Effect of solvents on the chiral recognition mechanisms of immobilized cellulose-based chiral stationary phase.

The effect of solvents on the enantioselectivities of four structurally similar chiral solutes with a cellulose derivative-based chiral stationary phase, Chiralpak IB, were studied using acetone (AC), 2-propanol (IPA), and tert-butanol (TBA) separately as polar modifiers. The enantioselectivities α of benzoin and methyl mandelate decrease with an increase in modifier concentration CM, whereas the enantioselectivity of pantolactone increased with increasing AC concentration. These results were attributed to the heterogeneous adsorption mechanisms of enantiomers. To interpret the dependence of enantioselectivity on modifier content, an enantioselectivity model based on a two-site adsorption model was proposed. The dependence of α on CM was inferred to be mainly due to the distinct modulating effects of modifier concentration on the two adsorption sites: the nonselective type-I site and enantioselective type-II site. The model fitted the benzoin data satisfactorily over a wide TBA concentration range. The retention factors as a function of TBA concentration were successfully deconvoluted for each site. With the use of the proposed model, it was inferred that the chiral recognitions of benzoin and methyl mandelate were mainly achieved by the presence of an aromatic group adjacent to the hydroxyl group. When using IPA and TBA separately as modifiers, the presence of an aromatic group adjacent to the ketone group mainly contributed to the nonselective π interactions and enantioselective steric interactions, respectively. These results, along with those of the modifier adsorption isotherms, determined using the perturbation method, as well as the retention behaviors of various achiral solutes, indicate that the molecular recognition mechanism of IB sorbent is highly sensitive to the adsorbate's molecular geometry. The molecular environment of the sorbent can be controlled using different modifiers, leading to distinct adsorption and retention mechanisms.