Chirogenesis and Amplification of Molecular Chirality Using Optical Vortices

Abstract

The study of chirogenesis of organic molecules is important to elucidate the origin of the homochirality of biomolecules on Earth. Here, we have accomplished chiral symmetry breaking from a racemate using optical vortices with orbital angular momentum and a helical wavefront. We propose a new methodology of asymmetric transformation by the combination of enantioselective crystal nucleation by irradiation with optical vortices and crystallization-induced dynamic optical resolution of conglomerate crystals. Chiral green vortices generated using a spiral phase plate (SPP) with a 532 nm CW-laser were used to irradiate a supersaturated solution of a racemic isoindolinone, leading to crystal nucleation. The handedness of the crystals were controlled by the winding direction of the chiral optical vortices. The molecular chirality of the isoindolinone was then amplified by dynamic crystallization.

Chirogenesis and Amplification of Molecular Chirality Using Optical Vortices

“…[28] In spontaneous dynamic crystallization, the chirality of the crystal was determined by the initially generated crystal nucleus and the nucleus was amplified under deracemization conditions based on dynamic crystal-lization. [29] One-handed enantiomorphic isoindolinone 1 was easily obtained by crystallization from solution by evaporation of the solvent in the presence of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) as a base. The racemization involving ring opening and closing reactions was accelerated by DBU, and almost optically pure enantiomorphic crystals were easily obtained after chiral symmetry breaking.…”

Reversible Controlling the Supramolecular Chirality of Side Chain Azobenzene Polymers: Chiral Induction and Modulation

“…[1] Generally, chirality appears at different hierarchical levels ranging from molecular to supramolecular levels, and chirality can be induced with the assembly of chiral substances or the combination of chiral and achiral substances with various structures, including helix, spiral, gyroid, toroid, and Moebius strips. [2,3] Recently, the origin Although a few works have reported the construction of chiroptical switches using azo polymers, including chiral gel, enantiopure tartaric acid, linearly polarized light, chiral solvents, and CPL. [18][19][20] However, a great challenge still remains.…”

Quantitative Difference in Solubility of Diastereomeric (2H/1H)-Isotopomers

“…Since Pasteur discovered molecular asymmetry, 1 the origin of biological chirality in nature has been an attractive mystery. 2 , 3 Among the theories, 4 − 9 isotopic chirality is a possibility 10 because many apparently achiral organic compounds become chiral when taking isotopic substitutions into consideration. 11 − 14 A higher deuterium-labeling ratio of meteoritic compounds than found in the same terrestrial compounds has been reported; 15 therefore, extra-terrestrial organic compounds may have isotopic chirality.…”

“…Since Pasteur discovered molecular asymmetry, the origin of biological chirality in nature has been an attractive mystery. , Among the theories, − isotopic chirality is a possibility because many apparently achiral organic compounds become chiral when taking isotopic substitutions into consideration. − A higher deuterium-labeling ratio of meteoritic compounds than found in the same terrestrial compounds has been reported; therefore, extra-terrestrial organic compounds may have isotopic chirality. Although chiral recognition technologies have been developed , and isotopically labeled compounds are often used to elucidate reaction mechanisms in the field of stereochemistry and biochemistry, chiral induction effects in asymmetric reactions are difficult to observe.…”