Rapid Depolymerization of Poly(ethylene Terephthalate) Thin Films by a Dual-enzyme System and Its Impact on Material Properties

Overview

Journal Chem Catal

Date 2023 Jun 23

PMID 37350932

Authors

Natalia A Tarazona

Ren Wei

Stefan Brott

Lara Pfaff

Uwe T Bornscheuer

Andreas Lendlein

Rainhard Machatschek

Affiliations

Soon will be listed here.

Abstract

Enzymatic hydrolysis holds great promise for plastic waste recycling and upcycling. The interfacial catalysis mode, and the variability of polymer specimen properties under different degradation conditions, add to the complexity and difficulty of understanding polymer cleavage and engineering better biocatalysts. We present a systemic approach to studying the enzyme-catalyzed surface erosion of poly(ethylene terephthalate) (PET) while monitoring/controlling operating conditions in real time with simultaneous detection of mass loss and changes in viscoelastic behavior. PET nanofilms placed on water showed a porous morphology and a thickness-dependent glass transition temperature () between 40°C and 44°C, which is >20°C lower than the of bulk amorphous PET. Hydrolysis by a dual-enzyme system containing thermostabilized variants of PETase and MHETase resulted in a maximum depolymerization of 70% in 1 h at 50°C. We demonstrate that increased accessible surface area, amorphization, and reduction speed up PET degradation while simultaneously lowering the threshold for degradation-induced crystallization.

Citing Articles

Molecular Details of Polyester Decrystallization via Molecular Simulation.

Lazarenko D, Schmidt G, Crowley M, Beckham G, Knott B Macromolecules. 2025; 58(4):1795-1803.

PMID: 40026450 PMC: 11866931. DOI: 10.1021/acs.macromol.4c02130.

From Bulk to Binding: Decoding the Entry of PET into Hydrolase Binding Pockets.

Jackering A, Gottsch F, Schaffler M, Doerr M, Bornscheuer U, Wei R JACS Au. 2024; 4(10):4000-4012.

PMID: 39483243 PMC: 11522925. DOI: 10.1021/jacsau.4c00718.

A High-Throughput Screening Platform for Engineering Poly(ethylene Terephthalate) Hydrolases.

Groseclose T, Kober E, Clark M, Moore B, Banerjee S, Bemmer V ACS Catal. 2024; 14(19):14622-14638.

PMID: 39386920 PMC: 11459431. DOI: 10.1021/acscatal.4c04321.

Interfacial Reactions in Chemical Recycling and Upcycling of Plastics.

Ong A, Teo J, Lim J ACS Appl Mater Interfaces. 2024; 16(36):46975-46987.

PMID: 39214617 PMC: 11403610. DOI: 10.1021/acsami.4c09315.

Efficient Depolymerization of Poly(ethylene 2,5-furanoate) Using Polyester Hydrolases.

Kumar V, Pellis A, Wimmer R, Popok V, de Claville Christiansen J, Varrone C ACS Sustain Chem Eng. 2024; 12(26):9658-9668.

PMID: 38966237 PMC: 11220789. DOI: 10.1021/acssuschemeng.4c00915.

References

Zhu B, Wang D, Wei N . Enzyme discovery and engineering for sustainable plastic recycling. Trends Biotechnol. 2021; 40(1):22-37. DOI: 10.1016/j.tibtech.2021.02.008. View

Palm G, Reisky L, Bottcher D, Muller H, Michels E, Walczak M . Structure of the plastic-degrading Ideonella sakaiensis MHETase bound to a substrate. Nat Commun. 2019; 10(1):1717. PMC: 6461665. DOI: 10.1038/s41467-019-09326-3. View

Tarazona N, Machatschek R, Balcucho J, Castro-Mayorga J, Saldarriaga J, Lendlein A . Opportunities and challenges for integrating the development of sustainable polymer materials within an international circular (bio)economy concept. MRS Energy Sustain. 2023; 9(1):28-34. PMC: 9127038. DOI: 10.1557/s43581-021-00015-7. View

Eberl A, Heumann S, Bruckner T, Araujo R, Cavaco-Paulo A, Kaufmann F . Enzymatic surface hydrolysis of poly(ethylene terephthalate) and bis(benzoyloxyethyl) terephthalate by lipase and cutinase in the presence of surface active molecules. J Biotechnol. 2009; 143(3):207-12. DOI: 10.1016/j.jbiotec.2009.07.008. View

Kawai F, Kawabata T, Oda M . Current knowledge on enzymatic PET degradation and its possible application to waste stream management and other fields. Appl Microbiol Biotechnol. 2019; 103(11):4253-4268. PMC: 6505623. DOI: 10.1007/s00253-019-09717-y. View

Badino S, Arnling Baath J, Borch K, Jensen K, Westh P . Adsorption of enzymes with hydrolytic activity on polyethylene terephthalate. Enzyme Microb Technol. 2021; 152:109937. DOI: 10.1016/j.enzmictec.2021.109937. View

Tarazona N, Machatschek R, Lendlein A . Unraveling the Interplay between Abiotic Hydrolytic Degradation and Crystallization of Bacterial Polyesters Comprising Short and Medium Side-Chain-Length Polyhydroxyalkanoates. Biomacromolecules. 2019; 21(2):761-771. DOI: 10.1021/acs.biomac.9b01458. View

Zhang W, Douglas J, Starr F . Why we need to look beyond the glass transition temperature to characterize the dynamics of thin supported polymer films. Proc Natl Acad Sci U S A. 2018; 115(22):5641-5646. PMC: 5984511. DOI: 10.1073/pnas.1722024115. View

Tarazona N, Machatschek R, Schulz B, Prieto M, Lendlein A . Molecular Insights into the Physical Adsorption of Amphiphilic Protein PhaF onto Copolyester Surfaces. Biomacromolecules. 2019; 20(9):3242-3252. DOI: 10.1021/acs.biomac.9b00069. View

10.

Sulaiman S, You D, Kanaya E, Koga Y, Kanaya S . Crystal structure and thermodynamic and kinetic stability of metagenome-derived LC-cutinase. Biochemistry. 2014; 53(11):1858-69. DOI: 10.1021/bi401561p. View

11.

Munstedt H . Rheological Measurements and Structural Analysis of Polymeric Materials. Polymers (Basel). 2021; 13(7). PMC: 8038039. DOI: 10.3390/polym13071123. View

12.

Wei R, Breite D, Song C, Grasing D, Ploss T, Hille P . Biocatalytic Degradation Efficiency of Postconsumer Polyethylene Terephthalate Packaging Determined by Their Polymer Microstructures. Adv Sci (Weinh). 2019; 6(14):1900491. PMC: 6662049. DOI: 10.1002/advs.201900491. View

13.

Wei R, von Haugwitz G, Pfaff L, Mican J, Badenhorst C, Liu W . Mechanism-Based Design of Efficient PET Hydrolases. ACS Catal. 2022; 12(6):3382-3396. PMC: 8939324. DOI: 10.1021/acscatal.1c05856. View

14.

Lyu S, Untereker D . Degradability of polymers for implantable biomedical devices. Int J Mol Sci. 2009; 10(9):4033-4065. PMC: 2769140. DOI: 10.3390/ijms10094033. View

15.

Pfaff L, Gao J, Li Z, Jackering A, Weber G, Mican J . Multiple Substrate Binding Mode-Guided Engineering of a Thermophilic PET Hydrolase. ACS Catal. 2022; 12(15):9790-9800. PMC: 9361285. DOI: 10.1021/acscatal.2c02275. View

16.

Brott S, Pfaff L, Schuricht J, Schwarz J, Bottcher D, Badenhorst C . Engineering and evaluation of thermostable PETase variants for PET degradation. Eng Life Sci. 2022; 22(3-4):192-203. PMC: 8961046. DOI: 10.1002/elsc.202100105. View

17.

Vegso K, Siffalovic P, Majkova E, Jergel M, Benkovicova M, Kocsis T . Nonequilibrium phases of nanoparticle Langmuir films. Langmuir. 2012; 28(28):10409-14. DOI: 10.1021/la301764t. View

18.

Werner A, Clare R, Mand T, Pardo I, Ramirez K, Haugen S . Tandem chemical deconstruction and biological upcycling of poly(ethylene terephthalate) to β-ketoadipic acid by Pseudomonas putida KT2440. Metab Eng. 2021; 67:250-261. DOI: 10.1016/j.ymben.2021.07.005. View

19.

Vollmer I, Jenks M, Roelands M, White R, van Harmelen T, de Wild P . Beyond Mechanical Recycling: Giving New Life to Plastic Waste. Angew Chem Int Ed Engl. 2020; 59(36):15402-15423. PMC: 7497176. DOI: 10.1002/anie.201915651. View

20.

Ballerstedt H, Tiso T, Wierckx N, Wei R, Averous L, Bornscheuer U . MIXed plastics biodegradation and UPcycling using microbial communities: EU Horizon 2020 project MIX-UP started January 2020. Environ Sci Eur. 2021; 33(1):99. PMC: 8380104. DOI: 10.1186/s12302-021-00536-5. View