Main chains, block copolymers solution self-assembly

Similarly, Wasserman and coworkers have studied a wide selection of polymeric materials in aqueous solution that are associative of some kind, i.e., that form some sort of self-assembly through non-covalent interactions [96]. Their study mainly deals with hydrogels of hydrophobically modified polymers, aqueous solutions of polymeric micelles created by block copolymers, and hydrogels based on poly (acrylic acid) and macrodiisocyanates. The spin probes of choice were hydrophobic, such as 5- and 16-DSA (see Eig. 2) or even spin labeled polymers. It was, e.g., possible to screen for the effect of chemical stmcture on the gel formation by recording and understanding the local mobility of the hydrophobic, long chain spin probes as a function of temperature. 

As already mentioned, there has been an extensive amount of studies on the self-assembly of amphiphilic block copolymers in selective solvents over the years. In this section, we will try to give representative examples of these studies divided into two main categories regarding the solvation medium, i.e. amphiphilic copolymers in organic solvents or in aqueous solutions. The latter can be further distinguished in nonionic or ionic containing copolymers. These examples will be limited to the more commonly studied di- and triblock linear copolymers, but concise reviews on the self-assembly of amphiphilic copolymers with more complex non-linear chain architectures can be found elsewhere [98-100]. 

This chapter focuses on polyferrocenylsilanes (PFSs) where iron and silicon are in the main chain. Subsequently, PFS block copolymers will be reviewed. These materials represent an area of rapidly growing interest as a result of their self-assembly into phase-separated metal-rich nanodomain structures in thin films and micelles in block-selective solvents. The resulting nanostructured materials have a wealth of potential applications and recent breakthroughs in this area are discussed. The subject matter of the chapter is divided up into subsections covering PFS homopolymer and block copolymer synthesis, solution and solid-state self-assembly and applications of the latter, which have been extensively developed by ourselves and our collaborators and also by other research groups. 

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