Cutinase-Catalyzed Polyester-Polyurethane Degradation: Elucidation of the Hydrolysis Mechanism

Polyurethanes (PU) are one of the most-used classes of synthetic polymers in Europe, having a considerable impact on the plastic waste management in the European Union. Therefore, they represent a major challenge for the recycling industry, which requires environmentally friendly strategies to be ab...

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Main Authors: Federico Di Bisceglie, Felice Quartinello, Robert Vielnascher, Georg M. Guebitz, Alessandro Pellis
Format: Article
Language:English
Published: MDPI AG 2022-01-01
Series:Polymers
Subjects:
Online Access:https://www.mdpi.com/2073-4360/14/3/411
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author Federico Di Bisceglie
Felice Quartinello
Robert Vielnascher
Georg M. Guebitz
Alessandro Pellis
author_facet Federico Di Bisceglie
Felice Quartinello
Robert Vielnascher
Georg M. Guebitz
Alessandro Pellis
author_sort Federico Di Bisceglie
collection DOAJ
description Polyurethanes (PU) are one of the most-used classes of synthetic polymers in Europe, having a considerable impact on the plastic waste management in the European Union. Therefore, they represent a major challenge for the recycling industry, which requires environmentally friendly strategies to be able to re-utilize their monomers without applying hazardous and polluting substances in the process. In this work, enzymatic hydrolysis of a polyurethane-polyester (PU-PE) copolymer using <i>Humicola insolens</i> cutinase (HiC) has been investigated in order to achieve decomposition at milder conditions and avoiding harsh chemicals. PU-PE films have been incubated with the enzyme at 50 °C for 168 h, and hydrolysis has been followed throughout the incubation. HiC effectively hydrolysed the polymer, reducing the number average molecular weight (M<sub>n</sub>) and the weight average molecular weight (M<sub>w</sub>) by 84% and 42%, respectively, as shown by gel permeation chromatography (GPC), while scanning electron microscopy showed cracks at the surface of the PU-PE films as a result of enzymatic surface erosion. Furthermore, Fourier Transform Infrared (FTIR) analysis showed a reduction in the peaks at 1725 cm<sup>−1</sup>, 1164 cm<sup>−1</sup> and 1139 cm<sup>−1</sup>, indicating that the enzyme preferentially hydrolysed ester bonds, as also supported by the nuclear magnetic resonance spectroscopy (NMR) results. Liquid chromatography time-of-flight/mass spectrometry (LC-MS-Tof) analysis revealed the presence in the incubation supernatant of all of the monomeric constituents of the polymer, thus suggesting that the enzyme was able to hydrolyse both the ester and the urethane bonds of the polymer.
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spelling doaj.art-91fbe535c7194043a5cbb0be21975d812023-11-23T17:33:22ZengMDPI AGPolymers2073-43602022-01-0114341110.3390/polym14030411Cutinase-Catalyzed Polyester-Polyurethane Degradation: Elucidation of the Hydrolysis MechanismFederico Di Bisceglie0Felice Quartinello1Robert Vielnascher2Georg M. Guebitz3Alessandro Pellis4Department of Agrobiotechnology, University of Natural Resources and Life Sciences Vienna, 3430 Tulln an der Donau, AustriaDepartment of Agrobiotechnology, University of Natural Resources and Life Sciences Vienna, 3430 Tulln an der Donau, AustriaDepartment of Agrobiotechnology, University of Natural Resources and Life Sciences Vienna, 3430 Tulln an der Donau, AustriaDepartment of Agrobiotechnology, University of Natural Resources and Life Sciences Vienna, 3430 Tulln an der Donau, AustriaDepartment of Agrobiotechnology, University of Natural Resources and Life Sciences Vienna, 3430 Tulln an der Donau, AustriaPolyurethanes (PU) are one of the most-used classes of synthetic polymers in Europe, having a considerable impact on the plastic waste management in the European Union. Therefore, they represent a major challenge for the recycling industry, which requires environmentally friendly strategies to be able to re-utilize their monomers without applying hazardous and polluting substances in the process. In this work, enzymatic hydrolysis of a polyurethane-polyester (PU-PE) copolymer using <i>Humicola insolens</i> cutinase (HiC) has been investigated in order to achieve decomposition at milder conditions and avoiding harsh chemicals. PU-PE films have been incubated with the enzyme at 50 °C for 168 h, and hydrolysis has been followed throughout the incubation. HiC effectively hydrolysed the polymer, reducing the number average molecular weight (M<sub>n</sub>) and the weight average molecular weight (M<sub>w</sub>) by 84% and 42%, respectively, as shown by gel permeation chromatography (GPC), while scanning electron microscopy showed cracks at the surface of the PU-PE films as a result of enzymatic surface erosion. Furthermore, Fourier Transform Infrared (FTIR) analysis showed a reduction in the peaks at 1725 cm<sup>−1</sup>, 1164 cm<sup>−1</sup> and 1139 cm<sup>−1</sup>, indicating that the enzyme preferentially hydrolysed ester bonds, as also supported by the nuclear magnetic resonance spectroscopy (NMR) results. Liquid chromatography time-of-flight/mass spectrometry (LC-MS-Tof) analysis revealed the presence in the incubation supernatant of all of the monomeric constituents of the polymer, thus suggesting that the enzyme was able to hydrolyse both the ester and the urethane bonds of the polymer.https://www.mdpi.com/2073-4360/14/3/411plastic degradationpolyurethanesenzyme catalysis
spellingShingle Federico Di Bisceglie
Felice Quartinello
Robert Vielnascher
Georg M. Guebitz
Alessandro Pellis
Cutinase-Catalyzed Polyester-Polyurethane Degradation: Elucidation of the Hydrolysis Mechanism
Polymers
plastic degradation
polyurethanes
enzyme catalysis
title Cutinase-Catalyzed Polyester-Polyurethane Degradation: Elucidation of the Hydrolysis Mechanism
title_full Cutinase-Catalyzed Polyester-Polyurethane Degradation: Elucidation of the Hydrolysis Mechanism
title_fullStr Cutinase-Catalyzed Polyester-Polyurethane Degradation: Elucidation of the Hydrolysis Mechanism
title_full_unstemmed Cutinase-Catalyzed Polyester-Polyurethane Degradation: Elucidation of the Hydrolysis Mechanism
title_short Cutinase-Catalyzed Polyester-Polyurethane Degradation: Elucidation of the Hydrolysis Mechanism
title_sort cutinase catalyzed polyester polyurethane degradation elucidation of the hydrolysis mechanism
topic plastic degradation
polyurethanes
enzyme catalysis
url https://www.mdpi.com/2073-4360/14/3/411
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AT robertvielnascher cutinasecatalyzedpolyesterpolyurethanedegradationelucidationofthehydrolysismechanism
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