Functional Chitosan-Calcium Carbonate Coatings for Enhancing Water and Fungal Resistance of Paper Materials.

The objective of this study was to increase the water resistance of paper while providing fungal resistance using a bio-based coating made from chitosan. The water resistance was improved through the surface control of roughness using modified calcium carbonate particles. The higher the quantity of particles in the film-forming solution, the higher the surface hydrophobicity of the paper. The addition of particles was found to counterbalance the chitosan hydrophilicity through the control of the coatings' penetration in the paper bulk. As a consequence, the wetting time and liquid water resistance were enhanced. The antifungal activity of the film-forming solutions and coated paper was also investigated against the growth of Chaetomium globosum, which was selected as a model strain able to contaminate paper materials. The results reveal that the antifungal activity of chitosan was improved by a possible synergic effect with the bicarbonate ions from the mineral particles.

Oxidative Depolymerization of Alkaline Lignin from Pinus Pinaster by Oxygen and Air for Value-Added Bio-Sourced Synthons.

In this work, an efficient 3-step process targeting the chemical modification and purification of lignin oligomers from industrial alkaline lignin is described. The oxidative depolymerization process of alkaline lignin with O2 or Air pressure, without use of metal catalyst, led to the production of two fractions of lignin oligomers named 'precipitated lignin' and 'hydrosoluble lignin' with 40% and 60% yield, respectively. These fractions were characterized with a wide range of methods including NMR spectroscopy (31P, 2D-HSQC), SEC (in basic media), FTIR. NMR analyses revealed the presence of carboxylic acid functions at a ratio of 1.80 mmol/g and 2.80 mmol/g for the precipitated and hydrosoluble lignin, respectively, values much higher than what is generally found in native lignin (between 0.2 and 0.5 mmol/g). SEC analyses revealed the formation of low molar masses for the precipitated (2200 g/mol) and hydrosoluble fractions (1500 g/mol) in contrast to the alkaline lignin (3900 g/mol). It is worth noting that the hydrosoluble fraction of lignin is soluble in water at any pH. Both processes (oxygen and air) were successfully scaled up and showed similar results in terms of yield and functionalization.

Extraction and Characterization of Hemicelluloses from a Softwood Acid Sulfite Pulp.

Hemicelluloses were extracted from a softwood acid sulfite pulp in a three-step procedure. Further delignification step resulted in a holocellulose pulp containing only 1.7 wt.% of the lignin left. Cold caustic extraction (CCE) with 18 wt.% NaOH at 60 °C for 1 h was performed to solubilize hemicelluloses of the holocellulose. An unbleached cellulose pulp was then obtained 97% pure, which indicates that 89% of the hemicelluloses were removed. After purification, extraction yields between 1.1 wt.% and 9.5 wt.% were obtained from the delignified pulp and the hemicelluloses' chemical compositions and structures were investigated by 1H, 13C nuclear magnetic resonance spectroscopy (NMR) and two-dimensional NMR by correlation spectroscopy (2D-COSY) and proton-detected heteronuclear single-quantum correlation (2D-HSQC), high-performance anion-exchange chromatography coupled with a pulsed amperometry detector (HPAEC-PAD), size-exclusion chromatography coupled with a refractive index detector (SEC-RI) and thermogravimetric analyses (TGA). Hemicelluloses were obtained with a purity of 96%, with short cellulosic chains as the only residue. Sulfite pulping modified the hemicelluloses' structure, and it was found that two types of hemicelluloses were isolated, glucomannans, predominant at 67%, and methylglucuronoxylans. Finally, alkali-soluble hemicelluloses displayed relatively narrow size distributions and low molar masses, Mw varying between 18,900 and 30,000 g/mol after acid sulfite pulping.

Synthesis and Self-Assembly of Xylan-Based Amphiphiles: From Bio-Based Vesicles to Antifungal Properties.

This work aims at designing functional biomaterials through selective chemical modification of xylan from beechwood. Acidic hydrolysis of xylan led to well-defined oligomers with an average of six xylose units per chain and with an aldehyde group at the reductive end. Reductive amination was performed on this aldehyde end group to introduce an azide reactive group. "Click chemistry" was then applied to couple these hydrophilic xylans moieties with different hydrophobic fatty acid methyl esters that were previously functionalized with complementary alkyne functions. The resulting amphiphilic bio-based conjugates were then self-assembled using three different methods, namely, direct solubilization, thin-film rehydration/extrusion, and microfluidics. Well-defined micelles and vesicles were obtained, and their high loading capacity with propiconazole as an antifungal active molecule was shown. The resulting vesicles loaded with propiconazole in a microfluidic process proved to significantly improve the antifungal activity of propiconazole, demonstrating the high potential of such xylan-based amphiphiles.

Periodate oxidation of 4-O-methylglucuronoxylans: Influence of the reaction conditions.

This work aims at studying the sodium periodate oxidation of 4-O-methylglucuronoxylans (MGX) in different experimental conditions for a control of the oxidation degree. A series of sodium periodate oxidation reactions were conducted at three NaIO4/xylose molar ratios: 0.05, 0.20 and 1.00. The effects of xylan molar mass, xylan concentration and reaction temperature on the reaction rate have been evaluated by UV/visible spectroscopy at 0.20 NaIO4/xylose ratio. No depolymerization is observed at 0.05 ratio while depolymerization occurs at 0.20 and is even complete at 1.00 NaIO4/xylose ratio. An increase of the reaction temperature - up to 80 °C - leads to an increase of the oxidation rate with no effect on the depolymerization. At high xylan concentrations, the oxidation rate increases but promotes chains aggregation.

Dispersibility and emulsion-stabilizing effect of cellulose nanowhiskers esterified by vinyl acetate and vinyl cinnamate.

The surface of cotton cellulose nanowhiskers (CNW's) was esterified by vinyl acetate (VAc) and vinyl cinnamate (VCin), in the presence of potassium carbonate as catalyst. Reactions were performed under microwave activation and monitored by Fourier transform infrared (FT-IR) spectroscopy. The supramolecular structure of CNW's before and after modification was characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). Distinctively from the acetylation treatment, an increase in particles dimensions was noted after esterification with VCin, which was assigned to π-π stacking interactions that may exist between cinnamoyl moieties. The dispersibility and emulsion stabilizing effect of acylated CNW's was examined in ethyl acetate, toluene, and cyclohexane, three organic solvents of medium to low polarity. The acylated nanoparticles could never be dispersed in toluene nor cyclohexane, but they formed stable dispersions in ethyl acetate while remaining dispersible in water. Stable ethyl acetate-in-water, toluene-in-water, and cyclohexane-in-water emulsions were successfully prepared with CNW's grafted with acetyl moieties, whereas the VCin-treated particles could stabilize only the cyclohexane-in-water emulsions. The impact of esterification treatment on emulsion stability and droplets size was particularly discussed.

Styrene-spaced copolymers including anthraquinone and ß-O-4 lignin model units: synthesis, characterization and reactivity under alkaline pulping conditions.

A series of random copoly(styrene)s has been synthesized via radical polymerization of functionalized anthraquinone (AQ) and ß-O-4 lignin model monomers. The copolymers were designed to have a different number of styrene spacer groups between the AQ and ß-O-4 lignin side chains aiming at investigating the distance effects on AQ/ß-O-4 electron transfer mechanisms. A detailed molecular characterization, including techniques such as size exclusion chromatography, MALDI-TOF mass spectrometry, and (1)H, (13)C, (31)P NMR and UV-vis spectroscopies, afforded quantitative information about the composition of the copolymers as well as the average distribution of the AQ and ß-O-4 groups in the macromolecular structures. TGA and DSC thermal analysis have indicated that the copolymers were thermally stable under regular pulping conditions, revealing the inertness of the styrene polymer backbone in the investigation of electron transfer mechanisms. Alkaline pulping experiments showed that close contact between the redox active side chains in the copolymers was fundamental for an efficient degradation of the ß-O-4 lignin model units, highlighting the importance of electron transfer reactions in the lignin degradation mechanisms catalyzed by AQ. In the absence of glucose, AQ units oxidized phenolic ß-O-4 lignin model parts, mainly by electron transfer leading to vanillin as major product. By contrast, in presence of glucose, anthrahydroquinone units (formed by reduction of AQ) reduced the quinone-methide units (issued by dehydration of phenolic ß-O-4 lignin model part) mainly by electron transfer leading to guaiacol as major product. Both processes were distance dependent.

Supramolecular structure characterization of cellulose II nanowhiskers produced by acid hydrolysis of cellulose I substrates.

Cellulose II nanowhiskers (CNW-II) were produced by treatment of microcrystalline cellulose with sulfuric acid by both controlling the amount of H(2)SO(4) introduced and the time of addition during the hydrolysis process. The crystalline structure was confirmed by both XRD and (13)C CP-MAS NMR spectroscopy. When observed between crossed polarizers, the cellulose II suspension displayed flow birefringence and was stable for several months. The CNW-II nanowhiskers were significantly smaller than the cellulose I nanowhiskers (CNW-I) and had a rounded shape at the tip. The CNW-II average length and height were estimated by AFM to be 153 ± 66 and 4.2 ± 1.5 nm, respectively. An average width of 6.3 ± 1.7 nm was found by TEM, suggesting a ribbon-shape morphology for these whiskers. The average dimensions of the CNW-II elementary crystallites were estimated from the XRD data, using Scherrer's equation. A tentative cross-sectional geometry consistent with both XRD and NMR data was then proposed and compared with the geometry of the CNW-I nanowhiskers.

Edible bioactive fatty acid-cellulosic derivative composites used in food-packaging applications.

To develop biodegradable packaging that both acts as a moisture barrier and as antimicrobial activity, nisin and stearic acid were incorporated into a hydroxy propyl methyl cellulose (HPMC) based film. Fifteen percent (w/w HPMC) of stearic acid improved film moisture barrier. However, film mechanical resistance and film antimicrobial activity on Listeria monocytogenes and Staphylococcus aureus pathogenic strains were both reduced. This lower film inhibitory activity was due to interactions between nisin and stearic acid. The molecular interaction was modeled, and an equation was developed to calculate the nisin concentration needed to be incorporated into the film matrix to obtain a desired residual antimicrobial activity. Because the molecular interactions were pH dependent, the impact of the pH of the film-forming solution on film inhibitory activity was investigated. Adjusting the pH to 3 totally avoided stearic acid and nisin interaction, inducing a high film inhibitory activity.