Antioxidant activity of phlorotannins from brown algae

Switchgrass was pretreated with sodium hydroxide (NaOH) at various concentrations and pretreatment times to investigate how delignification caused by NaOH affects its lignin chemistry. NaOH resulted in significant delignification ranging from 44.0 to 84.6% depending on pretreatment intensity. While there was no significant glucan loss due to NaOH pretreatment, higher NaOH concentrations removed xylan by up to 28.3%. Nitrobenzene oxidation (NBO) was used to study changes in lignin chemistry, and indicated that at higher NaOH concentrations, the amount of 4-hydroxygenzaldehyde (Hy) degraded from p-hydroxyphenyl propanol (H) lignin units was significantly reduced (p < 0.05). However, amounts of syringic (SA) and vanillic (VA) acids generated from syringyl (S) and guaiacyl (G) degradation were greater at higher NaOH concentration. S/G ratio (=0.62 raw switchgrass) did not significantly (p > 0.05) change with 15 min pretreatment, but it increased to 0.75 and 0.72, respectively, with 30 and 60 min pretreatments (p < 0.05). Increase in NaOH concentration did not significantly (p > 0.05) change S/G ratio, but H/G ratio (=0.48 raw switchgrass) decreased significantly to 0.14 regardless of pretreatment times. Overall, the H unit was found to be more susceptible to NaOH than S and G unit monolignols. Though changes in lignin chemistry due to NaOH concentration were observed, their impact on cellulolytic enzyme action during hydrolysis could not be fully understood. Further studies on lignin isolation may help to determine how these changes in lignin chemistry by NaOH impact cellulolytic enzymes.

In the present research, activated carbon-supported sulfonic acid catalysts were synthesized and tested as pretreatment agents for the conversion of switchgrass into glucose. The catalysts were synthesized by reacting sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid with activated carbon. The characterization of catalysts suggested an increase in surface acidities, while surface area and pore volumes decreased because of sulfonation. Batch experiments were performed in 125 mL serum bottles to investigate the effects of temperature (30, 60, and 90 °C), reaction time (90 and 120 min) on the yields of glucose. Enzymatic hydrolysis of pretreated switchgrass using Ctec2 yielded up to 57.13% glucose. Durability tests indicated that sulfonic solid-impregnated carbon catalysts were able to maintain activity even after three cycles. From the results obtained, the solid acid catalysts appear to serve as effective pretreatment agents and can potentially reduce the use of conventional liquid acids and bases in biomass-into-biofuel production.

Valorization of lignin into aromatics has driven researchers for decades. In this research, niobium was deposited on oyster shells (OSNC) and carbon rods (CRNC) and tested as a catalyst for depolymerization of lignin. Catalysts (2%, 5%, and 8% loading) were synthesized via wet impregnation. Batch experiments were performed at 95 °C, using 8 g of lignin, and 1 g of catalyst. Our research indicates that niobium supported catalysts are effective in partial oxidation of lignin. Maximum vanillin concentration for OSNC was found to be 86.25 mg L⁻¹ (0.1 wt%) at 5% niobium whereas, as for CRNC, maximum vanillin concentration was found to be 139.40 mg L⁻¹ (0.17 wt%) at 2% niobium loading. Addition of hydrogen peroxide into the batch reactor decreased the concentration of vanillin production.

The effect of binding between the lignin isolates from an alkali (NaOH)– and an acid (H₂SO₄)– pretreated Miscanthus and cellulolytic enzymes in Cellic^® CTec2 was investigated. Additonally, cellobiose and Avicel were enzymatically hydrolyzed with and without lignin isolates to study how enzyme binding onto lignin affects its conversion to glucose. Three carbohydrate–lignin loadings (0.5:0.25, 0.5:0.5, and 0.5:1.0% (w/v)) were employed. The results indicated that β-glucosidase (BG) had a strong tendency to bind to all lignin isolates. The overall tendency of enzyme binding onto lignin isolate was similar regardless of pretreatment chemical concentration. Though enzyme binding onto lignin isolates was observed, hydrolysis in the presence of these isolates did not have a significant (p > 0.05) impact on glucose production from cellobiose and Avicel. Cellobiose to glucose conversion of 99% was achieved via hydrolysis at both 5 and 10 FPU/g carbohydrate. Hydrolysis of Avicel with 5 and 10 FPU/g CTec2 resulted in 29.3 and 47.7% conversion to glucose, respectively.