Per-acetylated cyclic hexa-, hepta-, and octa-saccharide, (alpha-cyclodextrin octadecaacetate, beta-cyclodextrin henei-icosaacetate and gamma-cyclodextrin tetracosaacetate, respectively) exhibit melting point reduction and high solubility in dense CO2. Two-phase boundaries of the CO2-acetylated sugar mixtures were determined for per-acetylated cyclodextrin concentrations of 2-30 wt.%. The dew-point locus of the CO2 per-acetylated cyclodextrin binary systems shifted to higher pressures as the number of saccharides in the acetylated cyclodextrin increased. The CO2-solubility of per-acetylated cyclodextrins was comparable to oligomers of poly(vinyl acetate) (PVAc) (the Most CO2 soluble non-fluorous vinyl homopolymer) that contained an equivalent number of acetate groups. This very high degree of miscibility implies that the acyl groups of the per-acetylated cyclodextrins were readily accessible for favorable Lewis acid:Lewis base interactions with CO2 . Upon depressurization, each per-acetylated cyclodextrin formed rigid, brittle foams within the vessel as the boiling per-acetylated cyclodextrin-rich phase solidified during the removal Of CO2. (C) 2003 Elsevier B.V. All rights reserved.