Liquid-Crystalline Phase Behavior in Polypeptoid Diblock Copolymers

Polypeptoid homopolymers and block copolymers undergo thermal transitions in the solid state that can be detected by differential scanning calorimetry (DSC), but so far there is neither consensus on the underpinnings of the observed thermal transitions nor consensus on the expected number of transitions. We synthesized a series of polypeptoid diblock copolymers containing hydrophobic alkyl side chains and hydrophilic ethylene oxide side chains, systematically varying side-chain length (S), backbone main-chain length (N), block copolymer composition (n/m), and N-terminal group, and studied their thermal transitions by a combination of X-ray scattering and DSC. The thermal transitions are largely unaffected by S, N, and n/m but strongly affected by the N-terminal group. Block copolymers with an acetylated N-terminus exhibit two thermal transitions. The low temperature thermal transition is due to a transition from a crystalline phase to a sanidic liquid crystalline mesophase. The molecules adopt planar, boardlike conformations and are arranged in a rectangular crystal lattice with extended backbones that run parallel to each other. The side chains extend on either side and are located within the plane of the backbone. The liquid crystalline phase is characterized by conformational disorder in dimensions normal to the molecular plane. The high temperature thermal transition is due to melting of the liquid crystalline phase to give an isotropic phase. Block copolymers with a free N-terminus (non-acetylated) exhibit only one thermal transition and similar out-of-plane conformational disorder. This disorder appears to be due to a difference in the pendant side chain display angle of the terminal nitrogen atom.