Hydration and dehydration play crucial roles in hydrophobic effects (HE) and are yet to be understood. Poly(γ-benzyl-L-glutamate) (PBLG) homopolymers in THF/water with various water content was investigated. We discovered that...

It remains a great challenge to control the morphology and the size of the self-assembled homopolypeptide aggregates. In this work, the rod-like micelles including spindles and cylinders were prepared by...

The investigation of hydrophobic hydration as a hydrophobic effect (HE) on the conformations and self-assembling behaviors of terminally charged poly (L-lactide) (PLLA[PPh 2 Me]I) in tetrahydrofuran (THF)/water with various water contents is reported. The backbone was hydrated while the ionic end group was not hydrated at a lower water content (33.3%), and consequentially PLLA[PPh 2 Me]I self-assembled into fibers. As the water content increased to 50.0%, ion pair end groups were hydrated and exerted a long-range dehydrating effect on the backbone, endowing chain spiralization via intramolecular C−H•••O�C hydrogen bonds and leading to the formation of spheres. At 60.0% water content, the long-range effect of hydrated water on the ion pair end groups completely removed the hydration water from the backbone, and so the macromolecules possessed a certain degree of amphiphilicity and self-assembled into vesicles. The elucidation of hydrophobic hydration is desirable for improving HE-caused self-assembly and understanding biological systems.