The carbon quantum dot (CQD), a fluorescent carbon nanoparticle, has attracted considerable interest due to its photoluminescent property and promising applications in cell imaging and bioimaging. In this work, biocompatible, photostable, and sustainably sourced CQDs were synthesized from byproducts derived from a biorefinery process using one-pot hydrothermal treatment. The main components of byproducts were the degradation products (autohydrolyzate) of biomass pretreated by autohydrolysis. The as-synthesized CQDs had a size distribution from 2.0–6.0 nm and had high percentage of sp2 and sp3 carbon groups. The CQDs showed blue-green fluorescence with a quantum yield of ~13%, and the fluorescence behaviors were found to be stable with strong resistance to photobleaching and temperature change. In addition, it is found that the as-synthesized CQDs could be used for imaging of cells and tumors, which show potential applications in bioimaging and related fields such as phototherapy and imaging.
The lignin rendered
soluble by lignocellulosic biorefinery pretreatment
remains insufficiently understood along the lines of molecular properties
and chemical composition. To procure a representative soluble lignin
preparation, an aromatic-selective adsorptive resin was utilized.
Approximately 90% of soluble lignin could be recovered from autohydrolysis
pretreatment hydrolyzate (autohydrolyzate) produced from a hardwood
and a nonwood biomass. Adsorbate compositional characterization revealed
a befuddling magnitude of carbohydrate in selectively isolated lignin
adsorbates. Quantitative structural analysis of the lignin by NMR
suggested lignin–carbohydrate complexes (LCCs) as the cause
behind the pronounced carbohydrate contents. Analyzed spectra revealed
both hardwood and nonwood soluble lignin features of ∼10 total
LCC per 100 aromatic rings, with each lignin bearing unique LCC profiles.
In addition, native structures remained in large quantities. The improved
understanding of hydrolyzate-soluble lignin granted from this work
will aid biorefinery development by improving discourse around a biorefinery
lignin source.
Recent techno-economic studies of proposed lignocellulosic biorefineries have concluded that creating value from lignin will assist realization of biomass utilization into valuable fuels, chemicals, and materials due to co-valorization and the new revenues beyond carbohydrates. The pretreatment step within a biorefinery process is essential for recovering carbohydrates, but different techniques and intensities have a variety of effects on lignin. Acidic and alkaline pretreatments have been shown to produce diverse lignins based on delignification chemistry. The valorization potential of pretreated lignin is affected by its chemical structure, which is known to degrade, including inter-lignin condensation under high-severity pretreatment. Co-valorization of lignin and carbohydrates will require dampening of pretreatment intensities to avoid such effects, in spite of tradeoffs in carbohydrate production.
Fractionation
of Kraft lignin from black liquor is necessary to
reduce its heterogeneity, which exerts negative effects upon lignin-commercial
polymer composite materials. In this work, Kraft lignin was dissolved
in acetic acid to get low viscosity lignin solution and fractionated
into specific molecular weight fractions by sequential ultrafiltration
with different molecular weight cut-offs. The fractionated lignins
were characterized, and their suitability in polyethylene–lignin
composites was evaluated. After ultrafiltration with 5k and 3k Da
cutoff, fractionation resulted in three fractions of differing molecular
weights and lower polydispersity than the original Kraft lignin (F1
(7010 g/mol), F2 (3540 g/mol), and F3 (1890 g/mol)). The results from
spectroscopic characterization of lignin (31P, 13C, and 2D-HSQC NMR) and thermal stability analysis (TGA and DSC)
indicated that the contents of various linkages and functional groups
and the thermal properties of each fraction varied as a function of
its molecular weight. Compared to F1 and F2, F3 (lowest molecular
weight and high quantity of phenolic hydroxyl groups) most positively
contributed to the mechanical properties of a polyethylene–lignin
composite.
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