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Abstract Additive manufacturing (AM) of polymeric materials enables the manufacturing of complex structures for a wide range of applications. Among AM methods vat photopolymerization (VP) is desired owing to improved efficiency, excellent surface finish, and printing resolution at the micron-scale. Nevertheless, the major portion of resins available for VP are based on systems with limited or negligible recyclability. Here, we describe an approach that enables the printing of a resin that is amenable to re-printing with retained properties and appearance. To that end, we take advantage of the potential of polythiourethane chemistry, which not only permits the click reaction between polythiols and polyisocyanates in the presence of organic bases, allowing a fast-printing process but also chemical recycling, reshaping, and reparation of the printed structures, paving the way toward the development of truly sustainable recyclable photoprintable resins. We demonstrate that this closed-loop 3D printing process is feasible both at the macroscale and microscale via DLP or DLW, respectively.

Abstract Biocatalysis is a key technology enabling plastic recycling. However, despite advances done in the development of plastic-degrading enzymes, the molecular mechanisms that govern their catalytic performance are poorly understood, hampering the engineering of more efficient enzyme-based technologies. In this work, we study the hydrolysis of PET-derived diesters and PET trimers catalyzed by the highly promiscuous lipase B from Candida antarctica (CALB) through QM/MM molecular dynamics simulations supported by experimental Michaelis–Menten kinetics. The computational studies reveal the role of the pH on the CALB regioselectivity toward the hydrolysis of bis-(hydroxyethyl) terephthalate (BHET). We exploit this insight to perform a pH-controlled biotransformation that selectively hydrolyzes BHET to either its corresponding diacid or monoesters using both soluble and immobilized CALB. The discoveries presented here can be exploited for the valorization of BHET resulting from the organocatalytic depolymerization of PET.

Biodegradable plastics usually have poorer mechanical or transport properties compared to conventional plastics. Here the authors show a class of biorenewable and chemically recyclable plastics based on copolymers of γ-butyrolactone and its ring-fused derivative, with competitive properties compared to conventional plastics.