ABSTRACT
This chapter gives an overview of the key elements that need to be considered for understanding and triggering the microstructure of polyhydroxyalkanoate (PHA) copolymers. This family of microbial biopolyesters offers a large potential considering its broad spectrum of possible material properties due to the diversity of comonomers. It is, therefore, of great interest to study and understand the influences on the molecular composition and composition distribution to valorize this potential. PHA biosynthesis is described considering substrates, microbial producers, the polymerizing enzyme class, and its spatial structure, as well as the kinetics of the PHA synthesis.
In the second part of this chapter, a summary of in vitro approaches to synthesize sequence controlled PHA (e.g., block copolymers) is given to emphasize the importance of the molecular architecture. Furthermore, existing approaches for sequence controlled PHA syntheses in living microorganisms are described considering feed strategies, genetic modifications, and artificial genetic networks.
