Evaluation of microstructural features of a new polymeric organic stationary phase grafted on silica surface: A paradigm of characterization of HPLC-stationary phases by a combination of suspension-state 1H NMR and solid-state 13C-CP/MAS-NMR

Silica-supported poly(octadecylacrylate) (Sil-ODAn), polymeric octadecylsilyl silica (polymeric ODS), and monomeric octadecylsilyl silica (monomeric ODS) were studied by a combination of suspension-state 1H NMR and solid-state 13C CP/MAS-NMR to probe the mechanisms underlying their functions as stationary phases for RP-HPLC. Sil-ODAn, with a strong temperature dependent separation behaviour showed correspondent temperature dependent manifestations in both suspension-state 1H NMR and solid-state 13C CP/MAS-NMR experiments. With a gradual increase in temperature, intensity of proton signals (1H NMR) of octadecyl moieties (mainly methylene groups) rose dramatically. This dramatic rise was at the same temperature of an endothermic peak detectable in its DSC thermogram indicating a relatively complete solid to liquid phase transition. In addition temperature dependencies of the ratio of trans to gauche conformed well to temperature dependencies of the separation factor between naphthacene and triphenylene (as a simple indicator of shape selectivity). Therefore NMR spectra of Sil-ODAn were used as a reference for ascertaining percentage of octadecyl moieties of liquid type mobility in the two other stationary phases. Using this method we determined percentage of liquid phase in polymeric ODS and monomeric ODS at various temperatures. We suggest a combination of suspension-state 1H NMR and solid-state 13C CP/MAS-NMR for structure-dynamic characterization of various kinds of hydrocarbon chains grafted onto the silica particles.