927 resultados para Chitosan. Adsorption kinetics. Kinetic Model. Adsorption Isotherm.Tetracycline. Sodium Cromoglycate


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Since the advent of automobiles, alcohol has been considered a possible engine fuel1,2. With the recent increased concern about the high price of crude oil due to fluctuating supply and demand and environmental issues, interest in alcohol based fuels has increased2,3. However, using pure alcohols or blends with conventional fuels in high percentages requires changes to the engine and fuel system design2. This leads to the need for a simple and accurate conventional fuels-alcohol blends combustion models that can be used in developing parametric burn rate and knock combustion models for designing more efficient Spark Ignited (SI) engines. To contribute to this understanding, numerical simulations were performed to obtain detailed characteristics of Gasoline-Ethanol blends with respect to Laminar Flame Speed (LFS), autoignition and Flame-Wall interactions. The one-dimensional premixed flame code CHEMKIN® was applied to simulate the burning velocity and autoignition characteristics using the freely propagating model and closed homogeneous reactor model respectively. Computational Fluid Dynamics (CFD) was used to obtain detailed flow, temperature, and species fields for Flame-wall interactions. A semi-detailed validated chemical kinetic model for a gasoline surrogate fuel developed by Andrae and Head4 was used for the study of LFS and Autoignition. For the quenching study, a skeletal chemical kinetic mechanism of gasoline surrogate, having 50 species and 174 reactions was used. The surrogate fuel was defined as a mixture of pure n-heptane, isooctane, and toluene. For LFS study, the ethanol volume fraction was varied from 0 to 85%, initial pressure from 4 to 8 bar, initial temperature from 300 to 900K, and dilution from 0 to 32%. Whereas for Autoignition study, the ethanol volume fraction was varied between 0 to 85%, initial pressure was varied between 20 to 60 bar, initial temperature was varied between 800 to 1200K, and the dilution was varied between 0 to 32% at equivalence ratios of 0.5, 1.0 and 1.5 to represent the in-cylinder conditions of a SI engine. For quenching study three Ethanol blends, namely E0, E25 and E85 are described in detail at an initial pressure of 8 atm and 17 atm. Initial wall temperature was taken to be 400 K. Quenching thicknesses and heat fluxes to the wall were computed. The laminar flame speed was found to increase with ethanol concentration and temperature but decrease with pressure and dilution. The autoignition time was found to increase with ethanol concentration at lower temperatures but was found to decrease marginally at higher temperatures. The autoignition time was also found to decrease with pressure and equivalence ratio but increase with dilution. The average quenching thickness was found to decrease with an increase in Ethanol concentration in the blend. Heat flux to the wall increased with increase in ethanol percentage in the blend and at higher initial pressures. Whereas the wall heat flux decreased with an increase in dilution. Unburned Hydrocarbon (UHC) and CO % was also found to decrease with ethanol concentration in the blend.

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The nineteenth symposium was held at the University of Missouri–Columbia on April 22, 1989. A total of eighteen papers were scheduled for presentation, of which nine were in poster session. Finally, fifteen papers were presented and sixteen were submitted for this proceedings. It was attended by 53 participants from five institutions. A sixth group (from Colorado State University) was kept from attending the symposium due to mechanical problems on the road and we missed them. Since they worked hard at their presentations, I requested CSU-group to submit their papers for the proceedings and I am happy that they did. ContentsMathematical modelling of a flour milling system. K. Takahashi, Y. Chen, J. Hosokoschi, and L. T. Fan. Kansas State University A novel solution to the problem of plasmid segregation in continuous bacterial fermentations. K.L. Henry, R. H. Davis, and A. L. Taylor. University of Colorado Modelling of embryonic growth in avian and reptile Eggs. C.L. Krause, R. C. Seagrave, and R. A. Ackerman. Iowa State University Mathematical modeling of in situ biodegradation processes. J.C. Wu, L. T. Fan, and L. E. Erickson. Kansas State University Effect of molecular changes on starch viscosity. C.H. Rosane and V. G. Murphy. Colorado State University Analysis of two stage recombinant bacterial fermentations using a structured kinetic model. F. Miao and D. S. Kampala. University of Colorado Lactic acid fermentation from enzyme-thinned starch by Lactobacillus amylovorus. P.S. Cheng, E. L. Iannotti, R. K. Bajpai, R. Mueller, and s. Yaeger. University of Missouri–Columbia Solubilization of preoxidized Texas lignite by cell-free broths of Penicillium strains. R. Moolick, M. N. Karim, J. C. Linden, and B. L. Burback. Colorado State University Separation of proteins from polyelectrolytes by ultrafiltration. A.G. Bazzano and C. E. Glatz. Iowa State University Growth estimation and modelling of Rhizopus oligosporus in solid state fermentations. D.-H. Ryoo, V. G. Murphy, M. N. Karim, and R. P. Tengerdy. Colorado State University Simulation of ethanol fermentations from sugars in cheese whey. C.J. Wang and R. K. Bajpai. University of Missouri–Columbia Studies on protoplast fusion of B. licheniformis. B. Shi, Kansas State University Cell separations of non-dividing and dividing yeasts using an inclined settler. C.-Y. Lee, R. H. Davis, and R. A. Sclafani. University of Colorado Effect of·serum upon local hydrodynamics within an airlift column. G.T. Jones, L. E. Erickson, and L. A. Glasgow. Kansas State University Optimization of heterologous protein secretion in continuous culture. A. Chatterjee, W. F. Remirez, and R. H. Davis. University of Colorado An improved model for lactic acid fermentation. P. Yeh, R. K. Bajpai, and E. L. Iannotti. University of Missouri–Columbia

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Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

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X-ray diffraction analyses of the clay-sized fraction of sediments from the Nankai Trough and Shikoku Basin (Sites 1173, 1174, and 1177 of the Ocean Drilling Program) reveal spatial and temporal trends in clay minerals and diagenesis. More detrital smectite was transported into the Shikoku Basin during the early-middle Miocene than what we observe today, and smectite input decreased progressively through the late Miocene and Pliocene. Volcanic ash has been altered to dioctahedral smectite in the upper Shikoku Basin facies at Site 1173; the ash alteration front shifts upsection to the outer trench-wedge facies at Site 1174. At greater depths (lower Shikoku Basin facies), smectite alters to illite/smectite mixed-layer clay, but reaction progress is incomplete. Using ambient geothermal conditions, a kinetic model overpredicts the amount of illite in illite/smectite clays by 15%-20% at Site 1174. Numerical simulations come closer to observations if the concentration of potassium in pore water is reduced or the time of burial is shortened. Model results match X-ray diffraction results fairly well at Site 1173. The geothermal gradient at Site 1177 is substantially lower than at Sites 1173 and 1174; consequently, volcanic ash alters to smectite in lower Shikoku Basin deposits but smectite-illite diagenesis has not started. The absolute abundance of smectite in mudstones from Site 1177 is sufficient (30-60 wt%) to influence the strata's shear strength and hydrogeology as they subduct along the Ashizuri Transect.

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The effect of biochar on the soil carbon mineral- ization priming effect depends on the characteristics of the raw materials, production method and pyrolysis conditions. The goal of the present study is to evaluate the impact of three different types of biochar on physicochemical properties and CO2 emissions of a sandy loam soil. For this purpose, soil was amended with three different biochars (BI, BII and BIII) at a rate of 8 wt % and soil CO2 emissions were measured for 45 days. BI is produced from a mixed wood sieving from wood chip production, BII from a mixture of paper sludge and wheat husks and BIII from sewage sludge. Cumulative CO2 emissions of biochars, soil and amended soil were well fit to a simple first-order kinetic model with correlation coef- ficients (r 2 ) greater than 0.97. Results show a negative prim- ing effect in the soil after addition of BI and a positive prim- ing effect in the case of soil amended with BII and BIII. These results can be related to different biochar properties such as carbon content, carbon aromaticity, volatile matter, fixed carbon, easily oxidized organic carbon or metal and phenolic substance content in addition to surface biochar properties. Three biochars increased the values of soil field capacity and wilting point, while effects over pH and cation exchange capacity were not observed.

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Existing methods for assessing protein synthetic rates (PSRs) in human skeletal muscle are invasive and do not readily provide information about individual muscle groups. Recent studies in canine skeletal muscle yielded PSRs similar to results of simultaneous stable isotope measurements using l-[1-13C, methyl-2H3]methionine, suggesting that positron-emission tomography (PET) with l-[methyl-11C]methionine could be used along with blood sampling and a kinetic model to provide a less invasive, regional assessment of PSR. We have extended and refined this method in an investigation with healthy volunteers studied in the postabsorptive state. They received ≈25 mCi of l-[methyl-11C]methionine with serial PET imaging of the thighs and arterial blood sampling for a period of 90 min. Tissue and metabolite-corrected arterial blood time activity curves were fitted to a three-compartment model. PSR (nmol methionine⋅min−1⋅g muscle tissue−1) was calculated from the fitted parameter values and the plasma methionine concentrations, assuming equal rates of protein synthesis and degradation. Pooled mean PSR for the anterior and posterior sites was 0.50 ± 0.040. When converted to a fractional synthesis rate for mixed proteins in muscle, assuming a protein-bound methionine content of muscle tissue, the value of 0.125 ± 0.01%⋅h−1 compares well with estimates from direct tracer incorporation studies, which generally range from ≈0.05 to 0.09%⋅h−1. We conclude that PET can be used to estimate skeletal muscle PSR in healthy human subjects and that it holds promise for future in vivo, noninvasive studies of the influences of physiological factors, pharmacological manipulations, and disease states on this important component of muscle protein turnover and balance.

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A detailed quantitative kinetic model for the polymerase chain reaction (PCR) is developed, which allows us to predict the probability of replication of a DNA molecule in terms of the physical parameters involved in the system. The important issue of the determination of the number of PCR cycles during which this probability can be considered to be a constant is solved within the framework of the model. New phenomena of multimodality and scaling behavior in the distribution of the number of molecules after a given number of PCR cycles are presented. The relevance of the model for quantitative PCR is discussed, and a novel quantitative PCR technique is proposed.

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The invasive signal amplification reaction has been previously developed for quantitative detection of nucleic acids and discrimination of single-nucleotide polymorphisms. Here we describe a method that couples two invasive reactions into a serial isothermal homogeneous assay using fluorescence resonance energy transfer detection. The serial version of the assay generates more than 107 reporter molecules for each molecule of target DNA in a 4-h reaction; this sensitivity, coupled with the exquisite specificity of the reaction, is sufficient for direct detection of less than 1,000 target molecules with no prior target amplification. Here we present a kinetic analysis of the parameters affecting signal and background generation in the serial invasive signal amplification reaction and describe a simple kinetic model of the assay. We demonstrate the ability of the assay to detect as few as 600 copies of the methylene tetrahydrofolate reductase gene in samples of human genomic DNA. We also demonstrate the ability of the assay to discriminate single base differences in this gene by using 20 ng of human genomic DNA.

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The effect of different total enzyme concentrations on the flux through the bacterial phosphoenolpyruvate:carbohydrate phosphotransferase system (PTS) in vitro was determined by measuring PTS-mediated carbohydrate phosphorylation at different dilutions of cell-free extract of Escherichia coli. The dependence of the flux on the protein concentration was more than linear but less than quadratic. The combined flux–response coefficient of the four enzymes constituting the glucose PTS decreased slightly from values of ≈1.8 with increasing protein concentrations in the assay. Addition of the macromolecular crowding agents polyethylene glycol (PEG) 6000 and PEG 35000 led to a sharper decrease in the combined flux–response coefficient, in one case to values of ≈1. PEG 6000 stimulated the PTS flux at lower protein concentrations and inhibited the flux at higher protein concentrations, with the transition depending on the PEG 6000 concentration. This suggests that macromolecular crowding decreases the dissociation rate constants of enzyme complexes. High concentrations of the microsolute glycerol did not affect the combined flux–response coefficient. The data could be explained with a kinetic model of macromolecular crowding in a two-enzyme group-transfer pathway. Our results suggest that, because of the crowded environment in the cell, the different PTS enzymes form complexes that live long on the time-scale of their turnover. The implications for the metabolic behavior and control properties of the PTS, and for the effect of macromolecular crowding on nonequilibrium processes, are discussed.

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We present the results of two-pump and probe femtosecond experiments designed to follow the relaxation dynamics of the lowest excited state (S1) populated by different modes. In the first mode, a direct (S0 → S1) radiative excitation of the ground state is used. In the second mode, an indirect excitation is used where the S1 state is populated by the use of two femtosecond laser pulses with different colors and delay times between them. The first pulse excites the S0 → S1 transition whereas the second pulse excites the S1 → Sn transition. The nonradiative relaxation from the Sn state populates the lowest excited state. Our results suggest that the S1 state relaxes faster when populated nonradiatively from the Sn state than when pumped directly by the S0 → S1 excitation. Additionally, the Sn → S1 nonradiative relaxation time is found to change by varying the delay time between the two pump pulses. The observed dependence of the lowest excited state population as well as its dependence on the delay between the two pump pulses are found to fit a kinetic model in which the Sn state populates a different surface (called S′1) than the one being directly excited (S1). The possible involvement of the Ag type states, the J intermediate, and the conical intersection leading to the S0 or to the isomerization product (K intermediate) are discussed in the framework of the proposed model.

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The heart of oxygenic photosynthesis is photosystem II (PSII), a multisubunit protein complex that uses solar energy to drive the splitting of water and production of molecular oxygen. The effectiveness of the photochemical reaction center of PSII depends on the efficient transfer of excitation energy from the surrounding antenna chlorophylls. A kinetic model for PSII, based on the x-ray crystal structure coordinates of 37 antenna and reaction center pigment molecules, allows us to map the major energy transfer routes from the antenna chlorophylls to the reaction center chromophores. The model shows that energy transfer to the reaction center is slow compared with the rate of primary electron transport and depends on a few bridging chlorophyll molecules. This unexpected energetic isolation of the reaction center in PSII is similar to that found in the bacterial photosystem, conflicts with the established view of the photophysics of PSII, and may be a functional requirement for primary photochemistry in photosynthesis. In addition, the model predicts a value for the intrinsic photochemical rate constant that is 4 times that found in bacterial reaction centers.

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The biochemistry of visual excitation is kinetically explored by measuring the activity of the cGMP phosphodiesterase (PDE) at light levels that activate only a few tens of rhodopsin molecules per rod. At 23 degrees C and in the presence of ATP, the pulse of PDE activity lasts 4 s (full width at half maximum). Complementing the rod outer segments (ROS) with rhodopsin kinase (RK) and arrestin or its splice variant p44 does not significantly shorten the pulse. But when the ROS are washed, the duration of the signal doubles. Adding either arrestin or p44 back to washed ROS approximately restores the pulse width to its initial value, with p44 being 10 times more efficient than arrestin. This supports the idea that, in vivo, capping of phosphorylated R* is mostly done by p44. When myristoylated (14:0) recoverin is added to unwashed ROS, the pulse duration and amplitude increase by about 50% if the free calcium is 500 nM. This effect increases further if the calcium is raised to 1 microM. Whenever R* deactivation is changed--when RK is exogenously enriched or when ATP is omitted from the buffer--there is no impact on the rising slope of the PDE pulse but only on its amplitude and duration. We explain this effect as due to the unequal competition between transducin and RK for R*. The kinetic model issued from this idea fits the data well, and its prediction that enrichment with transducin should lengthen the PDE pulse is successfully validated.

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Neste estudo foi avaliada a remoção de metil paration - inseticida e atrazina - herbicida presentes em água, em reatores de bancada, com fungos. A pesquisa foi dividida em quatro etapas: operação em batelada com metil paration e micélio fúngico, com e sem glicose; teste de toxicidade em placas com Aspergillus niger AN400; operação em batelada com os pesticidas atrazina e metil paration e esporos de Aspergillus niger AN400, com e sem glicose; e operação em reatores de leito fixo e fluxo ascendente. Na primeira etapa, a remoção de metil paration foi de 97% nos reatores sem glicose e 94% nos reatores com glicose com 32 dias de reação. Na operação em batelada, com esporos, um modelo cinético de primeira ordem representou bem a velocidade de decaimento de metil paration nesta fase, principalmente, nos reatores que continham glicose. Para os experimentos sem adição de glicose, a constante cinética foi de 0,063 ± 0,005/h, enquanto que para os experimentos com glicose a constante foi de 0,162 ± 0,014/h. Dessa forma, a adição de glicose resultou efetivamente em aumento na velocidade de conversão do inseticida. Na fase experimental, com atrazina e esporos de Aspergillus niger AN400, a presença do substrato primário (glicose) não teve influência na remoção de atrazina, sendo que os percentuais de remoção foram muito próximos aos percentuais encontrados nos reatores sem glicose. O estudo cinético, nessa fase com atrazina e esporos, revelou que para os experimentos sem a adição de glicose, o valor da velocidade de conversão de atrazina (RATZo) foi de 0,023/d, enquanto que para os experimentos com glicose (RATZo) foi 0,022/d. Portanto, a adição de glicose parece não ter influenciado significativamente a velocidade de remoção do herbicida por Aspergillus niger AN400. O teste de toxicidade demonstrou que metil paration e atrazina não inibiram o crescimento do fungo nas várias concentrações testadas, inclusive nas mais elevadas, que foram 60 mg/L e 25 mg/L para metil paration e atrazina, respectivamente. No reator de leito fixo a remoção de metil paration foi de 40% com 12 h de tempo de detenção hidráulica, e 0,5 g glicose/L. Porém, quando a concentração de glicose foi duplicada a remoção de metil paration diminuiu para 35%. Neste reator o pH se manteve na faixa ácida 3,4 a 5,2, considerada ideal para os fungos. Os resultados encontrados mostram a viabilidade dos fungos para remoção desses pesticidas, considerados persistentes no ambiente.

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The pyrolysis and combustion of corn stover were studied by dynamic thermogravimetry and derivate thermogravimetry (TG-DTG) at heating rates of 5, 10, 20 and 50 K min−1 at atmospheric pressure. For the simulation of pyrolysis and combustion processes a kinetic model based on the distribution of activation energies was used, with three pools of reactants (three pseudocomponents) because of the complexity of the biomass samples of agricultural origin. The experimental thermogravimetric data of pyrolysis and combustion processes were simultaneously fitted to determine a single set of kinetic parameters able to describe both processes at the different heating rates. The model proposed achieves a good correlation between the experimental and calculated curves, with an error of less than 4% for fitting four heating rates simultaneously. The experimental results and kinetic parameters may provide useful data for the design of thermo decomposition processing system using corn stover as feedstock. On the other hand, analysis of the main compounds in the evolved gas is given by means of a microcromatograph.

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On the basis of laboratory experiments with model mixtures (active carbon + CuBr2 at different loads), this work studies the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) by de novo synthesis. For the different samples, the temperature of the maximum carbon oxidation rate was determined by thermogravimetric analysis, and a kinetic model was proposed for the degradation of the materials in an oxidizing atmosphere (synthetic air). The effect of the addition of different amounts of CuBr2 was studied, finding that its presence accelerates the degradation of the carbonaceous structure in the presence of oxygen. The thermal degradation of the samples in air is satisfactorily described by a first-order single-reaction model. In addition, combustion runs of one of the mixtures (consisting of activated carbon + 50 wt % CuBr2, pyrolyzed at 700 °C) were performed in a quartz horizontal laboratory furnace. The analysis of the emissions and the solid residue proved the formation of brominated dioxins and furans at 300, 400, and 500 °C, with a maximum yield at 300 °C (91.7 ng/g of total PBDD/Fs) and a higher bromination degree with increasing temperature.