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Hydrophobic Solutes (hydrophobic + solute)
Selected AbstractsMolecular dynamics simulations of hydrotropic solubilization and self-aggregation of nicotinamideJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 7 2010Yong Cui Abstract Hydrotropy is a phenomenon where the presence of a large quantity of one solute enhances the solubility of another solute. The mechanism of this phenomenon remains elusive and a topic of debate. This study employed molecular dynamics simulation to investigate the hydrotropic mechanism of a model system consisting of a hydrotropic agent, nicotinamide (NA), a poorly water-soluble solute, PG-300995 (PG), and water. Our study demonstrates that NA and PG undergo significant aggregation in the aqueous solution, a result correlating closely to the self-aggregation of NA under the same conditions. The correlations are found both structurally and dynamically, suggesting that the self-aggregation of NA may be a prerequisite, or at least a major contributor, to its hydrotropic effects. The self-aggregation of NA allows the segregation of the hydrophobic solute from water, a key step to ease the energy increase to the system. Energetic evidences directly show that the hydrotropic solubilization is favored in the presence of NA aggregation. These results are in strong support of the molecular aggregation hypothesis for hydrotropic solubilization. Additionally, it is found that the restoration of water,water HBs from the interference of the NA and PG molecules plays an important role for the aggregation. The HBs between the solute and the hydrotrope may contribute, but is not vital, to the aggregation and hence the hydrotropic effects. The dynamic data confirm that the aggregates, while remain in liquid state, are much more active dynamically than a pure NA amorphous/liquid phase under the same temperature and pressure. By equilibrating an NA amorphous agglomerate with water, it is found that the aggregation state, rather than an NA,water two phase system, is the equilibrium state of the NA,+,water system. © 2010 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 99:3048,3059, 2010 [source] Compositional effects on electrophoretic and chromatographic figures of merit in electrokinetic chromatography with cetyltrimethylammonium bromide/sodium octyl sulfate vesicles as the pseudostationary phase.ELECTROPHORESIS, Issue 5 2008Part 1: Effect of the phase ratio Abstract The effect of the phase ratio on the electrophoretic and chromatographic properties of unilamellar vesicles comprised of cetyltrimethylammonium bromide (CTAB) and sodium octyl sulfate (SOS) was investigated in EKC. The surfactant concentration of the vesicles was 0.9, 1.2, 1.5, and 1.8% w/v, with a mole ratio of 1:3.66 (CTAB/SOS). Results were compared to those obtained using SDS micelles at concentrations of 1.0% (w/v, 35,mM) and 1.5% (52,mM). The CTAB/SOS vesicles (0.9,1.8% w/v) provided a significantly larger elution range (5.7,,,tves/t0,,,8.7) and greater hydrophobic (methylene) selectivity (2.8,,,,CH2,,,3.1) than SDS micelles (3.1,,,tmc/t0,,,3.3; ,CH2,=,2.2). Whereas the larger elution range can be attributed to the 25% reduction in EOF due to the interaction of unaggregated CTAB cations and the negatively charged capillary wall, the higher methylene selectivity is likely due to the lower concentration of water expected in the CTAB/SOS vesicle bilayer compared to the Palisades layer of SDS micelles. For a given phase ratio, CTAB/SOS vesicles are somewhat less retentive than SDS micelles, although retention factors comparable to those observed in 1.0,1.5% SDS can be obtained with 1.5,1.8% CTAB/SOS. A linear relationship was observed between phase ratio and retention factor, confirming the validity of the phase ratio model for these vesicles. Unique polar group selectivities and positional isomer shape selectivities were obtained with CTAB/SOS vesicles, with both types of selectivities being nearly independent of the phase ratio. For four sets of positional isomers, the elution order was always para < ortho < meta. Finally, the thermodynamics of solute retention was qualitatively similar to that reported for other surfactant aggregates (micelles and microemulsions); the enthalpic contribution to retention was consistently favorable for all compounds, whereas the entropic contribution was favorable only to hydrophobic solutes. [source] Conformational effects on the performance and selectivity of a polymeric pseudostationary phase in electrokinetic chromatographyELECTROPHORESIS, Issue 4-5 2005Jonathan P. McCarney Abstract The effect of the conformation of a polymeric pseudostationary phase on performance and selectivity in electrokinetic chromatography was studied using an amphiphilic pH-responsive polymer that forms compact intramolecular aggregates (unimer micelles) at low pH and a more open conformation at high pH. The change in conformation was found to affect the electrophoretic mobility, retention, selectivity, and separation efficiency. The low-pH conformer has higher electrophoretic mobility and greater affinity for most solutes. The unimer micelle conformation was also found to provide a solvation environment more like that of micelles and other amphiphilic self-associative polymers studied previously. It was not possible to fully characterize the effect of conformation on efficiency, but very hydrophobic solutes with long alkyl chains appeared to migrate with better efficiency when the unimer micelle conformation was employed. The results imply that polymers with a carefully optimized lipophilic-hydrophilic balance that allow self-association will perform better as pseudostationary phases. In addition, the results show that electrokinetic chromatography is a useful method for determining the changes in solvation environment provided by stimuli-responsive polymers with changes in the conditions. [source] Mixed-mode ion-exchangers and their comparative chromatographic characterization in reversed-phase and hydrophilic interaction chromatography elution modesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 14 2008Michael Lämmerhofer Abstract A set of particulate silica-supported mixed-mode RP/weak anion-exchangers (RP/WAX) (obtained by bonding of N -undecenoylated 3-aminoquinuclidine, 3-aminotropane and 2-dimethylaminoethylamine as well as of N -butenoyl-(2S,4S,5R)-2-aminomethyl-5-[(2-octylthio)ethyl]-quinuclidine to thiol-modified silica) were chromatographically characterized in comparison to selected commercially available columns using two distinct isocratic elution modes, viz. an aqueous-rich RP-type elution mode (with 40% ACN and 60% buffer) as well as an organic solvent-rich hydrophilic interaction chromatography (HILIC)-type elution mode (95 and 90% ACN). The mixed-mode RP/WAX phases showed multimodal applicability, unlike a polar embedded RP material (Synergi Fusion RP), amino phases (Luna NH2, BioBasic AX) or typical HILIC packings (ZIC-HILIC, TSKGel Amide-80). Principal component analysis (PCA) of the RP test data confirmed that the in-house developed RP/WAX columns as well as the Acclaim Mixed-Mode WAX-1 phase resemble each other in their chromatographic characteristics having slightly lower hydrophobic selectivity (,CH2 of 1.5) than the tested Synergi Fusion RP (,CH2 ,1.8). In contrast, a decrease in mixed-mode character due to lowered ion-exchange capacity and concomitantly increased RP-like behavior could be identified for other mixed-mode phases in the order of Obelisc R > Primesep B2 > Uptisphere MM3. PCA on HILIC data revealed that the RP/WAX phases behave dissimilar to TSKGel Amide-80, ZIC-HILIC and polysulfoethyl A under the chosen elution conditions. Hence, they may be regarded as complementary to these commercial stationary phases with applicability profiles for hydrophilic but also hydrophobic solutes. [source] | ||||||||||