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Reductive Enzyme Cascades for Valorization of Polyethylene Terephthalate Deconstruction Products

  • Madan R. Gopal
    Madan R. Gopal
    Department of Chemical & Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States
    Center for Plastics Innovation, University of Delaware, Newark, Delaware 19716, United States
  • Roman M. Dickey
    Roman M. Dickey
    Department of Chemical & Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States
    Center for Plastics Innovation, University of Delaware, Newark, Delaware 19716, United States
  • Neil D. Butler
    Neil D. Butler
    Department of Chemical & Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States
  • Michael R. Talley
    Michael R. Talley
    Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States
    Center for Plastics Innovation, University of Delaware, Newark, Delaware 19716, United States
  • Daniel T. Nakamura
    Daniel T. Nakamura
    Center for Plastics Innovation, University of Delaware, Newark, Delaware 19716, United States
  • Ashlesha Mohapatra
    Ashlesha Mohapatra
    Department of Chemical & Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States
  • Mary P. Watson
    Mary P. Watson
    Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States
    Center for Plastics Innovation, University of Delaware, Newark, Delaware 19716, United States
  • Wilfred Chen
    Wilfred Chen
    Department of Chemical & Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States
    Center for Plastics Innovation, University of Delaware, Newark, Delaware 19716, United States
    More by Wilfred Chen
  • , and 
  • Aditya M. Kunjapur*
    Aditya M. Kunjapur
    Department of Chemical & Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, United States
    Center for Plastics Innovation, University of Delaware, Newark, Delaware 19716, United States
    *Email: [email protected]
Cite this: ACS Catal. 2023, 13, 7, 4778–4789
Publication Date (Web):March 24, 2023
https://doi.org/10.1021/acscatal.2c06219
Copyright © 2023 American Chemical Society

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    Abstract

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    To better incentivize the collection of plastic wastes, chemical transformations must be developed that add value to plastic deconstruction products. Polyethylene terephthalate (PET) is a common plastic whose deconstruction through chemical or biological means has received much attention. However, a limited number of alternative products have been formed from PET deconstruction, and only a small share could serve as building blocks for alternative materials or therapeutics. Here, we demonstrate the production of useful monoamine and diamine building blocks from known PET deconstruction products. We achieve this by designing one-pot biocatalytic transformations that are informed by the substrate specificity of an ω-transaminase and diverse carboxylic acid reductases (CAR) toward PET deconstruction products. We first establish that an ω-transaminase from Chromobacterium violaceum (cvTA) can efficiently catalyze amine transfer to potential PET-derived aldehydes to form monoamine para-(aminomethyl)benzoic acid (pAMBA) or diamine para-xylylenediamine (pXYL). We then identified CAR orthologs that could perform the bifunctional reduction of terephthalic acid (TPA) to terephthalaldehyde or the reduction of mono-(2-hydroxyethyl) terephthalic acid (MHET) to its corresponding aldehyde. After characterizing 17 CARs in vitro, we show that the CAR from Segniliparus rotundus (srCAR) had the highest observed activity on TPA. Given these elucidated substrate specificity results, we designed modular enzyme cascades based on coupling srCAR and cvTA in one pot with enzymatic cofactor regeneration. When we supply TPA, we achieve a 69 ± 1% yield of pXYL, which is useful as a building block for polymeric materials. When we instead supply MHET and subsequently perform base-catalyzed ester hydrolysis, we achieve 70 ± 8% yield of pAMBA, which is useful for therapeutic applications and as a pharmaceutical building block. This work expands the breadth of products derived from PET deconstruction and lays the groundwork for eventual valorization of waste PET to higher-value chemicals and materials.

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