Self-Assembly of Folic Acid Derivatives: Induction of Supramolecular Chirality by Hierarchical Chiral Structures

• Published in: Chemistry : a European journal Vol. 10; no. 23; pp. 5942 - 5951
• Main Authors: Kamikawa, Yuko, Nishii, Masayuki, Kato, Takashi
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 03-12-2004; WILEY‐VCH Verlag
• Subjects: chirality; hydrogen bonds; liquid crystals; self-assembly; supramolecular chemistry
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200400424

Hierarchical chiral structures made up of dendritic oligo(L‐ or D‐glutamic acid) moieties of folic acid derivatives induce supramolecular chirality in the self‐assembled columnar structures of the folic acids. These folic acids self‐assemble through the intermolecular hydrogen bonds of the pterin rings to form disklike tetramers. In the neat states, the stacked tetramers form thermotropic hexagonal columnar phases over wide temperature ranges, including room temperature. Addition of alkali metal salts induces chirality in the columnar phases. In dilute solution states in a relatively polar solvent (chloroform), the folic acid derivatives form non‐chiral, self‐assembled structures. In the presence of sodium triflate, the folic acid forms chiral columnar assemblies through the oligo(L‐glutamic acid) moiety, similar to those formed in the liquid‐crystalline (LC) states. The enantiomer of the folic acid induces columnar assemblies with reversed helicity. In the case of the diastereomer, no induced helicity is observed. Application of an apolar solvent (dodecane) drives the folic acid derivatives to form chiral assemblies in the absence of ions. In this case, lipophilic interactions promote nanophase segregation, which enhances the formation of chiral columns. Interestingly, the chiral supramolecular structure of the diastereomer induces the most intense circular dichroism. In both cases, the molecular chirality in the oligo(glutamate) moieties yields supramolecular chirality of the folic acids that self‐assemble through cooperative molecular interactions.
Chiral columnar assemblies of folic acid derivatives with hierarchical chiral oligo(glutamic acid) moieties are formed both in liquid‐crystalline and in dilute solution. Their molecular structural asymmetry greatly affects the supramolecular helical structures of the columns (see scheme).