Recently, cost-effective production of highly value-added furan chemicals from abundant and renewable bioresources has gained much attentions via chemoenzymatic approach in environmentally-friendly reaction system. In this work, chemoenzymatic cascade reaction...

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.

No abstract

Recently, the cost-effective production of high value-added furan chemicals from inexpensive, abundant, and renewable bioresources has gained much attention via a chemoenzymatic approach in an environmentally friendly reaction system. Furfurylamine is an important furan-based chemical for the production of additives, fibers, perfumes, agrochemicals, and pharmaceuticals. This study attempted to develop one sustainable approach for the production of furfurylamine via chemoenzymatic cascade catalysis of biomass into furfurylamine using a chemocatalyst and a biocatalyst. Using alkali-treated shrimp shells as the biobased support, a tin-based heterogeneous chemocatalyst (Sn-DAT-SS) was first prepared to transform corncob into furfural in 52.4% yield in deep eutectic solvent choline chloride:ethylene glycol (ChCl:EG)–water (10:90, v/v) at 170 °C within 0.5 h. Sn-DAT-SS was easy to recover and has good reusability. Detailed investigation using Fourier transform infrared (FT-IR) spectroscopy, Brunauer–Emmett–Teller (BET) analysis, temperature-programmed desorption of NH3 (NH3-TPD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) indicated that the Lewis and Brönsted acid sites existed on the surface of Sn-DAT-SS. The possible catalytic mechanism of the Sn-DAT-SS-catalyzed transformation of corncob into furfural in ChCl:EG–water was presented. To biologically synthesize furfurylamine, newly constructed recombinant Escherichia coli CCZU-XLS160 whole-cells harboring ω-transaminase and l-alanine dehydrogenase were used to catalyze biomass-derived furfural using available inexpensive NH4Cl (2.0 mol NH4Cl/mol furfural) as the amine donor in ChCl:EG–water (10:90, v/v) at 35 °C and pH 7.5. Within 71.5 h, 92.3 mM furfural derived from corncob was wholly transformed into furfurylamine with a productivity of 0.39 g furfurylamine/g xylan in corncob in ChCl:EG–water (10:90, v/v). This work demonstrated an environmentally friendly chemoenzymatic strategy for utilizing lignocellulosic biomass into furfurylamine via tandem chemocatalysis and biocatalysis in green reaction media. It was feasible to obtain furfurylamine from a renewable source consisting of corncob and shrimp shells.

No abstract