title: Enantioresolution in electrokinetic chromatography-complete filling technique using sulfated gamma-cyclodextrin. Software-free topological anticipation.
abstract: Few papers have tried to predict the resolution ability of chiral selectors in capillary electrophoresis for the separation of the enantiomers of chiral compounds. In a previous work, we have used molecular information available on-line to establish enantioresolution levels of basic compounds using highly sulfated β-CD (HS-β-CD) as chiral selector in electrokinetic chromatography-complete filling technique (EKC-CFT). The present study is a continuation of this previous work, introducing some novelties. In this work, the ability of sulfated γ-cyclodextrin (S-γ-CD) as chiral selector in EKC-CFT is modelled for the first time. Thirty-three structurally unrelated cationic and neutral compounds (drugs and pesticides) are studied. Categorical enantioresolution levels (RsC, 0 or 1) are assigned from experimental enantioresolution values obtained at different S-γ-CD concentrations. Novel topological parameters connected to the chiral carbon (C*-parameters) are introduced. Four C*-parameters and a topological parameter of the whole molecule (aromatic atom count) are the most important variables according to a discriminant partial least squares-variable selection process. It suggests the preponderance of the topology adjacent to the chiral carbon to anticipate the RsC levels. A software-free anticipation protocol for new molecules is proposed. Over the current set of molecules evaluated, 100% of correct anticipations (resolved and non-resolved compounds) are obtained, while anticipation of some compounds remains undetermined. A criterion is introduced to alert on compounds which should not be anticipated.
authors.affiliation: Departamento de Química Analítica, Universitat de València, Burjassot, Valencia, Spain.
authors.forename: Laura
authors.initials: L
authors.lastname: Escuder-Gilabert
authors.affiliation: Departamento de Química Analítica, Universitat de València, Burjassot, Valencia, Spain.
authors.forename: Yolanda
authors.initials: Y
authors.lastname: Martín-Biosca
authors.affiliation: Departamento de Química Analítica, Universitat de València, Burjassot, Valencia, Spain. Electronic address: maria.j.medina@uv.es.
authors.forename: María José
authors.initials: MJ
authors.lastname: Medina-Hernández
authors.affiliation: Departamento de Química Analítica, Universitat de València, Burjassot, Valencia, Spain; Instituto Interuniversitario de Investigación de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Valencia, Spain.
authors.forename: Salvador
authors.initials: S
authors.lastname: Sagrado
mesh_terms: D002412:Cations; D020374:Chromatography, Micellar Electrokinetic Capillary / Q000379:methods*; D016002:Discriminant Analysis; D007202:Indicators and Reagents; D016018:Least-Squares Analysis; D010575:Pesticides / Q000032:analysis; D004364:Pharmaceutical Preparations / Q000032:analysis; D012984:Software; D013237:Stereoisomerism; D047408:gamma-Cyclodextrins / Q000737:chemistry*
chemical_list: D002412:Cations; D007202:Indicators and Reagents; D010575:Pesticides; D004364:Pharmaceutical Preparations; D047408:gamma-Cyclodextrins
keywords: Complete filling technique; Discriminant partial least squares; Electrokinetic chromatography; Enantioresolution; Sulfated-γ-cyclodextrin; Topological parameters