Synthesis and hierarchical structures of amphiphilic polyphenyl acetylenes carrying L-valine pendants

In this work, we synthesized amino acid-containing poly(phenylacetylene)s and demonstrated the possibility of tuning their hierarchical structures by internal and external perturbations. A valine-acetylene adduct, 4-ethynylbenzoyl-L-valine methyl ester (5), was readily polymerized by [Rh(nbd)Cl](2), and the resultant "polyester" (1) was selectively hydrolyzed by KOH to its "polyacid" congener, poly(4-ethynylben zoyl-L-valine) (2). (Supra)molecular structures of the polymers were characterized by NMR, IR, UV, CD, and AFM techniques. The macromolecules took helical chain conformations in solutions. Their Cotton effects varied to different extents, when the polymer, solvent, and pH changed respectively from 1 to 2, from methanol to THF, and from neutral to basic. Upon evaporation of their methanol solutions, 1 and 2 self-assembled into micellar spheres and helical cables, respectively. Changing the solvent of 1 to THF changed its folding structure to helical cables, while increasing the pH of the methanol solution of 2 led to the formation of random threads. The denaturation from helical cables to random threads is probably caused by the cleavage of interstrand hydrogen bonds by base-mediated ionization of carboxyl groups of the valine pendants.