Ozone-activated lignocellulose films blended with chitosan for edible film production.

This work focuses on the influence of ozone pretreatment on the fractionation and solubilization of sugarcane bagasse and soda bagasse pulp fibers in sodium hydroxide/urea solution, as well as the application of regenerated cellulose for producing edible films. The methodology involved pretreating lignocelluloses with ozone for 20 to 120 min before dissolving in sodium hydroxide/urea solution. The influence of the pretreatment conditions on cellulose dissolution yield was investigated. Regenerated cellulose films were then formed, with and without the addition of 2 % chitosan. Mechanical, physical, structural, thermal, and antimicrobial attributes were determined as a function of ozonation conditions of raw materials and chitosan content. The findings exhibited positive effects of short ozonation on enhancing mechanical strength, cohesion, and hydrophobicity. The prolonged ozonation of 120 min demonstrated optimal improvements in continuity, swelling, and antibacterial resistance of obtained films. Incorporating chitosan enhanced tensile performance, stiffness, and vapor barriers but increased moisture absorption. Tailoring the activation of biomass through ozone pretreatment and chitosan addition resulted in renewable films with adjustable properties to meet diverse packaging requirements, particularly for fruit protective coatings, ensuring the preservation of post-harvest quality.

Oxidation Treatments Using Hydrogen Peroxide to Convert Paper-Grade Eucalyptus Kraft Pulp into Dissolving-Grade Pulp.

Converting paper-grade bleached Kraft pulp into dissolving pulp using eco-friendly chemicals on-site at the mill is a challenge for the pulp industry. In this study, two oxidation systems are evaluated: the first one is based on the use of hydrogen peroxide at various levels of alkalinity; the second one investigates the use of sodium periodate followed by hydrogen peroxide to convert aldehydes into carboxyls and enhance their hemicelluloses removal. Our results have shown that when using only peroxide, the removal of hemicelluloses was not sufficient to improve the pulp's dissolving ability. Conversely, the periodate-peroxide system proved to be more efficient. Results regarding the pulp purity, solubility, degradation (pulp viscosity and cellulose molecular mass distribution), brightness, and its potential applications were discussed.

ClO2-Mediated Oxidation of the TEMPO Radical: Fundamental Considerations of the Catalytic System for the Oxidation of Cellulose Fibers.

The reaction mechanism of ClO2-mediated TEMPO oxidation was investigated by EPR spectroscopy and UV-Vis spectroscopy in the context of an alternative TEMPO sequence for cellulose fiber oxidation. Without the presence of a cellulosic substrate, a reversibility between TEMPO and its oxidation product, TEMPO+, was displayed, with an effect of the pH and reagent molar ratios. The involvement of HOCl and Cl-, formed as byproducts in the oxidation mechanism, was also evidenced. Trapping HOCl partly inhibits the reaction, whereas adding methylglucoside, a cellulose model compound, inhibits the reversibility of the reaction to TEMPO.

Oxidation treatments to convert paper-grade Eucalyptus kraft pulp into microfibrillated cellulose.

Microfibrillated cellulose (MFC) is an emerging cellulosic material that has shown enormous potential in various industrial sectors such as food packaging, cosmetics, pharmaceuticals, filler for cement and paper, and others. Yet, there is still the need to improve its processing in order to reach its full potential. Despite research efforts for the production of MFC, the production volumes remain low because the costs of these products are hardly competitive with synthetic polymers. The present study investigates the conversion of bleached Kraft pulp into MFC using three different oxidative treatments: (1) oxidation with sodium periodate followed by oxidation with hydrogen peroxide to enrich the pulp with carboxyl groups; (2) activation of hydrogen peroxide with copper to produce hydroxyl radicals; and (3) use of hydrogen peroxide alone in alkaline medium. Treatments (1) and (2) allowed producing interesting MFC with reduced energy consumption.

Study of the Reactivity of Lignin Model Compounds to Fluorobenzylation Using 13C and 19F NMR: Application to Lignin Phenolic Hydroxyl Group Quantification by 19F NMR.

Lignin is an aromatic biopolymer derived from lignocellulosic biomass. Providing a comprehensive structural analysis of lignin is the primary motivation for the quantification of various functional groups, with a view to valorizing lignin in a wide range of applications. This study investigated the lignin fluorobenzylation reaction and performed a subsequent 19F-NMR analysis to quantify hydroxyl groups, based on a work developed two decades ago by Barrelle et al. The objectives were to check the assignments proposed in this previous study and to examine the reactivity of various types of lignin hydroxyls with the derivatization agent. Selected lignin model compounds containing phenolic and aliphatic hydroxyls were subjected to the fluorobenzylation reaction, and the obtained reaction medium was analyzed by 13C and 19F NMR spectroscopy. The model compound results showed that phenolic hydroxyls were totally derivatized, whereas aliphatic hydroxyls underwent minimal conversion. They also confirmed that 19F NMR chemical shifts from -115 ppm to -117.3 ppm corresponded to phenolic groups. Then, a 19F NMR analysis was successfully applied to Organosolv commercial lignin after fluorobenzylation in order to quantify its phenolic group content; the values were found to be in the range of the reported values using other analytical techniques after lignin acetylation.

Study of the Direct Red 81 Dye/Copper(II)-Phenanthroline System.

Recovered papers contain several chromophores, such as wood lignin and dyes. These have to be eliminated during paper recycling in order to produce white paper. Hydrogen peroxide under alkaline conditions is generally used to decolorize lignin, but its effect on dyes is limited. Copper(II)-phenanthroline (Cu-Phen) complexes can activate the oxidation of lignin by hydrogen peroxide. Hydrogen peroxide may also be activated during recycled fiber bleaching, thus enhancing its color-stripping efficiency towards unoxidizable azo dyes. The purpose of this paper was to determine the effect of Cu-Phen complexes on a model azo dye, Direct Red 81 (DR81), in aqueous solution. Different Cu-Phen solutions (with different initial Cu:Phen molar ratios) were prepared and mixed with the dye at different pHs. The geochemical computer program PHREEQC allowed precise calculation of the theoretical distribution between different possible coordinates (CuPhenOH⁺, Cu(Phen)22+, CuPhen(OH)2, Cu(Phen)32+, etc.) depending on pH and initial concentrations. UV-vis spectroscopic measurements were correlated with the major species theoretically present in each condition. The UV absorbance of the system was mainly attributed to the Cu-Phen complex and the visible absorbance was only due to the dye. Cu-Phen appeared to reduce the color intensity of the DR81 dye aqueous solution under specific conditions (more effective at pH 10.7 with Cu:Phen = 1:1), probably owing to the occurrence of a coordination phenomenon between DR81 and Cu-Phen. Hence, the ligand competition between phenanthroline and hydroxide ions would be disturbed by a third competitor, which is the dye molecule. Further investigation proved that the DR81 dye is able to form a complex with copper-phenanthroline, leading to partial color-stripping. This new "color-stripping effect" may be a new opportunity in paper and textile industries for wastewater treatment.

WITHDRAWN: Elucidation of structural condensation in lignin of eastern cottonwood.

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