Safer bio-based solvents to replace toluene and tetrahydrofuran for the biocatalyzed synthesis of polyesters

Pellis, Alessandro; Byrne, Fergal; Sherwood, James; Vastano, Marco; Comerford, James W.; Farmer, Thomas J.

doi:10.1039/c8gc03567a

Cited by 55 publications

(45 citation statements)

References 22 publications

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“…It must be noted that the use of biogenic solvents for biocatalytic continuous processes is still in infancy and represents a very promising research avenue to conduct sustainable chemical processes. Novel solvents have started to be routinely assessed for screenings in biocatalysis, with very promising results …”

Section: Other Environmentally‐friendly Solvents For Continuous Biocamentioning

confidence: 99%

Continuous Biocatalysis in Environmentally‐Friendly Media: A Triple Synergy for Future Sustainable Processes

Guajardo

Marı́a²

2019

ChemCatChem

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Enzyme catalysis (biocatalysis) is a mature strategy to perform organic synthesis with high selectivity and under mild reaction conditions. However, despite their origin and biodegradability, the simple use of enzymes is not sufficient to validate a process as green or sustainable. To reinforce the value that biocatalysis may offer, enzymatic processes can be established in environmentally‐friendly media, such as water, neoteric solvents (e. g. deep‐eutectic‐solvents, DES), biogenic solvents (e. g. 2‐MeTHF or terpenes), or even solvent‐free systems (if substrates allow that). Furthermore, these options can be conducted in continuous biocatalytic processes, which are more efficient and sustainable. Hence, a triple synergy is generated, and very promising environmentally‐friendly options can be envisaged. This conceptual paper discusses these alternatives, providing relevant, recently reported, successful examples.

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Section: Other Environmentally‐friendly Solvents For Continuous Biocamentioning

confidence: 99%

Continuous Biocatalysis in Environmentally‐Friendly Media: A Triple Synergy for Future Sustainable Processes

Guajardo

Marı́a²

2019

ChemCatChem

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“…Once GA was obtained and purified, we explored the enzymatic polymerization as an alternative to the protection strategies required in traditional chemo‐catalytic methods. For this aim, a commercial immobilized lipase from Candida antarctica (CaLB) was selected due to its known stability to high temperatures and different solvents . Solubility tests of GA in solvents suitable for the enzymatic polymerization highlighted the necessity of alternative strategies.…”

Section: Methodsmentioning

confidence: 99%

“…Biocatalyzed Polycondensation Reactions : The protocol was adapted from Pellis et. al . A total of 8 × 10 −4 mol of GA diester (0.2 m ) and 8 × 10 −4 mol of diol (BDO or ODO, 0.2 m ) (diester:diol ratio = 1:1) were added together with 4 mL of DPE or Cyrene in a 25 mL round bottom flask.…”

Section: Methodsmentioning

confidence: 99%

“…al. [26] A total of 8 × 10 −4 mol of GA diester (0.2 m) and 8 × 10 −4 mol of diol (BDO or ODO, 0.2 m) (diester:diol ratio = 1:1) were added together with 4 mL of DPE or Cyrene in a 25 mL round bottom flask. The mixture was then stirred at the desired operational temperature until complete dissolution of the monomers in the solvent.…”

Section: Methodsmentioning

confidence: 99%

“…For this aim, a commercial immobilized lipase from Candida antarctica (CaLB) was selected due to its known stability to high temperatures and different solvents. [26,27] Solubility tests of GA in solvents suitable for the enzymatic polymerization highlighted the necessity of alternative strategies. The high melting temperature of GA (>140 °C) does not allow enzymatic polymerization in bulk.…”

Section: Doi: 101002/marc201900361mentioning

confidence: 99%

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Sustainable Galactarate‐Based Polymers: Multi‐Enzymatic Production of Pectin‐Derived Polyesters

Vastano

Pellis

Machado

et al. 2019

Macromol. Rapid Commun.

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Large amounts of agricultural wastes are rich in pectins that, in many cases, disrupt the processing of food residues due to gelation. Despite pectins being a promising sustainable feedstock for bio‐based chemical production, the current pathways to produce platform molecules from this polysaccharide are hazardous and entail the use of strong acids. The present work describes a sequence of biocatalyzed reactions that involves 1) the extraction of pectin from sugar beet pulp and enzymatic recovery of galacturonic acid (GalA), followed by 2) the enzymatic oxidation of the GalA aldehyde and the recovery of galactaric acid (GA), and 3) the biocatalyzed polycondensation of GA to obtain fully bio‐based polyesters carrying lateral hydroxy functionalities. The acid‐free pectin extraction is optimized using enzymes and microwave technology. The conditions for enzymatic oxidation of GalA allow the separation of the GA produced by a simple centrifugation step that leads to the enzyme‐catalyzed polycondensation reactions.

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Continuous Flow Bioamination of Ketones in Organic Solvents at Controlled Water Activity using Immobilized ω‐Transaminases

et al. 2020

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Compared with biocatalysis in aqueous media, the use of enzymes in neat organic solvents enables increased solubility of hydrophobic substrates and can lead to more favorable thermodynamic equilibria, avoidance of possible hydrolytic side reactions and easier product recovery. ω-Transaminases from Arthrobacter sp. (AsRÀ ωTA) and Chromobacterium violaceum (CvÀ ωTA) were immobilized on controlled porosity glass metal-ion affinity beads (EziG) and applied in neat organic solvents for the amination of 1phenoxypropan-2-one with 2-propylamine. The reaction system was investigated in terms of type of carrier material, organic solvents and reaction temperature. Optimal conditions were found with more hydrophobic carrier materials and toluene as reaction solvent. The system's water activity (a w ) was controlled via salt hydrate pairs during both the biocatalyst immobilization step and the progress of the reaction in different nonpolar solvents. Notably, the two immobilized ωTAs displayed different optimal values of a w , namely 0.7 for EziG 3 À AsRÀ ωTA and 0.2 for EziG 3 À CvÀ ωTA. In general, high catalytic activity was observed in various organic solvents even when a high substrate concentration (450-550 mM) and only one equivalent of 2propylamine were applied. Under batch conditions, a chemical turnover (TTN) above 13000 was obtained over four subsequent reaction cycles with the same batch of EziG-immobilized ωTA. Finally, the applicability of the immobilized biocatalyst in neat organic solvents was further demonstrated in a continuous flow packedbed reactor. The flow reactor showed excellent performance without observable loss of enzymatic catalytic activity over several days of operation. In general, ca. 70% conversion was obtained in 72 hours using a 1.82 mL flow reactor and toluene as flow solvent, thus affording a space-time yield of 1.99 g L À 1 h À 1 . Conversion reached above 90% when the reaction was run up to 120 hours.

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Safer bio-based solvents to replace toluene and tetrahydrofuran for the biocatalyzed synthesis of polyesters

Abstract: Biocatalyzed synthesis of aliphatic and furan-based polyesters in safer, bio-derived solvents for the substitution of toluene and tetrahydrofuran.

Cited by 55 publications

References 22 publications

Continuous Biocatalysis in Environmentally‐Friendly Media: A Triple Synergy for Future Sustainable Processes

Continuous Biocatalysis in Environmentally‐Friendly Media: A Triple Synergy for Future Sustainable Processes

Sustainable Galactarate‐Based Polymers: Multi‐Enzymatic Production of Pectin‐Derived Polyesters

Continuous Flow Bioamination of Ketones in Organic Solvents at Controlled Water Activity using Immobilized ω‐Transaminases

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