Intriguingly, little
is known about the impact of dispersity on
the crystallization driven self-assembly (CDSA) of amphiphilic block
copolymers in aqueous media. Here, we investigate the influence of
dispersity on the CDSA of ABA-type amphiphilic block co-oligomers
(ABCOs). Two pairs of ABCOs are synthesized comprising discrete (Đ = 1.00) or disperse (Đ =
1.20) isotactic l-lactic acid 16-mers as the semicrystalline
hydrophobic block and either oligo(ethylene glycol) methyl ether (MeOoEG)
or oligo(tetraethylene glycol succinate) (oTEGSuc) as the discrete
hydrophilic block. Self-assembly studies in water with 10% THF reveal
uniform nanofibers/2D sheets for the discrete oligomers, but such
structural regularity is largely compromised in the disperse oligomers.
The results are corroborated by sharp melting transitions in both
solution and bulk for the discrete ABCOs, unlike their disperse analogues
that show a lack of crystallization. Interestingly, the discrete MeOoEG-LLA
oligomer reveals crystallization driven gelation, illustrating the
contrasting differences between the discrete oligomers and their disperse
counterparts.