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The use of linear expressions of solute boiling point versus retention to indicate special interactions with the molecular rings of modified cyclodextrin phases in gas chromatography

The boiling points (degrees C, 1 x 10) of diverse C10 polar solutes from volatile oils are set against their relative retention times versus n-undecane to calculate linear equations for 12 commercial modified cyclodextrin (CD) capillary phases. Ten data points are considered for each CD, then solutes are rejected until 5 or more remain that give an expression with a correlation coefficient of at least 0.990 and a standard deviation of less than 5.5. Three phases give almost perfect correlation, and 3 other CDs have difficulty complying. Solutes involved in the equations (most frequently cuminal, linalol, and carvone) are presumed to have a 'standard' polar transient interaction with the molecular rings of the CDs concerned. Several remaining solutes (mostly citral, fenchone, and menthol) exhibit extra retention over the calculated standard (up to 772%), which is believed to indicate a firm 'host' CD or 'guest' solute molecular fit in some cases. Other solutes show less retention than calculated (mostly citronellal, citronellol, estragole, and pulegone). This suggests rejection by the CD, which behaves merely as a conventional stationary phase to them. The intercept constant in the equation for each phase is suggested to be a numerical relative polarity indicator. These b values indicate that 3 hydroxypropyl CDs show the most polarity with values from 28 to 43; and CDs that are fully substituted with inert groups fall in the range of 15 to 20.