C(18) phases prepared by different synthetic pathways are examined by solid-state NMR spectroscopy. Silane functionality is clearly indicated by (29)Si CP/MAS NMR spectroscopy. Order and mobility of the alkyl chains are investigated with high-speed (1)H MAS and (13)C CP/MAS NMR spectroscopy. Differences in coverage are monitored by (1)H line widths,( 13)C chemical shifts, (13)C cross-polarization constants, and (1)H relaxation times in the rotating frame. It is shown that C(18) phases prepared by the surface polymerization technique exhibit a more regular surface coverage than sorbents prepared by conventional polymeric synthesis. The findings from solid-state NMR investigations are discussed in the context of liquid chromatography (LC) separations of linear and bulky polycyclic aromatic hydrocarbon (PAH) solutes.
The relationship between alkyl phase structure and chromatographic performance is investigated
for a series of docosyl (C22)-modified silica surfaces. The results of solid-state nuclear magnetic resonance
(NMR) spectroscopy and fluorescence spectroscopy are evaluated and correlated with liquid chromatographic
retention for relevant shape-selective separations. A set of four different stationary phases was prepared by
solution and surface polymerization approaches, yielding materials with surface coverages ranging from 3.6
to 7.0 μmol/m2. 13C cross polarization magic angle spinning (CP/MAS) NMR spectra indicate that a
predominance of trans conformations exists for high-coverage C22 phases (>4.0 μmol/m2). Two-dimensional
solid-state NMR spectroscopy (wide line separation, WISE) was utilized to evaluate the mobility of the trans
and gauche alkyl chain conformations. Temperature-dependent 13C CP/MAS NMR measurements of the bonded
phases exhibit large differences in the dynamic behavior of the immobilized C22 chains. Unusually high chain
rigidity was found for the self-assembled monolayer C22 phase (7.0 μmol/m2). Fluorescence lifetime
measurements of 1,6-diphenylhexatriene (DPH) exhibit two different lifetimes of τF ≈ 1 and 7 ns, which are
ascribed to probe molecule populations in the mobile and bonded phases, respectively. Quantitative evaluation
of the fluorescence decay curves shows that the partitioning of DPH into the alkyl phase is favored at higher
surface coverages, reaching a maximum at a ligand density of 4.9 μmol/m2. Time-resolved fluorescence
anisotropy measurements also revealed that probe mobility was minimized at this surface coverage. With
increasing temperature, the mobility of DPH was found to increase and the fraction of sorbed molecules to
decrease. A shape selectivity test mixture containing five polycyclic aromatic hydrocarbons including DPH
was employed for temperature-dependent chromatographic studies. In accord with the spectroscopic results,
shape selectivity is enhanced at low temperatures and at high surface coverages. The combination of these
spectroscopic and chromatographic tools provides a wealth of information on the surface morphology of
systematically prepared C22 sorbents and greater insight on the molecular recognition process in liquid
chromatography.
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