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The biologically-derived polymers polyhydroxyalkanoates (PHAs) are biodegradable and can be considered a valuable alternative to conventional fossil-based plastics. However, upstream and downstream processes for PHA production are characterized by high energy and chemical consumption and are not economically competitive with petroleum-based polymers. Aiming to improve both the environmental and economical sustainability of PHAs production, in this work, corn straw was used as raw material to obtain a mixture of fermentable sugars after microwave-assisted flash hydrolysis (2 min, 0.01 g/L, 50.7% yield). A mixed microbial culture enriched from dairy industry waste was used for fermentation in a shake flask, allowing us to achieve good poly(hydroxy-butyrate-co-hydroxy-valerate) yields (41.4%, after 72 h of fermentation). A scale-up in a stirred tank bioreactor (3 L) gave higher yields (76.3%, after 96 h), allowing in both cases to achieve a concentration of 0.42 g/L in the fermentation medium. The possibility of producing PHAs from agricultural waste using a mixed microbial culture from the food industry with enabling technologies could make the production of biopolymers more competitive.

Valorization of agri-food residues to produce bio-based platform chemicals will enhance the transition to the bio-economy era. To this end, a sustainable process has been developed for the overall valorization of grape stalks (GS) according to a circular approach, starting from the lignin fraction to further deal with the cellulose-rich residue. This non-conventional protocol fully adheres to green chemistry principles, exploiting the so-called enabling technologies—mainly ultrasound and microwaves—for energy-saving innovative processes. Firstly, ultrasound-assisted extraction (UAE, 40 kHz, 200 W) demonstrated to be an excellent technique for GS delignification combined with natural deep eutectic solvents (NaDESs). Delignification enables isolation of the pertinent lignin framework and the potential to obtain a polyphenol-rich liquid fraction, focusing on the valorization of GS as source of bioactive compounds (BACs). Among the NaDESs employed, the combination of choline chloride (ChCl) and levulinic acid (LevA) (ChLevA) presented noteworthy results, enabling a delignification higher than 70%. LevA is one of the top-value biobased platform chemicals. In this work, a flash microwave (MW)-assisted process was subsequently applied to the cellulose-rich fraction remained after delignification, yielding 85% LevA. The regeneration of this starting compound to produce ChLevA can lead to a further biomass delignification cycle, thus developing a new cascade protocol for a full valorization of GS.