Regulating the morphology and size of homopolypeptide self-assemblies via selective solvents

It remains a great challenge to control the morphology and size of self-assembled homopolypeptide aggregates. In this work, rod-like micelles including spindles and cylinders were prepared by a solution self-assembly of poly(gamma-benzyl-l-glutamate) (PBLG) homopolypeptides with different degrees of polymerization, in which their size was controlled precisely by tuning the ratio of water/methanol in selective cosolvents. The length of the rod-like micelles increased with an increasing amount of methanol in the selective cosolvents, which was confirmed using the combination of SEM, TEM and AFM. The self-assembly mechanism of PBLG in selective cosolvents was investigated by using complementary Fourier transform infrared (FT-IR), circular dichroism (CD) and low-field NMR analyses. It was found that the shrinkage and swelling of PBLG chains play important roles in the self-assembly process. The obtained results may provide a guideline for the study of regulating the assembled aggregate sizes.