Polyhydroxyalkanoates (PHAs) are ubiquitous prokaryotic storage compounds of carbon and energy, acting as sinks for reducing power during periods of surplus of carbon source relative to other nutrients. With close to 150 different hydroxyalkanoate monomers identified, the structure and properties of these polyesters can be adjusted to serve applications ranging from food packaging to biomedical uses. Despite its versatility and the intensive research in the area over the last three decades, the market share of PHAs is still low. While considerable rich literature has accumulated concerning biochemical, physiological, and genetic aspects of PHAs intracellular accumulation, the costs of substrates and processing costs, including the extraction of the polymer accumulated in intracellular granules, still hampers a more widespread use of this family of polymers. This review presents a comprehensive survey and critical analysis of the process engineering and metabolic engineering strategies reported in literature aimed at the production of chiral (R)-hydroxycarboxylic acids (RHAs), either from the accumulated polymer or by bypassing the accumulation of PHAs using metabolically engineered bacteria, and the strategies developed to recover the accumulated polymer without using conventional downstream separations processes. Each of these topics, that have received less attention compared to PHAs accumulation, could potentially improve the economy of PHAs production and use. (R)-hydroxycarboxylic acids can be used as chiral precursors, thanks to its easily modifiable functional groups, and can be either produced de-novo or be obtained from recycled PHA products. On the other hand, efficient mechanisms of PHAs release from bacterial cells, including controlled cell lysis and PHA excretion, could reduce downstream costs and simplify the polymer recovery process.

Biomass appears to be one of the most prominent renewable resources for biofuels such as bioethanol, mainly due to its better environmental performance compared with fossil fuels. This study addresses a comprehensive environmental performance of bioethanol production, employing empirical data from hybrid poplar grown in the U.S. The study considers 1 MJ as a functional unit and employs a cradle-to-grave approach, which entails the feedstock and harvesting production of poplar, transport to a biorefinery, bioconversion of the biomass process, and fuel use. On average, bioconversion is the main contributor to environmental degradation in all the categories evaluated (77%). The second main contributor is either the feedstock and harvesting production of poplar (17%) or fuel use (6%), depending on the environmental category. Thus, focusing on only one category may induce a misinterpretation of the environmental performance of bioethanol production. Finally, environmental credits in the global warming potential (GWP) category were obtained from the carbon sequestered in the biomass during the growing period and from avoided fossil fuel emissions due to electricity production from a renewable source. This means that the net GWP of the life cycle of bioethanol from poplar biomass is slightly negative (−1.05 × 10⁻³ kg CO₂-eq·MJ⁻¹).