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.
Yan Cao,Linfeng Zhang,Yingxue Geng,Yingjie Li,Qun Zhao,Jianhong Huang,Ping Ning,Senlin Tian
Polycyclic aromatic hydrocarbons (PAHs) can penetrate and accumulate in the pulmonary surfactant (PS) membranes, leading to abnormalities of biological macromolecules and the destruction of membrane structure and properties. In the present study, the bioavailability , apparent permeability, effective permeability and residual coefficient of 10 PAHs on PS membrane was assessed by the parallel artificial membrane permeability assay (PAMPA). The influence of various forces on permeability is obtained by analyzing the correlation between parameters and physicochemical properties . Research shows that octanol-water partition coefficient ( K ow ) cannot directly predict permeability, and permeability has no significant relationship with polarity. Dispersion, induction, coupling/polarization promote permeation, while hydrogen bonded acid and n-n electron pair inhibit permeation. Further surface pressure-area (π-A) isotherms test and Brewster angle microscope observation manifested that there are huge differences in the transmembrane ability and effects on the membrane of PAHs with different structures. This work has considerable significance that will help to evaluate the bioavailability and human health risk of PAHs.