title: Elucidation of the Chromatographic Enantiomer Elution Order Through Computational Studies.
abstract: During the last twenty years, the interest towards the development of chiral compound has exponentially been increased. Indeed, the set-up of suitable asymmetric enantioselective synthesis protocols is currently one of the focuses of many pharmaceutical research projects. In this scenario, chiral HPLC separations have gained great importance as well, both for analytical- and preparative-scale applications, the latter devoted to the quantitative isolation of enantiopure compounds. Molecular modelling and quantum chemistry methods can be fruitfully applied to solve chirality related problems especially when enantiomerically pure reference standards are missing. In this framework, with the aim to explain the molecular basis of the enantioselective retention, we performed computational studies to rationalize the enantiomer elution order with both low- and high-molecular weight chiral selectors. Semi-empirical and quantum mechanical computational procedures were successfully applied in the domains of chiral ligand-exchange and chiral ion-exchange chromatography, as well as in studies dealing with the use of polysaccharide-based enantioresolving materials.
authors.affiliation: Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123-Perugia, Italy.
authors.forename: Roccaldo
authors.initials: R
authors.lastname: Sardella
authors.affiliation: Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123-Perugia, Italy.
authors.forename: Federica
authors.initials: F
authors.lastname: Ianni
authors.affiliation: Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123-Perugia, Italy.
authors.forename: Antonio
authors.initials: A
authors.lastname: Macchiarulo
authors.affiliation: Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123-Perugia, Italy.
authors.forename: Lucia
authors.initials: L
authors.lastname: Pucciarini
authors.affiliation: Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123-Perugia, Italy.
authors.forename: Andrea
authors.initials: A
authors.lastname: Carotti
authors.affiliation: Department of Pharmaceutical Sciences, University of Perugia, Via Fabretti 48, 06123-Perugia, Italy.
authors.forename: Benedetto
authors.initials: B
authors.lastname: Natalini
mesh_terms: D002845:Chromatography / Q000379:methods*; D008958:Models, Molecular; D008970:Molecular Weight; D011134:Polysaccharides / Q000737:chemistry / Q000302:isolation & purification; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D011134:Polysaccharides
keywords: Chiral recognition mechanism; computational studies; enantiomeric elution order; high-performance liquid chromatography; low- and high-molecular weight chiral selectors; medicinal chemistry