The development of sustainable plastics from abundant renewable feedstocks has been limited by the complexity and efficiency of their production as well as their lack of competitive material properties. Here, we demonstrate the direct transformation of the hemicellulosic fraction of non-edible biomass into a diester plastic precursor at 83% yield (95% from commercial xylose) during integrated plant fractionation with glyoxylic acid. Melt polycondensation of the resulting xylose-based diester with a range of aliphatic diols led to high-molecular weight amorphous polyesters with combined high glass transition temperatures, tough mechanical properties, and strong gas barriers, which could be processed by injection-molding, thermoforming, and 3D-printing. These polyesters could then be chemically recycled from mixed plastic waste streams or digested under biologically relevant conditions. The transformation’s simplicity led to projected costs that were competitive with fossil alternatives and significantly reduced associated greenhouse gas emissions, especially if glyoxylic acid was sourced from CO2.
To explore the effect of chain length and conformation
on the nucleation
of peptides, the primary nucleation induction time of glycine homopeptides
in pure water at different supersaturation levels under various temperatures
has been determined. Nucleation data suggest that longer chains will
prolong the induction time, especially for chains longer than three,
where nucleation will occur over several days. In contrast, the nucleation
rate increased with an increase in the supersaturation for all homopeptides.
Induction time and nucleation difficulty increase at lower temperatures.
However, for triglycine, the dihydrate form was produced with an unfolded
peptide conformation (pPII) at low temperature. The interfacial energy
and activation Gibbs energy of this dihydrate form are both lower
than those at high temperature, while the induction time is longer,
indicating the classical nucleation theory is not suitable to explain
the nucleation phenomenon of triglycine dihydrate. Moreover, gelation
and liquid–liquid separation of longer chain glycine homopeptides
were observed, which was normally classified to nonclassical nucleation
theory. This work provides insight into how the nucleation process
evolves with increasing chain length and variable conformation, thereby
offering a fundamental understanding of the critical peptide chain
length for the classical nucleation theory and complex nucleation
process for peptides.
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