The mechanism of lignin carbohydrate complex formation by addition of polysaccharides on quinone methide (QM) generated during lignin polymerisation was investigated using a model approach. Dehydrogenation polymers (DHPs, lignin model compounds) were synthesized from coniferyl alcohol in the presence of a glucuronoarabinoxylan (GAX) extracted from oat spelts, by Zutropfverfahren (ZT) and Zulaufverfahren (ZL) methods. The methods ZT and ZL differed in their distribution of QM over the reaction period but generated roughly the same QM amount. Steric exclusion chromatography of the ZT and ZL reaction products showed that only the ZT reaction produced high molar mass compounds. Covalent linkages in the ZT reaction involving ether bonds between GAX moiety and alpha carbon of the lignin monomer were confirmed by (13)C NMR and xylanase-based fractionation. The underlying phenomena were further investigated by examining the interactions between GAX and DHP in sorption experiments. GAX and DHPs were shown to interact to form hydrophobic aggregates. In the ZT process, slow addition permitted polymer reorganisation which led to dehydration around the lignin-like growing chains thereby limiting the addition of water on the quinone methide formed during polymerisation and thus favoured lignin-carbohydrate complex (LCC) formation.

Well-dispersed suspensions are a prerequisite when preparing smooth model surfaces based on neutral bacterial cellulose nanocrystals (BCNs). However, neutral nanocrystal suspensions present pronounced particle aggregation. Carboxymethyl cellulose (CMC) or xyloglucan (XG) was therefore added to aggregated BCN suspensions. Turbidity measurements, polysaccharide content, and transmission electron microscopy (TEM) analysis revealed that aggregation of BCNs in CMC/BCN and XG/BCN suspensions is dependent on the concentration of CMC and XG in the suspensions. CMC enhances BCN dispersion above the concentration ratio of 0.05. In the case of XG, a better colloidal stability is observed above the concentration ratio of 0.5. Atomic force microscopy (AFM) investigations demonstrated that cellulose-based model surfaces, spin-coated from CMC/BCN or XG/BCN solutions, exhibited more uniform topography and less roughness than the reference BCN model surface.

Multilayered thin films have been prepared by means of the " spin-assisted electrostatic layer-by-layer self-assembly " method, in which cellulose nanocrystals (CN) and cationic xylans (CX) are alternatively deposited up to 10 times on a rotating silicon wafer. The film growth process was studied and the thickness increment was found to be equal to 23 nm per bilayer. This value is relatively high in comparison with that of previous studies. Atomic force microscopy revealed that the surface of the films consists of thick layers of CX, which are deposited as a compact network of aggregates on the CN layers. After a few deposition cycles, structural color appears. When the film is submitted to enzymatic hydrolysis of xylans, the thickness of the film decreases and a visible color change is induced. The sensitivity of the test was evaluated in comparison with a usual colorimetric measurement, which relies on the detection of reducing sugars set free by enzymatic hydrolysis. The assay sensitivity was found to be similar to that of the colorimetric method. The presented new method is simple, fast, and easy to use. These findings show that the method based on multilayer thin films might open new opportunities to optimize the screening assays for xylanase discovery.

This study aims at investigating the impact of ionic liquid extraction on lignin structure by studying the mechanism of lignin depolymerization in 1-ethyl-3-methylimidazolium acetate EMIM [OAc]) and comparing it with that of organosolv and milled wood methods. Ionic liquid mediated lignin (ILL) using EMIM[OAc]), ethanol organosolv lignin (EOL) and milled wood lignin (MWL) were isolated from Typha capensis (TC) and subjected to several analytical characterizations. Experimental data shows that ILL exhibited a relatively lower degree of condensation, lower aromatic C-C structures and a higher aliphatic OH with values of 0.42/Ar, 1.94/Ar and 1.33/Ar moieties compared with EOL values of 0.92/Ar, 2.22/Ar and 0.51/Ar moieties respectively. The ILL was depolymerized under mild conditions giving relatively higher β-aryl ether linkages content, higher molecular mass, and exhibited closer structures and reactivity to native lignin than EOL. These insights on TC lignin depolymerization in EMIM [OAc]) acetate may contribute to better value-addition of lignocellulosic biomass.

The sorption of arabinoxylan (AX) on bacterial cellulose was investigated by adding AX to the culture medium of Gluconacetobacter xylinus. The starting AX material was produced by alkaline extraction of oat spelts. To investigate the impact of varying AX quality, the residual lignin was reduced by ClO 2 bleaching. Furthermore, bleached and unbleached xylans were subjected to xylanase hydrolysis in order to produce fractions of varying molar mass. Of all samples only the water soluble fractions were used for sorption experiments. A reduced molar mass resulted in a lower sorption of AX to the cellulose, while the lignin content increased the sorption of AX on bacterial cellulose. The sorption of AX resulted in a reduction of bacterial cellulose crystallinity and cellulose Ia content. In combined treatments of AX with xyloglucan and b-glucan no synergistic effect of those polysaccharides on the AX sorption was found.

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During biomass fractionation, any native acetylation of lignin and heteropolysaccharide may affect the process and the resulting lignin structure. In this study, Typha capensis (TC) and its lignin isolated by milling (MWL), ionosolv (ILL) and organosolv (EOL) methods were investigated for acetyl group content using FT-Raman, 1 H NMR, 2D-NMR, back-titration, and Zemplén transesterification analytical methods. The study revealed that TC is a highly acetylated grass; extractive free TC (TC extr ) and TC MWL exhibited similar values of acetyl content: 6 wt % and 8 wt % by Zemplén transesterification, respectively, and 11 wt % by back-titration. In contrast, lignin extracted from organosolv and [EMIm][OAc] pulping lost 80% of the original acetyl groups. With a high acetyl content in the natural state, TC could be an interesting raw material in biorefinery in which acetic acid could become an important by-product.

Emulsions are usually metastable systems of two non-miscible phases stabilized by surface active species like surfactant molecules. Emulsions stabilized by solid colloidal particles adsorbed at the interface (Pickering emulsions) offer some competitive advantages with respect to classical emulsions. Most studies published up to now concern emulsions stabilized by inorganic (metallic oxides, exfoliated clays, carbonates and phosphates) or polymeric particles while biomass derived alternatives have only been explored to a limited extent. For the first time, we report the stabilization of emulsions by unmodified cellulose nanocrystals [1, 2] . Cellulose nanocrystals were produced from bacterial cellulose and used to form Pickering emulsions. We demonstrate by SEM that the nanocrystals are adsorbed at the oil/water interface. We also study the size distribution of the droplets that was found to range around 4μm in diameter with very narrow dispersity. The stability of the emulsions was also investigated. The fabrication of new armored microparticles exposing cellulose acicular nanocrystals from cellulose nanocrystals opens opportunities to build materials from low cost and environmental friendly resource.