Recent Theoretical Insights into the Oxidative Degradation of Biopolymers and Plastics by Metalloenzymes

Abstract

Molecular modeling techniques have become indispensable in many fields of molecular sciences in which the details related to mechanisms and reactivity need to be studied at an atomistic level. This review article provides a collection of computational modeling works on a topic of enormous interest and urgent relevance: the properties of metalloenzymes involved in the degradation and valorization of natural biopolymers and synthetic plastics on the basis of both circular biofuel production and bioremediation strategies. In particular, we will focus on lytic polysaccharide monooxygenase, laccases, and various heme peroxidases involved in the processing of polysaccharides, lignins, rubbers, and some synthetic polymers. Special attention will be dedicated to the interaction between these enzymes and their substrate studied at different levels of theory, starting from classical molecular docking and molecular dynamics techniques up to techniques based on quantum chemistry.

A novel laccase from Trametes polyzona with high performance in the decolorization of textile dyes

“…2 B). The active site of laccases consists of a type 1 (T1) copper site that catalyzed the substrate oxidation, and a trinuclear copper cluster (T2 and T3 coppers) where the oxygen is reduced (Jones and Solomon 2015 ; Rovaletti et al 2023 ). Residues involved in Cu ions coordination are conserved and identified by combining structural information and multiple sequence alignments (Figs.…”

“…Laccases are able to catalyze the oxidation of a diverse array of chemical compounds including polyphenols, diamines and aromatic amines and inorganic ions. Consequently, they are employed in different processes including lignin valorisation, (bio) polymers degradation and water bioremediation (Riva 2006 ; Ostadhadi-Dehkordi et al 2012 ; Rovaletti et al 2023 ). Promoting the advancement of more sustainable processes involves expanding the range of substrates and applications for laccases, for instance, by combining these enzymes with aromatic molecules, creating the so-called laccase/mediator system (LMS) (Riva 2006 ; Morozova et al 2007 ).…”

Mechanism of non-phenolic substrate oxidation by the fungal laccase Type 1 copper site from Trametes versicolor: the case of benzo[a]pyrene and anthracene

“…Finally, the present work provides new insights on the C–H oxidation mechanism by laccases, which can be generalized inspiring future theoretical/experimental investigations focused on hydrocarbons of different nature, such as other aromatic pollutants or plastics. 82…”

Natural, Designed and Engineered Metalloenzymes: Structure, Catalytic Mechanisms and Applications

“…Moreover, two excellent review articles have been reported on related topics. Arrigoni, Bertini, and coworkers have presented an overview of theoretical investigations for elucidating the mechanism of metalloenzymes involved in the degradation and valorization of natural biopolymers and synthetic plastics [ 8 ]. Further, Leone, Lombardi, and coworkers have described the most recent advances in the development of homogeneous hydrogen evolution catalysts envisioned to mimic hydrogenases [ 9 ].…”