Supramolecular Copolymerization of Bichromophoric Chiral and Achiral Perylenediimide Dyes

Propagation and amplification of chirality are considered to play an important role in the chemical evolution of biological homochirality. Stereochemical communications have been demonstrated to have a significant effect on the formation of chiral hierarchical structures in helical polymers, surface assemblies and supramolecular polymers. The formation of supramolecular copolymers based on chiral and achiral bichromophoric perylenediimide (PDI) dyes having a binaphtyl- and biphenyl-core-bridging unit, respectively, was investigated in terms of chiral amplification and propagation. The biphenyl-bridged PDI dye was expected to perform as a prochiral component to adopt both right- and left-handed twisting structures with the free rotation over the phenyl-phenyl linkage upon partnered with the chiral binaphtly PDI dye in the coassemblies. The coassemblies between the chiral and achiral PDI dyes with dissimilar core units demonstrated the composition dependent control in the length of supramolecular nanofibers as well as amplification of optical activity.

Chirality: The Backbone of Chemistry as a Natural Science

Chemistry as a natural science occupies the length and temporal scales ranging between the formation of atoms and molecules as quasi-classical objects, and the formation of proto-life systems showing catalytic synthesis, replication, and the capacity for Darwinian evolution. The role of chiral dissymmetry in the chemical evolution toward life is manifested in how the increase of chemical complexity, from atoms and molecules to complex open systems, accompanies the emergence of biological homochirality toward life. Chemistry should express chirality not only as molecular structural dissymmetry that at the present is described in chemical curricula by quite effective pedagogical arguments, but also as a cosmological phenomenon. This relates to a necessarily better understanding of the boundaries of chemistry with physics and biology.

Autocatalytic Models for the Origin of Biological Homochirality

Mechanistic studies of the Soai autocatalytic reaction in the context of biological homochirality.

Autocatalytic Models for the Origin of Biological Homochirality

Mechanistic studies of the Soai autocatalytic reaction in the context of biological homochirality.

Possible Roles of Amphiphilic Molecules in the Origin of Biological Homochirality

A review. The question of homochirality is an intriguing problem in the field of chemistry, and is deeply related to the origin of life. Though amphiphiles and their supramolecular assembly have attracted less attention compared to biomacromolecules such as RNA and proteins, the lipid world hypothesis sheds new light on the origin of life. This review describes how amphiphilic molecules are possibly involved in the scenario of homochirality. Some prebiotic conditions relevant to amphiphilic molecules will also be described. It could be said that the chiral properties of amphiphilic molecules have various interesting features such as compositional information, spontaneous formation, the ability to exchange components, fission and fusion, adsorption, and permeation. This review aims to clarify the roles of amphiphiles regarding homochirality, and to determine what kinds of physical properties of amphiphilic molecules could have played a role in the scenario of homochirality.