ABSTRACT

The self-assembly process, serving to hierarchically build supramolecular structures by starting with the corresponding building blocks, represents a key process in nature. The result of the self-assembly process appears in a variety of 3D systems, such as the tertiary structure of proteins, the helical structure of DNA, or the bilayer morphology of cellular membrane. The driving forces involve various interactions such as van der Waals interactions, hydrogen bonds, and hydrophobic/hydrophilic balance. Of particular interest is to use the self-assembly process to generate 3D supramolecular structures based on natural and synthetic building blocks because it allows the creation of new hybrid materials and modulation of their properties. In terms of applications, the 3D assemblies resulting from hierarchical organization via self-assembly should posses enough mechanical and chemical stability, preserve the functionality of the building blocks, and add new properties/functionality due to the specicity of the supramolecular structure. In this respect, polymers and copolymers are synthetic macromolecules that can be chemically engineered to possess a specically tailored composition, function, and structure. They represent the building blocks for generation of a variety of 3D assemblies (Mai and

Eisenberg 2012). Depending on their chemical nature and conditions in which the self-assembly process takes place, the synthetic and natural polymers/copolymers generate a variety of different supramolecular architectures ranging from a few nanometers in diameter up to several micrometers. This versatility has been explored extensively in the past, giving access to a library of different structures including micelles, worms, or vesicles in solution as well as planar membranes and hydrogels (Kopeček and Yang 2012; Kataoka et al. 2012; Kowal et al. 2014).Here, the aim is to discuss these different architectures and their characteristics together with the typical methods for their preparation and characterization. The controlled design of such nanoobjects plays a pivotal role in a variety of scientic elds such as medicine, chemistry, electronics, environmental sciences, food sciences, and technology. Important areas for applications of these supramolecular architectures, especially in combination with biomolecules introducing functionality, are presented in this chapter by highlighting some of the most promising examples from recent literature (Kowal et  al. 2014; van Oers et  al. 2014). Overall, this chapter provides an overview of the different 3D shapes accessible via self-assembly of synthetic macromolecules (polymers and copolymers).