Cryogenic transmission electron microscopy (cryo-TEM) of micelles and vesicles formed in water by polyethylene oxide)-based block copolymers

We investigated the micellar polymorphism of poly(ethylene oxide)(PEO)-based block copolymers to illustrate the possibility of a rational control of the aggregation structure through synthetic manipulation of the molecular characteristics. Boundaries for the micellar shape transitions from bilayers to cylinders to spheres with increasing PEO composition were determined with direct cryogenic transmission electron microscopic (cryo-TEM) imaging of the microstructures in the form of thin vitreous hydrated specimens. Analyses of cryo-TEM images lead to determination of the packing properties of the hydrophobic block in terms of the interfacial area per chain and the degree of chain stretching. Also, the micellar phases of the block copolymers are characterized by anomalous structural behaviors such as coexistence of different structures and formation of exotic compound structures, which are discussed in terms of metastability inherent in the system comprising polymeric materials.