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- W2008759926 abstract "Calixarenes are synthetic macrocyclic compounds, described as molecular baskets as they possess high ionophoric selectivity and form inclusion complexes with many important ionic guests. In our initial work, hexameric and tetrameric tert-butylcalixarenes, unfunctionalized at the lower rim, are shown to be separable on a diol column using supercritical fluid chromatography with methanol/chloroform-modified CO(2) as mobile phase. The variation in capacity factors for these calixarenes was studied as a function of modifier composition. However, the solubility of these molecular baskets in unmodified supercritical CO(2) is enhanced by fluorination at the upper rim. For example, when p-allylcalix[4]arene is derivatized by a thiol-ene addition reaction with heptadecafluorodecanethiol, CF(3)(CF(2))(7)(CH(2))(2)SH, a solubility of >0.12 mol L(-)(1) in supercritical CO(2) is measured for the p-heptadecafluorodecylthio-n-propylcalix[4]arene at 60 °C and 200 atm. However, subsequent lower rim functionalization to form the tetrahydroxamate derivative, while reducing the solubility, allows supercritical fluid extraction of Fe(III) by the fluorinated calix[4]arene ligands to be studied as a function of temperature and pressure and monitored using UV/visible and atomic absorption spectrometry. In particular, the visible absorption spectra obtained for the extracted Fe(III)-calix[4]arene tetrahydroxamate complex, collected in dimethyl sulfoxide, are indicative of octahedral Fe(III) complexation in a manner similar to that displayed by water-soluble siderophores. Studies on the efficiency and selectivity of Fe(III) extraction are also reported." @default.
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- W2008759926 date "1997-06-01" @default.
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- W2008759926 title "Molecular Baskets in Supercritical CO<sub>2</sub>" @default.
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- W2008759926 doi "https://doi.org/10.1021/ac960850q" @default.
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