ABSTRACT
Polyhydroxyalkanoate oligomers (oligo-PHA) are low molar mass PHA consisting of a small number of 3-hydroxyacid repeat units (usually not more than 200 residue units). They can be synthesized either naturally in eukaryotic cells and in prokaryotic cells through intracellular or extracellular degradation of storage PHA to yield natural oligomers, or via several chemical modifications such as basic hydrolysis or transesterification. The synthetic analogs of natural PHA oligomers are obtained by anionic ring-opening polymerization (ROP) of β-substituted β-lactones. These synthetic and biodegradable oligomers, through various chemical modifications, can further allow the preparation of bioactive oligomers with attractive properties for novel and high value-added applications, especially in medicine, agrochemistry, and cosmetology. Bioactive oligomers are also biodegradable: they possess enhanced properties, controlled functional end groups, and thus can be potential components of copolymers or blends with other biodegradable polymers. The natural and synthetic routes used for the preparation of selected bioactive PHA oligomers and their detailed characterization by mass spectrometry are discussed in this chapter.
