Academic literature on the topic 'Pseudo-first order rate constant and second order rate constant'
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Journal articles on the topic "Pseudo-first order rate constant and second order rate constant"
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Wigfield, Donald C., and Douglas M. Goltz. "Kinetics of reconstitution of apotyrosinase by copper." Biochemistry and Cell Biology 68, no. 2 (February 1, 1990): 476–79. http://dx.doi.org/10.1139/o90-067.
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The kinetics of the reconstitution reaction of apotyrosinase with copper (II) ions are reported. The reaction is pseudo first order with respect to apoenzyme and the values of these pseudo first order rate constants are reported as a function of copper (II) concentration. Two copper ions bind to apoenzyme, and if the second one is rate limiting, the kinetically relevant copper concentration is the copper originally added minus the amount used in binding the first copper ion to enzyme. This modified copper concentration is linearly related to the magnitude of the pseudo first order rate constant, up to a copper concentration of 1.25 × 10−4 M (10-fold excess), giving a second order rate constant of 7.67 × 102 ± 0.93 × 102 M−1∙s−1.Key words: apotyrosinase, copper, tyrosinase.
2
Ho, Y. S., and G. McKay. "Kinetic Model for Lead(II) Sorption on to Peat." Adsorption Science & Technology 16, no. 4 (April 1998): 243–55. http://dx.doi.org/10.1177/026361749801600401.
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The kinetics of lead sorption on to peat have been investigated. The batch sorption model, based on the assumption of a pseudo-second order mechanism, has been developed to predict the rate constant of sorption, the equilibrium capacity and initial sorption rate with the effect of initial lead(II) concentration, peat particle size and temperature. An equilibrium capacity of sorption has been evaluated with the pseudo-second order rate equation. In addition, an activation energy of sorption has also been determined based on the pseudo-second order rate constants.
3
Wigfield, Donald C., and Season Tse. "Oxidation of the mercurous ion by peroxidase." Canadian Journal of Chemistry 64, no. 5 (May 1, 1986): 969–72. http://dx.doi.org/10.1139/v86-162.
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The kinetics of oxidation of the mercurous ion by peroxidase have been measured by following the disappearance of mercurous ion using cold-vapour atomic absorption spectroscopy. Pseudo-first-order kinetics are observed with respect to mercurous ion, and the pseudo-first-order rate constants are linearly related to peroxidase concentration, showing first-order dependence on peroxidase. This behaviour is identical to oxidation of elemental mercury, and the second-order rate constant, 1.44 × 104 M−1 s−1 at 23 °C, is also, within experimental error, the same as that for elemental mercury oxidation. The data are interpreted in terms of peroxidase-induced disproportionation of the mercurous dimer, followed by two-electron oxidation of zero-valent mercury.
4
Pe, Justin Alfred, Sung-Phil Mun, and Min Lee. "Fe–Doped TiO2–Carbonized Medium–Density Fiberboard for Photodegradation of Methylene Blue under Visible Light." Materials 14, no. 17 (August 27, 2021): 4888. http://dx.doi.org/10.3390/ma14174888.
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Fe–doped titanium dioxide–carbonized medium–density fiberboard (Fe/TiO2–cMDF) was evaluated for the photodegradation of methylene blue (MB) under a Blue (450 nm) light emitting diode (LED) module (6 W) and commercial LED (450 nm + 570 nm) bulbs (8 W, 12 W). Adsorption under daylight/dark conditions (three cycles each) and photodegradation (five cycles) were separately conducted. Photodegradation under Blue LED followed pseudo-second-order kinetics while photodegradation under commercial LED bulbs followed pseudo-first-order kinetics. Photodegradation rate constants were corrected by subtracting the adsorption rate constant except on the Blue LED experiment due to their difference in kinetics. For 8 W LED, the rate constants remained consistent at ~11.0 × 10−3/h. For 12 W LED, the rate constant for the first cycle was found to have the fastest photodegradation performance at 41.4 × 10−3/h. After the first cycle, the rate constants for the second to fifth cycle remained consistent at ~28.5 × 10−3/h. The energy supplied by Blue LED or commercial LEDs was sufficient for the bandgap energy requirement of Fe/TiO2–cMDF at 2.60 eV. Consequently, Fe/TiO2–cMDF was considered as a potential wood-based composite for the continuous treatment of dye wastewater under visible light.
5
Djordjevic, Dragan, Dragan Stojiljkovic, and Miodrag Smelcerovic. "Adsorption Kinetics of Reactive Dyes on Ash from Town Heating Plant." Archives of Environmental Protection 40, no. 3 (December 11, 2014): 123–35. http://dx.doi.org/10.2478/aep-2014-0024.
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Abstract In order to investigate the mechanism of adsorption of reactive dyes from the textile industry on ash from heating plant produced by brown coal combustion, some characteristic sorption constants are determined using Langergren adsorption equations for pseudo-fi rst and pseudo-second order. Combined kinetic models of pseudo-first order and pseudo-second order can provide a simple but satisfactory explanation of the adsorption process for a reactive dye. According to the characteristic diagrams and results of adsorption kinetic parameters of reactive dyes on ashes, for the applied amounts of the adsorbents and different initial dye concentrations, it can be concluded that the rate of sorption is fully functionally described by second order adsorption model. According to the results, the rate constant of pseudo-second order decreases with increasing initial dye concentration and increases with increasing amount of adsorbent – ash.
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Aviram, I., and M. Sharabani. "Kinetic studies of the reduction of neutrophil cytochrome b-558 by dithionite." Biochemical Journal 237, no. 2 (July 15, 1986): 567–72. http://dx.doi.org/10.1042/bj2370567.
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The reduction with dithionite of neutrophil cytochrome b-558, implicated in superoxide generation by activated neutrophils, was investigated by a stopped-flow technique in non-ionic-detergent extracts of the membranes and in crude membrane particles. The dependence of the pseudo-first-order rate constants on the concentration of dithionite was consistent with a mechanism of reduction that involves the dithionite anion monomer SO2.- as the reactive species. The estimated second-order rate constant was 7.8 × 10(6) M-1 × S-1 for Lubrol PX-solubilized cytochrome b-558 and 5.1 × 10(6) M-1 × S-1 for the membrane-bound protein. The similarity of the kinetic constants suggests that solubilization did not introduce gross changes in the reactive site. Imidazole and p-chloromercuribenzoate, known as inhibitors of NADPH oxidase, did not affect significantly cytochrome b-558 reduction rates. The reaction rate of cytochrome b-558 with dithionite exhibited a near-zero activation energy. The first-order rate constant for reduction decreased with increasing ionic strength, indicating a positive effective charge on the reacting protein.
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Filatova, Elena G., and Yury N. Pozhidaev. "Kinetics and Adsorption Ions of Heavy Metal by Modified Alumino-Silicates." Solid State Phenomena 316 (April 2021): 170–74. http://dx.doi.org/10.4028/www.scientific.net/ssp.316.170.
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Adsorption isotherms of Ni (II) and Cu (II) ions by alumino-silicates, modified with N, N'-bis (3-triethoxysilylpropyl) thiocarbamide (BTM-3), and HCl, were obtained. The adsorption kinetics of heavy metal ions is studied, using the kinetic pseudo-first and pseudo-second order models. It is shown that, when alumino-silicates are modified, the rate and energy of adsorption increase. It is established that the kinetics of the adsorption of the studied ions is best described by a pseudo-second order model. The maximum value of the adsorption rate constant of 33.7∙10-5 g/ (mmol min) corresponds to nickel (II) ions for alumino-silicates, modified with HCl. The maximum value of the adsorption rate constant value of 2.91∙10-5 g/ (mmol min) for alumino-silicates, modified with BTM-3, corresponds to Cu (II) ions.
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Galezowski, Wlodzimierz, and Arnold Jarczewski. "Study of the dissociation of the products of some proton transfer reactions in acetonitrile solvent." Canadian Journal of Chemistry 70, no. 3 (March 1, 1992): 935–42. http://dx.doi.org/10.1139/v92-126.
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The conductometric study of the products of the proton transfer reactions of C-acids (nitriles, nitroalkanes, and 2,4,6-trinitrotoluene) with the strong amine bases (1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,8-bis(dimethylamino)naphthalene (DMAN), and piperidine) in acetonitrile shows their large degree of dissociation into free ions. The dissociation constant values have been estimated at 25 °C to be larger than 1 × 10−4 M. This weakens the formalism commonly accepted in spectrophotometric kinetic studies of these systems of reactions, based on the assumption that the product is an ion pair. Spectrophotometric equilibrium and kinetic measurements provided evidence that reverse reaction is a second-order process (pseudo-first order because cation concentration is controlled by side reactions). The influence of the common cation (TMGH+) on the equilibria of the proton abstraction from 2-methyl-1-(4-nitrophenyl)-1-nitropropane and 4-nitrophenylcyanomethane with TMG base in acetonitrile at 25 °C was examined and was found to be compatible with the assumption of large dissociation of the reaction product for free ions. "Equilibrium constants" estimated by the Benesi and Hildebrand method (which assumes an ion-pair product) decreased with increasing concentration of added TMGH+ cation, but these "equilibrium constants" multiplied by [TMGH+] are constant. The observed pseudo-first-order rate constants of the proton transfer reaction, measured at large excess of the base over C-acid, grow with the cation concentration due to the increase of the backward reaction rate. The concentration of added common cation shows a negligible influence on the observed rate constants of deuteron transfer reaction. Thus, as a result of side reactions, in which extra amounts of cation are formed, some second-order rate constants [Formula: see text] and also kinetic isotope effects (KIEs) [Formula: see text] that have been measured in acetonitrile can be substantially overestimated. Keywords: ion-pair dissociation, proton transfer reactions, kinetic isotope effects.
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Holle, Rizky B., Audy D. Wuntu, and Meiske S. Sangi. "Kinetika Adsorpsi Gas Benzena Pada Karbon Aktif Tempurung Kelapa." Jurnal MIPA 2, no. 2 (July 8, 2013): 100. http://dx.doi.org/10.35799/jm.2.2.2013.2997.
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Telah diteliti kinetika adsorpsi gas benzena pada karbon aktif tempurung kelapa yang diaktivasi dengan NaCl dengan tujuan menentukan model kinetika yang dapat diaplikasikan untuk adsorpsi gas benzena pada karbon aktif tempurung kelapa. Data adsorpsi dianalisis dengan menggunakan empat model persamaan laju adsorpsi yaitu (1) persamaan laju order pertama pseudo Lagergren, (2) persamaan laju order kedua pseudo Ho, (3) persamaan Elovich, dan (4) persamaan Ritchie. Hasil kajian menunjukkan bahwa model kinetika dengan persamaan laju order ke-2 pseudo Ho adalah yang paling sesuai diaplikasikan untuk adsorpsi gas benzena pada karbon aktif tempurung kelapa. Dari model kinetika order ke-2 pseudo Ho diperoleh konstanta adsorpsi benzena sebesar 1,63x10-4 g mg-1 min-1. Nilai energi adsorpsi menunjukkan bahwa benzena teradsorpsi secara fisik pada adsorben.Kinetics of gaseous benzene adsorption on coconut shell NaCl-activated carbon had been studied. The research was aimed to determine the appropriate kinetic model applied to gaseous benzene adsorption on the adsorbent. Adsorption data was analyzed using four kinetic models of adsorption rate equation, which were (1) Lagergren’s pseudo first order rate equation, (2) Ho’s pseudo second order rate equation, (3) Elovich‘s equation, and (4) Ritchie’s equation. The results showed that the Ho’s pseudo second order rate equation was best applied to gaseous benzene adsorption on coconut shell activated carbon. The second order rate constant for benzene adsorption was 1.63x10-4 g mg-1 min-1. The value of adsorption energy showed that benzene was physically adsorbed on the adsorbent.
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João, Jair Juarez, Walter Satiro Júnior, and José Luiz Vieira. "Use of zeolite synthesized from coal ashl from Santa Catarina for removal of iron, manganese and methylene blue dye in water." Ambiente e Agua - An Interdisciplinary Journal of Applied Science 13, no. 4 (July 5, 2018): 1. http://dx.doi.org/10.4136/ambi-agua.2224.
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The fly ash of coal, generated in a thermoelectric plant, was used to synthesize zeolite by hydrothermal treatment with a sodium hydroxide solution. The zeolite synthesized was used as an adsorbent of metals (Fe and Mn) and of the methylene blue dye in water. The characterization of the zeolite showed that silicon oxide is the main compound in its composition, followed by aluminum, iron, sodium and calcium, which together correspond to more than 86% of its composition. These were used to investigate the kinetic parameters of adsorption and the isotherm of the metals and the methylene blue dye in aqueous solutions. Three kinetic models, pseudo-first order, pseudo-second order and intraparticle diffusion were used to predict adsorption rate constants. The adsorption kinetics of the dye and metals followed the pseudo-second order kinetics and reached equilibrium in 15 minutes with a 99% removal rate for metals, independently of the pH. The values of the diffusion constants (K2) for iron in pH 5, 7 and 8 were 1.3158; 1.3881 e 0.6053 mg.g-1.min-1 and for manganese 1.2511; 1.5239 and 1.4336 mg.g-1.min-1, respectively. For methylene blue, the removal rate was 90% and the constant (K2) value was 0.5437 mg.g-1.min-1. The studies showed the existence of different stages in the adsorption of the metals and the methylene blue dye in zeolite.
Dissertations / Theses on the topic "Pseudo-first order rate constant and second order rate constant"
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Tshabalala, Oupa Samuel. "The development of FT-Raman techniques to quantify the hydrolysis of Cobalt (III) nitrophenylphosphate complexes using multivariate data analysis." Diss., 2007. http://hdl.handle.net/10500/23202.
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The FT-Raman techniques were developed to quantify reactions that
follow on mixing aqueous solutions of bis-(1,3-diaminopropane)diaquacobalt(
III) ion ([Co(tn)2(0H)(H20)]2+) and p-nitrophenylphosphate
(PNPP).
For the development and validation of the kinetic modelling
technique, the well-studied inversion of sucrose was utilized. Rate
constants and concentrations could be estimated using calibration
solutions and modelling methods. It was found that the results
obtained are comparable to literature values. Hence this technique
could be further used for the [Co(tn)2(0H)(H20)]2+ assisted
hydrolysis of PNPP.
It was found that rate constants where the pH is maintained at 7.30
give results which differ from those where the pH is started at 7.30
and allowed to change during the reaction. The average rate
constant for 2:1 ([Co(tn)2(0H)(H20)]2+:PNPP reactions was found to
be approximately 3 x 104 times the unassisted PNPP hydrolysis rate.Chemistry
M. Sc. (Chemistry)
Books on the topic "Pseudo-first order rate constant and second order rate constant"
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Henriksen, Niels E., and Flemming Y. Hansen. Theories of Molecular Reaction Dynamics. Oxford University Press, 2018. http://dx.doi.org/10.1093/oso/9780198805014.001.0001.
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This book deals with a central topic at the interface of chemistry and physics—the understanding of how the transformation of matter takes place at the atomic level. Building on the laws of physics, the book focuses on the theoretical framework for predicting the outcome of chemical reactions. The style is highly systematic with attention to basic concepts and clarity of presentation. Molecular reaction dynamics is about the detailed atomic-level description of chemical reactions. Based on quantum mechanics and statistical mechanics or, as an approximation, classical mechanics, the dynamics of uni- and bimolecular elementary reactions are described. The first part of the book is on gas-phase dynamics and it features a detailed presentation of reaction cross-sections and their relation to a quasi-classical as well as a quantum mechanical description of the reaction dynamics on a potential energy surface. Direct approaches to the calculation of the rate constant that bypasses the detailed state-to-state reaction cross-sections are presented, including transition-state theory, which plays an important role in practice. The second part gives a comprehensive discussion of basic theories of reaction dynamics in condensed phases, including Kramers and Grote–Hynes theory for dynamical solvent effects. Examples and end-of-chapter problems are included in order to illustrate the theory and its connection to chemical problems. The book has ten appendices with useful details, for example, on adiabatic and non-adiabatic electron-nuclear dynamics, statistical mechanics including the Boltzmann distribution, quantum mechanics, stochastic dynamics and various coordinate transformations including normal-mode and Jacobi coordinates.
Book chapters on the topic "Pseudo-first order rate constant and second order rate constant"
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Milhé, C. "Determination by 1H NMR of a Slow Conformational Transition and Hydration Change in the Consensus TATAAT Prsbnow Box." In Biological NMR Spectroscopy. Oxford University Press, 1997. http://dx.doi.org/10.1093/oso/9780195094688.003.0027.
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The conformational dynamics and hydration of a DNA 14-mer containing the consensus Pribnow box sequence TATAAT have been measured using rotating frame T1 measurements and NOESY and ROESY in water. The H2 proton resonances of adenines show fast intermediate exchange behavior which can be attributed to a conformational transition that affects the distances between H2 protons of neighboring adenine residues, both sequential and cross-strand. The relaxation rate constant of the transition was measured at 4000s-1 at 25°C. Bound water close to the H2 proton of adenines was observed with residence times of >lns. At low temperature (5°C), the Pribnow box is in a closed state in which hydration water in the minor groove is tightly bound. At higher temperatures, the conformation opens up as judged by the increase in separation between sequential H2 protons of adenines and water exchanges freely from the minor groove. The conformational transition and the altered hydration pattern may be related to promoter function. The control of gene expression in procaryotes depends on the specific recognition by RNA polymerase of a six base-pair sequence (consensus: TTGACA) located at -35 from the transcription site, and a second one, named the Pribnow box (consensus: TATAAT) at about 10 base-pairs upstream the initiation site (Rosenberg and Court, 1979). It has been shown (Hawley and McClure, 1983) that strong promoters exhibit a high degree of homology with the consensus sequences, separated by an optimum consensus spacer length of 17 base pairs. The strength of a promoter depends on, among other thing, the rate of the initiation of transcription. This rate depends on the product between the thermodynamic and kinetic constants KB and k2 (McClure, 1980). The initial binding of RNA polymerase to the promoter results in the formation of a transcriptionally inactive ‘closed’ complex, characterized by the association constant KB. Isomerization to the active ‘open’ complex then occurs, and is characterized by the first order rate constant k2. Hence, the frequency of transcription initiation depends both on the strength of the polymerase-promoter interaction, and the ease with which this complex can isomerize to the productive state. Both of these events are likely to depend on the physical properties of the promoter.
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Bokstein, Boris S., Mikhail I. Mendelev, and David J. Srolovitz. "Kinetics of heterogeneous processes." In Thermodynamics and Kinetics in Materials Science. Oxford University Press, 2005. http://dx.doi.org/10.1093/oso/9780198528036.003.0013.
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Most practical reactions that occur in synthesizing or processing materials are heterogeneous. These include oxidation, reduction reactions, dissolution of solids in liquids, and most solid-state phase transformations. Consider the oxidation of a metal by exposure of a solid metal to an atmosphere with a finite partial pressure of oxygen. In order for oxidation to occur, molecular oxygen must dissociate into atomic oxygen on the metal surface. In some cases, atomic oxygen diffuses into the metal and reacts to form an internal oxide, while in others, the reaction occurs at the surface. In the latter case, thickening of the oxide layer requires either metal or oxygen diffusion through the growing oxide layer. This example demonstrates that heterogeneous processes commonly involve several steps. The first step is usually the transport of a reactant through one of the phases to the interface. The second is the adsorption (segregation) or chemical reaction on the interface. Finally, the last third step is the diffusion of the products into the growing phase or the desorption of the product. Since the entire heterogeneous process is a type of complex reaction, there is usually one step that controls the rate of the process, that is, is the rate-determining step. Recall that the rate-determining step is the slowest (fastest) step for a consecutive (parallel) reaction (see Sections 8.2.1 and 8.2.2). Consider the case of a consecutive heterogeneous reaction in which one of the reactants is transported through the fluid phase to the solid–fluid interface, where a first-order reaction takes place. The reaction rate ωr in such a case is ωr=kcx, where cx is the concentration of the reactant on the interface. Since the reactant is consumed at the interface, cx is smaller than the reactant concentration far from the interface, c0. It is usually easier to measure the reactant concentration in the bulk fluid. Therefore, it is convenient, to rewrite the reaction rate in terms of the bulk concentration in the fluid and an effective rate constant . . . ωr = kcx = keffc0. (11.1) . . . It is easiest to see the relation between keff and k by considering the steady-state case.
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Cornish-Bowden, Athel. "Steady-state kinetics." In Spectrophotometry and Spectrofluorimetry. Oxford University Press, 2000. http://dx.doi.org/10.1093/oso/9780199638130.003.0010.
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All of chemical kinetics is based on rate equations, but this is especially true of steady-state enzyme kinetics: in other applications a rate equation can be regarded as a differential equation that has to be integrated to give the function of real interest, whereas in steady-state enzyme kinetics it is used as it stands. Although the early enzymologists tried to follow the usual chemical practice of deriving equations that describe the state of reaction as a function of time there were too many complications, such as loss of enzyme activity, effects of accumulating product etc., for this to be a fruitful approach. Rapid progress only became possible when Michaelis and Menten (1) realized that most of the complications could be removed by extrapolating back to zero time and regarding the measured initial rate as the primary observation. Since then, of course, accumulating knowledge has made it possible to study time courses directly, and this has led to two additional subdisciplines of enzyme kinetics, transient-state kinetics, which deals with the time regime before a steady state is established, and progress-curve analysis, which deals with the slow approach to equilibrium during the steady-state phase. The former of these has achieved great importance but is regarded as more specialized. It is dealt with in later chapters of this book. Progress-curve analysis has never recovered the importance that it had at the beginning of the twentieth century. Nearly all steps that form parts of the mechanisms of enzyme-catalysed reactions involve reactions of a single molecule, in which case they typically follow first-order kinetics: . . . v = ka . . . . . . 1 . . . or they involve two molecules (usually but not necessarily different from one another) and typically follow second-order kinetics: . . . v = kab . . . . . . 2 . . . In both cases v represents the rate of reaction, and a and b are the concentrations of the molecules involved, and k is a rate constant. Because we shall be regarding the rate as a quantity in its own right it is not usual in steady-state kinetics to represent it as a derivative such as -da/dt.
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Esonye, Chizoo, Okechukwu Donminic Onukwuli, Akuzuo Uwaoma Ofoefule, Cyril Sunday Ume, and Nkiruka Jacintha Ogbodo. "Sea Almond as a Promising Feedstock for Green Diesel: Statistical Optimization and Power Rate Law Based Chemical Kinetics of Its Consecutive Irreversible Methanolysis." In Prunus. IntechOpen, 2020. http://dx.doi.org/10.5772/intechopen.93880.
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For successful industrial scale-up and effective cost analysis of transesterification process, presentation of complimentary research data from process optimization using statistical design techniques, chemical kinetics and thermodynamics are essential. Full factorial central composite design (FFCCD) was applied for the statistical optimization of base methanolysis of sea almond (Terminalia catappa) seed oil using response surface methodology (RSM) coupled with desirability function analysis on quadratic model. Reaction time had the most significant impact on the biodiesel yield. Optimum conditions for biodiesel yield of 93.09 wt% validated at 92.58 wt% were 50.03°C, 2.04 wt% catalyst concentration, 58.5 min and 4.66 methanol/oil molar ratio with overall desirability of 1.00. Ascertained fuel properties of the FAME were in compliance with international limits. GC–MS, FTIR and NMR characterizations confirmed unsaturation and good cold-flow qualities of the biodiesel. Based on power rate law, second-order kinetic model out-performed first-order kinetic model. Rate constants of the triglyceride (TG), diglycerides (DG) and monoglycerides (MG) hydrolysis were in the range of 0.00838–0.0409 wt%/min while activation energies were 12.76, 15.83 and 22.43 kcal/mol respectively. TG hydrolysis to DG was the rate determining step. The optimal conditions have minimal error and would serve as a springboard for industrial scale-up of biodiesel production from T. catappa seed oil.
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Affam, Augustine Chioma, Ezerie Henry Ezechi, and Malay Chaudhuri. "Classical Fenton and Sequencing Batch Reactor Treatment of Pesticide Wastewater." In Handbook of Research on Resource Management for Pollution and Waste Treatment, 373–403. IGI Global, 2020. http://dx.doi.org/10.4018/978-1-7998-0369-0.ch016.
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This chapter examined Fenton and sequencing batch reactor (SBR) treatment of pesticide industrial wastewater. The optimum operating conditions for Fenton pretreatment of the pesticide wastewater were H2O2/COD molar ratio 3.0, H2O2/Fe2+ molar ratio 10, pH 3 and reaction time 60 min. The COD and TOC removal were 58.51 and 39.76%, respectively and biodegradability (BOD5/COD ratio) increased from 0.02 to ~ 0.30 after 60 min reaction time. The reaction followed pseudo-first order kinetics with a rate constant (k) of 0.0083 min−1. In the post-treatment by aerobic SBR, five different Fenton operating conditions were investigated and H2O2/COD molar ratio 3.0, H2O2/Fe2+ molar ratio 25, pH 3 and reaction time 60 min appeared to be the most significant (p < 0.05) operating conditions. The Fenton–SBR treatment at 12 hr HRT achieved COD, TOC and BOD5 removal efficiency of 96.7, 97.7 and 93.3%, respectively. The Fenton-SBR process was effective for the treatment of pesticide wastewater.
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Goody, R. M., and Y. L. Yung. "Band Models." In Atmospheric Radiation. Oxford University Press, 1989. http://dx.doi.org/10.1093/oso/9780195051346.003.0006.
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Radiative heating calculations in the atmosphere involve four distinguishable scales of frequency. First, there is the comparatively slow variation with frequency of the Planck function and its derivative with respect to temperature. About one-half of the radiation from a black body at terrestrial temperatures lies in a wave number range of 500 cm-1. The second scale is that of the unresolved contour of a band. For atmospheric molecules other than water vapor, the Planck function is effectively constant over a single band; water vapor bands must be divided into sections of the order of 50 cm-1 wide before this is so. For a rotating molecule, the next relevant scale of frequency is that of the spacing between rotation lines, approximately 1-5 cm-1. Finally, there is the monochromatic scale on which the absorption coefficient may be treated as a constant, and for which Lambert’s absorption law is obeyed: of the order of one-fifth of a line width ≃ 2 x 10-2 cm-1 for a gas at atmospheric pressure, down to 2 x 10-4cm-1 for a Doppler line in the middle atmosphere. This step takes us to a division of the frequency scale that, when taken together with other features of the calculation, presents a formidable computation task. Calculations can, of course, be made and are made at this limiting spectral resolution (line-by-line calculations) but, despite the fact that they are technically feasible with modern computers, such calculations are rare and are usually performed to provide a few reference cases. The great majority of investigations make use of averages over many lines, embracing spectral ranges that are small compared to a band contour (narrow-band models), or over complete bands (wide-band models), or over the entire thermal spectrum (emissivity models.) There are a number of reasons for working with spectral averages. Practical considerations are that important classes of laboratory measurements, and most atmospheric observations (e.g., satellite radiometry) are made with some spectral averaging, often comparable to that of narrow-band models.
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Phan-Thien, Nhan, and Sangtae Kim. "Numerical Implementation." In Microstructures in Elastic Media. Oxford University Press, 1994. http://dx.doi.org/10.1093/oso/9780195090864.003.0008.
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Analytical solutions to a set of boundary integral equations are rare, even with simple geometries and boundary conditions. To make any reasonable progress, a numerical technique must be used. There are basically four issues that must be discussed in any numerical scheme dealing with integral equations. The first and most basic one is how numerical integration can be effected, together with an effective way of dealing with singular kernels of the type encountered in elastostatics. Numerical integration is usually termed numerical quadrature, meaning mathematical formulae for numerical integration. The second issue is the boundary discretization: when integration over the whole boundary is replaced by a sum of the integrations over the individual patches on the boundary. Each patch would be a finite element, or in our case, a boundary element on the surface. Obviously a high-order integration scheme can be devised for the whole domain, thus eliminating the need for boundary discretization. Such a scheme would be problem dependent and therefore would not be very useful to us. The third issue has to do with the fact that we are constrained by the very nature of the numerical approximation process to search for solutions within a certain subspace of L2, say the space of piecewise constant functions in which the unknowns are considered to be constant over a boundary element. It is the order of this subspace, together with the order and the nature of the interpolation of the geometry, that gives rise to the names of various boundary element schemes. Finally, one is faced with the task of solving a set of linear algebraic equations, which is usually dense (the system matrix is fully populated) and potentially ill-conditioned. A direct solver such as Gauss elimination may be very efficient for small- to medium-sized problems but will become stuck in a large-scale simulation, where the only feasible solution strategy is an iterative method. In fact, iterative solution strategies lead naturally to a parallel algorithm under a suitable parallel computing environment. This chapter will review various issues involved in the practical implementation of the CDL-BIEM on a serial computer and on a distributed computing environment.
Conference papers on the topic "Pseudo-first order rate constant and second order rate constant"
1
van Rij, Jennifer, Tim Ameel, and Todd Harman. "Constant Wall Temperature Nusselt and Poiseuille Numbers in Rectangular Microchannels." In ASME/JSME 2007 Thermal Engineering Heat Transfer Summer Conference collocated with the ASME 2007 InterPACK Conference. ASMEDC, 2007. http://dx.doi.org/10.1115/ht2007-32465.
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Slip flow convective heat transfer and friction loss characteristics are numerically evaluated for constant wall temperature rectangular microchannels. The effects of rarefaction, accommodation coefficients, aspect ratio, second-order slip boundary conditions, axial conduction, and viscous dissipation with flow work are each considered. Second-order slip boundary conditions, axial conduction, and viscous dissipation with flow work effects have not been studied previously for rectangular channel slip flows. The effects of each of these parameters on the numerically computed convective heat transfer rate and friction loss are evaluated through the Nusselt number and Poiseuille number respectively. The numerical results are obtained using a continuum-based computational fluid dynamics algorithm that includes second-order slip flow and temperature jump boundary conditions. Numerical results for the three-dimensional, fully developed Nusselt and Poiseuille numbers are presented as functions of Knudsen number, first- and second-order velocity slip and temperature jump coefficients, aspect ratio, Brinkman number, and Peclet number. Effects of rarefaction, accommodation coefficients, and aspect ratio are consistent with previously reported analytical results for rectangular channel constant wall temperature flows. The effects of second-order slip terms, axial conduction and viscous dissipation are also shown to significantly affect the Nusselt and Poiseuille numbers.
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Krishnaswamy, S., K. Jones, and K. Mann. "STOPPED-FLOW KINETICS OF PROTHROMBINASE COMPLEX ASSEMBLY." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1643279.
Full textAbstract:
Prothrombinase is the multi -component enzyme composed of factor Xa and the cofactor, factor Va, that assemble on a phospholipid surface in the presence of calcium ion. Fluoresence stopped-flow kinetic studies of prothrombinase assembly in the absence of the substrate, prothrombin were undertaken at saturating concentrations of calcium ion, using phospholipid vesicles (PCPS), factor Va and factor Xa modified at the active-site with the fluorophore dansyl-glutamylglycinylarginylchloro methylketone (DEGR-Xa). The substantial fluorescence enhancement of DEGR-Xa in the presence of factor Va, PCPS and calcium ion was used as a continuous measure of prothrombinase complex formation. The rate of complex formation studied under pseudo-first order conditions was most rapid when factor Va was reacted with the DEGR-Xa-PCPS binary complex. Under these conditions, the rate increased linearly with increasing PCPS concentrations and was independent of the concentration of factor Va. The reaction between Va and PCPS assessed by stopped-flow light scattering produced identical rates. The data indicate that the rate-limiting step in the reaction between Va and PCPS-bound DEGR-Xa is the initial formation of a Va-PCPS binary complex (8.4×107M−1s−1) followed by the very rapid reaction (>3×109M−1s−1) between PCPS-bound DEGR-Xa and Va. When complex formation was initiated by mixing DEGR-Xa and Va with PCPS or by mixing DEGR-Xa with Va-PCPS, the pseudo-first order rates were substantially lower. Under these conditions, increasing concentrations of factor Va inhibited the rate of prothrombinase complex formation which could be overcome by increasing PCPS concentrations. The data are consistent with the interpretation that the initial formation of the DEGR-Xa-PCPS complex is a prerequisite for prothrombinase assembly. The second order rate constant for the reaction between DEGR-Xa and PCPS (9.5×109M−1s−1 ) was independently determined by stopped-flow light scattering. Collectively, the data indicate that prothrombinase assembly proceeds via the initial formation of DEGR-Xa-PCPS and Va-PCPS binary complexes. The lipid-bound constituents then rapidly react via diffusion over the vesicle surface to form prothrombinase.(Supported by NIH grants HL-35058 and HL-34575)
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Kazemi, Reza, Ali Asghar Jafari, and Mohammad Faraji Mahyari. "Increasing Penetration Rate of Drill String by Optimum Positioning of Stabilizers." In ASME 2010 10th Biennial Conference on Engineering Systems Design and Analysis. ASMEDC, 2010. http://dx.doi.org/10.1115/esda2010-25196.
Full textAbstract:
In this research, optimum arrangements of drill string’s stabilizers are investigated. The optimum arrangement leads to biggest WOB without buckling. So the penetration rate of the drill bit can be increases. To this goal, the potential energy of drill string for axial and lateral vibration is written in an integral equation. In this equation, the effect of geometrical shortening, which causes nonlinear coupling between axial and lateral vibration, is considered. The work done by WOB force and weight of drill string is calculated. The mode summation method is employed to convert the integral potential energy of the continuous system to a discrete one. The effects of stabilizers are modeled by linear springs with large stiffness constant. Dropping and considering third and fourth order tensor of potential energy lead to linear and nonlinear stability analysis, respectively. Taking first and second order derivatives of discrete potential energy, the stability of drill string can be analyzed. Repeating this procedure for different numbers and positions of stabilizers, the optimum arrangement of stabilizers can be found. This method is employed to find the best arrangement of one and two stabilizers, by linear and nonlinear method.
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Pieters, J., G. willems, H. C. Hemker, and T. Lindout. "EFFECT OF ANTITHROMBIN III AND HEPARIN ON FACTOR X ACTIVATION BY FACTOR IXa." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1643767.
Full textAbstract:
The heparin-catalyzed inactivation of activated coagulation factors by antithrombin III (AT III) has mostly been studied for isolated serine proteases. However, we decided to study the action of heparin and AT III under more physiological conditions, i.e. during the activation of factor X by factor IXa in the presence of phospholipid and calcium. Thereby we made use of a mathematical model which describes the generation of factor Xa by factor IXa, phospholipid and calcium in the presence of AT III and heparin. Fitting the experimental factor Xa generation curve to a set of equations gave the pseudo-first-order rate constants of factor Xa and factor IXa. In a first approach we examined the effect of AT III alone on factor X activation. We found that the second order rate constant of inhibition of formed factor Xa was 2 x 10 5M-1min-1 , whereas that of factor Xa in free solution was 5 x 10 5M-1min-1 , indicating that phospholipid-bound factor X competes with AT III for factor Xa. The second order rate constant of inhibiton of factor IXa, either in the presence or absence of accessory components, was 8 x 103 M-1min-1. Unfractionated heparin (UFH; 168 USP units/mg) was found to stimulate the inhibition of generated factor Xa by AT III (200 nM) with 0.1 min-1 per nM of UFH, and a synthetic pentasaccharide (PS; 4000 anti-Xa units/mg) stimulated this inhibition with only 0.03 min-1per nM. Due to the presence of phospholipid-bound factor X this stimulation was 4-fold less when compared with factor Xa in free solution. At UFH concentrations higher than 3 nM, and PS concentrations exceeding 10 nM hardly any active factor Xa generation could be measured because of the rapid inactivation of factor Xa whereas factor IXa was not inhibited. Using a factor IXa assay we found that PS, even at relatively high concentrations, had no effect on factor IXa inactivation by AT III (200 nM), both in the presence and absence of accessory components. The inactivation of factor IXa by AT III (200 nM) during factor X activation was stimulated by UFH with 1.6 x 10 -2min-1 per nM of UFH. Surprisingly, this was 4-fold more when compared with factor IXa in the absence of accessory components. We established that calcium stimulates the heparin-dependent inhibition of factor IXa.
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Jackson, Craig M. "A DEFINITION OF HEPARIN ANTICOAGULANT POTENCY APPLICABLE TO ALL HEPARINS AND HEPARIN-LIKE SUBSTANCES AND ITS PRACTICAL APPLICATION IN ASSAYING HEPARIN." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1642928.
Full textAbstract:
Heparins increase the rate of inactivation of proteinases by antithrombin without being consumed in the inactivation reaction. The anticoagulant activity of any heparin or heparin preparation is thus determined by the increase in the inactivaton rate which it produces. This rate increase is dependent on the concentration of the heparin in the sample and on some now well known structural properties of the individual heparin molecules that produce high affinity for antithrombin . All proteinases are not inactivated by antithrombin equally rapidly in the absence of heparin, nor are heparins and heparin derivatives of different molecular weight equally effective in the inactivation of the same proteinase. Under appropriate conditions, the observed rate constant (kObs) for the heparin catalyzed proteinase inactivation reaction is simply related to the intrinsic potencies and concentrations of the individual high affinity heparin molecules in the sample. The intrinsic potency of a high affinity heparin molecule is the efficiency with which it catalyzes the inactivation of the particular proteinase, e.g. Factor Xa or thrombin, i.e., it is a second order rate constant, (designated k*) . After k* has been determined from kobs for a known heparin or heparin preparation and a particular proteinase, the concentration of heparin in an unknown sample can be calculated from the equation[H] = [HAT] = kobs/k* In general terms, the appropriate conditions, i.e.,the antithrombin and proteinase concentrations, the pH, and ionic strength, required for this equation to be used are those conditions for which all of the high affinity heparin is bound to the antithrombin and pseudo first order kinetic behavior occurs. At very low heparin concentrations, a correction for the inactivation of the proteinase by antithrombin alone is necessary, but is easily made.Supported by Organon Teknika Corporation and an Established Investigator Award from the American National Red Cross
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Owen, B. A., and W. G. Owen. "ASSOCIATION OF HEPARIN AND FACTOR Xa: INFLUENCE ON THE RATE OF INHIBITION OF FACTOR Xa BY ANTITHROMBIN III-HEPARIN." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1643837.
Full textAbstract:
Association of heparin non-covalently with bovine factor Xa was analyzed by Superose-12 gel chromatography. In 0.05 M NaCl, 0.02 M Tris, pH 7.5, DEGR-Xa (factor Xa inactivated by dans-Glu-Gly-Arg-CH2Cl) was eluted as a single, sharp peak at Ve/Vt=0-65 (elution volume/internal volume). Mixtures of heparin and DEGR-Xa were eluted as two partially resolved peaks of protein at Ve/Vt=0.59 and 0.65. The fraction of DEGFUXa in the leading peak was directly proportional to [heparin], and at 100 yM heparin the leading peak contained more than half the total protein. When 0.02 M HEPES was substituted for Tris a single, slightly broadened peak at Ve/Vt=0.64 was obtained on chromatography of 100 μM heparin and 10 μM DEGR-Xa. In a buffer system comprising 0.02 M Tris, 0.02 M HEPES, 0.03 M NaCl, pH 7.5, two peaks were eluted at Ve/Vt=0.59 and 0.65. Therefore, Tris increases the affinity of DEGR-Xa for heparin.Solutions buffered with Tris or HEPES were compared for effects on the kinetics of inhibition of factor Xa by antithrombin III-heparin. Reaction mixtures containing 1 nM factor Xa, 30 nM heparin and 600 nM antithrombin III were assayed with S-2222 at intervals of 2-10 sec. Reagent concentrations were chosen (a) to assure pseudo-first-order kinetics, (b) to have [heparin]<< Kq for factor Xa-heparin, and (c) to bind virtually all available heparin to antithrombin III. The same second-order rate constant, Kobs=2.5×107 M−1s−1, was obtained in both buffer systems. We conclude that the association of factor Xa with heparin observed directly by gel chromatography does not contribute to the reaction rate of factor Xa with antithrombin III-heparin.
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Verhamme, I. M. A., and G. W. K. van Dedem. "EFFECT OF THE BUFFER COMPOSITION AND THE PRESENCE OF ORG 10172 AND SOME GLYCOSAMINOGLYCANS ON THE INHIBITION OF ALPHA-THROMBIN BY HEPARIN COFACTOR II." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1644351.
Full textAbstract:
Heparin cofactor II (HCII) inhibits alpha-thrombin (Ila) with formation of a 1:1 complex.The inhibition is accelerated by heparin and dermatan sulfate (DS).The present study describes the pH and ionic strength dependence of the second order inactivation constant k2nd for the simple IIa-HCII interaction and for the interaction catalysed by heparin, dermatan sulfate and the antithrombotic Org 10172 containing low molecular DS.In all cases we found a bell-shaped pH profile for k2nd with characteristic maxima and pK values. Org 10172 accelerates the HCII mediated inhibition of Ila though not to the same extent as heparin and DS. Substantial narrowing of the pH profile occurs under influence of glycosaminoglycans , the alkaline limb of the profiles being displaced towards a more acidic pH. The ionic strength is critical for the determination of k2nd. A nonlinear decrease is observed with increasing ionic strength, due to the screening effect of the ions in solution. Ca++ ions do not accelerate the inactivation process in absence of GAG, in contrast to the findings for the Ila-ATIII interaction. The pseudo-first order model for Ila inactivation is only valid for : a) the uncatalysed reaction irrespective of ionic strength, b) the inactivation in buffers of intermediate ionic strength and in the presence of low GAG concentration and c) the inactivation in media of high ionic strength irrespective of GAG concentration. In all other reaction conditions the inactivation rate substantially deviates from a pseudo-first order plot.Suicide substrates are known to exhibit a comparable behavior. However this model appeared inadequate for describing our experiments. An appropriate model for these aberrant inactivation profiles is not evident.Deviation from pseudo-first order kinetics occurs more readily with heparin than with dermatan sulfate and is probably related with their difference in charge density.
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Latallo, Zbigniew S., and Craig M. Jackson. "HUMAN MEIZOTHROMBIN 1, ITS ISOLATION AND PROPERTIES." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1644661.
Full textAbstract:
Meizothrombin (MT) and meizothrombin des Fragment 1 (MT1) are intermediates in the conversion of prothrombin to α-thrombin (αTH). Due to their transient character, properties of these enzymes are difficult to establish. Isolation of MT1 was achieved by affinity chromatography on D-Phe-Pro-Arginal (FPRal)immobilized on Affi-Gel 10 as originally employed for thrombin purification (Patel et al. Biochim.Biophys. Acta 748,321 (1983)). Human prethrombin 1 was activated with the purified activator from Echis carinatus venom in the presence of Ca++;, benzamidine and FPRal gel at pH 7.8. After exhaustive washing the MT1 was eluted with 0.1 M hydroxylamine in 0.15 M Na acetate buffer, pH 5.5. Under these conditions the MT1 is stable and can bestored at -70°C. Upon changing the pH of the preparation to 8.0, complete conversion into aTH occurred atroom temperature within 48 hours. Homogeneity of both preparations wasdemonstrated by PAGE. The Km and ke, values for MT1 measured on Tos-Gly-Pro-Arg pNA(0.1 M NaCl, 0.01 M TRIS, 0.01 M HEPES, 0.1% PEG, pH 7.8, 25°C) were 15.7 /iM and 126 s-1. The kinetic con stants for the aTH resulting from autocatalytic degradation of MT1 were indistinguishable from those previously established forαTH obtained by Xa activation i.e. 4.77 /μM and 126 s-1. Clotting activity of MT1 was found to be only one fifth as high as that of the resulting μTH(746 u/mg vs. 3900 u/mg as tested using the NIH standard) .Inhibitionof MTl by antithrombin III was alsomuch less rapid than αTH andmost importantly, it was not affected by high affinity heparin( Mr20,300). Under conditions of the experiment (0.3 M NaCl, 0.0rl M TRIS, 0.01 M HEPES, 2.5 mM EDTA, 0.1% PEG, pH 7.8, 25°C; [ATIII] 100 nM, [E] 10 nM), the pseudo first order rate constants in the absence of heparin were 4.04 × 10-3V1 (MTl) and 1.13 × 10-3V1 (αTH), giving apparent second order rate constants of 4.04 × 103 and 1.13 × 10-4M-1s-1. In the presence of 4.5 nM of heparin the observed first order rate constant for MTl remained unchanged whereas it increased to 6.241 × 10-3s-1 (5.5 fold) for αTH. This apparent lack of an effect of heparin may be of significance in vivo.Supported by a Matching Grant from the American National Red Cross and by the Southeastern Michigan Blood Service.
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Schoen, P., H. C. Hemker, and T. Lindhoubt. "INHIBITION OF FACTOR Xa AND THROMBIN BY ANTITHROMBIN III AND HEPARIN DURING HUMAN PROTHROMBIN ACTIVATION." In XIth International Congress on Thrombosis and Haemostasis. Schattauer GmbH, 1987. http://dx.doi.org/10.1055/s-0038-1643766.
Full textAbstract:
Prothrombin-catalyzed human prothrombin activation results in the generation of thrombin and meizothrombin- des FI (MDF1) as was demonstrated by an immunoblot technique. Theheparin-independent second order rate -.onstants of inhibition of both thrombin and MDF1were 3.7 x 105 M-1min-1, whereas the rate constant of inhibition of purified thrombin was 6.5 x 105 M-1min-1 . In the presence of heparin the decay of amidolytic thrombin activity appeared to be bi-exponential and could be modelled by a 4-parameter equation. Fitting the experimental data to this equation gave the pseudo-first-order rate constants of inhibition, as well asthe composition of the reaction with respectto the levels of thrombin and MDF1. The occurence of MDF1 rather than meizothrombin (MT)suggests that MT is very rapidly converted into prothrombin fragment 1 (FI) and MDF1, a "dead-end" product of prothrombin activation. At high prothrombin concentrations (1.0 μM) predominantly MDF1 and not thrombin is formed, indicating that MT itself and/or MDF1 cleaves at Argl56 - Serl57 to produce FI and MDF1. Interestingly, heparin is unable to stimulate the inhibition of MT and MDF1 by AT III. We could demonstrate that MT and MDF1 have a low affinity, if any, for heparin.The kinetics of the heparin-dependent inhibition of prothrom-binase formed thrombin differ from those of purified thrombin added to the prothrombin activation reaction. A lower rate of inactivation of endogenous formed thrombin was observed and,moreover, could not be modelled as a simple random order bi-reactant enzyme-catalyzed reaction. Theseeffects might be caused by the presence of prothrombin activation fragments.Taking the factor Xa inactivation also into account, it appeared that the major effect of heparin onthe thrombin generation was to enhance the inhibition of thrombin rather thanthat of factor Xa. When unfractionated heparin (UFH; mean Mr = 14000, 168 USP units/mg) was compared with a synthetic pentasaccharide (PS; Mr = 1714, 4000 anti-Xa U/mg) on basis of equal anti-Xa U/ml, UFH shortened the half-life time of factor Xa 190-fold, whereas PS shortened the half-life time 17-fold.
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Vorreiter, A., S. Fischer, H. Saathoff, R. Radespiel, and J. R. Seume. "Numerical Investigations of the Efficiency of Circulation Control in a Compressor Stator." In ASME Turbo Expo 2010: Power for Land, Sea, and Air. ASMEDC, 2010. http://dx.doi.org/10.1115/gt2010-22721.
Full textAbstract:
Airfoil active flow control has been attempted in the past in order to increase the permissible loading of boundary layers in gas turbine components. The present paper presents a stator with active flow control for a high speed compressor using a Coanda surface near the trailing edge in order to inhibit boundary layer separation. The design intent is to reduce the number of vanes while — in order to ensure a good matching with the downstream rotor — the flow turning angle is kept constant. In a first step, numerical simulations of a linear compressor cascade with circulation control are conducted. The Coanda surface is located behind an injection slot on the airfoil suction side. Small blowing rates lead to a gain in efficiency associated with a rise in static pressure. In a second step, this result is transferred to a 4-stage high speed research compressor, where the circulation control is applied in the first stator. The design method and the first results are based on steady numerical calculations. The analysis of these results shows performance benefits of the concept. For both, the cascade and the research compressor, the pressure gain and efficiency are shown as a function of blowing rate and jet power ratio. The comparison is performed based on a dimensionless efficiency which takes into account the change of power loss.