Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study
Abstract Our reliance on synthetic polymers (plastics) is causing immeasurable damage to the environment. Better alternatives are actively being sought‐after, such as biodegradable polyesters obtained by enzymatic synthesis. Here we compare in detail the catalytic mechanisms for poly(caprolactone) s...
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crwiley:10.1002/cctc.202000780 2024-06-02T07:57:20+00:00 Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study Figueiredo, Pedro R. Almeida, Beatriz C. Dourado, Daniel F. A. R. Sousa, Andreia F. Silvestre, Armando J. D. Carvalho, Alexandra T. P. 2020 http://dx.doi.org/10.1002/cctc.202000780 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fcctc.202000780 https://onlinelibrary.wiley.com/doi/pdf/10.1002/cctc.202000780 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/cctc.202000780 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor ChemCatChem volume 12, issue 19, page 4845-4852 ISSN 1867-3880 1867-3899 journal-article 2020 crwiley https://doi.org/10.1002/cctc.202000780 2024-05-03T11:00:02Z Abstract Our reliance on synthetic polymers (plastics) is causing immeasurable damage to the environment. Better alternatives are actively being sought‐after, such as biodegradable polyesters obtained by enzymatic synthesis. Here we compare in detail the catalytic mechanisms for poly(caprolactone) synthesis by the enzymes Archaeoglobus fulgidus carboxylesterase (AfEST) and Candida antarctica lipase B (CalB) using Quantum Mechanics/Molecular Mechanics Molecular Dynamics simulations. In the ring‐opening step (rate‐limiting) the significantly higher free energy barrier found for AfEST is a consequence of the larger distance between the histidine‐aspartate pair and the oxygen of the lactone, and a shorter distance to the serine nucleophile, favouring the reverse reaction towards the initial reactants. Our results give important insights towards the design of enzymatic variants which combine high activity and high thermostability in the synthesis of poly(caprolactone), which due to its bioresorbability is of great importance for biomedical applications. Article in Journal/Newspaper Antarc* Antarctica Wiley Online Library ChemCatChem 12 19 4845 4852 |
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Wiley Online Library |
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crwiley |
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English |
description |
Abstract Our reliance on synthetic polymers (plastics) is causing immeasurable damage to the environment. Better alternatives are actively being sought‐after, such as biodegradable polyesters obtained by enzymatic synthesis. Here we compare in detail the catalytic mechanisms for poly(caprolactone) synthesis by the enzymes Archaeoglobus fulgidus carboxylesterase (AfEST) and Candida antarctica lipase B (CalB) using Quantum Mechanics/Molecular Mechanics Molecular Dynamics simulations. In the ring‐opening step (rate‐limiting) the significantly higher free energy barrier found for AfEST is a consequence of the larger distance between the histidine‐aspartate pair and the oxygen of the lactone, and a shorter distance to the serine nucleophile, favouring the reverse reaction towards the initial reactants. Our results give important insights towards the design of enzymatic variants which combine high activity and high thermostability in the synthesis of poly(caprolactone), which due to its bioresorbability is of great importance for biomedical applications. |
format |
Article in Journal/Newspaper |
author |
Figueiredo, Pedro R. Almeida, Beatriz C. Dourado, Daniel F. A. R. Sousa, Andreia F. Silvestre, Armando J. D. Carvalho, Alexandra T. P. |
spellingShingle |
Figueiredo, Pedro R. Almeida, Beatriz C. Dourado, Daniel F. A. R. Sousa, Andreia F. Silvestre, Armando J. D. Carvalho, Alexandra T. P. Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study |
author_facet |
Figueiredo, Pedro R. Almeida, Beatriz C. Dourado, Daniel F. A. R. Sousa, Andreia F. Silvestre, Armando J. D. Carvalho, Alexandra T. P. |
author_sort |
Figueiredo, Pedro R. |
title |
Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study |
title_short |
Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study |
title_full |
Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study |
title_fullStr |
Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study |
title_full_unstemmed |
Enzymatic Synthesis of Poly(caprolactone): A QM/MM Study |
title_sort |
enzymatic synthesis of poly(caprolactone): a qm/mm study |
publisher |
Wiley |
publishDate |
2020 |
url |
http://dx.doi.org/10.1002/cctc.202000780 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fcctc.202000780 https://onlinelibrary.wiley.com/doi/pdf/10.1002/cctc.202000780 https://onlinelibrary.wiley.com/doi/full-xml/10.1002/cctc.202000780 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
ChemCatChem volume 12, issue 19, page 4845-4852 ISSN 1867-3880 1867-3899 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/cctc.202000780 |
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ChemCatChem |
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12 |
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19 |
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4845 |
op_container_end_page |
4852 |
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1800740491347623936 |