title: A Kinetic/Thermodynamic Origin of Regular Chiral Fluctuation or Symmetry Breaking Unique to Preferential Enrichment.
abstract: The kinetic/thermodynamic origin of preferential enrichment (PE), which is a spontaneous enantiomeric resolution phenomenon applicable to racemic crystals, is described. The mechanism of PE, which was unveiled with respect to the first-generation of chiral organic compounds showing PE, has been interpreted in terms of a nonlinear complexity phenomenon including two unique processes: a solvent-assisted solid-to-solid polymorphic transition and subsequent selective redissolution of the excess one enantiomer from the transformed disordered crystals into the mother liquor. The present works confirm that PE takes place because of the unique nonlinear solubility properties of the two enantiomers after the occurrence of a polymorphic transition under PE crystallization conditions at high supersaturation. Furthermore, a ternary phase diagram that is consistent with the mechanism of PE is proposed.
authors.affiliation: Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 606-8502, Japan.|PRESTO (Japan) Science and Technology Agency, Kawaguchi, Saitama, 332-0012, Japan.
authors.forename: Yoshiaki
authors.initials: Y
authors.lastname: Uchida
authors.affiliation: Faculty of Law, Meijigakuin University, Minato-ku, Tokyo, 108-8636, Japan.
authors.forename: Sekai
authors.initials: S
authors.lastname: Iwama
authors.affiliation: Normandie Université, SMS, EA 3233, Univ Rouen, Crystal Genesis Unit, 76821, Mont Saint-Aignan Cedex, France.
authors.forename: Gérard
authors.initials: G
authors.lastname: Coquerel
authors.affiliation: Graduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto, 606-8501, Japan. tamura.rui.8c@kyoto-u.ac.jp.
authors.forename: Rui
authors.initials: R
authors.lastname: Tamura
keywords: chiral resolution; chirality; density functional calculations; nonequilibrium processes; phase diagrams