“Supramolecular” Amphiphiles Created by Wrapping Poly(styrene) with the Helix‐Forming β‐1,3‐Glucan Polysaccharide

We have demonstrated that giant polymer micelles with a uniform diameter (ca. 200 nm) can be fabricated by “supramolecular wrapping” of poly(styrene) (PS) with the β‐1,3‐glucan polysaccharide, with the β‐1,3‐glucan fastening the PS chains together in a noncovalent fashion to facilitate the formation of a supramolecular polymer network on the O/W emulsion surface. Various spectroscopic and microscopic investigations have revealed that the inner cores of the micelles are comprised of a hydrophobic PS network, whereas the surfaces consist of a hydrophilic β‐1,3‐glucan layer. Accordingly, functional guest molecules can easily be encapsulated inside the cavity through hydrophobic interactions. The encapsulated molecules can simply be released from the micelle cores by peeling off the β‐1,3‐glucan shell in a supramolecular manner. As functional groups can be introduced into the glucose side‐chain unit in a straightforward manner by chemical modification, the micellar surface can acquire further functions useful for molecular recognition. These results show that the micelles obtained could have applications as novel soft nanoparticles, which would be indispensable not only for nanotechnologies, but also for biotechnologies aimed at gene or drug delivery systems.