Reductive Enzyme Cascades for Valorization of Polyethylene Terephthalate Deconstruction Products
| Author(s) | Gopal, Madan R. | |
| Author(s) | Dickey, Roman M. | |
| Author(s) | Butler, Neil D. | |
| Author(s) | Talley, Michael R. | |
| Author(s) | Nakamura, Daniel T. | |
| Author(s) | Mohapatra, Ashlesha | |
| Author(s) | Watson, Mary P. | |
| Author(s) | Chen, Wilfred | |
| Author(s) | Kunjapur, Aditya M. | |
| Date Accessioned | 2023-05-11T17:36:15Z | |
| Date Available | 2023-05-11T17:36:15Z | |
| Publication Date | 2023-04-07 | |
| Description | This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © 2023 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acscatal.2c06219. The Supporting Information is available free of charge at https://doi.org/10.1021/acscatal.2c06219. This article will be embargoed until 04/07/2024. | |
| Abstract | 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. | |
| Sponsor | A.M.K., W.C., M.P.W., M.R.G., R.M.D., and M.R.T. acknowledge the Center for Plastics Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (grant number DESC0021166). Cloning work was performed under proposal 506446 by the U.S. Department of Energy Joint Genome Institute, a DOE Office of Science User Facility, supported by the Office of Science of the U.S. Department of Energy operated under contract no. DE-AC02-05CH11231. More information can be found at 10.46936/10.25585/60001335 and https://ror.org/04xm1d337. | |
| Citation | Gopal, Madan R., Roman M. Dickey, Neil D. Butler, Michael R. Talley, Daniel T. Nakamura, Ashlesha Mohapatra, Mary P. Watson, Wilfred Chen, and Aditya M. Kunjapur. “Reductive Enzyme Cascades for Valorization of Polyethylene Terephthalate Deconstruction Products.” ACS Catalysis 13, no. 7 (April 7, 2023): 4778–89. https://doi.org/10.1021/acscatal.2c06219. | |
| ISSN | 2155-5435 | |
| URL | https://udspace.udel.edu/handle/19716/32734 | |
| Language | en_US | |
| Publisher | ACS Catalysis | |
| Keywords | plastics | |
| Keywords | polyethylene terephthalate | |
| Keywords | valorization | |
| Keywords | upcycling | |
| Title | Reductive Enzyme Cascades for Valorization of Polyethylene Terephthalate Deconstruction Products | |
| Type | Article |
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