Screw-sense inversion characteristic of alpha-helical poly(beta-p-chlorobenzyl L-aspartate) and comparison with other related polyaspartates

This is one of a series of studies on the reversal of the helix sense of polyaspartates originated from the pioneering work of Goodman and his associates in 1960s. Poly(beta-p-chlorobenzyl L-aspartate) (PClBLA) is one of the well-studied polyaspartate derivatives in both solution and the solid state. The chemical structure of PClBLA differs from those of poly(beta-benzyl L-aspartate) (PBLA) and poly(beta-phenethyl L-aspartate) (PPLA) only at the terminal of the relatively long side chain. PBLA takes a left-handed form (L) in conventional helicoidal solvents and does not exhibit any screw-sense inversion. In contrast to PBLA, both PClBLA and PPLA form a right-handed helix (R) in chlorinated alkane solvents and exhibits a reversal of alpha-helix sense at higher temperatures. Yet the transition behaviors in the presence of denaturant acid are quite different between these two polymers. While PPLA exhibits transitions such as R --> L --> coil by lowering temperature, PClBLA directly goes into the coil state without showing the reentrant L form. The cause of these phenomenological differences among these polymers has been investigated by constructing the phase diagram.