Structure-antioxidant activity relationship of active oxygen catalytic lignin and lignin-carbohydrate complex.

Lignin, as a natural antioxidant, has a great potential to replace the chemosynthetic ones due to this material benefits of being biodegradable, eco-friendly, abundant and low-cost. However, the commonly-used lignins, such as acid, kraft and alkali lignins, have the poor antioxidant ability, and their antioxidative mechanism and kinetics remain poorly understood. Moreover, the understanding of the effect of polysaccharides in lignin-carbohydrate complex (LCC) on lignin antioxidant activity is also extremely insufficient. Herein, we isolated lignin and LCC from rice straw and its alkali-oxygen spent liquor to investigate their structure-antioxidant activity relationship and antioxidative mechanism. Experimental results illustrated that the alkali-oxygen treatment can significantly enhance the antioxidant activity of lignin. Demethoxylation, ring-opening and the cleavage of aryl ether bonds occur to lignin structure leading to the decrease of molecular weight, while the more stable condensed β-1', 5-5' and β-5' linkages maintain the thermostability of this antioxidant. The synergistic effect of adjacent methoxyl with phenolic hydroxyl is the key factor that endows lignin with the outstanding antioxidant activity. In contrast, oligosaccharides formed by alkali-oxygen treatment have a negative influence on the antioxidant activity of lignin. This work demonstrates that alkali-oxygen lignin is a promising antioxidant to replace chemosynthetic ones for polymeric materials.