Partition of the natural dye carmine has been studied in aqueous two-phase systems prepared by mixing aqueous solutions of polymer or copolymer with aqueous salt solutions (Na(2)SO(4) and Li(2)SO(4)). The carmine dye partition coefficient was investigated as a function of system pH, polymer molar mass, hydrophobicity, system tie-line length and nature of the electrolyte. It has been observed that the carmine partition coefficient is highly dependent on the electrolyte nature and pH of the system, reaching values as high as 300, indicating the high potential of the two-phase extraction with ATPS in the purification of carmine dye. The partition relative order was Li(2)SO(4)"Na(2)SO(4). Carmine molecules were concentrated in the polymer-rich phase, indicating an enthalpic specific interaction between carmine and the pseudopolycation, which is formed by cation adsorption along the macromolecule chain. When the enthalpic carmine-pseudopolycation interaction decreases, entropic forces dominate the natural dye-transfer process, and the carmine partitioning coefficient decreases. The optimization of the extraction process was obtained by a central composite face-centered (CCF) design. The CCF design was used to evaluate the influence of Li(2)SO(4) and PEO 1500 concentration and of the pH on the partition coefficient of carmine. The conditions that maximize the partition of carmine into the top phase were determined to be high concentrations of PEO and Li(2)SO(4) and low pH values within the ranges studied.
Bovine serum albumin (BSA)/curcumin binding and dye photodegradation stability were evaluated. BSA/curcumin complex showed 1:1 stoichiometry, but the thermodynamic binding parameters depended on the technique used and BSA conformation. The binding constant was of the order of 10L·mol by fluorescence and microcalorimetric, and 10 and 10L·mol by surface plasmon resonance (steady-state equilibrium and kinetic experiments, respectively). For native BSA/curcumin, fluorescence indicated an enthalpic and entropic driven process based on the standard enthalpy change (ΔH=-8.67kJ·mol), while microcalorimetry showed an entropic driven binding process (ΔH=29.11kJ·mol). For the unfolded BSA/curcumin complex, it was found thatp ΔH=-16.12kJ·mol and ΔH=-42.63kJ·mol. BSA (mainly native) increased the curcumin photodegradation stability. This work proved the importance of using different techniques to characterize the protein-ligand binding.
The effect of different ionic cosolutes (NaCl, Na(2)SO(4), Li(2)SO(4), NaSCN, Na(2)[Fe(CN)(5)NO], and Na(3)[Co(NO)(6)]) on the interaction between sodium dodecyl sulfate (SDS) and poly(ethylene oxide) (PEO) was examined by small-angle X-ray scattering (SAXS) and isothermal titration calorimetric techniques. The critical aggregation concentration values (cac), the saturation concentration (C(2)), the integral enthalpy change for aggregate formation (ΔH(agg)(int)) and the standard free energy change of micelle adsorption on the macromolecule chain (ΔΔG(agg)) were derived from the calorimetric titration curves. In the presence of 1.00 mmol L(-1) cosolute, no changes in the parameters were observed when compared with those obtained for SDS-PEO interactions in pure water. For NaCl, Na(2)SO(4), Li(2)SO(4), and NaSCN at 10.0 and 100 mmol L(-1), the cosolute presence lowered cac, increased C(2), and the PEO-SDS aggregate became more stable. In the presence of Na(2)[Fe(CN)(5)NO], the calorimetric titration curves changed drastically, showing a possible reduction in the PEO-SDS degree of interaction, possibility disrupting the formed nanostructure; however, the SAXS data confirmed, independent of the small energy observed, the presence of aggregates adsorbed on the polymer chain.
Phase diagrams, densities and refractive indexes of poly(ethylene oxide) + organic salts + water aqueous two-phase systems: Effect of temperature, anion and molar mass, Fluid Phase Equilibria http://dx. Graphical abstractHighlights The segregation process is endothermic and entropically driven for all ATPS. The biphasic region on the phase diagrams increase as the molar mass of PEO increase. The biphasic region increased in relation to the anions studied: citrate > tartrate > succinate. AbstractThe application of aqueous two-phase systems (ATPSs) at the industrial level requires systems formed by non-toxic substances to decrease the negative impact on the environment. Organic salts such as sodium citrate, sodium tartrate and sodium succinate have been utilized in order to fulfill this objective. In this work, ATPSs formed by poly(ethylene oxide), PEO, with molar mass 10,000 or 35,000 g mol -1 , organic salts and water, namely PEO10000 + sodium citrate + water, PEO10000 + sodium tartrate + water, PEO10000 + sodium succinate + water and PEO35000 + sodium citrate + water ATPSs at (283.15, 298.15 and 313.15) K have been studied. Effects of temperature, anion and polymer molar mass on the phase diagrams, as well as, the densities and refractive indexes of both phases of the ATPSs were evaluated. The segregation process was endothermic and entropically driven for all ATPSs. The biphasic region on the phase diagrams increased as the molar mass of PEO increased. In addition, the biphasic region also increased in relation to the anions studied: citrate > tartrate > succinate. The consistency of the tie-line data was ascertained by applying the Othmer-Tobias correlation.
The interaction between Allura Red and bovine serum albumin (BSA) was studied in vitro at pH 7.4. The fluorescence quenching was classified as static quenching due to the formation of AR-BSA complex, with binding constant (K) ranging from 3.26±0.09 to 8.08±0.0610(4)L.mol(-1), at the warfarin binding site of BSA. This complex formation was driven by increasing entropy. Isothermal titration calorimetric measurements also showed an enthalpic contribution. The Allura Red diffusion coefficient determined by the Taylor-Aris technique corroborated these results because it reduced with increasing BSA concentration. Interfacial tension measurements showed that the AR-BSA complex presented surface activity, since interfacial tension of the water-air interface decreased as the colorant concentration increased. This technique also provided a complexation stoichiometry similar to those obtained by fluorimetric experiments. This work contributes to the knowledge of interactions between BSA and azo colorants under physiological conditions.
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