The enzymatic depolymerization is a promising route to valorize the lignin polymers by turning the cross-linked polymers into monomers or oligomers. However, the lignin polymers cannot be effectively converted into small chemicals, as the oligomers are prone to polymerization, which is particularly challenging to monitor and thus regulate. Here, we develop a microstructured fiber Bragg grating (mFBG) sensor to probe the dynamic polymerization process of typical lignin oligomer surrogates─guaiacol (monomer) and guaiacylglycerol-β-guaiacyl ether (GBG, dimer)─catalyzed by laccase in an operando way. The mFBG sensor was developed with its reliability well validated by control experiments at first. Further, operando monitoring of the polymerization reaction process of the typical lignin monomer (i.e., guaiacol) and dimer (guaiacylglycerol-β-guaiacyl ether, GBG) was demonstrated under various conditions with the mFBG sensor. The GC-MS and UV–vis absorption measurements were carried out as a further check. Finally, the specific polymerization characteristics and reaction mechanism were studied. The mFBG sensor enables operando monitoring of the heterogeneous polymerization process of lignin monomers and oligomers and can potentially be tailored to probe more complex lignin depolymerization processes and unveil enzymatic synergistic mechanisms for the biological transition of biomass.
Deep eutectic solvents (DES) are promising green solvents for depolymerization and reconstruction of lignin. Revealing the transformations of lignin during DES treatment is beneficial for high potential lignin applications. In this study, bagasse lignin was treated with a binary DES and three ternary DESs, respectively. The results showed that net hydrogen bonding acidity(α-β) value of DES was positively correlated to the increment of phenolic hydroxyl of lignin, and the ternary DES of choline chloride-formic acid-oxalic acid (ChCl-FA-OA) exhibited the best phenolation performances. The phenolic hydroxyl content of ChCl-FA-OA treated lignin was increased by 50.4 %, reaching 2.41 mmol/g under optimum conditions (120 °C, 4 h, ChCl-FA-OA = 1:2:1). Moreover, it was found that the cleavage of β-O-4′ aryl ether bond and ester bond were dominant reactions during the treatment, accompanied by condensation reactions. Additionally, the obtained lignin oil contained various syringyl and guaiacyl derived phenolic compounds. Especially, the content of acetovanillone in lignin oil reached 29.94 %, much higher than in previous studies. Finally, the degradation mechanism of lignin in ChCl-FA-OA system was proposed. The present work provided insights into the relationship between lignin phenolation and DES properties. The novel ChCl-FA-OA system can achieve efficient lignin depolymerization, and convert lignin biomass into value-added chemical products.
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