Structure−Function Relationships in High-Density Docosylsilane Bonded Stationary Phases by Raman Spectroscopy and Comparison to Octadecylsilane Bonded Stationary Phases: Effects of Common Solvents

Abstract

The effects of common solvents on alkyl chain conformational order in a series of high-density C22 stationary phases with surface coverage ranging from 3.61 to 6.97 micromol/m2 are investigated by Raman spectroscopy. Conformational order is evaluated using the intensity ratio of the antisymmetric and symmetric nu(CH2) modes as well as the frequencies at which these Raman bands are observed. Solvents studied include methanol-d4, acetonitrile-d3, water-d2, toluene-d8, chloroform-d. and benzene-d6. Alkyl chain conformational order and, hence, solvation of the stationary phase, is dependent on the Gibbs free energy change for these molecules at infinite dilution in hexadecane (DeltaG(o)HD), as well as stationary-phase properties (polymerization method and surface coverage). In general, polar solvents increase slightly the conformational order of these C22 stationary phases, while nonpolar solvents decrease conformational order. A comparison is made between C22 and C18 bonded-phase systems to further understand the role of alkyl chain length on solvent-stationary phase interactions. The change in alkyl chain conformational order induced by solvent is also compared to that induced by temperature, which provides insight into the effect of chromatographic conditions on stationary-phase shape selectivity, an important application of these materials.