Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers
Isohexides are versatile carbohydrate-based building blocks for designing biodegradable polymers with tunable biodegradability and enhanced material properties owing to their unique high structural rigidity and hydrophilicity. However, the limited reactivity and thermal stability of isohexides, espe...
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ftsmithonian:oai:figshare.com:article/13607832 2023-05-15T13:40:33+02:00 Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers Jing Wu (54032) Jiefei Qi (6041855) Yiming Lin (174403) Yong Chen (109188) Xu Zhang (49484) Rongliang Wu (117506) Huaping Wang (3632671) 2021-01-19T00:00:00Z https://doi.org/10.1021/acssuschemeng.0c06733.s001 unknown https://figshare.com/articles/journal_contribution/Lipase-Catalyzed_Fully_Aliphatic_Copolyesters_Based_on_Renewable_Isohexide_Isomers/13607832 doi:10.1021/acssuschemeng.0c06733.s001 CC BY-NC 4.0 CC-BY-NC Biophysics Biochemistry Medicine Biotechnology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified EP process stability wide-angle X-ray diffraction OH carbohydrate-based building blocks Renewable Isohexide Isomers Isohexides WAXD tetrahedral transition-state interm. MD MP polymerization endo isohexide M n values IM CALB Text Journal contribution 2021 ftsmithonian https://doi.org/10.1021/acssuschemeng.0c06733.s001 2021-02-03T09:34:44Z Isohexides are versatile carbohydrate-based building blocks for designing biodegradable polymers with tunable biodegradability and enhanced material properties owing to their unique high structural rigidity and hydrophilicity. However, the limited reactivity and thermal stability of isohexides, especially the isomers with endo -hydroxyl groups, hamper their practical applications. In this work, fully aliphatic copolyesters based on two isohexide stereoisomers, isosorbide (IS) and isomannide (IM), were comparatively synthesized via a mild lipase-catalyzed polymerization [enzymatic polymerization (EP)] technique. The products were obtained with fairly high molecular weights ( M n values: 15,300–31,500 g·mol –1 ), negligible degree of discoloration, and 20–40 °C higher thermal stabilities ( T d,5% : 335–360 °C) compared to those of their counterparts obtained by melt polymerization (MP). Molecular dynamics (MD) simulation revealed that the endo -OH is preferred to the exo -OH under the EP process having a high hydrogen-bonding frequency with the catalytic site of CALB (lipase immobilized from Candida antarctica, CALB), and it also requires considerably low energy (70–100 kJ·mol –1 ) to form the second tetrahedral transition-state intermediates. The wide-angle X-ray diffraction (WAXD) study further elucidates the interesting influence of the EP process on inducing specific β-type crystalline structures. Other Non-Article Part of Journal/Newspaper Antarc* Antarctica Unknown |
institution |
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Unknown |
op_collection_id |
ftsmithonian |
language |
unknown |
topic |
Biophysics Biochemistry Medicine Biotechnology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified EP process stability wide-angle X-ray diffraction OH carbohydrate-based building blocks Renewable Isohexide Isomers Isohexides WAXD tetrahedral transition-state interm. MD MP polymerization endo isohexide M n values IM CALB |
spellingShingle |
Biophysics Biochemistry Medicine Biotechnology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified EP process stability wide-angle X-ray diffraction OH carbohydrate-based building blocks Renewable Isohexide Isomers Isohexides WAXD tetrahedral transition-state interm. MD MP polymerization endo isohexide M n values IM CALB Jing Wu (54032) Jiefei Qi (6041855) Yiming Lin (174403) Yong Chen (109188) Xu Zhang (49484) Rongliang Wu (117506) Huaping Wang (3632671) Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers |
topic_facet |
Biophysics Biochemistry Medicine Biotechnology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified Physical Sciences not elsewhere classified EP process stability wide-angle X-ray diffraction OH carbohydrate-based building blocks Renewable Isohexide Isomers Isohexides WAXD tetrahedral transition-state interm. MD MP polymerization endo isohexide M n values IM CALB |
description |
Isohexides are versatile carbohydrate-based building blocks for designing biodegradable polymers with tunable biodegradability and enhanced material properties owing to their unique high structural rigidity and hydrophilicity. However, the limited reactivity and thermal stability of isohexides, especially the isomers with endo -hydroxyl groups, hamper their practical applications. In this work, fully aliphatic copolyesters based on two isohexide stereoisomers, isosorbide (IS) and isomannide (IM), were comparatively synthesized via a mild lipase-catalyzed polymerization [enzymatic polymerization (EP)] technique. The products were obtained with fairly high molecular weights ( M n values: 15,300–31,500 g·mol –1 ), negligible degree of discoloration, and 20–40 °C higher thermal stabilities ( T d,5% : 335–360 °C) compared to those of their counterparts obtained by melt polymerization (MP). Molecular dynamics (MD) simulation revealed that the endo -OH is preferred to the exo -OH under the EP process having a high hydrogen-bonding frequency with the catalytic site of CALB (lipase immobilized from Candida antarctica, CALB), and it also requires considerably low energy (70–100 kJ·mol –1 ) to form the second tetrahedral transition-state intermediates. The wide-angle X-ray diffraction (WAXD) study further elucidates the interesting influence of the EP process on inducing specific β-type crystalline structures. |
format |
Other Non-Article Part of Journal/Newspaper |
author |
Jing Wu (54032) Jiefei Qi (6041855) Yiming Lin (174403) Yong Chen (109188) Xu Zhang (49484) Rongliang Wu (117506) Huaping Wang (3632671) |
author_facet |
Jing Wu (54032) Jiefei Qi (6041855) Yiming Lin (174403) Yong Chen (109188) Xu Zhang (49484) Rongliang Wu (117506) Huaping Wang (3632671) |
author_sort |
Jing Wu (54032) |
title |
Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers |
title_short |
Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers |
title_full |
Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers |
title_fullStr |
Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers |
title_full_unstemmed |
Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers |
title_sort |
lipase-catalyzed fully aliphatic copolyesters based on renewable isohexide isomers |
publishDate |
2021 |
url |
https://doi.org/10.1021/acssuschemeng.0c06733.s001 |
genre |
Antarc* Antarctica |
genre_facet |
Antarc* Antarctica |
op_relation |
https://figshare.com/articles/journal_contribution/Lipase-Catalyzed_Fully_Aliphatic_Copolyesters_Based_on_Renewable_Isohexide_Isomers/13607832 doi:10.1021/acssuschemeng.0c06733.s001 |
op_rights |
CC BY-NC 4.0 |
op_rightsnorm |
CC-BY-NC |
op_doi |
https://doi.org/10.1021/acssuschemeng.0c06733.s001 |
_version_ |
1766136960486735872 |