title: Understanding chiral molecular micellar separations using steady-state fluorescence anisotropy, capillary electrophoresis, and NMR.
abstract: Chiral separations employing four diastereomers of poly sodium N-undecanoyl leucylvalinate (p-SULV) as chiral selectors are probed by use of MEKC, steady-state fluorescence anisotropy, and NMR. By employing diastereomers and thus altering the stereochemistry of a single amino acid in a systematic way, one may control the enantiorecognition ability of the chiral selector. As a result, one can gain a better understanding of the mechanisms of chiral recognition for the two classes of neutral or anionic chiral analytes studied. Evaluation of the chiral interactions leading to chiral separations confirmed our earlier observation of a strong relationship between the selectivity (alpha) observed using a chromatographic separation technique (MEKC) and that determined from the spectroscopic parameter, beta. A linear alpha versus beta relationship was observed for the molecular micelle p-(L)-SULV with all eight analytes included in this study. However, as we earlier predicted, different groups of analytes had different slopes, i.e., values of m, suggesting different chiral separation mechanisms. Evaluation of the data allowed a grouping of the analytes according to the primary site of chiral interaction with the leucine or valine moiety of molecular micelle chiral headgroup.
authors.affiliation: Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA.
authors.forename: Bertha C
authors.initials: BC
authors.lastname: Valle
authors.forename: Kevin F
authors.initials: KF
authors.lastname: Morris
authors.forename: Kristin A
authors.initials: KA
authors.lastname: Fletcher
authors.forename: Vivian
authors.initials: V
authors.lastname: Fernand
authors.forename: Drew M
authors.initials: DM
authors.lastname: Sword
authors.forename: Stacie
authors.initials: S
authors.lastname: Eldridge
authors.forename: Cynthia K
authors.initials: CK
authors.lastname: Larive
authors.forename: Isiah M
authors.initials: IM
authors.lastname: Warner
mesh_terms: D016880:Anisotropy; D002627:Chemistry, Physical / Q000379:methods; D002845:Chromatography / Q000379:methods; D002855:Chromatography, Thin Layer; D004573:Electrolytes / Q000737:chemistry; D019075:Electrophoresis, Capillary / Q000379:methods*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D008823:Micelles; D008856:Microscopy, Fluorescence / Q000379:methods*; D008956:Models, Chemical; D011522:Protons; D013050:Spectrometry, Fluorescence / Q000379:methods; D013237:Stereoisomerism; D013501:Surface-Active Agents / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D004573:Electrolytes; D008823:Micelles; D011522:Protons; D013501:Surface-Active Agents