Solid-state NMR characterization of amylose tris(3,5-dimethylphenylcarbamate) chiral stationary-phase structure as a...

Solid-state NMR (1H/13C CPMAS) was utilized to identify structural differences in amylose tris(3,5-dimethylphenylcarbamate) chiral stationary phase (Chiralpak AD), as a function of mobile-phase composition. Dry Chiralpak AD stationary phase displayed an amorphous CPMAS NMR spectrum. However, CPMAS spectra of Chiralpak AD flushed with organic mobile phases clearly displayed evidence of solvent complexes. Chiralpak AD flushed with nonpolar hexane exhibited solvent complexes with minimal structural perturbation. For Chiralpak AD flushed with hexane containing alcohol modifiers, however, solvent incorporation caused significant difference in conformation distribution as evidenced by increased resolution of 13C peaks in the CPMAS spectrum of the stationary phase. 2-Propanol modifier displayed more efficient displacement of incorporated hexane while forming relatively more distinct/ordered solvent complexes with Chiralpak AD in comparison to ethanol modifier. Reversed elution order and unusual retention behavior on Chiralpak AD as a function of mobile-phase modifier was reported earlier. These chromatographic behaviors are believed to be due to different alterations of the steric environment of the chiral cavities in the CSP by the different mobile-phase modifiers. In addition, on the basis of the chemical shift of C-1 carbon on the amylose backbone, it is possible that Chiralpak AD's structure is a helix with a number of fold less than six.