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.

Assessing the suitability of recovering shrub biowaste involved in wildland fires in the South of Europe through torrefaction mobile units.

Several types of shrubs and oak inducing high wildland fire risk in the South of Europe were evaluated for their potential valorization through torrefaction. Biomasses were firstly characterized in terms of macromolecular and elemental composition. Lab-scale TGA-GC/MS torrefaction experiments allowed the in-depth study of the solid mass transformation and the production profile of 23 volatile species (200 to 300 °C at 3 °C·min-1 and 300 °C for 30 min). The proportion of the torrefied products (solid, CO, CO2, water and volatile species) was evaluated through mass balance in a lab-scale furnace under typical torrefaction conditions (300 °C, 40 min). The results show a similar characterization and behavior in torrefaction for oak and shrublands, and slightly different characteristics for fern. However, fern may grow separately from shrublands and is considered to present a low fire risk. This suggests that the in-situ direct valorization of these biomasses through torrefaction mobile units seems promising. However, other properties, such as density, flowability and grindability need to be studied to confirm the feasibility of the process. Regarding torrefaction products, a higher carbon content and an interesting increase in heating value were measured for the torrefied solid, which makes it suitable for energetic valorization, among other uses. The composition of permanent gases was evaluated and found in agreement with previous studies. Finally, the volatile species released were studied in function of the torrefaction temperature, in view of their possible valorization as green chemicals.

Evaluating river driftwood as a feedstock for biochar production.

Driftwood in river catchments might pose a hazard for the safety of infrastructures, such as dams and river dwellers, and thus is often removed. Génissiat dam in France presents a case study where annually approximately 1300 tons of driftwood are removed to prevent driftwood sinking and to protect the dam infrastructure. Collected river driftwood is rarely studied for utilization purposes and is commonly combusted or landfilled. However, driftwood can be valorized for biochar production through pyrolysis or hydrothermal carbonization (HTC). This study follows a novel approach in characterizing river driftwood by identifying the different common genera present at Génissiat dam on the upper Rhône, France. Moreover, the research provides for the first time a comprehensive analysis of river driftwood different physico-chemical properties, such as moisture content, major elemental composition (CHNSO), HHV, and macromolecular composition (cellulose, hemicellulose, lignin, and extractives). The study shows that the transportation of driftwood through rivers can enhance its properties by reducing the bark content resulting in lower ash content. Results indicate that driftwood can be mixed and further processed as a feedstock regardless of their genera and type for biochar production by pyrolysis or hydrothermal carbonization.

Molecular and phenotypic profiling from the base to the crown in maritime pine wood-forming tissue.

Environmental, developmental and genetic factors affect variation in wood properties at the chemical, anatomical and physical levels. Here, the phenotypic variation observed along the tree stem was explored and the hypothesis tested that this variation could be the result of the differential expression of genes/proteins during wood formation. Differentiating xylem samples of maritime pine (Pinus pinaster) were collected from the top (crown wood, CW) to the bottom (base wood, BW) of adult trees. These samples were characterized by Fourier transform infrared spectroscopy (FTIR) and analytical pyrolysis. Two main groups of samples, corresponding to CW and BW, could be distinguished from cell wall chemical composition. A genomic approach, combining large-scale production of expressed sequence tags (ESTs), gene expression profiling and quantitative proteomics analysis, allowed identification of 262 unigenes (out of 3512) and 231 proteins (out of 1372 spots) that were differentially expressed along the stem. A good relationship was found between functional categories from transcriptomic and proteomic data. A good fit between the molecular mechanisms involved in CW-BW formation and these two types of wood phenotypic differences was also observed. This work provides a list of candidate genes for wood properties that will be tested in forward genetics.

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.

TEMPO-mediated oxidation of cellulose III.

Various cellulose samples converted into cellulose III by two different ammonia treatments, either liquid or gaseous, were reacted with catalytic amounts of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO), sodium hypochlorite, and sodium bromide in water. A substantial increase in the reactivity of cellulose III samples was observed in comparison to those in cellulose I, and a relationship between oxidation conditions and cellulose primary hydroxyl groups accessibility was directly established. For the characterization, we have used several methods, mainly (13)C NMR, methylene blue adsorption, FTIR, and conductometric titration. In all samples, the primary alcohol groups were selectively oxidized into carboxyl groups, provided the sodium hypochlorite is added dropwise and the reaction is performed at constant pH 10.

Theoretical and experimental studies on the adsorption of aromatic compounds onto cellulose.

The adsorption of several aromatic compounds over microcrystalline cellulose was studied by molecular modeling and experimentally using gas chromatography. Experimental adsorption enthalpies were obtained from an equation based on Clausius-Clapeyron formalism and the temperature dependence of retention volume at infinite dilution. Four different cellulose surfaces (three crystalline (110, 100, and 010) and one amorphous) were modeled. Overall strong agreement was observed between the experimental and theoretical work with 84% of the adsorbate-cellulose systems having differences between measured and predicted values of less than 20%. Based on both calculated and experimental data, a morphology for the microcrystalline cellulose as a weighted combination of the four surfaces was proposed: 39% (110), 28% (100), 10% (010), and 23% amorphous. By adopting this distribution, differences between experimental and weighted average predicted adsorption energies were 10% or less for 14 out of 17 compounds; a maximum of 15% was observed for guaiacol. Experimental results for monosubstituted aromatic compounds revealed that adsorption enthalpies are related to the hydrophilic/hydrophobic character of the substituent groups: 3.5 kJ mol(-1) for a methyl group, 15.7 kJ mol(-1) for a double bond, 21.0 kJ mol(-1) for a methoxyl group, 22.8 kJ mol(-1) for a carbonyl group, and 27.6 kJ mol(-1) for a hydroxyl group. These tendencies were confirmed by modeling, except for the aldehyde carbonyl group, where an overestimation of 10.8 kJ mol(-1) was observed. Analysis of experimental and predicted adsorption enthalpies of multisubstituted aromatic compounds suggests that the efficiency of their interaction with cellulose depends on a compromise between the roughness of the cellulose surface and their conformational adaptability.