Comparative study of the radiation-induced grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) and polypropylene substrates. I: Kinetics and structural investigation

A comparative study has been made of the radiation grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) and polypropylene (PP) substrates, using the simultaneous irradiation method. Effects of grafting conditions such as monomer concentrations, type of solvent, dose rate and irradiation dose on the grafting yield were investigated. Under the same grafting conditions it was found that a higher degree of grafting of styrene was obtained using a mixture of dichloromethane/methanol solvents for PFA and methanol for PP and the degree of grafting was higher in PP than in PFA at all doses. However, the micro-Raman spectroscopy analysis of the graft revealed that, for the same degree of grafting, the penetration depth of the grafted polystyrene into the substrate was higher in PFA than in PP substrates. In both polymers the crystallinity was hardly affected by the grafting process and the degree of crystallinity decreased slightly with grafting dose. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be 0.6 and 1.4 order for PFA and 0.15 and 2.2 for PP, respectively. The degree of grafting increased with increasing radiation dose in both polymers. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield for PFA and PP was accompanied by a proportional increase in the penetration depth of the graft into the substrates. (C) 2003 Society of Chemical Industry.

Influence of shapes of selected vegetable materials on drying kinetics during fluidized bed drying

Three different particular geometrical shapes of parallelepiped, cylinder and sphere were taken from cut green beans (length:diameter = 1:1, 2:1 and 3:1) and potatoes (aspect ratio = 1:1, 2:1 and 3:1) and peas, respectively. Their drying behaviour in a fluidised bed was studied at three different drying temperatures of 30, 40 and 50 degreesC (RH = 15%). Drying curves were constructed using non-dimensional moisture ratio (MR) and time and their behaviour was modelled using exponential (MR = exp(-kt)) and Page (MR = exp(-kt(n))) models. The effective diffusion coefficient of moisture transfer was determined by Fickian method using uni- and three-dimensional moisture movements. The diffusion coefficient was least affected by the size when the moisture movement was considered three-dimensional, whereas the drying temperature had a significative effect on diffusivity as expected. The drying constant and diffusivity coefficients were on the descending order for potato, beans and peas. The Arrhenius activation energy for the peas was also highest, indicating a strong barrier to moisture movement in peas as compared to beans and skinless cut potato pieces. (C) 2003 Elsevier Science Ltd. All rights reserved.

Analysis of multicomponent adsorption kinetics on activated carbon

An integrated mathematical model for the kinetics of multicomponent adsorption on microporous carbon was developed. Transport in this bidisperse solid is represented by balance equations in the macropore and micropore phases, in which gas-phase diffusion dominates the mass transfer in the macropores, with the phenomenological diffusivities represented by the generalized Maxwell-Stefan (GMS) formulation. Viscous flow also contributes to the macropore fluxes and is included in the MS expressions. Diffusion of the adsorbed phase controls the mass transfer in the micro ore phase, p which is also described in a similar way by the MS method. The adsorption isotherms are represented by a new heterogeneous modified vacancy solution theory formulation of adsorption, which has proved to be a robust method for adsorption on activated carbons. The model is applied to the coadsorption and codesorption of C2H6 and C3H8 on Ajax and Norit carbon, as well as the displacement on Ajax carbon. The effect of the viscous flow in the macropore phase is not significant for the cases studied. The model accurately predicts the overshoot behavior and rollup of C2H6 during coadsorption. The prediction for the heavier compound C3H8 is always satisfactory, though at higher C3H8 mole fraction, the overshoot extent of C2H6 is overpredicted, possibly due to neglect of heat effects.

Drying kinetics of jatropha seeds

Given the necessity of developing jatropha cultivation equipment, this work adjusted different mathematical models to experimental data obtained from the drying of jatropha seeds submitted to different drying conditions and selected the best model to describe the drying process. The experiment was carried out at the Federal Institute of Goiás - Rio Verde Campus. Seeds with initial moisture content of approximately 0.50 (kg water/kg dry matter) were dried in a forced air-ventilated oven, at temperatures of 45, 60, 75, 90 and 105°C to moisture content of 0.10 ± 0.005 (kg water/kg dry matter). The experimental data were adjusted to 11 mathematical models to represent the drying process of agricultural products. The models were compared using the coefficient of determination, chi-square test, relative mean error, estimated mean error and residual distribution. It was found that the increase in the air temperature caused a reduction in the drying time of seeds. The models Midilli and Two Terms were suitable to represent the drying process of Jatropha seeds and between them the use of the Midili model is recommended due to its greater simplicity.

Kinetics of solute leachate from imbibing Caesalpinia echinata Lam. (Brazilwood) seeds

The electrical conductivity of leachates from imbibing seeds has been used as a vigor test for several species. The adaptation of this methodology to different species requires knowledge on the leaching kinetics of electrolytes. For Brazilwood seeds, the classic method was not satisfactory and rapid tests are essential because they have low storage capacity at room temperature. Leaching kinetics during seed imbibition is a function of physiological quality, presence or absence of seed coat, imbibing temperature and the initial moisture content of seed. In this study, the electrolyte leaching rate of six different categories of seeds, from two regions, was evaluated in seeds with and without seed coat and incubated with different moisture contents and at different temperatures. The results showed that the electrolyte leaching rate in Brazilwood seeds is independent of the physiological quality, the presence or absence of seed coat and imbibition temperature, but these factors changed the total amount of electrolytes leached. The leaching rate increased in the first few minutes of imbibition, suggesting that the adjustment of the methodology must consider the reduction in imbibition time, reduction in temperature, use of a controlled and slower pre-imbibition, and replacement of the imbibition solution after the first few minutes.

Ecosapentanoic acid (EPA) does not affect cell kinetics in peripheral lymphocites from patients with Crohn's disease (CD) according to IL6 174G/C polymorphism

Rationale: Omega 3 fatty acids have been shown to be of potential benefit in patients with CD. The aim of the present study was to evaluate whether EPA can modulate the inflammatory response according to different genotypes of IL6G174G/C polymorphism. Methods: Peripheral blood cells were collected from CD patients with different genotypes for IL6 174G/C (GG, n = 16, GC, n = 8, CC, n = 7), and lymphocytes were established in culture media. Replicates with the addition of EPA (25 mM) were analysed in a period of 24h, 48h and 72h. Expression of IL6 e a PGE2 was assessed by ELISA. Apoptosis and cellular proliferation was determined by flow cytometry.

Heterogeneous kinetics of the reduction of chromium (VI) by elemental iron

Zero valent iron (ZVI) has been extensively used as a reactive medium for the reduction of Cr(VI) to Cr(III) in reactive permeable barriers. The kinetic rate depends strongly on the superficial oxidation of the iron particles used and the preliminary washing of ZVI increases the rate. The reaction has been primarily modelled using a pseudo-first-order kinetics which is inappropriate for a heterogeneous reaction. We assumed a shrinking particle type model where the kinetic rate is proportional to the available iron surface area, to the initial volume of solution and to the chromium concentration raised to a power ˛ which is the order of the chemical reaction occurring at surface. We assumed α= 2/3 based on the likeness to the shrinking particle models with spherical symmetry. Kinetics studies were performed in order to evaluate the suitability of this approach. The influence of the following parameters was experimentally studied: initial available surface area, chromium concentration, temperature and pH. The assumed order for the reaction was confirmed. In addition, the rate constant was calculated from data obtained in different operating conditions. Digital pictures of iron balls were periodically taken and the image treatment allowed for establishing the time evolution of their size distribution.

Adsorption kinetics of removal of yellow lanasol dyestuff using gallinaceous feathers

Gallinaceous feathers are an abundant solid waste from the poultry processing industries, which poses disposal problems. A kinetic study dealing with the adsorption process of wool reactive dye, Yellow Lanasol 4G (CI Reactive Yellow 39), on gallinaceous (Gallus gallus, Cobb 500) feathers was carried out. The main research goals of this work were to evaluate the viability of using this waste as adsorbent and to study the kinetics of the adsorption process, using a synthetic effluent. The characterization of feathers was performed by scanning electron microscopy, mercury porosimetry and B.E.T. method. The study of several factors (stirring, particles size, initial dye concentration and temperature) showed their influence over the adsorption process. An adapted version of the Schumckler and Goldstein´s unreacted core model fitted the experimental data. The best fit was obtained when the rate-limiting step was the diffusion through the reacted layer, which was expected considering the size of the dyestuff molecules. The comparison with the granular activated carbon (GAC) Sutcliffe GAC 10-30 indicate that in spite of the high adsorption capacities shown by feathers the GAC presented higher values, the values obtained were respectively 150 and 219 mg g-1, for an initial concentration of 500 mg L-1. The results obtained might open future perspectives both to the valorization of feathers and to the economical treatment of textile wastewaters.

Experimental design methodologies for the identification of Michaelis-Menten type kinetics

The main objective of this work was to investigate the application of experimental design techniques for the identification of Michaelis-Menten kinetic parameters. More specifically, this study attempts to elucidate the relative advantages/disadvantages of employing complex experimental design techniques in relation to equidistant sampling when applied to different reactor operation modes. All studies were supported by simulation data of a generic enzymatic process that obeys to the Michaelis-Menten kinetic equation. Different aspects were investigated, such as the influence of the reactor operation mode (batch, fed-batch with pulse wise feeding and fed-batch with continuous feeding) and the experimental design optimality criteria on the effectiveness of kinetic parameters identification. The following experimental design optimality criteria were investigated: 1) minimization of the sum of the diagonal of the Fisher information matrix (FIM) inverse (A-criterion), 2) maximization of the determinant of the FIM (D-criterion), 3) maximization of the smallest eigenvalue of the FIM (E-criterion) and 4) minimization of the quotient between the largest and the smallest eigenvalue (modified E-criterion). The comparison and assessment of the different methodologies was made on the basis of the Cramér-Rao lower bounds (CRLB) error in respect to the parameters vmax and Km of the Michaelis-Menten kinetic equation. In what concerns the reactor operation mode, it was concluded that fed-batch (pulses) is better than batch operation for parameter identification. When the former operation mode is adopted, the vmax CRLB error is lowered by 18.6 % while the Km CRLB error is lowered by 26.4 % when compared to the batch operation mode. Regarding the optimality criteria, the best method was the A-criterion, with an average vmax CRLB of 6.34 % and 5.27 %, for batch and fed-batch (pulses), respectively, while presenting a Km’s CRLB of 25.1 % and 18.1 %, for batch and fed-batch (pulses), respectively. As a general conclusion of the present study, it can be stated that experimental design is justified if the starting parameters CRLB errors are inferior to 19.5 % (vmax) and 45% (Km), for batch processes, and inferior to 42 % and to 50% for fed-batch (pulses) process. Otherwise equidistant sampling is a more rational decision. This conclusion clearly supports that, for fed-batch operation, the use of experimental design is likely to largely improve the identification of Michaelis-Menten kinetic parameters.

Reactivity of syringyl and guaiacyl lignin units and delignification kinetics in the kraft pulping of eucalyptus globulus wood using Py-Gc-Ms/FID

Eucalyptus globulus sapwood and heartwood showed no differences in lignin content (23.0% vs. 23.7%) and composition: syringyl-lignin (17.9% vs. 18.0%) and guaiacyl-lignin (4.8% vs. 5.2%). Delignification kinetics of S- and G-units in heartwood and sapwood was investigated by Py-GC–MS/FID at 130, 150 and 170 °C and modeled as double first-order reactions. Reactivity differences between S and G-units were small during the main pulping phase and the higher reactivity of S over G units was better expressed in the later pulping stage. The residual lignin composition in pulps was different from wood or from samples in the initial delignification stages, with more G and H-units. S/G ratio ranged from 3 to 4.5 when pulp residual lignin was higher than 10%, decreasing rapidly to less than 1. The S/H was initially around 20 (until 15% residual lignin), decreasing to 4 when residual lignin was about 3%.

Modelling of the kinetics of municipal solid waste composting in full-scale mechanical-biological treatment plants

A thesis submitted in fulfilment of the requirements for the Degree of Doctor of Philosophy in Sanitary Engineering in the Faculty of Sciences and Technology of the New University of Lisbon

Kinetics of growth of Leishmania (Leishmania) chagasi cycle in McCoy cell culture

The kinetics of growth of Leishmania performed in vitro after internalization of the promastigote form in the cell and the occurrence of the transformation of the parasite into the amastigote form have been described by several authors. They used explants of macrophages in hamster spleen cell culture or in a human macrophage lineage cell, the U937. Using microscopy, the description of morphologic inter-relationship and the analysis of the production of specific molecules, it has been possible to define some of the peculiarities of the biology of the parasite. The present study shows the growth cycle of Leishmania chagasi during the observation of kinetic analysis undertaken with a McCoy cell lineage that lasted for a period of 144 hours. During the process, the morphologic transformation was revealed by indirect immunofluorescence (IF) and the molecules liberated in the extra cellular medium were observed by SDS-PAGE at 24-hour intervals during the whole 144-hour period. It was observed that in the first 72 hours the promastigote form of L. chagasi adhered to the cell membranes and assumed a rounded (amastigote-like) form. At 96 hours the infected cells showed morphologic alterations; at 120 hours the cells had liberated soluble fluorescent antigens into the extra cellular medium. At 144 hours, new elongated forms of the parasites, similar to promastigotes, were observed. In the SDS-PAGE, specific molecular weight proteins were observed at each point of the kinetic analysis showing that the McCoy cell imitates the macrophage and may be considered a useful model for the study of the infection of the Leishmania/cell binomial.

Mediated catalysis of Paracoccus pantotrophus cytochrome c peroxidase by P. pantotrophus pseudoazurin: kinetics of intermolecular electron transfer

J Biol Inorg Chem (2007) 12:691–698 DOI 10.1007/s00775-007-0219-9

Kinetics studies of the superoxide-mediated electron transfer reactions between rubredoxin-type proteins and superoxide reductases

J Biol Inorg Chem (2006) 11: 433–444 DOI 10.1007/s00775-006-0090-0

Kinetics of the cercaria-schistosomulum transformation in vivo

Sitice most studies on the cercaria-schistosomulum transformation have been carried out in vitro, the authors used the inoculation ofcercariae into the peritoneal cavity of mice tofollow the steps involved in this progressive adaptation of cercarie to the vertebmte host. The main conclusions were: 1. Most cercariae reach the schistosomular stage between 90-120 min after intraperitoneal inoculation. 2. Changes usuallystart with detachment of the tail followed by loss, rupture or changes of the glycocalix. 3. After 120 min most larvae loss their tails and present water sensitivity. 4. Acetabular grands depletion usually does not occur in cercaria-shistosomulum changes in the peritoneal cavity of mice. These steps differ in some way from those described in the kinetics of the in vitro observations performed by other investigators, and is more like those described in the penetration in the skin of living vertebrates.