Estudos de adsorção de tetraciclina e cromoglicato em partículas de quitosana

Among the polymers that stand out most in recent decades, chitosan, a biopolymer with physico-chemical and biological promising properties has been the subject of a broad field of research. Chitosan comes as a great choice in the field of adsorption, due to their adsorbents properties, low cost and abundance. The presence of amino groups in its chain govern the majority of their properties and define which application a sample of chitosan may be used, so it is essential to determine their average degree of deacetylation. In this work we developed kinetic and equilibrium studies to monitor and characterize the adsorption process of two drugs, tetracycline hydrochloride and sodium cromoglycate, in chitosan particles. Kinetic models and the adsorption isotherms were applied to the experimental data. For both studies, the zeta potential analyzes were also performed. The adsorption of each drug showed distinct aspects. Through the studies developed in this work was possible to describe a kinetic model for the adsorption of tetracycline on chitosan particles, thus demonstrating that it can be described by two kinetics of adsorption, one for protonated tetracycline and another one for unprotonated tetracycline. In the adsorption of sodium cromoglycate on chitosan particles, equilibrium studies were developed at different temperatures, allowing the determination of thermodynamic parameters

Estudos de adsorção de tetraciclina em partículas de quitosana

Due to its physico-chemical and biological properties, related to the abundance and low cost of raw material, chitosan has been recognized as a material of wide application in various fields, such as in drug delivery systems. Many of these properties are associated with the presence of amino groups in its polymer chain. A proper determination of these amino groups is very important, in order to properly specify if a given chitosan sample can be used in a particular application. Thus, in this work, initially, a comparison between the determination of the deacetylation degree by conductometry and elemental analysis was carried out using a detailed analysis of error propagation. It was shown that the conductometric analysis resulted in a simple and safe method for the determining the degree of deacetylation of chitosan. Subsequently, experiments were performed to monitor and characterize the adsorption of tetracycline on chitosan particles through kinetic and equilibrium studies. The main models of kinetics and adsorption isotherms, widely used to describe the adsorption on wastewater treatment systems and the drug loading, were used to treat the experimental data. Firstly, it was shown that an apparent linear t/q(t) × t relationship did not imply in a pseudo-second-order adsorption kinetics, differently of what has been repeatedly reported in the literature. It was found that this misinterpretation can be avoided by using non-linear regression. Finally, the adsorption of tetracycline on chitosan particles was analyzed using insights obtained from theoretical analysis, and the parameters generated were used to analyze the kinetics of adsorption, the isotherm of adsorption and to ropose a mechanism of adsorption

Characterization of micro-mesoporous carbonaceous materials. Calculations of adsorption isotherm of hydrocarbons

In this paper we apply a method recently developed by Do and co-workers(1) for the prediction of adsorption isotherms of pure vapors on carbonaceous materials. The information required for the prediction is the pore size distribution and the BET constant, C, of a corresponding nonporous surface (graphite). The dispersive adsorption force is assumed to be the dominant force in adsorption mechanism. This applies to nonpolar and weakly polar hydrocarbons. We test this predictive model against the adsorption data of benzene, toluene, n-pentane, n-hexane, and ethanol on a commercial activated carbon. It is found that the predictions are excellent for all adsorbates tested with the exception of ethanol where the predicted values are about 10% less than the experimental data, and this is probably attributed to the electrostatic interaction between ethanol molecules and the functional groups on the carbon surfaces.

Effects of adsorbate-adsorbate interaction in the description of adsorption isotherm of hydrocarbons in micro-mesoporous carbonaceous materials

In this paper, we present a model accounting for the adsorbate-adsorbate interaction in the adsorbed phase in the description of adsorption of pure vapors on carbonaceous materials. The details of the adsorbate-adsorbate interaction of a particular species are obtained from the analysis of its adsorption data on non-porous carbon black. The predictability of the model is tested against the adsorption isotherm data for benzene, toluene, n-pentane, n-hexane, carbon tetrachloride, methanol and ethanol on microporous activated carbon. It was found that the model prediction for non-polar adsorbates are satisfactory while it under-predicts for polar adsorbates, which is attributed to their additional interaction with functional groups. (C) 2002 Elsevier Science B.V. All rights reserved.

The influence of carbon surface oxygen groups on Dubinin–Astakhov equation parameters calculated from CO2 adsorption isotherm

We present the results of a systematic study of the influence of carbon surface oxidation on Dubinin–Astakhov isotherm parameters obtained from the fitting of CO2 adsorption data. Using GCMC simulations of adsorption on realistic VPC models differing in porosity and containing the most frequently occurring carbon surface functionalities (carboxyls, hydroxyls and carbonyls) and their mixtures, it is concluded that the maximum adsorption calculated from the DA model is not strongly affected by the presence of oxygen groups. Unfortunately, the same cannot be said of the remaining two parameters of this model i.e. the heterogeneity parameter (n) and the characteristic energy of adsorption (E0). Since from the latter the pore diameters of carbons are usually calculated, by inverse-type relationships, it is concluded that they are questionable for carbons containing surface oxides, especially carboxyls.

Adsorption of flexible n-alkane on graphitized thermal carbon black: analysis of adsorption isotherm by means of GCMC simulation

In this paper, we investigate the suitability of the grand canonical Monte Carlo in the description of adsorption equilibria of flexible n-alkane (butane, pentane and hexane) on graphitized thermal carbon black. Potential model of n-alkane of Martin and Siepmann (J. Phys. Chem. 102 (1998) 2569) is employed in the simulation, and we consider the flexibility of molecule in the simulation. By this we study two models, one is the fully flexible molecular model in which n-alkane is subject to bending and torsion, while the other is the rigid molecular model in which all carbon atoms reside on the same plane. It is found that (i) the adsorption isotherm results of these two models are close to each other, suggesting that n-alkane model behaves mostly as rigid molecules with respect to adsorption although the isotherm for longer chain n-hexane is better described by the flexible molecular model (ii) the isotherms agree very well with the experimental data at least up to two layers on the surface.

Adsorption isotherm studies of Cd (II), Pb (II) and Zn (II) ions bioremediation from aqueous solution using unmodified and EDTA-modified maize cob

The need to clean-up heavy metal contaminated environment can not be over emphasized. This paper describes the adsorption isotherm studies of Cd (II), Pb (II) and Zn (II) ions from aqueous solution using unmodified and EDTA-modified maize cob. Maize cob was found to be an excellent adsorbent for the removal of these metal ions. The amount of metal ions adsorbed increased as the initial concentration increased. Also, EDTA - modification enhanced the adsorption capacity of maize cob probably due to the chelating ability of EDTA. Among the three adsorption isotherm tested, Dubinin-Radushkevich gave the best fit with R² value ranging from 0.9539 to 0.9973 and an average value of 0.9819. This is followed by Freundlich isotherm (Ave. 0.9783) and then the Langmuir isotherm (Ave. 0.7637). The sorption process was found to be a physiosorption process as seen from the apparent energy of adsorption which ranged from 2.05KJ\mol to 4.56KJ\mol. Therefore, this study demonstrates that maize cob which is an environmental pollutant could be used to adsorb heavy metals and achieve cleanliness thereby abating environmental nuisance caused by the maize cob.

Adsorption isotherm studies of BOD, TSS and colour reduction from palm oil mill effluent (POME) using boiler fly ash

Palm oil is one of the two most important vegetable oils in the world's oil and fats market. The extraction and purification processes generate different kinds of waste generally known as palm oil mill effluent (POME). Earlier studies had indicated the possibility of using boiler fly ash to adsorb impurities and colour in POME treatment. The adsorption treatment of POME using boiler fly ash was further investigated in detail in this work with regards to the reduction of BOD, colour and TSS from palm oil mill effluent. The amount of BOD, colour and TSS adsorbed increased as the weight of the boiler fly ash used was increased. Also, the smaller particle size of 425µm adsorbed more than the 850µm size. Attempts were made to fit the experimental data with the Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The R² values, which ranged from 0.8974-0.9898, 0.8848-0.9824 and 0.6235-0.9101 for Freundlich, Langmuir and Dubinin-Radushkevich isotherms respectively, showed that Freundlich isotherm gave a better fit followed by Langmuir and then Dubinin-Radushkevich isotherm. The sorption trend could be put as BOD > Colour > TSS. The apparent energy of adsorption was found to be 1.25, 0.58 and 0.97 (KJ/mol) for BOD, colour and TSS respectively, showing that sorption process occurs by physiosorption. Therefore, boiler fly ash is capable of reducing BOD, Colour and TSS from POME and hence could be used to develop a good adsorbent for POME treatment.

A kinetic model of phosphorus metabolism in growing goats

The effect of increasing phosphorus (P) intake on P utilization was investigated in balance experiments using 12 Saanen goats, 4 to 5 mo of age and weighing 20 to 30 kg. The goats were given similar diets with various concentrations of P, and 32P was injected to trace the movement of P in the body. A P metabolism model with four pools was developed to compute P exchanges in the system. The results showed that P absorption, bone resorption, and excretion of urinary P and endogenous and fecal P all play a part in the homeostatic control of P. Endogenous fecal output was positively correlated to P intake (P < .01). Bone resorption of P was not influenced by intake of P, and P recycling from tissues to the blood pool was lesser for low P intake. Endogenous P loss occurred even in animals fed an inadequate P diet, resulting in a negative P balance. The extrapolated minimum endogenous loss in feces was .067 g of P/d. The minimum P intake for maintenance in Saanen goats was calculated to be .61 g of P/ d or .055 g of P/(kg.75·d) at 25 kg BW. Model outputs indicate greater P flow from the blood pool to the gut and vice versa as P intake increased. Intake of P did not significantly affect P flow from bone and soft tissue to blood. The kinetic model and regressions could be used to estimate P requirement and the fate of P in goats and could also be extrapolated to both sheep and cattle.

A macroscopic kinetic model for DNA polymerase elongation and high-fidelity nucleotide election

The enzymatically catalyzed template-directed extension of ssDNA/primer complex is an impor-tant reaction of extraordinary complexity. The DNA polymerase does not merely facilitate the insertion of dNMP, but it also performs rapid screening of substrates to ensure a high degree of fidelity. Several kinetic studies have determined rate constants and equilibrium constants for the elementary steps that make up the overall pathway. The information is used to develop a macro-scopic kinetic model, using an approach described by Ninio [Ninio J., 1987. Alternative to the steady-state method: derivation of reaction rates from first-passage times and pathway probabili-ties. Proc. Natl. Acad. Sci. U.S.A. 84, 663–667]. The principle idea of the Ninio approach is to track a single template/primer complex over time and to identify the expected behavior. The average time to insert a single nucleotide is a weighted sum of several terms, in-cluding the actual time to insert a nucleotide plus delays due to polymerase detachment from ei-ther the ternary (template-primer-polymerase) or quaternary (+nucleotide) complexes and time delays associated with the identification and ultimate rejection of an incorrect nucleotide from the binding site. The passage times of all events and their probability of occurrence are ex-pressed in terms of the rate constants of the elementary steps of the reaction pathway. The model accounts for variations in the average insertion time with different nucleotides as well as the in-fluence of G+C content of the sequence in the vicinity of the insertion site. Furthermore the model provides estimates of error frequencies. If nucleotide extension is recognized as a compe-tition between successful insertions and time delaying events, it can be described as a binomial process with a probability distribution. The distribution gives the probability to extend a primer/template complex with a certain number of base pairs and in general it maps annealed complexes into extension products.

Kinetic Model for Micro Algae Cell Concentration and Size Distribution: Application to Nannochloropsis gaditana

The cell concentration and size distribution of the microalgae Nannochloropsis gaditana were studied over the whole growth process. Various samples were taken during the light and dark periods the algae were exposed to. The distributions obtained exhibited positive skew, and no change in the type of distribution was observed during the growth process. The size distribution shifted to lower diameters in dark periods while in light periods the opposite occurred. The overall trend during the growth process was one where the size distribution shifted to larger cell diameters, with differences between initial and final distributions of individual cycles becoming smaller. A model based on the Logistic model for cell concentration as a function of time in the dark period that also takes into account cell respiration and growth processes during dark and light periods, respectively, was proposed and successfully applied. This model provides a picture that is closer to the real growth and evolution of cultures, and reveals a clear effect of light and dark periods on the different ways in which cell concentration and diameter evolve with time.

A mechanistic kinetic model for phenol degradation by the Fenton process

The objective of this paper is to develop and validate a mechanistic model for the degradation of phenol by the Fenton process. Experiments were performed in semi-batch operation, in which phenol, catechol and hydroquinone concentrations were measured. Using the methodology described in Pontes and Pinto [R.F.F. Pontes, J.M. Pinto, Analysis of integrated kinetic and flow models for anaerobic digesters, Chemical Engineering journal 122 (1-2) (2006) 65-80], a stoichiometric model was first developed, with 53 reactions and 26 compounds, followed by the corresponding kinetic model. Sensitivity analysis was performed to determine the most influential kinetic parameters of the model that were estimated with the obtained experimental results. The adjusted model was used to analyze the impact of the initial concentration and flow rate of reactants on the efficiency of the Fenton process to degrade phenol. Moreover, the model was applied to evaluate the treatment cost of wastewater contaminated with phenol in order to meet environmental standards. (C) 2009 Elsevier B.V. All rights reserved.

A compartmental model of hepatic disposition kinetics: 1. Model development and application to linear kinetics

The conventional convection-dispersion model is widely used to interrelate hepatic availability (F) and clearance (Cl) with the morphology and physiology of the liver and to predict effects such as changes in liver blood flow on F and Cl. The extension of this model to include nonlinear kinetics and zonal heterogeneity of the liver is not straightforward and requires numerical solution of partial differential equation, which is not available in standard nonlinear regression analysis software. In this paper, we describe an alternative compartmental model representation of hepatic disposition (including elimination). The model allows the use of standard software for data analysis and accurately describes the outflow concentration-time profile for a vascular marker after bolus injection into the liver. In an evaluation of a number of different compartmental models, the most accurate model required eight vascular compartments, two of them with back mixing. In addition, the model includes two adjacent secondary vascular compartments to describe the tail section of the concentration-time profile for a reference marker. The model has the added flexibility of being easy to modify to model various enzyme distributions and nonlinear elimination. Model predictions of F, MTT, CV2, and concentration-time profile as well as parameter estimates for experimental data of an eliminated solute (palmitate) are comparable to those for the extended convection-dispersion model.

On modified simple reacting spheres kinetic model for chemically reactive gases

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A kinetic model for the formation of acrylamide during the finish-frying of commercial French fries

Acrylamide is formed from reducing sugars and asparagine during the preparation of French fries. The commercial preparation of French fries is a multi-stage process involving the preparation of frozen, par-fried potato strips for distribution to catering outlets where they are finish fried. The initial blanching, treatment in glucose solution and par-frying steps are crucial since they determine the levels of precursors present at the beginning of the finish frying process. In order to minimize the quantities of acrylamide in cooked fries, it is important to understand the impact of each stage on the formation of acrylamide. Acrylamide, amino acids, sugars, moisture, fat and color were monitored at time intervals during the frying of potato strips which had been dipped in varying concentrations of glucose and fructose during a typical pretreatment. A mathematical model of the finish-frying was developed based on the fundamental chemical reaction pathways, incorporating moisture and temperature gradients in the fries. This showed the contribution of both glucose and fructose to the generation of acrylamide, and accurately predicted the acrylamide content of the final fries.