide copolymer filled with different amounts of bentonite (from 1 to 5 wt.% were synthesized. Collapse kinetics of hydrogel composites was studied in solutions of different concentrations of polyvalent metal salts at a constant temperature of 25 °C. The mass of water given away from hydrogels into the solution was determined by gravimetric method. It has been found that the presence of bentonite in the polyelectrolyte hydrogel composites prevents to some extent collapse in electrolyte solutions, due to steric and electrostatic interactions between the filler particles. These interactions preclude further collapse of hydrogels. The Peleg's kinetic model, most precisely describing experimental data, was applied to calculation of kinetic constants of polymer hydrogels collapse. It is shown that the initial collapse rate and the kinetic constant of collapse and swelling depend non-monotonically on the concentration (ionic strength in the electrolyte solution. At the identical concentration of salts in the solution the kinetic constant of hydrogel collapse is independent of the radius of ions of metals of the studied salts.

  11. Adsorption of methyl orange and salicylic acid on a nano-transition metal composite: Kinetics, thermodynamic and electrochemical studies.

    Science.gov (United States)

    Arshadi, M; Mousavinia, F; Amiri, M J; Faraji, A R

    2016-12-01

    In this work synthesis of Mn-nanoparticles (MnNPs) supported on the Schiff base modified nano-sized SiO2Al2O3 mixed-oxides (Si/Al) and its implementation as an adsorbent for the removal of organic pollutions such as methyl orange (MO) and salicylic acid (SA) was investigated. Si/Al were functionalized by grafting Schiff base ligand and in the next step, MnNPs were prepared over the modified nano sol-gel Si/Al. Structures and adsorption characteristics of the obtained organometallic-modified SiO2/Al2O3 mixed oxide were studied by several methods such as elemental analysis, diffuse reflectance UV-vis spectroscopy, FT-IR spectroscopy, nitrogen adsorption/desorption, scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive X-ray (EDX), inductively coupled plasma (ICP-AES), Electron Paramagnetic Resonance (EPR), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). EPR data of the immobilized manganese ions resulted that the transition state of active sites in the nano-adsorbent are in the form of Mn(II) ions at the surface. The adsorption properties of heterogeneous Mn(II) ions showed that this nano-adsorbent has very good potential to remove MO and SA ions from aqueous solution. The removal efficiency of the SAPAS@MnNPs towards MO reached out to 89.3 and 29.1% and for SA approached to 54.6 and 18.9% at 150 and 500mg/dm(3) initial organic pollution concentrations, respectively. To investigate the adsorption kinetic of Mn(II) ions onto the nano-sized support, pseudo first and pseudo second order kinetics, and the Freundlich, Langmuir and Langmuir-Freundlich isotherm models have also been applied to the equilibrium adsorption data. The contact time to obtain equilibrium for maximum adsorption capacity was 45min. The adsorption process was spontaneous and endothermic in nature and it was well explained with pseudo-second-order kinetic model. No remarkable loss of removal capacity even after 8th times regeneration

  12. A Three-Component Assembly Promoted by Boronic Acids Delivers a Modular Fluorophore Platform (BASHY Dyes).

    Science.gov (United States)

    Santos, Fábio M F; Rosa, João N; Candeias, Nuno R; Carvalho, Cátia Parente; Matos, Ana I; Ventura, Ana E; Florindo, Helena F; Silva, Liana C; Pischel, Uwe; Gois, Pedro M P

    2016-01-26

    The modular assembly of boronic acids with Schiff-base ligands enabled the construction of innovative fluorescent dyes [boronic acid salicylidenehydrazone (BASHY)] with suitable structural and photophysical properties for live cell bioimaging applications. This reaction enabled the straightforward synthesis (yields up to 99%) of structurally diverse and photostable dyes that exhibit a polarity-sensitive green-to-yellow emission with high quantum yields of up to 0.6 in nonpolar environments. These dyes displayed a high brightness (up to 54,000 M(-1) cm(-1)). The promising structural and fluorescence properties of BASHY dyes fostered the preparation of non-cytotoxic, stable, and highly fluorescent poly(lactide-co-glycolide) nanoparticles that were effectively internalized by dendritic cells. The dyes were also shown to selectively stain lipid droplets in HeLa cells, without inducing any appreciable cytotoxicity or competing plasma membrane labeling; this confirmed their potential as fluorescent stains.

  13. Synthesis and degradation of nucleic acid components by formamide and iron sulfur minerals.

    Science.gov (United States)

    Saladino, Raffaele; Neri, Veronica; Crestini, Claudia; Costanzo, Giovanna; Graciotti, Michele; Di Mauro, Ernesto

    2008-11-19

    We describe the one-pot synthesis of a large panel of nucleic bases and related compounds from formamide in the presence of iron sulfur and iron-copper sulfur minerals as catalysts. The major products observed are purine, 1H-pyrimidinone, isocytosine, adenine, 2-aminopurine, carbodiimide, urea, and oxalic acid. Isocytosine and 2-aminopurine may recognize natural nucleobases by Watson-Crick and reverse Watson-Crick interactions, thus suggesting novel scenarios for the origin of primordial nucleic acids. Since the major problem in the origin of informational polymers is the instability of their precursors, we also investigate the effects of iron sulfur and iron-copper sulfur minerals on the stability of ribooligonucleotides in formamide and in water. All of the iron sulfur and iron-copper sulfur minerals stimulated degradation of RNA. The relevance of these findings with respect to the origin of informational polymers is discussed.

  14. Kinetics and Mechanistic Approach to the Benzimidazolium fluorochromate Oxidation of Indole-2-aldehyde in various percentages of Acetic acid and Water mixture

    Directory of Open Access Journals (Sweden)

    V. Saleem Malik

    2015-03-01

    Full Text Available The kinetics of benzimidazolium fluorochromate (BIFC catalysed oxidation of indole-2-aldehyde (2-InA with perchloric acid in 50% acetic acid–50% water solvent mixture at 303 K has been followed spectrophotometrically. The reaction is first order with respect to [BIFC], [2-InA] and [H+] and the reaction is catalyzed by hydrogen ions. A suitable mechanism has been proposed.

  15. Kinetic and thermodynamic studies on the adsorption of U(VI) ions on densely crosslinked poly(methacrylic acid) from aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Oezeroglu, C.; Keceli, G. [Istanbul Univ., Dept. of Chemistry, Avcilar Istanbul (Turkey)

    2009-07-01

    In this study, densely crosslinked poly(methacrylie acid) was used to adsorb uranium(VI) ions from aqueous solution. For this purpose, the crosslinked copolymer of ethylene glycol dimethacrylate (EGDM) and methacrylic acid (MA) containing 25% (w/w) methacrylic acid (MA) was synthesized by using dibenzoyl peroxide-N,N-dimethylaniline (BPO-DMA) initiator system at room temperature. The adsorption of uranium(Vl) ions on the copolymer sample (0.02 g copolymer/5 mL solution of U(VI) ions) was carried out in a batch reactor. The parameters which effect the uranium adsorption process, such as, contact time. pH of solution, initial uranium(VI) concentration and temperature were investigated. It was observed that an increase in these parameters enhanced the removal of U(VI) ions from aqueous solution. The adsorption data were modelled by the Freundlich. Langmuir and Dubinin-Radushkevich (D-R) isotherms. The adsorption capacity of the crosslinked copolymer and free energy change were calculated by using D-R isotherms. Thermodynamic parameters ({delta}H , {delta}S and {delta}G ) were determined for the adsorption of U(VI) ions from aqueous solutions by the crosslinked copolymer bearing methacrylic acid functional groups. Experimental adsorption data were analyzed using sorption kinetic models of the pseudo-first order and pseudo-second order kinetic models. It was observed that pseudo-second order kinetic model provided a high goodness of fit with experimental data for the adsorption of U(VI) ions on the crosslinked copolymer bearing methacrylic acid functional groups. The densely crosslinked poly(methacrylic acid) might be of interest in large scale uranium removals from aqueous solution, since it had high uranyl sorption capacities ranging from 0.16 to 2.37 mmol/g copolymer at pH 2.7 (293 K). (orig.)

  16. A study of pH-dependent photodegradation of amiloride by a multivariate curve resolution approach to combined kinetic and acid-base titration UV data.

    Science.gov (United States)

    De Luca, Michele; Ioele, Giuseppina; Mas, Sílvia; Tauler, Romà; Ragno, Gaetano

    2012-11-21

    Amiloride photostability at different pH values was studied in depth by applying Multivariate Curve Resolution Alternating Least Squares (MCR-ALS) to the UV spectrophotometric data from drug solutions exposed to stressing irradiation. Resolution of all degradation photoproducts was possible by simultaneous spectrophotometric analysis of kinetic photodegradation and acid-base titration experiments. Amiloride photodegradation showed to be strongly dependent on pH. Two hard modelling constraints were sequentially used in MCR-ALS for the unambiguous resolution of all the species involved in the photodegradation process. An amiloride acid-base system was defined by using the equilibrium constraint, and the photodegradation pathway was modelled taking into account the kinetic constraint. The simultaneous analysis of photodegradation and titration experiments revealed the presence of eight different species, which were differently distributed according to pH and time. Concentration profiles of all the species as well as their pure spectra were resolved and kinetic rate constants were estimated. The values of rate constants changed with pH and under alkaline conditions the degradation pathway and photoproducts also changed. These results were compared to those obtained by LC-MS analysis from drug photodegradation experiments. MS analysis allowed the identification of up to five species and showed the simultaneous presence of more than one acid-base equilibrium.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1985-01-01

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

  18. Investigation of Self-Assembly of Two-Component Organogel System Based on Trigonal Acids and Aminobenzothiazole Derivatives

    Directory of Open Access Journals (Sweden)

    Youbo Di

    2013-01-01

    Full Text Available We reported here the gelation behaviors of two-component organogel system based on different acids and aminobenzothiazole derivatives in various organic solvents. Their gelation behaviors in 20 solvents were tested as new organic gelators. It was shown that the molecular skeletons and substituted groups in these compounds played a crucial role in the gelation behavior of the mixtures. Only the binary mixture of 2-aminobenzothiazole and trigonal 1,3,5-benzenetricarboxylic acid with aromatic core could form organogels in ethanol and acetone. Morphological observations reveal that the microstructures of both xerogels showed similar wrinkle-shaped domains composed of sheet-like aggregates with many holes. Spectral studies reveal the hydrogen bonding interaction between the amide of the gelator and lamellar-like structure of the aggregates in both gels. The present investigation is a perspective to provide new clues for the design of new nanomaterials and functional textile materials with special microstructures.

  19. Myo-inositol esters of indole-3-acetic acid are endogenous components of Zea mays L. shoot tissue

    Science.gov (United States)

    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.

  20. Biomass torrefaction: modeling of volatile and solid product evolution kinetics.

    Science.gov (United States)

    Bates, Richard B; Ghoniem, Ahmed F

    2012-11-01

    The aim of this work is the development of a kinetics model for the evolution of the volatile and solid product composition during torrefaction conditions between 200 and 300°C. Coupled to an existing two step solid mass loss kinetics mechanism, this model describes the volatile release kinetics in terms of a set of identifiable chemical components, permitting the solid product composition to be estimated by mass conservation. Results show that most of the volatiles released during the first stage include highly oxygenated species such as water, acetic acid, and carbon dioxide, while volatiles released during the second step are composed primarily of lactic acid, methanol, and acetic acid. This kinetics model will be used in the development of a model to describe reaction energy balance and heat release dynamics.

  1. Effect of Span 60 on the Microstructure, Crystallization Kinetics, and Mechanical Properties of Stearic Acid Oleogels: An In-Depth Analysis.

    Science.gov (United States)

    Uvanesh, K; Sagiri, S S; Senthilguru, K; Pramanik, K; Banerjee, I; Anis, Arfat; Al-Zahrani, S M; Pal, Kunal

    2016-02-01

    Modulation of crystallization of stearic acid and its derivatives is important for tuning the properties of stearate oleogels. The present study delineates the crystallization of stearic acid in stearate oleogels in the presence of Span 60. Microarchitecture analysis revealed that stearic acid crystals in the oleogels changed its shape from plate-like structure to a branched architecture in the presence of Span 60. Consequently, a significant variation in the mobility of the solute molecules inside the oleogel (Fluorescence recovery after photobleaching studies, FRAP analysis) was observed. Thermal analysis (gelation kinetics and DSC) revealed shortening of nucleation induction time and secondary crystallization with an increase in the Span 60 concentration. Furthermore, isosolid diagram suggested better physical stability of the formulations at higher proportions of Span 60. XRD analysis indicated that there was a decrease in the crystal size and the crystallinity of the stearic acid crystals with an increase in Span 60 concentration in the Span 60 containing oleogels. However, crystal growth orientation was unidirectional and found unaltered with Span 60 concentration (Avarmi analysis using DSC data). The mechanical study indicated a composition-dependent variation in the viscoelastic properties (instantaneous [τ1 ], intermediate [τ2 ], and delayed [τ3 ] relaxation times) of the formulations. In conclusion, Span 60 can be used to alter the kinetics of the crystallization, crystal habit and crystal structure of stearic acid. This study provides a number of clues that could be used further for developing oleogel based formulation.

  2. Ruthenium(III) catalyzed oxidation of sulfanilic acid by diperiodatocuprate(III) in aqueous alkaline medium. A kinetic and mechanistic approach

    Science.gov (United States)

    Munavalli, D. S.; Patil, R. K.; Chimatadar, S. A.; Nandibewoor, S. T.

    2009-12-01

    The kinetics of ruthenium(III) catalyzed oxidation of sulfanilic acid by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of (0.50 mol dm-3) has been studied spectrophoto-metrically. The reaction between sulfanilic acid and DPC in alkaline medium exhibits 1: 4 stoichiometry (sulfanilic acid: DPC). The reaction is first order with respect to [DPC] and [RuIII] and has less than unit order both in [sulfanilic acid] and [alkali]. The active species of catalyst and oxidant have been identified. Intervention of free radicals was observed in the reaction. The main products were identified by spot test and IR. Probable mechanism is proposed and discussed. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to the slow step of the mechanism are computed and discussed. Thermodynamic quantities are also determined.

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

    Directory of Open Access Journals (Sweden)

    Sanjay Kumar Singh

    2011-09-01

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

  4. The chemistry of escapin: identification and quantification of the components in the complex mixture generated by an L-amino acid oxidase in the defensive secretion of the sea snail Aplysia californica.

    Science.gov (United States)

    Kamio, Michiya; Ko, Ko-Chun; Zheng, Shilong; Wang, Binghe; Collins, Stacy L; Gadda, Giovanni; Tai, Phang C; Derby, Charles D

    2009-01-01

    Escapin is an L-amino acid oxidase in the ink of a marine snail, the sea hare Aplysia californica, which oxidizes L-lysine (1) to produce a mixture of chemicals which is antipredatory and antimicrobial. The goal of our study was to determine the identity and relative abundance of the constituents of this mixture, using molecules generated enzymatically with escapin and also using products of organic syntheses. We examined this mixture under the natural range of pH values for ink-from approximately 5 at full strength to approximately 8 when fully diluted in sea water. The enzymatic reaction likely forms an equilibrium mixture containing the linear form alpha-keto-epsilon-aminocaproic acid (2), the cyclic imine Delta(1)-piperidine-2-carboxylic acid (3), the cyclic enamine Delta(2)-piperidine-2-carboxylic acid (4), possibly the linear enol 6-amino-2-hydroxy-hex-2-enoic acid (7), the alpha-dihydroxy acid 6-amino-2,2-dihydroxy-hexanoic acid (8), and the cyclic aminol 2-hydroxy-piperidine-2-carboxylic acid (9). Using NMR and mass spectroscopy, we show that 3 is the major component of this enzymatic product at any pH, but at more basic conditions, the equilibrium shifts to produce relatively more 4, and at acidic conditions, the equilibrium shifts to produce relatively more 2, 7, and/or 9. Studies of escapin's enzyme kinetics demonstrate that because of the high concentrations of escapin and L-lysine in the ink secretion, millimolar concentrations of 3, H(2)O(2), and ammonia are produced, and also lower concentrations of 2, 4, 7, and 9 as a result. We also show that reactions of this mixture with H(2)O(2) produce delta-aminovaleric acid (5) and delta-valerolactam (6), with 6 being the dominant component under the naturally acidic conditions of ink. Thus, the product of escapin's action on L-lysine contains an equilibrium mixture that is more complex than previously known for any L-amino acid oxidase.

  5. Asymmetric synthesis of quaternary aryl amino acid derivatives via a three-component aryne coupling reaction

    Directory of Open Access Journals (Sweden)

    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.

  6. Influence of organic acids on kinetic release of chromium in soil contaminated with leather factory waste in the presence of some adsorbents.

    Science.gov (United States)

    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.

  7. Protective Effects of Dihydrocaffeic Acid, a Coffee Component Metabolite, on a Focal Cerebral Ischemia Rat Model

    Directory of Open Access Journals (Sweden)

    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.

  8. Formation of flavor components by the reaction of amino acid and carbonyl compounds in mild conditions.

    Science.gov (United States)

    Pripis-Nicolau, L; de Revel, G; Bertrand, A; Maujean, A

    2000-09-01

    This work describe products of reactions between four alpha-dicarbonyl compounds (diacetyl, pentan-2,3-dione, glyoxal, and methylglyoxal) or two alpha-hydroxy ketones, (acetoine and acetol) and amino acids present in wines. The results shows the formation of odorous products or strong-smelling additives resulting from the Maillard and Strecker reaction in a primarily aqueous medium, at low temperature and low pH ( approximately pH 3.5) of the wine. GC/FID, GC/FPD, GC/NPD and GC/MS techniques were used. The olfactive characteristics of the products are described. In the presence of sulfur amino acids and in particular cysteine, many products were formed with a heterocycle production such as pyrazines and methylpyrazines, methylthiazoles, acetylthiazoles, acetylthiazolines, acetylthiazolidines, trimethyloxazole, and dimethylethyloxazoles. These various compounds present odors of sulfur, cornlike, pungent, nut, popcorn, roasted hazelnut, toasted, roasted, and ripe fruits. The chemical conditions of the model reactions are specified. The influence of temperature and pH on the reactions in the presence of cysteine were also studied.

  9. KINETIKA FERMENTASI ASAM ASETAT (VINEGAR) OLEH BAKTERI Acetobacter aceti B 127 DARI ETANOL HASIL FERMENTASI LIMBAH CAIR PULP KAKAO [Kinetics of Acetic Acid (Vinegar) Fermentation By Acetobacter aceti B127 from Ethanol Produced by Fermentation of Liquid Waste of Cacao Pulp

    OpenAIRE

    M. Supli Effendi

    2002-01-01

    Acetic acid concentration is one of vinegar’s quality parameter. Acetic acid concentration in vinegar is influenced by the activity of acetic acid bacteria. This research studied the kinetics of anaerobic fermentation of liquid waste of cacao pulp by Saccharomyces cerevisiae R60 to produce ethanol and the kinetics of acetic acid fermentation from ethanol by Acetobacter aceti B127. The kinetics of acetic acid fermentation from ethanol by Acetobacter aceti B127 can be used as a basic of biopro...

  10. Coffee component 3-caffeoylquinic acid increases antioxidant capacity but not polyphenol content in experimental cerebral infarction.

    Science.gov (United States)

    Ruiz-Crespo, Silvia; Trejo-Gabriel-Galan, Jose M; Cavia-Saiz, Monica; Muñiz, Pilar

    2012-05-01

    Although coffee has antioxidant capacity, it is not known which of its bioactive compounds is responsible for it, nor has it been analyzed in experimental cerebral infarction. We studied the effect one of its compounds, 3-caffeoylquinic acid (3-CQA), at doses of 4, 25 and 100 μg on plasma antioxidant capacity and plasma polyphenol content, measuring the differences before and after inducing a cerebral infarction in an experimental rat model. We compared them with 3-caffeoylquinic-free controls. The increase in total antioxidant capacity was only higher than in controls in 3-CQA treated animals with the highest dose. This increase in antioxidant capacity was not due to an increase in polyphenols. No differences between the experimental and control group were found regarding polyphenol content and cerebral infarction volume. In conclusion, this increase in antioxidant capacity in the group that received the highest dose of 3-CQA was not able to reduce experimental cerebral infarction.

  11. Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

    Science.gov (United States)

    Zhu, Chen; Hu, Fang Q.; Burden, David S.

    2001-11-01

    Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH) 3(a), and Fe(OH) 3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO 42- transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.

  12. Two-Component Regulatory Systems – implication in the quorum sensing mechanisms and bacteriocin production in lactic acid bacteria

    Directory of Open Access Journals (Sweden)

    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.

  13. 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

    Institute of Scientific and Technical Information of China (English)

    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.

  14. Evaluation of the Organic Acids Ability for Extraction of Anthocyanins and Phenolic Compounds from Different Sources and Their Degradation Kinetics During Cold Storage

    Directory of Open Access Journals (Sweden)

    Hosseini Sepideh

    2016-12-01

    Full Text Available The study of anthocyanin and phenolic acids has always received much attention due to their extensive range of colors and potential beneficial health effects. In this study extraction of anthocyanins from barberry, eggplant peel and red cabbage was investigated by using different organic solvents. Soluble solid content, antioxidant capacity, total monomeric anthocyanins and total phenolic content were determined and then degradation kinetics of anthocyanin in different solution during freezing process was assayed. In order to examine the effect of different acids on the degree of extraction of anthocyanin and total phenol, varied concentration of hydrochloric, citric and acetic acids were dissolved in a mixture of water and ethanol to prepare acidified aqueous solution. Results indicated that citric acid solution is one of the best solvents for phenolic and anthocyanin extraction which showed the best scavenging activity of DPPH radical. Results from degradation kinetics of total monomeric anthocyanins revealed that stability of anthocyanins in the solution depended on temperature and other ingredients which are present in the medium. Moreover, the present data confirmed that barberry and red cabbage acidified extracts could be one of the more stable natural food colorants based on anthocyanins.

  15. Thermodynamics of axial substitution and kinetics of reactions with amino acids for the paddlewheel complex tetrakis(acetato)chloridodiruthenium(II,III).

    Science.gov (United States)

    Santos, Rodrigo L S R; van Eldik, Rudi; de Oliveira Silva, Denise

    2012-06-18

    The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru(2)(CH(3)COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters ΔH°, ΔS°, and ΔV° were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru(2) substituted species. The results revealed that the [Ru(2)(CH(3)COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.

  16. The YvqE two-component system controls biofilm formation and acid production in Streptococcus pyogenes.

    Science.gov (United States)

    Isaka, Masanori; Tatsuno, Ichiro; Maeyama, Jun-Ichi; Matsui, Hideyuki; Zhang, Yan; Hasegawa, Tadao

    2016-07-01

    In Streptococcus pyogenes, proteins involved in determining virulence are controlled by stand-alone response regulators and by two-component regulatory systems. Previous studies reported that, compared to the parental strain, the yvqE sensor knockout strain showed significantly reduced growth and lower virulence. To determine the function of YvqE, we performed biofilm analysis and pH assays on yvqE mutants, and site-directed mutagenesis of YvqE. The yvqE deletion mutant showed a slower acid production rate, indicating that YvqE regulates acid production from sugar fermentation. The mutant strain, in which the Asp(26) residue in YvqE was replaced with Asn, affected biofilm formation, suggesting that this amino acid senses hydrogen ions produced by fermentative sugar metabolism. Signals received by YvqE were directly or indirectly responsible for inducing pilus expression. This study shows that at low environmental pH, biofilm formation in S. pyogenes is mediated by YvqE and suggests that regulation of pilus expression by environmental acidification could be directly under the control of YvqE.

  17. The electrooxidation mechanism of formic acid on platinum and on lead ad-atoms modified platinum studied with the kinetic isotope effect

    Science.gov (United States)

    Bełtowska-Brzezinska, M.; Łuczak, T.; Stelmach, J.; Holze, R.

    2014-04-01

    Kinetics and mechanism of formic acid (FA) oxidation on platinum and upd-lead ad-atoms modified platinum electrodes have been studied using unlabelled and deuterated compounds. Poisoning of the electrode surface by CO-like species was prevented by suppression of dissociative chemisorption of FA due to a fast competitive underpotential deposition of lead ad-atoms on the Pt surface from an acidic solution containing Pb2+ cations. Modification of the Pt electrode with upd lead induced a catalytic effect in the direct electrooxidation of physisorbed FA to CO2. With increasing degree of H/D substitution, the rate of this reaction decreased in the order: HCOOH > DCOOH ≥ HCOOD > DCOOD. HCOOH was oxidized 8.5-times faster on a Pt/Pb electrode than DCOOD. This primary kinetic isotope effect proves that the C-H- and O-H-bonds are simultaneously cleaved in the rate determining step. A secondary kinetic isotope effect was found in the dissociative chemisorption of FA in the hydrogen adsorption-desorption range on a bare Pt electrode after H/D exchange in the C-H bond, wherein the influence of deuterium substitution in the O-H group was negligibly small. Thus the C-H bond cleavage is accompanied by the C-OH and not the O-H bond split in the FA decomposition, producing CO-like species on the Pt surface sites.

  18. Enthalpies of hydrogen bonding of quinoline with o-phenylphenol and of hydrogen-bonding reactions involving the acid and base components of a coal-derived asphaltene

    Energy Technology Data Exchange (ETDEWEB)

    Dietz, A.G.; Blaha, C.; Li, N.C.

    1977-01-01

    Calorimetric studies are reported of hydrogen bonding between quinoline (Qu) and o-phenylphenol (OPP). The enthalpies of hydrogen-bonding of the acid and base components of a coal-derived asphaltene with OPP and Qu are also reported. The results provide strong evidence that the acid and base components of asphaltene function substantially as hydrogen donor and acceptor, respectively. 1 figure, 1 table.

  19. Heterogeneity of the electron exchange capacity of kitchen waste compost-derived humic acids based on fluorescence components.

    Science.gov (United States)

    Yuan, Ying; Tan, Wen-Bing; He, Xiao-Song; Xi, Bei-Dou; Gao, Ru-Tai; Zhang, Hui; Dang, Qiu-Ling; Li, Dan

    2016-11-01

    Composting is widely used for recycling of kitchen waste to improve soil properties, which is mainly attributed to the nutrient and structural functions of compost-derived humic acids (HAs). However, the redox properties of compost-derived HAs are not fully explored. Here, a unique framework is employed to investigate the electron exchange capacity (EEC) of HAs during kitchen waste composting. Most components of compost-derived HAs hold EEC, but nearly two-thirds of them are found to be easily destroyed by Shewanella oneidensis MR-1 and thus result in an EEC lower than the electron - donating capacity in compost-derived HAs. Fortunately, a refractory component also existed within compost-derived HAs and could serve as a stable and effective electron shuttle to promote the MR-1 involved in Fe(III) reduction, and its EEC was significantly correlated with the aromaticity and the amount of quinones. Nevertheless, with the increase of composting time, the EEC of the refractory component did not show an increasing trend. These results implied that there was an optimal composting time to maximize the production of HAs with more refractory and redox molecules. Recognition of the heterogeneity of EEC of the compost-derived HAs enables an efficient utilization of the composts for a variety of environmental applications. Graphical abstract Microbial reduction of compost-derived HAs.

  20. Aroma components of acid-hydrolyzed vegetable protein made by partial hydrolysis of rice bran protein.

    Science.gov (United States)

    Jarunrattanasri, Arporn; Theerakulkait, Chockchai; Cadwallader, Keith R

    2007-04-18

    Hydrolyzed vegetable protein (HVP) was prepared from rice bran protein concentrate (RBPc) by partial hydrolysis with aqueous 0.5 N HCl at 95 degrees C for 12 or 36 h (H-RBPc-12 and H-RBPc-36, respectively). Aroma components of the RBPc and the HVPs were characterized by gas chromatography-olfactometry, gas chromatography-mass spectrometry, aroma extract dilution analysis, and calculation of odor activity values (OAVs). The predominant odorants in RBPc were 3-methylbutanal, hexanal, 2-aminoacetophenone, (E)-2-nonenal, phenylacetaldehyde, and beta-damascenone. Among these, the odor of 2-aminoacetophenone, present at 59 ng/g in RBPc, was reminiscent of the typical odor of RBPc. Most of the predominant odorants had higher log3FD factors in the H-RBPc-36 as compared to H-RBPc-12. Aroma impact compounds of H-RBPc-12 and H-RBPc-36 were 2-methoxyphenol (guaiacol), 4-hydroxy-2,5-dimethyl-3(2H)furanone, 3-hydroxy-4,5-dimethyl-2(5H)furanone (sotolon), vanillin, 3-methylbutanal, (E)-2-nonenal, 4-vinyl-2-methoxyphenol (p-vinylguaiacol), and beta-damascenone. Guaiacol had the highest OAV values of 2770 and 17650 in H-RBPc-12 and H-RBPc-36, respectively.

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

    Directory of Open Access Journals (Sweden)

    GOVINDASAMY RAJARAJAN

    2009-02-01

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

  2. Difference between Extra- and IntracellularT1Values of Carboxylic Acids Affects the Quantitative Analysis of Cellular Kinetics by Hyperpolarized NMR

    DEFF Research Database (Denmark)

    Karlsson, Magnus; Jensen, Pernille Rose; Ardenkjær-Larsen, Jan Henrik;

    2016-01-01

    Incomplete knowledge of the longitudinal relaxationtime constant (T1) leads to incorrect assumptions in quantita-tive kinetic models of cellular systems, studied by hyper-polarized real-time NMR. Using an assay that measures theintracellular signal of small carboxylic acids in living cells......, theintracellular T1of the carboxylic acid moiety of acetate, keto-isocaproate, pyruvate, and butyrate was determined. Theintracellular T1is shown to be up to four-fold shorter thanthe extracellular T1. Such a large difference in T1valuesbetween the inside and the outside of the cell has significantinfluence...... on the quantification of intracellular metabolicactivity. It is expected that the significantly shorter T1valueof the carboxylic moieties inside cells is a result of macro-molecular crowding. An artificial cytosol has been preparedand applied to predict the T1of other carboxylic acids. Wedemonstrate the value...

  3. Difference between Extra- and Intracellular T1 Values of Carboxylic Acids Affects the Quantitative Analysis of Cellular Kinetics by Hyperpolarized NMR

    DEFF Research Database (Denmark)

    Karlsson, Magnus; Jensen, Pernille Rose; Ardenkjær-Larsen, Jan Henrik;

    2016-01-01

    Incomplete knowledge of the longitudinal relaxation time constant (T1) leads to incorrect assumptions in quantitative kinetic models of cellular systems, studied by hyperpolarized real-time NMR. Using an assay that measures the intracellular signal of small carboxylic acids in living cells......, the intracellular T1 of the carboxylic acid moiety of acetate, ketoisocaproate, pyruvate, and butyrate was determined. The intracellular T1 is shown to be up to four-fold shorter than the extracellular T1. Such a large difference in T1 values between the inside and the outside of the cell has significant influence...... on the quantification of intracellular metabolic activity. It is expected that the significantly shorter T1 value of the carboxylic moieties inside cells is a result of macromolecular crowding. An artificial cytosol has been prepared and applied to predict the T1 of other carboxylic acids. We demonstrate the value...

  4. Difference between Extra- and Intracellular T1 Values of Carboxylic Acids Affects the Quantitative Analysis of Cellular Kinetics by Hyperpolarized NMR.

    Science.gov (United States)

    Karlsson, Magnus; Jensen, Pernille Rose; Ardenkjaer-Larsen, Jan Henrik; Lerche, Mathilde H

    2016-10-17

    Incomplete knowledge of the longitudinal relaxation time constant (T1 ) leads to incorrect assumptions in quantitative kinetic models of cellular systems, studied by hyperpolarized real-time NMR. Using an assay that measures the intracellular signal of small carboxylic acids in living cells, the intracellular T1 of the carboxylic acid moiety of acetate, keto-isocaproate, pyruvate, and butyrate was determined. The intracellular T1 is shown to be up to four-fold shorter than the extracellular T1 . Such a large difference in T1 values between the inside and the outside of the cell has significant influence on the quantification of intracellular metabolic activity. It is expected that the significantly shorter T1 value of the carboxylic moieties inside cells is a result of macromolecular crowding. An artificial cytosol has been prepared and applied to predict the T1 of other carboxylic acids. We demonstrate the value of this prediction tool.

  5. Structural Characterisation of FabG from Yersinia pestis, a Key Component of Bacterial Fatty Acid Synthesis.

    Directory of Open Access Journals (Sweden)

    Jeffrey D Nanson

    Full Text Available Ketoacyl-acyl carrier protein reductases (FabG are ubiquitously expressed enzymes that catalyse the reduction of acyl carrier protein (ACP linked thioesters within the bacterial type II fatty acid synthesis (FASII pathway. The products of these enzymes, saturated and unsaturated fatty acids, are essential components of the bacterial cell envelope. The FASII reductase enoyl-ACP reductase (FabI has been the focus of numerous drug discovery efforts, some of which have led to clinical trials, yet few studies have focused on FabG. Like FabI, FabG appears to be essential for survival in many bacteria, similarly indicating the potential of this enzyme as a drug target. FabG enzymes are members of the short-chain alcohol dehydrogenase/reductase (SDR family, and like other SDRs, exhibit highly conserved secondary and tertiary structures, and contain a number of conserved sequence motifs. Here we describe the crystal structures of FabG from Yersinia pestis (YpFabG, the causative agent of bubonic, pneumonic, and septicaemic plague, and three human pandemics. Y. pestis remains endemic in many parts of North America, South America, Southeast Asia, and Africa, and a threat to human health. YpFabG shares a high degree of structural similarity with bacterial homologues, and the ketoreductase domain of the mammalian fatty acid synthase from both Homo sapiens and Sus scrofa. Structural characterisation of YpFabG, and comparison with other bacterial FabGs and the mammalian fatty acid synthase, provides a strong platform for virtual screening of potential inhibitors, rational drug design, and the development of new antimicrobial agents to combat Y. pestis infections.

  6. Palladium(II)-catalyzed oxidation of L-tryptophan by hexacyanoferrate(III) in perchloric acid medium: a kinetic and mechanistic approach

    Indian Academy of Sciences (India)

    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.

  7. Thermal degradation kinetics and solid state, temperature dependent, electrical conductivity of charge–transfer complex of phenothiazine with chloranil and picric acid

    Indian Academy of Sciences (India)

    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. An efficient tandem approach for the synthesis of functionalized 2-pyridone-3-carboxylic acids using three-component reaction in aqueous media.

    Science.gov (United States)

    Mehrparvar, Saber; Balalaie, Saeed; Rabbanizadeh, Mahnaz; Ghabraie, Elmira; Rominger, Frank

    2014-08-01

    Novel analogs of 2-pyridone-3-carboxylic acids 4a-l have been prepared by the three-component reaction of 3-formyl chromone, Meldrum's acid, and primary amines in the presence of a catalytic amount of diammonium hydrogen phosphate in water. Good-to-high yields, easy work-up, and an environmentally friendly profile are the advantages of this method for the synthesis of 2-pyridone-3-carboxylic acid derivatives.

  9. Development of multi-component diesel surrogate fuel models – Part I: Validation of reduced mechanisms of diesel fuel constituents in 0-D kinetic simulations

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Pang, Kar Mun; Ng, Hoon Kiat

    2016-01-01

    In the present work, development and validation of reduced chemical kinetic mechanisms for several different hydrocarbons are performed. These hydrocarbons are potential representative for practical diesel fuel constituents. n-Hexadecane (HXN), 2,2,4,4,6,8,8-heptamethylnonane (HMN), cyclohexane...... (CHX) and toluene are selected to represent straight-alkane, branched-alkane, cyclo-alkane and aromatic compounds in the diesel fuel. A five-stage chemical kinetic mechanism reduction scheme formulated in the previous work is applied to develop the reduced HMN and CHX models based on their respective...... developed fuel constituent reduced mechanisms, together with the formerly derived reduced HXN mechanism are comprehensively validated in zero-dimensional chemical kinetic simulations under a wide range of shock tube and jet-stirred reactor (JSR) conditions. Well agreement between the reduced and detailed...

  10. Kinetics of Cd2+ and Cr3+ Sorption from Aqueous Solutions Using Mercaptoacetic Acid Modified and Unmodified Oil Palm Fruit Fibre(Elaeis guineensis) Adsorbents

    Institute of Scientific and Technical Information of China (English)

    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).

  11. Effect of humic acid and transition metal ions on the debromination of decabromodiphenyl by nano zero-valent iron: kinetics and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    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+}.

  12. Peak alignment and robust principal component analysis of gas chromatograms of fatty acid methyl esters and volatiles

    DEFF Research Database (Denmark)

    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...... that the usage of ROPCA is advantageous, compared with traditional PCA, when analysing the entire profile of chromatographic data in cases of sub-optimally aligned data. It also demonstrates how choosing the most robust PCA (sample or element-wise) depends on the type of outliers present in the data set....

  13. Studies of heteropoly acid/polyvinylidenedifluoride-hexafluoroproylene composite membranes and implication for the use of heteropoly acids as the proton conducting component in a fuel cell membrane

    Energy Technology Data Exchange (ETDEWEB)

    Malers, Jennifer L.; Sweikart, Mary-Ann [Department of Chemical Engineering, Colorado School of Mines, Golden, CO 80401 (United States); Hydrogen Technologies and Systems Center, National Renewable Energy Laboratory, Golden, CO 80401 (United States); Horan, James L. [Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, CO 80401 (United States); Turner, John A. [Hydrogen Technologies and Systems Center, National Renewable Energy Laboratory, Golden, CO 80401 (United States); Herring, Andrew M. [Department of Chemical Engineering, Colorado School of Mines, Golden, CO 80401 (United States)

    2007-10-11

    Complete polarization curves for a number of heteropoly acids (HPAs), H{sub 3}PW{sub 12}O{sub 40}, {alpha}-H{sub 3}P{sub 2}W{sub 18}O{sub 62}, H{sub 6}P{sub 2}W{sub 21}O{sub 71}, and H{sub 6}As{sub 2}W{sub 21}O{sub 69} as the only proton conducting component are presented for the first time. Both thin pellets of HPA and composite membranes of 1:1 (w/w) of HPA and polyvinylidenedifluoride-hexafluoropropylene (PVDF-HFP) are investigated. Although the pellets are somewhat variable, the HPA phase changes can be observed by electrochemistry and these materials show promise for solid acid fuel cell performance at >200 C. The high proton conductivities reported for HPAs at RT are demonstrated in fuel cells using HPA/PVDF-HFP composites with limiting current densities as high as 1.6 A cm{sup -2} using dry O{sub 2} and H{sub 2}. Moderate fuel cell activity is demonstrated for {alpha}-H{sub 3}PW{sub 18}O{sub 62} at 120 C and 25%RH. Unfortunately all of the materials studied were somewhat porous and the open circuit potentials observed were somewhat low. We were also able to show that an HPA fuel cell could be shorted by reduction of the HPA to a heteropoly blue under exceptional circumstances. (author)

  14. Studies of heteropoly acid/polyvinylidenedifluoride-hexafluoroproylene composite membranes and implication for the use of heteropoly acids as the proton conducting component in a fuel cell membrane

    Science.gov (United States)

    Malers, Jennifer L.; Sweikart, Mary-Ann; Horan, James L.; Turner, John A.; Herring, Andrew M.

    Complete polarization curves for a number of heteropoly acids (HPAs), H 3PW 12O 40, α-H 3P 2W 18O 62, H 6P 2W 21O 71, and H 6As 2W 21O 69 as the only proton conducting component are presented for the first time. Both thin pellets of HPA and composite membranes of 1:1 (w/w) of HPA and polyvinylidenedifluoride-hexafluoropropylene (PVDF-HFP) are investigated. Although the pellets are somewhat variable, the HPA phase changes can be observed by electrochemistry and these materials show promise for solid acid fuel cell performance at >200 °C. The high proton conductivities reported for HPAs at RT are demonstrated in fuel cells using HPA/PVDF-HFP composites with limiting current densities as high as 1.6 A cm -2 using dry O 2 and H 2. Moderate fuel cell activity is demonstrated for α-H 3PW 18O 62 at 120 °C and 25%RH. Unfortunately all of the materials studied were somewhat porous and the open circuit potentials observed were somewhat low. We were also able to show that an HPA fuel cell could be shorted by reduction of the HPA to a heteropoly blue under exceptional circumstances.

  15. Amino acid efflux by asexual blood-stage Plasmodium falciparum and its utility in interrogating the kinetics of hemoglobin endocytosis and catabolism in vivo.

    Science.gov (United States)

    Dalal, Seema; Klemba, Michael

    2015-06-01

    The endocytosis and catabolism of large quantities of host cell hemoglobin is a hallmark of the intraerythrocytic asexual stage of the human malaria parasite Plasmodium falciparum. It is known that the parasite's production of amino acids from hemoglobin far exceeds its metabolic needs. Here, we show that P. falciparum effluxes large quantities of certain non-polar (Ala, Leu, Val, Pro, Phe, Gly) and polar (Ser, Thr, His) amino acids to the external medium. That these amino acids originate from hemoglobin catabolism is indicated by the strong correlation between individual amino acid efflux rates and their abundances in hemoglobin, and the ability of the food vacuole falcipain inhibitor E-64d to greatly suppress efflux rates. We then developed a rapid, sensitive and precise method for quantifying flux through the hemoglobin endocytic-catabolic pathway that is based on leucine efflux. Optimization of the method involved the generation of a novel amino acid-restricted RPMI formulation as well as the validation of D-norvaline as an internal standard. The utility of this method was demonstrated by characterizing the effects of the phosphatidylinositol-3-kinase inhibitors wortmannin and dihydroartemisinin on the kinetics of Leu efflux. Both compounds rapidly inhibited Leu efflux, which is consistent with a role for phosphtidylinositol-3-phosphate production in the delivery of hemoglobin to the food vacuole; however, wortmannin inhibition was transient, which was likely due to the instability of this compound in culture medium. The simplicity, convenience and non-invasive nature of the Leu efflux assay described here makes it ideal for characterizing the in vivo kinetics of hemoglobin endocytosis and catabolism, for inhibitor target validation studies, and for medium-throughput screens to identify novel inhibitors of cytostomal endocytosis.

  16. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Directory of Open Access Journals (Sweden)

    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.

  17. Acid rock drainage and metal leaching from mine waste material (tailings) of a Pb-Zn-Ag skarn deposit: environmental assessment through static and kinetic laboratory tests

    OpenAIRE

    Blanca Adriana Méndez Ortiz; Alejandro Carrillo Chávez; Marcos Gustavo Monroy Fernández

    2007-01-01

    In this work, the processes and products involved in the generation of acid rock drainage – metal leaching (ARD-ML) from mine waste material (tailings) derived from the exploitation of an ore type Pb- Zn-Ag skarn were characterized. Laboratory tests (static and kinetic) of historic and recent tailings were conducted along with the mineralogical characterization of solids, and chemical analyses of solids and leachates. Pyrite (FeS2) is the most abundant sulfi de phase, and one of the main mine...

  18. Synthesis of interpenetrating network hydrogel from poly(acrylic acid-co-hydroxyethyl methacrylate) and sodium alginate: modeling and kinetics study for removal of synthetic dyes from water.

    Science.gov (United States)

    Mandal, Bidyadhar; Ray, Samit Kumar

    2013-10-15

    Several interpenetrating network (IPN) hydrogels were made by free radical in situ crosslink copolymerization of acrylic acid (AA) and hydroxy ethyl methacrylate in aqueous solution of sodium alginate. N,N'-methylenebisacrylamide (MBA) was used as comonomer crosslinker for making these crosslink hydrogels. All of these hydrogels were characterized by carboxylic content, FTIR, SEM, XRD, DTA-TGA and mechanical properties. Swelling, diffusion and network parameters of the hydrogels were studied. These hydrogels were used for adsorption of two important synthetic dyes, i.e. Congo red and methyl violet from water. Isotherms, kinetics and thermodynamics of dye adsorption by these hydrogels were also studied.

  19. Assessment of two kinetic tests to predict the acid mine drainage in waste rock samples of a uranium mine

    OpenAIRE

    Abreu, Adriana Trópia de; Faria, Efigênia Miranda de; Chaves, Carla Thamilis Fonseca; Leite,Adilson do Lago; Lena,Jorge Carvalho de

    2014-01-01

    Acid mine drainage is the result of the oxidation process of sulfide bearing rocks. This process occurs when the sulfide material is exposed to atmospheric conditions. Under these conditions, successive oxidation reactions yield sulfuric acid generating acidic waters. This problem becomes more serious when the surrounding rocks are not able to neutralize the acid. The low pH condition of the drained water accelerates the solubility process of solid materials (rocks, soils and sediments) and f...

  20. Sorption kinetics of ofloxacin in soils and mineral particles.

    Science.gov (United States)

    Pan, Bo; Wang, Peng; Wu, Min; Li, Jing; Zhang, Di; Xiao, Di

    2012-12-01

    The environmental behavior of antibiotics is not well known and the precise environmental risk assessment is not practical. This study investigated the sorption kinetics of ofloxacin, a widely used antibiotics, on soil particles with different organic carbon contents as well as soil components (a humic acid, ferric oxide and kaolinite). Two-compartment sorption kinetics were mathematically recognized (except ferric oxide because of its very fast sorption). The apparent sorption rate and the contribution of fast sorption compartment decreased with the increased organic carbon content with the exception of humic acid, suggesting that the slow sorption sites were partially located in organo-mineral complex. The OFL concentration-dependent sorption kinetics suggested that the slow sorption compartment was not controlled by diffusion process as indicated by slower sorption at higher OFL loading. The difference between OFL sorption kinetics and those of hydrophobic organic contaminants was discussed and possible mechanism of OFL two-compartment sorption was proposed.