R.S. Mohamed

Phase equilibrium and insulin partitioning in aqueous two-phase systems containing block copolymers and potassium phosphate

Abstract In this work, phase diagrams of aqueous two-phase systems (ATPS) containing PEO–PPO–PEO block copolymers and potassium phosphate as well as the partitioning behavior of insulin in these systems are presented. Experiments aimed at the identification of the effects of copolymer structure (by varying the number of EO units per polymer molecule), temperature (283.15 and 298.15xa0K) and pH (5.0 and 7.0) on the phase behavior of these systems were carried out. The results indicated the enlargement of the two-phase region upon increasing the temperature, pH and copolymer hydrophobicity (expressed as the PO/EO ratio in the copolymer molecule). Experimental measurements of the partitioning of human insulin in these ATPS also indicated the dependency of the partition coefficients on temperature, pH, and copolymer hydrophobicity, with the latter being the most influential factor. Finally, experimental data on the phase behavior and insulin partitioning were correlated using an excess Gibbs energy virial-type model modified in order to account for coulombic interactions and ionization equilibrium between the various forms of the phosphate ion.

Extraction of caffeine, chlorogenic acids and lipids from green coffee beans using supercritical carbon dioxide and co-solvents

The paper reports on experimental data on the extraction of caffeine, coffee oil and chlorogenic acids from green coffee beans using pure supercritical CO2 and supercritical CO2 modified with ethanol (5% w/w) and isopropyl alcohol (5% w/w) at 50 and 60oC and 15.2 24.8 e 35.2 MPa. In this study extraction kinetics were obtained for all assays i.e. samples were collected at several time intervals for each solvent and mixed solvent. When pure CO2 and CO2-ethanol mixed solvent were used, an increase in pressure resulted in an increase in the amount of oil extracted. When CO2 was modified with isopropyl alcohol, the amount of coffee oil extracted also increased with pressure. Caffeine extraction initially increased and subsequently decreased with pressure. Chlorogenic acids were only extracted when isopropyl alcohol was used as a co-solvent. An increase in extraction temperature resulted in a decrease of caffeine and oil extraction (retrograde condensation) when only CO2 was used as solvent. With the use of co-solvent this retrograde behavior was no longer observed and the increase in temperature resulted in the increase in the extracted amounts of caffeine, coffee oil and chlorogenic acids.

Supercritical carbon dioxide extraction of methylxanthines from maté tea leaves

Methylxanthines are alkaloids found in natural products such as tea, coffee and guarana. These alkaloids are commonly used in cola drinks and pharmaceutical products due principally to their stimulant and diuretic effects on the human organism. In this work, experimental data on the supercritical CO2 extraction of caffeine, theophylline and theobromine from herbal mate tea, a beverage traditionally consumed by the gauchos of southern Brazil, the Argentine, Paraguay and Uruguay, were obtained using high pressure extraction equipment that allows adequate control of temperature and pressure. The continuous extraction/fractionation of mate tea leaves, Ilex paraguariensis in natura using carbon dioxide was carried out at 313.2 and 343.2 K and pressures of 13.8 and 25.5 MPa. Extraction/fractionation curves revealed the large influence of temperature and pressure on extraction yield. CO2 was also found to show a higher selectivity for caffeine than for theophylline and theobromine.

A modified UNIQUAC equation for mixtures containing self-associating compounds

The UNIQUAC model for the excess Gibbs energy is modified using chemical theory to account for chain-like association occurring in self-associating compounds such as alcohols. The equation considers the alcohol to be a mixture of clusters in chemical equilibrium. The UNIQUAC equation is used to model the behavior of the mixture of clusters, with size and surface parameters related to the number of alcohol molecules involved in their formation. The values of association enthalpy and entropy were obtained through fitting vapor pressure data. The model is used to correlate phase behavior of alcohol-hydrocarbon mixtures at low pressures, presenting excellent results in bubble point calculations. A further extension was made to allow for cross-association, the formation of a hydrogen bond between the molecules of an alcohol and an active solute. This extension was used to model alcohol-aromatic mixtures with equally good results.

A chemical theory based equation of state for self-associating compounds

Abstract The Redlich–Kwong–Soave equation of state commonly used to describe the volumetric behavior of pure fluids and mixtures is modified using chemical theory to account for chain-like association occurring in self-associating compounds such as alcohols. The equation treats the pure fluid as a mixture of clusters, with parameters a and b related to the number of molecules involved in their formation and obtained by regression of vapor pressure data using hydrocarbons as homomorphs. The model is extended to mixtures of a self-associating compound and inert ones, and used to correlate the phase behavior of alcohol–hydrocarbon mixtures. The model resulted in excellent correlation of bubble point pressure experimental data and good predictions of vapor phase composition, especially at low temperatures, situation in which equations of state are usually inaccurate.

A SOLVATION-BASED THERMODYNAMIC MODEL FOR AQUEOUS TWO-PHASE SYSTEMS

Aqueous two-phase systems (ATPSs) have found wide application in the separation of biological molecules such as amino acids, peptides and proteins. Most of the research in this area has been dedicated to experimental determination and less effort has been devoted to the proper thermodynamic modeling of these systems. This work presents a new model for ATPS that accounts for solvation effects between polymer and water molecules, which are commonly reported to be responsible for phase separation. The model uses the Flory-Huggins equation as a starting point and modifies the combinatorial term by considering the presence of a hydration shell. The modified equation parameters were fit to a number of isotherms of poly(ethylene glycol) - dextran systems, and the results obtained are reported herein. These results show that the adopted modification leads to remarkable improvements in the performance of the model.

Biological phosphate removal using a degradable carbon source produced by hydrothermal treatment of excess sludge

The possibility of reusing excess sludge treated by hydrothermal reaction for the purpose of improving the efficiency of the enhanced biological phosphate removal (EBPR) process was investigated. Excess sludge from a fish-processing industry located in Japan was treated in high-temperature and high-pressure water, at a reaction temperature ranging from 200 to 400oC, a pressure of 1.8 to 30MPa and a constant reaction time of 7 min. For the conditions tested, the results showed that when the reaction temperature was increased the content of readily biodegradable substrate in the total CODCr increased. In addition, the amount of some volatile fatty acids (VFAs) produced by the hydrothermal reaction increased as reaction temperature increased. From the phosphate release tests under anaerobic conditions, it was possible to demonstrate that not only the VFAs, but also the readily and slowly biodegradable substrates are used as potential carbon source by the phosphate-accumulating organisms (PAOs).

Calculation of liquid-liquid equilibrium of aqueous two-phase systems using a chemical-theory-based excess Gibbs energy model

Abstract - Mixtures containing compounds that undergo hydrogen bonding show large deviations from ideal behavior. These deviations can be accounted for through chemical theory, according to which the formation of a hydrogen bond can be treated as a chemical reaction. This chemical equilibrium needs to be taken into account when applying stability criteria and carrying out phase equilibrium calculations. In this work, we illustrate the application of the stability criteria to establish the conditions under which a liquid-phase split may occur and the subsequent calculation of liquid-liquid equilibrium using a chemical-theory-modified Flory-Huggins equation to describe the non ideality of aqueous two -phase systems composed of poly(ethylene glycol) and dextran. The model was found to be able to correlate ternary liquid-liquid diagrams reasonably well by simple adjustment of the polymer -polymer binary interaction parameter. Keywords : Aqueous two -phase systems, thermodynamic modeling, Gibbs energy, liquid-liquid equilibrium .