Preparation and supramolecular self-assembly of a polypeptide-block-polypseudorotaxane

Abstract

We have successfully prepared a new class of self-assembled biomaterial: a polypeptide-block-polypseudorotaxane diblock copolymer. This diblock copolymer is comprised of an a-helical polypeptide rod, based on gamma-benzyl-L-glutamate, and an originally coiled segment P(EO19-r-PO3); it forms inclusion complexes with a-cyclodextrins (alpha-CDs) to give crystalline polypseudorotaxanes. Formation of the polypseudorotaxane converts the conformation of P(EO19-r-PO3) from a flexible chain into a rodlike structure, which results in a novel block copolymer exhibiting a rod-rod conformation. Intrinsic interactions (e.g., the polypseudorotaxane's channel-type crystallization, the polypeptide's secondary structure, and microphase separation) within and between these rod-rod diblock copolymers contribute to their hierarchical self-assembly behavior, which we characterized using DSC, H-1 NMR spectroscopy, C-13 CP/MAS NMR spectroscopy, WAXS, and SAXS. The data obtained from the WAXS and SAXS studies clearly indicate the formation of juxtaposed bilayer-like nanostructure featuring hexagonally packed PBLG stacks and channel-type polypseudorotaxane moieties.