On the enzymatic synthesis of ketone-containing oligomers and their processing into sustainable crosslinked materials
6 affiliations
- 1Department of Chemistry and Industrial Chemistry
- 2University of Genoa
- 3Faculty of Chemical Engineering, Biotechnologies and
- 4Environmental Protection
- 5Mines Paris, PSL University, CEMEF (CNRS UMR 7635), Sophia Antipolis
- 6Nice Institute of Chemistry (CNRS UMR, University Côte d’Azur, Valrose Avenue, 28, Nice, France, 06100
Abstract
In this work, two ketone-containing pre-polyesters based on dimethyl 2-oxoglutarate (pDMOG) and dimethyl 1,3-acetonedicarboxylate (pDADC), were obtained via a solventless polymerization reaction in presence of Lipase B from Candida antarctica as the biocatalyst. 1 H-NMR indicated diol conversions over 90% for both monomers, while GPC analysis revealed differences between the two systems, with pDMOG reaching a M n of ≈ 8 kDa ( M w ≈ 30kDa) while pDADC reached a M n of ≈1.5 kDa ( M w ≈ 2.5 kDa). Molecular docking studies were performed to investigate the productive accommodation of the substrates and corresponding oligomeric products within the CaLB active site. Priamine TM 1071 (PR) was then used to crosslink these polymers using a solvent-free and catalyst-free reaction, showing that the network formation was directly governed by the molecular structure of the ketone-containing pre-polyester precursor. The thermal stability of the obtained materials showed an improvement at higher temperatures when compared with the neat pre-polyesters. DSC analyses showed that pDMOG and pDADC are semicrystalline materials, while the crosslinked materials led to fully amorphous systems. The rheological behaviour was also analysed, confirming that the crosslinked materials have temperature-dependent viscoelastic properties. These results can provide new perspectives for the design of processable crosslinked polymer systems obtained from bio-derived precursors by using chemo-enzymatic methods.
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BibTeX
@misc{daescu2026enzymatic,
title = {{On the enzymatic synthesis of ketone-containing oligomers and their processing into sustainable crosslinked materials}},
author = {Diana-Ionela Dăescu and Nathan Jourdainne and Christian Vigo and Giacomo Damonte and Anamaria Todea and Orietta Monticelli and Nathanael Guigo and Alessandro Pellis},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009729/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009729/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - On the enzymatic synthesis of ketone-containing oligomers and their processing into sustainable crosslinked materials
AU - Diana-Ionela Dăescu
AU - Nathan Jourdainne
AU - Christian Vigo
AU - Giacomo Damonte
AU - Anamaria Todea
AU - Orietta Monticelli
AU - Nathanael Guigo
AU - Alessandro Pellis
PY - 2026
DA - 2026/10/01
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009729/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009729/v1
AB - In this work, two ketone-containing pre-polyesters based on dimethyl 2-oxoglutarate (pDMOG) and dimethyl 1,3-acetonedicarboxylate (pDADC), were obtained via a solventless polymerization reaction in presence of Lipase B from Candida antarctica as the biocatalyst. 1 H-NMR indicated diol conversions over 90% for both monomers, while GPC analysis revealed differences between the two systems, with pDMOG reaching a M n of ≈ 8 kDa ( M w ≈ 30kDa) while pDADC reached a M n of ≈1.5 kDa ( M w ≈ 2.5 kDa). Molecular docking studies were performed to investigate the productive accommodation of the substrates and corresponding oligomeric products within the CaLB active site. Priamine TM 1071 (PR) was then used to crosslink these polymers using a solvent-free and catalyst-free reaction, showing that the network formation was directly governed by the molecular structure of the ketone-containing pre-polyester precursor. The thermal stability of the obtained materials showed an improvement at higher temperatures when compared with the neat pre-polyesters. DSC analyses showed that pDMOG and pDADC are semicrystalline materials, while the crosslinked materials led to fully amorphous systems. The rheological behaviour was also analysed, confirming that the crosslinked materials have temperature-dependent viscoelastic properties. These results can provide new perspectives for the design of processable crosslinked polymer systems obtained from bio-derived precursors by using chemo-enzymatic methods.
ER -