A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone
Abstract A three‐step enzymatic reaction sequence for the synthesis of poly‐ϵ‐caprolactone (PCL) was designed running in a fed‐batch operation. The first part of the cascade consisted of two oxidation steps starting with alcohol dehydrogenase catalyzed oxidation from cyclohexanol to cyclohexanone an...
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crwiley:10.1002/cctc.201600806 2024-06-02T07:58:06+00:00 A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone Scherkus, Christian Schmidt, Sandy Bornscheuer, Uwe T. Gröger, Harald Kara, Selin Liese, Andreas 2016 http://dx.doi.org/10.1002/cctc.201600806 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fcctc.201600806 https://onlinelibrary.wiley.com/doi/full/10.1002/cctc.201600806 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor ChemCatChem volume 8, issue 22, page 3446-3452 ISSN 1867-3880 1867-3899 journal-article 2016 crwiley https://doi.org/10.1002/cctc.201600806 2024-05-03T11:03:55Z Abstract A three‐step enzymatic reaction sequence for the synthesis of poly‐ϵ‐caprolactone (PCL) was designed running in a fed‐batch operation. The first part of the cascade consisted of two oxidation steps starting with alcohol dehydrogenase catalyzed oxidation from cyclohexanol to cyclohexanone and further oxidation to ϵ‐caprolactone (ECL) by means of a Baeyer–Villiger monooxygenase. As a third step, lipase‐catalyzed hydrolysis of the lactone to 6‐hydroxyhexanoic acid (6‐HHA) was designed. With this biocatalytic multistep process reported herein, severe substrate surplus and product inhibition could be circumvented by the fed‐batch operation by adding the cyclohexanol substrate and by in situ product removal of ECL by hydrolysis, respectively. Up to 283 m m product concentration of 6‐HHA was reached in the fed‐batch operated process without loss in productivity within 20 h. After extraction and subsequent polymerization catalyzed by Candida antarctica lipase B, analysis of the unfractionated polymer revealed a bimodal distribution of the polymer population, which reached a mass average molar mass ( M w ) value of approximately 63 000 g mol −1 and a dispersity ( M w / M n ) of 1.1 for the higher molecular weight population, which thus revealed an alternative route to the conventional synthesis of PCL. Article in Journal/Newspaper Antarc* Antarctica Wiley Online Library ChemCatChem 8 22 3446 3452 |
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English |
description |
Abstract A three‐step enzymatic reaction sequence for the synthesis of poly‐ϵ‐caprolactone (PCL) was designed running in a fed‐batch operation. The first part of the cascade consisted of two oxidation steps starting with alcohol dehydrogenase catalyzed oxidation from cyclohexanol to cyclohexanone and further oxidation to ϵ‐caprolactone (ECL) by means of a Baeyer–Villiger monooxygenase. As a third step, lipase‐catalyzed hydrolysis of the lactone to 6‐hydroxyhexanoic acid (6‐HHA) was designed. With this biocatalytic multistep process reported herein, severe substrate surplus and product inhibition could be circumvented by the fed‐batch operation by adding the cyclohexanol substrate and by in situ product removal of ECL by hydrolysis, respectively. Up to 283 m m product concentration of 6‐HHA was reached in the fed‐batch operated process without loss in productivity within 20 h. After extraction and subsequent polymerization catalyzed by Candida antarctica lipase B, analysis of the unfractionated polymer revealed a bimodal distribution of the polymer population, which reached a mass average molar mass ( M w ) value of approximately 63 000 g mol −1 and a dispersity ( M w / M n ) of 1.1 for the higher molecular weight population, which thus revealed an alternative route to the conventional synthesis of PCL. |
format |
Article in Journal/Newspaper |
author |
Scherkus, Christian Schmidt, Sandy Bornscheuer, Uwe T. Gröger, Harald Kara, Selin Liese, Andreas |
spellingShingle |
Scherkus, Christian Schmidt, Sandy Bornscheuer, Uwe T. Gröger, Harald Kara, Selin Liese, Andreas A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone |
author_facet |
Scherkus, Christian Schmidt, Sandy Bornscheuer, Uwe T. Gröger, Harald Kara, Selin Liese, Andreas |
author_sort |
Scherkus, Christian |
title |
A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone |
title_short |
A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone |
title_full |
A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone |
title_fullStr |
A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone |
title_full_unstemmed |
A Fed‐Batch Synthetic Strategy for a Three‐Step Enzymatic Synthesis of Poly‐ϵ‐caprolactone |
title_sort |
fed‐batch synthetic strategy for a three‐step enzymatic synthesis of poly‐ϵ‐caprolactone |
publisher |
Wiley |
publishDate |
2016 |
url |
http://dx.doi.org/10.1002/cctc.201600806 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fcctc.201600806 https://onlinelibrary.wiley.com/doi/full/10.1002/cctc.201600806 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
ChemCatChem volume 8, issue 22, page 3446-3452 ISSN 1867-3880 1867-3899 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/cctc.201600806 |
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ChemCatChem |
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8 |
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22 |
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3446 |
op_container_end_page |
3452 |
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1800741378834038784 |