Biorefineries aim to convert biomass into a spectrum of products ranging from biofuels to specialty chemicals. To achieve economically sustainable conversion, it is crucial to streamline the catalytic and downstream processing steps. In this work, a route that combines bio- and electrocatalysis to convert glucose into bio-based unsaturated nylon-6,6 is reported. An engineered strain of Saccharomyces cerevisiae was used as the initial biocatalyst for the conversion of glucose into muconic acid, with the highest reported muconic acid titer of 559.5 mg L(-1) in yeast. Without any separation, muconic acid was further electrocatalytically hydrogenated to 3-hexenedioic acid in 94 % yield despite the presence of biogenic impurities. Bio-based unsaturated nylon-6,6 (unsaturated polyamide-6,6) was finally obtained by polymerization of 3-hexenedioic acid with hexamethylenediamine.
Biorefineries aim to convert biomass into aspectrum of products ranging from biofuels to specialty chemicals.T o achieve economically sustainable conversion, it is crucial to streamline the catalytic and downstream processing steps.I n this work, ar oute that combines bio-and electrocatalysis to convert glucose into bio-based unsaturated nylon-6,6 is reported. An engineered strain of Saccharomyces cerevisiae was used as the initial biocatalyst for the conversion of glucose into muconic acid, with the highest reported muconic acid titer of 559.5 mg L À1 in yeast. Without any separation, muconic acid was further electrocatalytically hydrogenated to 3-hexenedioic acid in 94 %y ield despite the presence of biogenic impurities. Bio-based unsaturated nylon-6,6 (unsaturated polyamide-6,6) was finally obtained by polymerization of 3-hexenedioic acid with hexamethylenediamine.
The shikimate pathway serves an essential role in many organisms. Not only are the three aromatic amino acids synthesized through this pathway, but many secondary metabolites also derive from it. Decades of effort have been invested into engineering Saccharomyces cerevisiae to produce shikimate and its derivatives. In addition to the ability to express cytochrome P450, S. cerevisiae is generally recognized as safe for producing compounds with nutraceutical and pharmaceutical applications. However, the intrinsically complicated regulations involved in central metabolism and the low precursor availability in S. cerevisiae has limited production levels. Here we report the development of a new platform based on Scheffersomyces stipitis, whose superior xylose utilization efficiency makes it particularly suited to produce the shikimate group of compounds. Shikimate was produced at 3.11 g/L, representing the highest level among shikimate pathway products in yeasts. Our work represents a new exploration toward expanding the current collection of microbial factories.
Depolymerization
of lignocellulosic biomass in concentrated metal
salts and more specifically in acidified LiBr molten salt hydrate
(AMSH) results in high glucose yields at low acid concentrations,
low temperatures, and very short times with potentially considerable
economic benefits. However, our understanding of this promising medium
is limited. Here, we study the effect of different LiBr concentrations
on acidity and hydrolysis of cellobiose, a cellulose surrogate molecule,
in dilute H2SO4 solutions. We use thermodynamic
modeling to predict the H+(hydron) activity and the speciation
and correlate these with the experimentally measured reaction rates.
We find that the main contribution of the salt to the reactivity stems
from the dramatic increase in H+ activity and secondary
to an interaction of salt with the acid species that effectively renders
the inorganic acid very strong. We perform molecular dynamics simulations
and reveal that the increased hydron activity can be attributed to
the decrease in the number of water molecules in the hydron solvation
shell upon salt addition. Additionally, we extend the analysis to
other salts and acids, concluding that the effects of different cations,
anions, and acids in cellobiose hydrolysis likewise can be attributed
to primarily changes in acidity. A key physicochemical descriptor
of various salts is their enthalpy of dissolution. Finally, we explore
the use of 13C NMR spectroscopy to estimate the pH of AMSH
solutions.
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