Solubility enhancement and QSPR correlations for polycyclic aromatic hydrocarbons complexation with α, β, and γ cyclodextrins

Abstract

Through batch equilibrium experiments, hydroxypropyl substituted α, β, and γ cyclodextrin (CDs) were shown to greatly increase the apparent solubility of eight common polycyclic aromatic hydrocarbons (PAHs) in aqueous solutions. Equations based on the volume fraction of solution composed of water and CDs have been developed to determine guest phase distribution. Based on these equations, the results of this and similar studies for CD showed that a log–log relationship exists between the fraction of CD occupied with a guest organic compound and the aqueous solubility of those guests (rsq 0.980). Analysis of potential quantitative structure property relationship (QSPR) found strong correlations between structural properties of the guests (e.g. aqueous solubility, octanol/water partitioning coefficient, molar volume, molecular surface area, and polarizability) and water/CD partitioning coefficients, phase distribution of the PAH between water and CD phases, and the fraction of CD molecules occupied with a guest PAH. Noteworthy among these, is the inverse relationship between the log of the fraction of CD molecules occupied under saturated conditions and the ratio of the molar volume of the PAH to the volume of the CD cavities (rsq for α, β, and γ: 0.887–0.892). Comparisons of the three CDs shows that while the size of the guest compound reduces its propensity to enter into the CD cavity, the effect of the guest size is lessened as the width of the CD ring increases. Development of these QSPR correlations provides a means to predict and evaluate guest/CD interactions for homologous series of compounds.