In Situ Adsorption of Red Onion (Allium cepa) Natural Dye on Cellulose Model Films and Fabrics Exploiting Chitosan as a Natural Mordant.

Synthetic dyes and chemicals create an enormous impact on environmental pollution both in textile manufacturing and after the product's lifetime. Biobased plant-derived colorants and mordants have great potential for the development of more sustainable textile dyeing processes. Colorants isolated from biomass residues are renewable, biodegradable, and usually less harmful than their synthetic counterparts. Interestingly, they may also bring additional functions to the materials. However, the extraction and purification of the biocolorants from biomass as well as their dyeing efficiency and color fastness properties require a more thorough examination. Here, we extracted red onion (Allium cepa) skins to obtain polyphenolic flavonoids and anthocyanins as biocolorants, characterized the chemical composition of the mixture, and used a quartz crystal microbalance and thin films of cellulose nanofibrils to study the adsorption kinetics of dyes onto cellulose substrates in situ. The effect of different mordants on the adsorption behavior was also investigated. Comparison of these results with conventional dyeing experiments of textiles enabled us to determine the interaction mechanism of the dyes with substrates and mordants. Chitosan showed high potential as a biobased mordant based both on its ability to facilitate fast adsorption of polyphenols to cellulose and its ability to retain the purple color of the red onion dye (ROD) in comparison to the metal mordants FeSO4 and alum. The ROD also showed excellent UV-shielding efficiency at low concentrations, suggesting that biocolorants, due to their more complex composition compared to synthetic ones, can have multiple actions in addition to providing aesthetics.

Fractionation of Technical Lignin from Enzymatically Treated Steam-Exploded Poplar Using Ethanol and Formic Acid.

Lignocellulosic biorefineries produce lignin-rich side streams with high valorization potential concealed behind their recalcitrant structure. Valorization of these residues to chemicals, materials, and fuels increases the profitability of biorefineries. Fractionation is required to reduce the lignins' structural heterogeneity for further processing. We fractionated the technical biorefinery lignin received after steam explosion and saccharification processes. More homogeneous lignin fractions were produced with high ß-O-4' and aromatic content without residual carbohydrates. Non-toxic biodegradable organic solvents like ethanol and formic acid were used for fractionation and can be adapted to the existing biorefinery processes. Macromolecular properties of the isolated fractions were carefully characterized by structural, chemical, and thermal methods. The ethanol organosolv treatment produced highly soluble lignin with a reasonable yield, providing a uniform material for lignin applications. The organosolv fractionation with formic acid and combined ethanol-formic acid produced modified lignins that, based on thermal analysis, are promising as thermoresponsive materials.

Vanillic acid and methoxyhydroquinone production from guaiacyl units and related aromatic compounds using Aspergillus niger cell factories.

BACKGROUND: The aromatic compounds vanillin and vanillic acid are important fragrances used in the food, beverage, cosmetic and pharmaceutical industries. Currently, most aromatic compounds used in products are chemically synthesized, while only a small percentage is extracted from natural sources. The metabolism of vanillin and vanillic acid has been studied for decades in microorganisms and many studies have been conducted that showed that both can be produced from ferulic acid using bacteria. In contrast, the degradation of vanillin and vanillic acid by fungi is poorly studied and no genes involved in this metabolic pathway have been identified. In this study, we aimed to clarify this metabolic pathway in Aspergillus niger and identify the genes involved. RESULTS: Using whole-genome transcriptome data, four genes involved in vanillin and vanillic acid metabolism were identified. These include vanillin dehydrogenase (vdhA), vanillic acid hydroxylase (vhyA), and two genes encoding novel enzymes, which function as methoxyhydroquinone 1,2-dioxygenase (mhdA) and 4-oxo-monomethyl adipate esterase (omeA). Deletion of these genes in A. niger confirmed their role in aromatic metabolism and the enzymatic activities of these enzymes were verified. In addition, we demonstrated that mhdA and vhyA deletion mutants can be used as fungal cell factories for the accumulation of vanillic acid and methoxyhydroquinone from guaiacyl lignin units and related aromatic compounds. CONCLUSIONS: This study provides new insights into the fungal aromatic metabolic pathways involved in the degradation of guaiacyl units and related aromatic compounds. The identification of the involved genes unlocks new potential for engineering aromatic compound-producing fungal cell factories.

Fungal Treatment Modifies Kraft Lignin for Lignin- and Cellulose-Based Carbon Fiber Precursors.

The kraft lignin's low molecular weight and too high hydroxyl content hinder its application in bio-based carbon fibers. In this study, we were able to polymerize kraft lignin and reduce the amount of hydroxyl groups by incubating it with the white-rot fungus Obba rivulosa. Enzymatic radical oxidation reactions were hypothesized to induce condensation of lignin, which increased the amount of aromatic rings connected by carbon-carbon bonds. This modification is assumed to be beneficial when aiming for graphite materials such as carbon fibers. Furthermore, the ratio of remaining aliphatic hydroxyls to phenolic hydroxyls was increased, making the structure more favorable for carbon fiber production. When the modified lignin was mixed together with cellulose, the mixture could be spun into intact precursor fibers by using dry-jet wet spinning. The modified lignin leaked less to the spin bath compared with the unmodified lignin starting material, making the recycling of spin-bath solvents easier. The stronger incorporation of modified lignin in the precursor fibers was confirmed by composition analysis, thermogravimetry, and mechanical testing. This work shows how white-rot fungal treatment can be used to modify the structure of lignin to be more favorable for the production of bio-based fiber materials.