Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction
Six‐membered cyclic carbonates with hydroxyl and methoxycarbonyloxy functional groups were prepared by transesterification of trimethylolpropane (TMP) with dimethylcarbonate (DMC) by solvent‐free lipase‐mediated flow reaction followed by thermal cyclization. The flow reaction efficiency was evaluate...
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crwiley:10.1002/btpr.2406 2024-06-23T07:47:51+00:00 Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction Bornadel, Amin Ismail, Mohamed Sayed, Mahmoud Hatti‐Kaul, Rajni Pyo, Sang‐Hyun 2016 http://dx.doi.org/10.1002/btpr.2406 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fbtpr.2406 https://onlinelibrary.wiley.com/doi/full/10.1002/btpr.2406 en eng Wiley http://onlinelibrary.wiley.com/termsAndConditions#vor Biotechnology Progress volume 33, issue 2, page 375-382 ISSN 8756-7938 1520-6033 journal-article 2016 crwiley https://doi.org/10.1002/btpr.2406 2024-06-11T04:41:19Z Six‐membered cyclic carbonates with hydroxyl and methoxycarbonyloxy functional groups were prepared by transesterification of trimethylolpropane (TMP) with dimethylcarbonate (DMC) by solvent‐free lipase‐mediated flow reaction followed by thermal cyclization. The flow reaction efficiency was evaluated using different configurations of reactor consisting of packed beds of Novozym®435 (immobilized Candida antarctica lipase B—CalB—a.k.a. N435) and molecular sieves, flowrate, and biocatalyst loads. The mixed column of the biocatalyst and molecular sieves, allowing rapid and efficient removal of the by‐product—methanol—was the most efficient setup. Higher conversion (81.6%) in the flow reaction compared to batch process (72%) was obtained using same amount of N435 (20% (w/w) N435:TMP) at 12 h, and the undesirable dimer and oligomer formation were suppressed. Moreover, the product was recovered easily without extra separation steps, and the biocatalyst and the molecular sieves remained intact for subsequent regeneration and recycling. The reaction of CalB with DMC and the primary transesterification product, monocarbonated TMP, respectively, as acyl donors was evaluated by in silico modeling and empirically to determine the role of the enzyme in the formation of cyclic carbonates and other side products. DMC was shown to be the preferred acyl donor, suggesting that TMP and its carbonated derivatives serve only as acyl acceptors in the lipase‐catalyzed reaction. Subsequent cyclization to cyclic carbonate is catalyzed at increased temperature and not by the enzyme. © 2016 American Institute of Chemical Engineers Biotechnol. Prog. , 33:375–382, 2017 Article in Journal/Newspaper Antarc* Antarctica Wiley Online Library Biotechnology Progress 33 2 375 382 |
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English |
description |
Six‐membered cyclic carbonates with hydroxyl and methoxycarbonyloxy functional groups were prepared by transesterification of trimethylolpropane (TMP) with dimethylcarbonate (DMC) by solvent‐free lipase‐mediated flow reaction followed by thermal cyclization. The flow reaction efficiency was evaluated using different configurations of reactor consisting of packed beds of Novozym®435 (immobilized Candida antarctica lipase B—CalB—a.k.a. N435) and molecular sieves, flowrate, and biocatalyst loads. The mixed column of the biocatalyst and molecular sieves, allowing rapid and efficient removal of the by‐product—methanol—was the most efficient setup. Higher conversion (81.6%) in the flow reaction compared to batch process (72%) was obtained using same amount of N435 (20% (w/w) N435:TMP) at 12 h, and the undesirable dimer and oligomer formation were suppressed. Moreover, the product was recovered easily without extra separation steps, and the biocatalyst and the molecular sieves remained intact for subsequent regeneration and recycling. The reaction of CalB with DMC and the primary transesterification product, monocarbonated TMP, respectively, as acyl donors was evaluated by in silico modeling and empirically to determine the role of the enzyme in the formation of cyclic carbonates and other side products. DMC was shown to be the preferred acyl donor, suggesting that TMP and its carbonated derivatives serve only as acyl acceptors in the lipase‐catalyzed reaction. Subsequent cyclization to cyclic carbonate is catalyzed at increased temperature and not by the enzyme. © 2016 American Institute of Chemical Engineers Biotechnol. Prog. , 33:375–382, 2017 |
format |
Article in Journal/Newspaper |
author |
Bornadel, Amin Ismail, Mohamed Sayed, Mahmoud Hatti‐Kaul, Rajni Pyo, Sang‐Hyun |
spellingShingle |
Bornadel, Amin Ismail, Mohamed Sayed, Mahmoud Hatti‐Kaul, Rajni Pyo, Sang‐Hyun Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction |
author_facet |
Bornadel, Amin Ismail, Mohamed Sayed, Mahmoud Hatti‐Kaul, Rajni Pyo, Sang‐Hyun |
author_sort |
Bornadel, Amin |
title |
Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction |
title_short |
Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction |
title_full |
Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction |
title_fullStr |
Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction |
title_full_unstemmed |
Six‐membered cyclic carbonates from trimethylolpropane: Lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction |
title_sort |
six‐membered cyclic carbonates from trimethylolpropane: lipase‐mediated synthesis in a flow reactor and in silico evaluation of the reaction |
publisher |
Wiley |
publishDate |
2016 |
url |
http://dx.doi.org/10.1002/btpr.2406 https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fbtpr.2406 https://onlinelibrary.wiley.com/doi/full/10.1002/btpr.2406 |
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Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_source |
Biotechnology Progress volume 33, issue 2, page 375-382 ISSN 8756-7938 1520-6033 |
op_rights |
http://onlinelibrary.wiley.com/termsAndConditions#vor |
op_doi |
https://doi.org/10.1002/btpr.2406 |
container_title |
Biotechnology Progress |
container_volume |
33 |
container_issue |
2 |
container_start_page |
375 |
op_container_end_page |
382 |
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1802638056956624896 |