Experimental probing and modeling of key sorbent-solute interactions of norephedrine enantiomers with polysaccharide-based chiral stationary phases.
The key interactions of a chiral solute, norephedrine or 2-amino-1-phenyl-1-propanol (PPA), with three commercially important polysaccharide-based chiral stationary phases, amylose Tris(3,5-dimethylphenylcarbamate) (ADMPC), amylose Tris((S)-alpha-methylbenzylcarbamate) (ASMBC) and cellulose Tris(3,5-dimethylphenylcarbamate) (CDMPC) are studied in detail using different experimental techniques and molecular simulations. The HPLC retention factors of the enantiomers of PPA in n-hexane/2-propanol (90/10, v/v) at 298 K vary significantly with these sorbents. The enantioselectivities of -PPA versus +PPA are 2.4, 1.0, and 0.8 (reversal in the elution order), respectively. The observed changes in the wavenumbers and the intensities of the amide bands of these polymers in the attenuated total reflection-infrared spectroscopy (ATR-IR) spectra upon absorption of each enantiomer are different. The IR wavenumbers, and the H-bonding interaction energies of the polymer side chains with each enantiomer (polymer-solute) in four different binding configurations are estimated and ranked using the density functional theory (the DFT/B3LYP/6-311+g(d,p) level of theory). X-ray diffraction (XRD) results show that the polymer crystallinity increases significantly upon absorption of each enantiomer. The helical pitches and the inter-rod packing for these polymers are inferred from the XRD results and incorporated into the molecular dynamics (MD) simulations. The elution orders predicted for the enantiomers of PPA using MD simulations of the polymer-PPA binary systems are consistent with the chromatography results. The enantioselectivity observed in ADMPC is hypothesized to be due to having three simultaneous interactions (two H-bond and one pi-pi) of the polymer with -PPA versus two interactions (one H-bond and one pi-pi) with +PPA.
Kasat
Rahul B
RB
School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN 47907-2100, USA.
Wang
Nien-Hwa Linda
NH
Franses
Elias I
EI
D002851:Chromatography, High Pressure Liquid; D008958:Models, Molecular; D008962:Models, Theoretical; D010665:Phenylpropanolamine / Q000737:chemistry*; D011134:Polysaccharides / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D014961:X-Ray Diffraction
D011134:Polysaccharides; D010665:Phenylpropanolamine