Structural properties and antioxidation activities of lignins isolated from sequential two-step formosolv fractionation

Abstract

In order to investigate the solubility behavior of lignin in formic acid (FA) solution Phragmites australis biomass was subjected to a sequential two-step formosolv fractionation using 88% FA followed by 70% FA to obtain four specific lignin fractions, designated as IFL-88%, IFSL-70%, IFIL-70% and IFL-EtAc. The structures of the four isolated lignin fractions were successfully characterized by gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance spectroscopy (2D-HSQC NMR), thermogravimetric analysis (TGA), and gas chromatography-mass spectroscopy (GC/MS). Furthermore, the total phenolic content of the four isolated lignin samples was assessed by Folin-Ciocalteu analysis. The data from structural properties revealed that depolymerization of the isolated lignin fractions occurred via β-O-4 cleavage, accompanied by competitive condensation reaction. Interestingly, 70% aqueous FA could separate specific lignin fractions with different antioxidant capacities of ABTS˙⁺ and DPPH radical scavenging activity. Due to the high total phenolic hydroxyl content (25%) and low molecular weight (Mw = 2760 Da) and polydispersity index (PDI = 1.5), IFL-EtAc lignin showed excellent antioxidant activity at the same concentration of 2.0 mg mL⁻¹ in comparison with three other isolated lignin fractions, and it was even equal to that of commercial antioxidant butylated hydroxytoluene (BHT). These findings are helpful to separate specific lignins with higher value as potential antioxidants by sequential two-step formosolv fractionation in lignin chemistry.