Tuning the functional properties of lignocellulosic films by controlling the molecular and supramolecular structure of lignin.

This study investigated the relationships between lignin molecular and supramolecular structures and their functional properties within cellulose-based solid matrix, used as a model biodegradable polymer carrier. Two types of derivatives corresponding to distinct structuration levels were prepared from a single technical lignin sample (PB1000): phenol-enriched oligomer fractions and colloidal nanoparticles (CLP). The raw lignin and its derivatives were formulated with cellulose nanocrystals or nanofibrils to prepare films by chemical oxidation or pressure-assisted filtration. The films were tested for their water and lignin retention capacities, radical scavenging capacity (RSC) and antimicrobial properties. A structural investigation was performed by infrared, electron paramagnetic resonance spectroscopy and microscopy. The composite morphology and performance were controlled by both the composition and structuration level of lignin. Phenol-enriched oligomers were the compounds most likely to interact with cellulose, leading to the smoothest film surface. Their RSC in film was 4- to 6-fold higher than that of the other samples. The organization in CLP led to the lowest RSC but showed capacity to trap and stabilize phenoxy radicals. All films were effective against S. aureus (gram negative) whatever the lignin structure. The results show the possibility to tune the performances of these composites by exploiting lignin multi-scale structure.

Abiotic and enzymatic degradation of wheat straw cell wall: a biochemical and ultrastructural investigation.

The action of an abiotic lignin oxidant and a diffusible xylanase on wheat straw was studied and characterized at the levels of the molecular structures by chemical analysis and of the cell wall ultrastructure by transmission electron microscopy. While distinct chemical changes in the target polymers were observed when each system was used separately, a combination of the two types of catalysts did not significantly increase either lignin oxidation or hemicellulose hydrolysis. Microscopic observations however revealed that the supramolecular organization of the cell wall polymers was significantly altered. This suggests that the abiotic Mn-oxalate complex and the xylanase cooperate in modifying the cell wall architecture, without noticeably enhancing the degradation of the constitutive polymers.

Hydrolysis of wheat bran and straw by an endoxylanase: production and structural characterization of cinnamoyl-oligosaccharides.

Hydrolysis of wheat bran and wheat straw by a 20.7 kDa thermostable endoxylanase released 35 and 18% of the cell-wall xylan content, respectively. Separation of the cinnamoyl-oligosaccharides (accounting for 6%) from the bulk of total oligosaccharides was achieved by specific anion-exchange chromatography. The cinnamoyl-oligosaccharides were further purified by preparative paper chromatography (PPC) and their molecular weight was determined by MALDI-TOF mass spectrometry. The partially purified hydrolysis end-products contained from 4 to 16 and from 4 to 12 pentose residues for wheat bran and straw, respectively, and only one cinnamic acid per molecule. The primary structure of the new feruloyl arabinoxylopentasaccharide from wheat bran hydrolysis, which has been determined using 2D NMR spectroscopy, is O-beta-D-xylopyranosyl-(1-->4)-O-[5-O- (feruloyl)-alpha-L-arabinofuranosyl-(1-->3)]-O-beta-D-xylopyranosy l-(1-->4) -O-beta-D-xylopyranosyl-(1-->4)-D-xylopyranose.

Oxidation of spruce wood sawdust by MnO(2) plus oxalate: a biochemical investigation.

This paper reports the modification/degradation of lignin within spruce sawdust by manganese complexes formed by the association of MnO(2) and oxalate. The Mn oxidants formed are shown to modify both the chemical and physical properties of the wood cell wall. Scanning electron microscopy analysis of oxidized tracheids revealed a smoothing of the cell wall surface from the lumen side due to the removal of some material. Thioacidolysis analysis of the oxidized lignin showed reductions of up to 30% in the recovery of ether-linked guaiacyl monomers and up to 45% for the some dimers composing the polymer. The MnO(2)/oxalate system also slightly modified polysaccharides, corresponding to a 10% loss in weight of arabinose and glucose in the oxidized sample. However, no delignification occurred, according to the acid insoluble lignin content of spruce. Oxalic acid at pH 2.5 did not induce detectable changes in the chemical structures of the lignin or of the polysaccharides.

Is horseradish peroxidase a ligninolytic enzyme?

Structural modifications of spruce liginins catalyzed by plant horseradish peroxidase (HRP) were studied. Changes in lignin structure were characterized by monomeric composition determination and hydrodynamic property analysis. Results show that HRP modifies lignin monomeric composition without alteration of polymer gel permeation pattern. This indicates that HRP and LiP have similar but different biodegradative effects.

An improved method for the purification of lignin peroxidases from Phanerochaete chrysosporium INA-12: properties of two major isoforms.

1. Phanerochaete chrysosporium INA-12 secretes several lignin peroxidase isoenzymes. This paper reports an improved procedure for the purification of the different isoforms compared to those previously described. 2. Lignin peroxidases are first concentrated and prefractionated on fast-flow ion-exchangers which avoid concentration by ultrafiltration and dialysis. 3. Further purification is achieved by hydrophobic interaction chromatography and anion-exchange FPLC. 4. Two major forms were purified to homogeneity. Kinetic measurements and protein characterization (isoelectric points, phosphate content) suggest that they are similar to those produced by P. chrysosporium BKM strain.