Eco-friendly and facile preparation of chitosan-based biofilms of novel acetoacetylated lignin for antioxidant and UV-shielding properties.

The development of eco-friendly, sustainable, biodegradable, and biocompatible green biopolymer composites is becoming increasingly important. In this study, acetoacetylated lignin (ATL) was obtained via an eco-friendly, facile one-step synthesis reaction, and chitosan (CS)-containing ATL films (CSL) were prepared. The chemical structural analysis of ATL confirmed that the acetoacetyl groups were successfully grafted onto kraft lignin (KL). ATL with adequate acetoacetyl groups exhibited enhanced molecular weight and antioxidant and ultraviolet (UV)-shielding properties. In particular, ATL, with a half maximal inhibitory concentration (IC50) of 23.8 µg·mL-1, exhibited superior antioxidant activity than butylated hydroxytoluene (38.3 µg·mL-1) and KL (50.0 µg·mL-1). When ATL was incorporated into the CS solution to prepare biofilms, the antioxidant activity, UV-shielding property, water resistance, and thermal stability of the CSL greatly improved. Notably, the UV-A and UV-B shielding properties of the 2 % CSL were 130 % and 78 % higher than those of the pure CS film, respectively. Therefore, ATL designed with lignin-derived multifunctional properties has potential applications as an antioxidant and UV-shielding bio-additive and shows significant prospects in food packaging and biomedical applications.

One-step silanization and amination of lignin and its adsorption of Congo red and Cu(II) ions in aqueous solution.

In this work, silanized and aminated lignin (SAL) was synthesized in one step and its adsorption of Congo red and Cu(II) ions in aqueous solution was explored. Lignin was subjected to amine-silanization with (3-aminopropyl) triethoxysilane (APTES). Structural characterization substantiated successful amine-silanzation of lignin and formation of multi-layer APTES intermolecular crosslinked structure. The prepared SAL (nitrogen content = 6.1%) exhibited enhanced molecular weight, thermal stability, and water- and organic solvent-resistance properties. Additionally, the present of the porous structure of particle surface and an increase in the specific surface area and zeta potential promoted the accessibility of contaminants to the effective adsorption sites of SAL. Adsorption experiments showed that both Congo red and Cu(II) ion could be completely removed at original pH value, and their adsorption involved electrostatic attraction and complexation, respectively. The adsorption isotherms and kinetics were well described by the Langmuir and pseudo-second-order equations, respectively. The results showed that SAL is a promising adsorbent for the treatment of effluents.

Peracetic acid-induced kraft lignin solubilization and its characterization for selective production of macromolecular biopolymers.

This study was conducted to investigate the degradation characteristics of kraft lignin (KL) during peracetic acid (PAA) treatment, and to produce potentially valuable polymers of low molecular weight lignin by controlling the reaction conditions. For the peracetic acid treatment, acetic acid (AA) and hydrogen peroxide (HP) were directly mixed at ratios of 4:1, 1:1, and 1:4 (v/v) and employed as reaction media. After PAA treatment of kraft lignin at 80 °C, complete dissolution of the lignin and reduction in the molecular weight were observed. When the PAA reaction was performed at high HP concentration (1:4, v/v), the aromatic lignin skeleton opened and converted to a structure containing large amounts of carboxyl groups. On the other hand, the treatment at high AA concentration (4:1, v/v) decomposed lignin while maintaining its aromatic structure. Hence, we demonstrated that the selective production of lignin-derived polymers can be controlled depending on PAA and HP concentrations.

Characterization of solvent-fractionated lignins from woody biomass treated via supercritical water oxidation.

Crude supercritical lignin (SCL) extracted from hardwood (Quercus mongolica) treated via supercritical water (SCW) oxidation was subjected to sequential fractionation with four organic solvents; five lignin fractions (F1-F4 and FIN) were thus obtained. The molecular weight (MW) of the fractionated lignins gradually increased as fractionation proceeded. However, the content of methoxyl groups and phenolic hydroxyl groups tended to decrease with increasing molecular weight of the lignins. The functional groups of SCL and the fractionated lignins were very similar based on Fourier-transform infrared analysis. The syringyl/guaiacyl ratio (S/G ratio) of the fractionated lignins increased with an increase in the MW. The thermal stability decreased with decreasing MW of the fractionated lignins, and all fractions except for F1 had a maximum degradation temperature of around 360 °C. The glass transition temperature (Tg) of the fractions increased from 83 °C to 137 °C with increasing MW.

Phanerochaete chrysosporium Multienzyme Catabolic System for in Vivo Modification of Synthetic Lignin to Succinic Acid.

Whole cells of the basidiomycete fungus Phanerochaete chrysosporium (ATCC 20696) were applied to induce the biomodification of lignin in an in vivo system. Our results indicated that P. chrysosporium has a catabolic system that induces characteristic biomodifications of synthetic lignin through a series of redox reactions, leading not only to the degradation of lignin but also to its polymerization. The reducing agents ascorbic acid and α-tocopherol were used to stabilize the free radicals generated from the ligninolytic process. The application of P. chrysosporium in combination with reducing agents produced aromatic compounds and succinic acid as well as degraded lignin polymers. P. chrysosporium selectively catalyzed the conversion of lignin to succinic acid, which has an economic value. A transcriptomic analysis of P. chrysosporium suggested that the bond cleavage of synthetic lignin was caused by numerous enzymes, including extracellular enzymes such as lignin peroxidase and manganese peroxidase, and that the aromatic compounds released were metabolized in both the short-cut and classical tricarboxylic acid cycles of P. chrysosporium. In conclusion, P. chrysosporium is suitable as a biocatalyst for lignin degradation to produce a value-added product.

Evaluation of correlation between glucan conversion and degree of delignification depending on pretreatment strategies using Jabon Merah.

The main purpose of this study was to investigate the glucan conversion rate after enzymatic hydrolysis depending on the treatment methods and conditions with changes in the chemical composition of treated solid fraction of Jabon Merah. The glucan conversion rate (17.4%) was not significantly improved after liquid hot water treatment (1st step) even though most of the hemicellulose was dissolved into liquid hydrolysate. Subsequently, dilute acid, organosolv, and peracetic acid treatment (2nd step) was conducted under various conditions to enhance glucan conversion. Among the 2nd step treatment, the glucan conversion rate of organosolv (max. 46.0%) and peracetic acid treatment (max. 65.9%) was increased remarkably through decomposition of acid-insoluble lignin (AIL). Finally, the glucan conversion rate and AIL content were highly correlated, which was revealed by the R-squared value (0.84), but inhibitory factors including cellulose crystallinity must be considered for advanced glucan conversion from highly recalcitrant biomasses, such as Jabon Merah.