Chemoenzymatic Conversion of Corncob to Furfurylamine via Tandem Catalysis with Tin-Based Solid Acid and Transaminase Biocatalyst

Abstract

Furfurylamine (FLA) is known as an important biobased product for the production of food additives, fuel additives, polymers, fibers, perfumes, and pharmaceuticals. In this study, recombinant Escherichia coli CV-PRSFDuet whole cells harboring transaminase were used for converting biomass-derived furfural into furfurylamine at pH 7.5 and 35 °C using l-alanine as the amine donor. Whole-cell-catalyzed conversion of 300 mM furfural gave 84.0% yield of furfurylamine with 100% selectivity. 90.3 mM furfural was obtained from the alkali pretreatment of dewaxed corncob (75 g/L) at 170 °C for 0.5 h with an acidified Sn-ZRD catalyst (3.6 wt %, pH 1.0) in the aqueous media, which could be biconverted into furfurylamine at 76.3% yield (0.267 g furfurylamine/g xylan in corncob) within 8.5 h in the presence of 10 mol l-alanine/mol furfural. Clearly, chemoenzymatic synthesis of furfurylamine from corncob could be conducted in a one-pot manner. Finally, an efficient recycling and reuse of the Sn-ZRD catalyst and immobilized whole cell biocatalyst were developed for the chemoenzymatic synthesis of FLA from corncob in the one-pot reaction system. In summary, an initial approach for high-value utilization of biomass into FLA and its derivatives was successfully provided under relatively mild performance conditions.

Highly Efficient Chemoenzymatic Cascade Catalysis of Biomass into Furfurylamine by a Heterogeneous Shrimp Shell-Based Chemocatalyst and an ω-Transaminase Biocatalyst in Deep Eutectic Solvent–Water

“…Using tin-based sulfonated kaolin (3.5 wt %) as the catalyst, FAL (67.3 mM) was obtained in 74.3% yield from corncob-derived D-xylose in the water− toluene (2:1, v/v) system containing 10 mM OP-10 at 170 °C for 0.5 h. 18 The FAL yield reached 46% from CC with ChCl− oxalic acid as the catalyst at 120 °C for 0.5 h. 30 170 °C for 0.5 h using the Sn-ZRD catalyst (3.6 wt %) in water. 38 Sulfonated vermiculite (4.0 wt %) catalyzed the conversion of reeds into FAL (55.0 mM) in a yield of 38% at 170 °C within 20 min. 53 Sulfonated sepiolite (3.0 wt %) was used to transform rice straw into FAL in 42% yield in 20 min at 170 °C.…”

“…58 Compared with chemical amination, biological amination with an ω-transaminase biocatalyst can be conducted under environmentally friendly reaction conditions. Using D-alanine (16:1 Dalanine to FAL ratio), 34 L-alanine (10:1 of L-alanine to FAL ratio), 38 or isopropylamine (3:1 isopropylamine to FAL ratio) as the amine donor, 36 FLA could be obtained in a yield of 74.0, 76.3, or 88.2% at 35 °C and pH 7.5. In these cases, high loading of expensive amine donors (alanine and isopropylamine) was supplemented into the biotransamination reaction system, but the FLA yields were still not high (<90%), accompanied by a large amount of pyruvic acid and acetone.…”

“…CCZU-XLS160 cells showed high biotransamination activity toward CC-derived FAL, and a higher FLA yield (0.39 g of FLA/g of xylan in CC) was obtained compared to that in the previous report (0.267 of g FLA/g of xylan in CC). 38 Cleaner production of biobased chemicals from available and renewable bioresource CC and SS is crucial to achieve a sustainable biorefinery process. Chemoenzymatic cascade transformation of lignocellulose into FLA with high yield is of great interest via tandem chemocatalysis and biocatalysis reactions.…”

“…37 Using amine donor L-alanine (10 mol Lalanine/mol FAL), CV-PRSFDuet cells harboring ω-trans-aminase could catalyze the transamination of FAL into FLA with 76% yield at 35 °C and pH 7.5. 38 Bioamination of FAL with AT2018 cells harboring ω-transaminase at a D-alanine to FAL ratio of 16:1 (mol/mol), FLA could be obtained in a yield of 74.0% at 35 °C and pH 7.5. 34 At an isopropylamine to FAL ratio of 3:1 (mol/mol) as the amine donor, PRSFDuet cells could biologically aminate FAL to FLA in a yield of 88.2% at 35 °C and pH 7.5.…”

“…In recent years, ω-transaminases have emerged as a biocatalytic alternative for the synthesis of FLA and its derivatives via bioamination . Using amine donor l -alanine (10 mol l -alanine/mol FAL), CV-PRSFDuet cells harboring ω-transaminase could catalyze the transamination of FAL into FLA with 76% yield at 35 °C and pH 7.5 . Bioamination of FAL with AT2018 cells harboring ω-transaminase at a d -alanine to FAL ratio of 16:1 (mol/mol), FLA could be obtained in a yield of 74.0% at 35 °C and pH 7.5 .…”