Nicolas Brosse

Effect of autohydrolysis of Miscanthus x giganteus on lignin structure and organosolv delignification.

The influence of the operating conditions of Miscanthus x Giganteus autohydrolysis on the composition of the solid residues and hydrolysates was examined. Milled wood lignin (MWL) extracted after autohydrolysis treatments performed at the same severity but at different temperatures were studied by (13)C and (31)P NMR in order to obtain a more complete picture of the changes in lignin structure occurring during the autohydrolysis. It was proposed that (1) the lignin homolytical fragmentation route should be enhanced with an increase of the temperature of the autohydrolysis treatment and (2) addition of a catalytic amount of 2-naphthol during the autohydrolysis step not only enhanced the dissolution of lignin but also allowed a better recovery of the hemicellulose sugars. A combined process involving an optimized autohydrolysis step (carried out in presence or not of 2-naphthol) and a low severity ethanol organosolv treatment was described for the separation and recovery of lignin, cellulose and hemicelluloses.

Combination of enzymatic hydrolysis and ethanol organosolv pretreatments: Effect on lignin structures, delignification yields and cellulose-to-glucose conversion

Enzymatic pre-hydrolysis using the industrial enzymatic cocktail Cellulyve® was assessed as a first step in a pretreatment process of Miscanthus biomass involving an aqueous-ethanol organosolv treatment. (13)C and (31)P Nuclear Magnetic Resonance and size exclusion chromatography were used to analyze the cellulose and lignin before and after treatment. It was demonstrated that despite a very low impact on the fibre structure (observed by Scanning Electron Microscopy) and composition (in terms of sugars and polyphenolics content), the enzymatic pre-treatment disrupted the lignocellulosic matrix to a considerable extend. This weakening permitted enhanced removal of lignin during organosolv pulping and increased hydrolysability of the residual cellulosic pulp for the production of monomeric glucose. Using this combined treatment, a delignification yield of 93% and an enzymatic cellulose-to-glucose conversion of 75% were obtained.

Physico-chemical properties and thermal stability of microcrystalline cellulose isolated from Alfa fibres.

In this study, microcrystalline cellulose (Alfa-MCC) was extracted from Alfa fibres using acid hydrolysis method. The molecular weight of the cellulose samples was determined by gel permeation chromatography. The crystallinities were studied by means of X-ray diffraction and solid state cross polarization magic angle spinning (13)C nuclear magnetic resonance spectroscopy, revealing that Alfa-MCC was more crystalline than the native cellulose isolated from Alfa fibres. The morphology of the celluloses was investigated using scanning electron microscopy, showing a compact structure and a rough surface. Furthermore, a good thermal stability was shown for Alfa-MCC. Based on these analyses, Alfa-MCC showed tremendous potential use as composites reinforcing agent, foods stabilizer and pharmaceutical additive.

Influence of the gelator structure and solvent on the organisation and chirality of self-assembling fibrillar networks

Chromophoric probes of naphthalimide moieties enable evaluation of their assembling behaviour photophysically through fluorescence spectroscopy and microscopy, and circular dichroism. These experiments highlight the influence of the nature of the chemical substitution of the organogelator. Very interesting results were also obtained by performing CD experiments showing that the nature of the solvent should modify the chirality of self-assembled aggregates. Highly oriented network structures were observed in the gel state and disappeared in isotropic solution. Microfibrous self-aggregation of organogels is in situ observed via fluorescence and SHG imaging and confirmed by transmission electron microscopic analysis of the dried sample.

UPLC method for the determination of vitamin E homologues and derivatives in vegetable oils, margarines and supplement capsules using pentafluorophenyl column.

A sensitive and rapid reversed-phase ultra performance liquid chromatographic (UPLC) method for the simultaneous determination of tocopherols (α-, β-, γ-, δ-), tocotrienols (α-, β-, γ-, δ-), α-tocopherol acetate and α-tocopherol nicotinate is described. The separation was achieved using a Kinetex pentafluorophenyl (PFP) column (150 × 2.1mm, 2.6 µm) with both photodiode array (PDA) and fluorescence (FL) detectors that were connected in series. Column was thermostated at 42°C. Under a gradient system consisting of methanol and water at a constant flow rate of 0.38 mL min(-1), all the ten analytes were well separated in less than 9.5 min. The method was validated in terms of linearity, limits of detection and quantitation, precision and recoveries. Calibration curves of the ten compounds were well correlated (r(2)>0.999) within the range of 100 to 25,000 μg L(-1) for α-tocopherol acetate and α-tocopherol nicotinate, 10 to 25,000 μg L(-1) for α-tocotrienol and 5 to 25,000 μg L(-1) for the other components. The method is simple and sensitive with detection limits (S/N, 3) of 1.0 to 3.0 μg L(-1) (FL detection) and 30 to 74 μg L(-1) (PDA detection). Relative standard deviations for intra- and inter-day retention times (<1%) and peak areas (≤ 4%) were obtained. The method was successfully applied to the determination of vitamin E in vegetable oils (extra virgin olive, virgin olive, pomace olive, blended virgin and refined olive, sunflower, soybean, palm olein, carotino, crude palm, walnut, rice bran and grape seed), margarines and supplements.

Effect of different pretreatments on delignification pattern and enzymatic hydrolysability of miscanthus, oil palm biomass and typha grass

Cumulative pretreatments methods were evaluated for delignification ability and enzymatic digestibility using miscanthus (M×G), empty palm fruit bunch (EFB) and typha grass as feedstocks. Despite their close chemical composition, the three feedstocks unveiled quite different behavior under the same condition of pretreatment. Characterization of ethanol organosol lignins extracted from the three feedstocks by (13)C NMR and FTIR revealed information concerning S/G/H ratios which was important to rationalize the differences among the feedstock behavior. The S/G/H ratios for MxG, EFB and typha, were established to levels of ~52/44/4, ~68/30/2 and ~46/27/27 respectively. The xylans hydrolytic susceptibility were a major cause of difference in behavior of feedstock during the pretreatment process. The influence of the presence of naphthol during autohydrolysis on the delignification ability was studied. A good relationship was observed between S+H/G ratio and the scavenging effect of naphthol.

The Origin of Molecular Mobility During Biomass Pyrolysis as Revealed by In situ 1H NMR Spectroscopy

The thermochemical conversion of lignocellulosic biomass feedstocks offers an important potential route for the production of biofuels and value-added green chemicals. Pyrolysis is the first phenomenon involved in all biomass thermochemical processes and it controls to a major extent the product composition. The composition of pyrolysis products can be affected markedly by the extent of softening that occurs. In spite of extensive work on biomass pyrolysis, the development of fluidity during the pyrolysis of biomass has not been quantified. This paper provides the first experimental investigation of proton mobility during biomass pyrolysis by in situ (1)H NMR spectroscopy. The origin of mobility is discussed for cellulose, lignin and xylan. The effect of minerals on cellulose mobility is also investigated. Interactions between polymers in the native biomass network are revealed by in situ (1)H NMR analysis.

High resolution solid state 2D NMR analysis of biomass and biochar.

Solid state NMR methods are required to analyze biomass as a function of its chemical or biological treatment for biofuels, chemicals, or biochar production. The native polymers network in lignocellulosic biomass and other solid materials, such as coal, coke, or biochar, can hardly be analyzed by liquid state NMR due to their poor swelling ability without chemical modification. A (1)H-(13)C two-dimensional heteronuclear correlation (HETCOR) experiment with frequency-switched Lee-Goldburg (FSLG) irradiation is performed on a high field spectrometer (750 MHz). This method leads to previously unattained resolution for biomass and biochar and offers a unique ability to reveal their chemical composition. The formation of aromatic moieties from carbohydrates and lignin thermal conversion is clearly distinguished. This method can be applied to all other carbonaceous materials.

Biomass to Bioethanol: Initiatives of the Future for Lignin

Lignin, which is one of the most abundant natural materials, represents a vastly underutilized natural polymer. With the emerging necessity to develop alternative sustainable transportation fuels, bioethanol produced from lignocellulosic biomass is considered as a viable option to petroleum-derived fuels. The effective utilization of biomass feedstock necessitates the development of cost-effective pretreatment technologies that are necessary to separate the three main biopolymers (cellulose, hemicellulose, and lignin). One of the key issues concerning the pretreatment process is the full recovery of the feedstock through optimum utilization of all lignocellulosic components, including nonsugar compounds, as marketable products. Thus, availability of high-quality lignin in large quantities should stimulate development in new lignin applications in the fields of fibres, biodegradable polymers, adhesives, and surface treatment (rust converter).

Extraction, Characterization and Utilization of Organosolv Miscanthus Lignin for the Conception of Environmentally Friendly Mixed Tannin/Lignin Wood Resins

Lignin was extracted from Miscanthus × giganteus using two procedures: an aqueous-ethanol organosolv treatment and a two-step process involving a dilute acid pre-soaking step followed by an aqueous-ethanol organosolv treatment. The organosolv lignin was subjected to a comprehensive structural characterization by 13C and MALDI-TOF MS and used for the formulation of a green wood adhesive prepared with 100% natural resins. The best formulation was composed of 60% of mimosa tannin and 40% of glyoxalated lignin extracted using a 1-step organosolv treatment. This formulation, when applied to wooden test panels yielded good internal bond strength results, which was good enough to pass relevant international standard specifications for interior-grade panels.