Untersuchung von stationären Phasen mittels dynamischer Festkörper-NMR

A polymer-based RP sorbent was prepared by immobilizing a poly(ethylene-co-acrylic acid) copolymer with an acid mass fraction of 5% on silica by using a 3-glycidoxypropyl linkage. 13C cross-polarization/magic angle spinning (CP/MAS) NMR spectroscopy of the sorbent, either in the dry state or suspended in the mobile phase, showed an increase in mobility at elevated temperatures. Alkyl chain segments with gauche conformations were more mobile than chain segments with trans conformations. The strength of the 13C-1H dipolar couplings in the alkyl chains was measured using the constant time dipolar and chemical shift pulse sequence revealing less molecular motion for the trans conformation. Non-linear van t Hoff plots were observed for separations of shape-constrained solutes (such as geometric ß-carotene isomers and polycyclic aromatic hydrocarbons (PAHs)). At higher temperatures, the retention behavior was similar to monomeric C18 sorbents, whereas at ambient and lower temperatures, enhanced shape selective properties were exhibited similar to polymeric C30 sorbents.