Abstract
Polyhydroxyalkanoates (PHA) comprises a set of natural polyesters of bacterial origins, biosynthesized from intracellular fatty acid feedstocks. Although modern studies have maintained a limited focus on the chemical properties of the feedstocks employed for PHA production, it is clear that in order to diversify their applications and value, concerted efforts must be applied to exploring and augmenting the chemical tractability of these polymers. In this chapter, the current state of the science is discussed, and selected recent strategies developed to access chemically modifiable polyhydroxyalkanoates are explored, including, but not limited to, multistep modifications of isolated polymers, short syntheses of monomer feedstocks, and metabolic engineering of monomer pathways. Selected examples from the literature will be emphasized to demonstrate the appeal and utility of these techniques.