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.