Cargando…
Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation
Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael add...
Autores principales: | , , , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2021
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8707784/ https://www.ncbi.nlm.nih.gov/pubmed/34946753 http://dx.doi.org/10.3390/molecules26247672 |
_version_ | 1784622522409418752 |
---|---|
author | Kayishaer, Aihemaiti Fadlallah, Sami Mouterde, Louis M. M. Peru, Aurélien A. M. Werghi, Yasmine Brunois, Fanny Carboué, Quentin Lopez, Michel Allais, Florent |
author_facet | Kayishaer, Aihemaiti Fadlallah, Sami Mouterde, Louis M. M. Peru, Aurélien A. M. Werghi, Yasmine Brunois, Fanny Carboué, Quentin Lopez, Michel Allais, Florent |
author_sort | Kayishaer, Aihemaiti |
collection | PubMed |
description | Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free treatment of HBO-citro with NaBH(4) at room temperature led to the full reduction of the lactone moiety which gave a novel fully renewable triol monomer having a citronellol side chain (Triol-citro). Noticeably, by simply changing the reducing agent, temperature and reaction duration, the partial reduction of HBO-citro can be achieved to yield a mixture of 5- and 6-membered Lactol-citro molecules. Triol-citro was chosen to prepare functional renewable polyesters having citronellol pendant chains via polycondensation reactions with diacyl chlorides having different chain lengths. Good thermal stability (T(d5%) up to 170 °C) and low glass transition temperatures (as low as −42 °C) were registered for the polyesters obtained. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan(®) 50 BG) to assess their biodegradability. A higher degradation profile was found for the polyesters prepared using co-monomers (acyl chlorides) having longer chain lengths. This is likely due to the decreased steric hindrance around the ester bonds which allowed enhanced accessibility of the enzyme. |
format | Online Article Text |
id | pubmed-8707784 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-87077842021-12-25 Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation Kayishaer, Aihemaiti Fadlallah, Sami Mouterde, Louis M. M. Peru, Aurélien A. M. Werghi, Yasmine Brunois, Fanny Carboué, Quentin Lopez, Michel Allais, Florent Molecules Article Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free treatment of HBO-citro with NaBH(4) at room temperature led to the full reduction of the lactone moiety which gave a novel fully renewable triol monomer having a citronellol side chain (Triol-citro). Noticeably, by simply changing the reducing agent, temperature and reaction duration, the partial reduction of HBO-citro can be achieved to yield a mixture of 5- and 6-membered Lactol-citro molecules. Triol-citro was chosen to prepare functional renewable polyesters having citronellol pendant chains via polycondensation reactions with diacyl chlorides having different chain lengths. Good thermal stability (T(d5%) up to 170 °C) and low glass transition temperatures (as low as −42 °C) were registered for the polyesters obtained. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan(®) 50 BG) to assess their biodegradability. A higher degradation profile was found for the polyesters prepared using co-monomers (acyl chlorides) having longer chain lengths. This is likely due to the decreased steric hindrance around the ester bonds which allowed enhanced accessibility of the enzyme. MDPI 2021-12-18 /pmc/articles/PMC8707784/ /pubmed/34946753 http://dx.doi.org/10.3390/molecules26247672 Text en © 2021 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Kayishaer, Aihemaiti Fadlallah, Sami Mouterde, Louis M. M. Peru, Aurélien A. M. Werghi, Yasmine Brunois, Fanny Carboué, Quentin Lopez, Michel Allais, Florent Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation |
title | Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation |
title_full | Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation |
title_fullStr | Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation |
title_full_unstemmed | Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation |
title_short | Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation |
title_sort | unprecedented biodegradable cellulose-derived polyesters with pendant citronellol moieties: from monomer synthesis to enzymatic degradation |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8707784/ https://www.ncbi.nlm.nih.gov/pubmed/34946753 http://dx.doi.org/10.3390/molecules26247672 |
work_keys_str_mv | AT kayishaeraihemaiti unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation AT fadlallahsami unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation AT mouterdelouismm unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation AT peruaurelienam unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation AT werghiyasmine unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation AT brunoisfanny unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation AT carbouequentin unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation AT lopezmichel unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation AT allaisflorent unprecedentedbiodegradablecellulosederivedpolyesterswithpendantcitronellolmoietiesfrommonomersynthesistoenzymaticdegradation |