Biomedical subjects
Publications and source records attributed to SK Singh.
Explore the source record for details and available documents.
A titration calorimetric study of the interaction between nonionic cellulose ethers and ionic surfactant (SDS) has been extended to a larger number of polymers to explore the effect of variation of polymer hydrophobicity on the energetics of the process. "Hydrophobicity" as used here is an overall effect of the nature, degree, and number of substituents and is characterized by the cloud point and (aqueous) surface tension lowering abilities of the polymer. A direct correlation is found between the extent of "hydrophobicity" and the endo-enthalpic peak in the initial SDS concentration region of interaction. However, the overall mechanism of interaction is similar for all the polymers, being dominated by polymer-surfactant interactions initially and converting into a surfactant-surfactant interaction process at higher SDS concentrations. The importance of polymer characteristics thus becomes weaker at the later stages of the process. Differences between the polymers is also reduced by an increase of temperature, leading to a near overlap of observed enthalpy curves at 40 degrees C. The energetics of interaction are also mirrored by the isothermal surfactant binding curves and the changes in macroscopic and microviscosity of the system. Copyright 1999 Academic Press.
The interaction between certain nonionic cellulose ethers (ethyl hydroxyethyl cellulose and hydroxypropyl methyl cellulose) and sodium dodecyl sulphate (SDS) has been investigated using isothermal titration microcalorimetry at temperatures between 25-50 degrees C. The observed heat flow curves have been interpreted in terms of a plausible mechanism of the interaction of the substituent groups with SDS monomers and clusters. The data have been related to changes occuring in the system at the macro- and microscopic levels with the addition of surfactants and with temperature. The process consists predominantly of polymer-surfactant interactions initially and surfactant-surfactant interactions at the later stages. A phenomenological model of the cooperative interaction (adsorption) process has been derived, and earlier published equilibrium binding data have been used to recover binding constants and Gibbs energy changes for this process. The adsorption enthalpies and entropies have been recovered along with the heat capacity change. The enthalpic cost of confining the nonpolar regions of the polymers in surfactant clusters is high, but the entropy gain from release of hydration shell water molecules as well as increased freedom of movement of these nonpolar regions in the clusters gives the process a strong entropic driving force. The process is entropy-driven initially and converts to being both enthalpy and entropy-driven at high SDS concentrations. An enthalpy-entropy compensation behavior is seen. Strongly negative heat capacity changes have been obtained resulting from the transfer of nonpolar groups from aqueous into nonpolar environments, as well as a reduction of conformational domains that the chains can populate. Changes in these two components cause the heat capacity change to become less negative at the higher binding levels. The system can be classified as exhibiting nonclassical hydrophobic binding at the later stages of binding. Copyright 1999 Academic Press.
The adsorption of amphiphilic drug molecules to a polyelectrolyte, kappa-carrageenan, has been shown to be related to hydrophobicity of drug and the conformation of the polyanion which in turn can be regulated by choice of counterion. The binding is of a strongly cooperative nature and the degree of cooperativity has been found to be related to the self-aggregation tendency of the drug molecules. This system has been examined by titration microcalorimetry and capillary viscometry to determine the thermodynamics of the binding phenomenon. The titration calorimetry data confirms the trends and conclusions drawn regarding the factors that control the binding. Viscometry shows that although there is a change in size of the polymeric chains when the drug molecules are adsorbed, the effect is primarily due to charge neutralization and not a conformation change. This allows the microcalorimetry data to be analyzed to recover the enthalpy of binding of the drug molecules to the polymer. Earlier published equilibrium binding data has been analyzed to determine the binding constants and free energy changes in the process (-25 to -90 kJ/mol). A phenomenological model has been derived for the cooperative binding process for this purpose. The binding process is primarily enthalpy driven with the major part of enthalpy change (-10 to -40 kJ/mol) arising from the aggregation of bound drug molecules, i.e., from hydrophobic interactions; the process is also entropically favorable. The size of these aggregates in polymer-bound state is of the order of 2-5 molecules of drug, similar to the pre-micellar aggregates of the drugs in solution. Copyright 1998 Academic Press.
Explore the source record for details and available documents.
Explore the source record for details and available documents.
Explore the source record for details and available documents.
Explore the source record for details and available documents.