Abstract
n-Butyl levulinate (n-BL) has numerous applications in biofuel and green
solvents. In this paper, we have reported mechanistic accounts of
sonoenzymatic synthesis of n-BL using Novozym 435. Esterification
parameters were optimized with statistical design of experiments.
Application of 35 kHz sonication boosted n-BL yield from 70.9% to
92.22%. Mechanistic investigation using Ping-Pong Bi-Bi kinetics model
and molecular docking simulations revealed interesting influence of
sonication on esterification reaction. Exposure to sonication induced
significant changes in the secondary structure of enzyme, as revealed in
ATR-FTIR analysis. Sonication increased α-helix content of enzyme that
increased enzyme activity by opening of flapping lid and widening the
catalytic cavity. Sonication also caused unfolding of secondary
structural motifs with rise in random coil content that favored
formation of enzyme-ligand complexes. These effects enhanced reaction
velocity and substrate affinity with reduction in inhibition and
unfavorable dissociation of intermediate complexes, which ultimately
enhanced n-BL yield.