Softwood lignocellulose is a potential
feedstock for the production
of biofuels and bioproducts. However, the highly cross-linked nature
of softwood lignocellulose restricts enzyme access to its sugars.
Thus, harsh pretreatment conditions (180–280 °C) and/or
high enzyme loading are required to unlock sugars. These requirements
negatively affect the economic viability of softwoods in biorefineries.
Here we show that H3PO4 pretreatment of pine
and Douglas fir under a mild reaction temperature (50 °C) and
atmospheric pressure enabled a high (∼80%) glucan digestibility
with low enzyme loading (5 filter paper units (FPU)/g glucan). The
dissolution and regeneration of softwoods disrupted the hydrogen bonding
between cellulose chains, thereby increasing the cellulose accessibility
to cellulase (CAC) values by ∼38-fold (from ∼0.4 to
15 m2/g biomass). Examination of H3PO4-pretreated softwoods by cross-polarization/magic angle spin (CP/MAS), 13C- nuclear magnetic resonance (NMR), and Fourier-transform
infrared spectroscopy (FTIR) revealed that breaking of the orderly
hydrogen bonding of crystalline cellulose caused the increase in CAC
(higher than 11 m2/g biomass), which, in turn, was responsible
for the high glucan digestibility of pretreated softwoods. The H3PO4 pretreatment process was feedstock independent.
Lastly, 2D 13C–1H heteronuclear single
quantum coherence (HSQC) NMR showed that the lignin was depolymerized
but not condensed; thus, the lignin can be available for producing
high-value products.