TY - JOUR
T1 - Environment-friendly transesterification to seawater-degradable polymers expanded
T2 - Computational construction guide to breaking points
AU - Pokora, Mateusz
AU - Rheinberger, Timo
AU - Wurm, Frederik R.
AU - Paneth, Agata
AU - Paneth, Piotr
N1 - Funding Information:
This research was conducted as a part of the International Research Agendas PLUS programme of the Foundation for Polish Science, co-financed by the European Union under the European Regional Development Fund (MAB PLUS/2019/11). This work has been completed while the first author was Doctoral Candidate in the Interdisciplinary Doctoral School at the Lodz University of Technology, Poland. Computer time allocation at PL-GRID via Cyfronet, Kraków, Poland is gratefully acknowledged. F.R.W. thanks the Deutsche Forschungsgemeinschaft (DFG WU/750 6-2) for funding.
Funding Information:
This research was conducted as a part of the International Research Agendas PLUS programme of the Foundation for Polish Science, co-financed by the European Union under the European Regional Development Fund (MAB PLUS/2019/11). This work has been completed while the first author was Doctoral Candidate in the Interdisciplinary Doctoral School at the Lodz University of Technology, Poland. Computer time allocation at PL-GRID via Cyfronet, Kraków, Poland is gratefully acknowledged. F.R.W. thanks the Deutsche Forschungsgemeinschaft ( DFG WU/750 6-2 ) for funding.
Publisher Copyright:
© 2022 The Authors
PY - 2022/12
Y1 - 2022/12
N2 - Marine plastic pollution caused by non-biodegradable polymers is a major worldwide concern. So-called “biodegradable” polymers should reduce plastic pollution in the environment by the safeguard of biodegradation. However, many polyesters degrade very slowly in seawater. We therefore designed a systematic library of “breaking points” that are installed into a polylactide backbone and simulated their degradation mechanisms, including internal and external SN2 mechanisms, Addition-Elimination (AE) mechanisms, and RNA-inspired mechanisms. The breaking points are composed of phosphoesters with pendant nucleophiles directly at the P-atom, or structurally similar silicones, or side-chain functional polyesters. All P-containing breaking points react via the RNA-inspired mechanism, while Si-containing linkers undergo decomposition via the A-E mechanism. For C-containing linkers, only when a long pendant chain (4 carbon atoms) is present can the reaction proceed via the RNA-inspired mechanism. In cases of shorter pendants, the Addition-Elimination (AE) mechanism is energetically favorable. We believe that these calculations will pave the way for the synthesis of exceptionally seawater-degradable polyesters in the future that can act as a safeguard to prevent microplastic formation after eventual littering.
AB - Marine plastic pollution caused by non-biodegradable polymers is a major worldwide concern. So-called “biodegradable” polymers should reduce plastic pollution in the environment by the safeguard of biodegradation. However, many polyesters degrade very slowly in seawater. We therefore designed a systematic library of “breaking points” that are installed into a polylactide backbone and simulated their degradation mechanisms, including internal and external SN2 mechanisms, Addition-Elimination (AE) mechanisms, and RNA-inspired mechanisms. The breaking points are composed of phosphoesters with pendant nucleophiles directly at the P-atom, or structurally similar silicones, or side-chain functional polyesters. All P-containing breaking points react via the RNA-inspired mechanism, while Si-containing linkers undergo decomposition via the A-E mechanism. For C-containing linkers, only when a long pendant chain (4 carbon atoms) is present can the reaction proceed via the RNA-inspired mechanism. In cases of shorter pendants, the Addition-Elimination (AE) mechanism is energetically favorable. We believe that these calculations will pave the way for the synthesis of exceptionally seawater-degradable polyesters in the future that can act as a safeguard to prevent microplastic formation after eventual littering.
KW - Degradable polymers
KW - DFT calculations
KW - Intramolecular transesterification
KW - Marine litter
UR - http://www.scopus.com/inward/record.url?scp=85138020540&partnerID=8YFLogxK
U2 - 10.1016/j.chemosphere.2022.136381
DO - 10.1016/j.chemosphere.2022.136381
M3 - Article
C2 - 36088968
AN - SCOPUS:85138020540
SN - 0045-6535
VL - 308
JO - Chemosphere
JF - Chemosphere
IS - Part 2
M1 - 136381
ER -