The recently developed protocol for isolating enzymatic mild acidolysis lignins (EMAL) coupled with the novel combination of derivatization followed by reductive cleavage (DFRC) and quantitative (31)P NMR spectroscopy were used to better understand the lignin isolation process from wood. The EMAL protocol is shown to offer access at lignin samples that are more representative of the overall lignin present in milled wood. The combination of DFRC/(31)P NMR provided a detailed picture on the effects of the isolation conditions on the lignin structure. More specifically, we have used vibratory and ball milling as the two methods of wood pulverization and have compared their effects on the lignin structures and molecular weights. Vibratory-milling conditions cause substantial lignin depolymerization. Lignin depolymerization occurs via the cleavage of uncondensed beta-aryl ether linkages, while condensed beta-aryl ethers and dibenzodioxocins were found to be resistant to such mechanical action. Condensation and side chain oxidations were induced mechanochemically under vibratory-milling conditions as evidenced by the increased amounts of condensed phenolic hydroxyl and carboxylic acid groups. Alternatively, the mild mechanical treatment offered by ball milling was found not to affect the isolated lignin macromolecular structure. However, the overall lignin yields were found to be compromised when the mechanical action was less intense, necessitating longer milling times under ball-milling conditions. As compared to other lignin preparations isolated from the same batch of milled wood, the yield of EMAL was about four times greater than the corresponding milled wood lignin (MWL) and about two times greater as compared to cellulolytic enzyme lignin (CEL). Molecular weight distribution analyses also pointed out that the EMAL protocol allows the isolation of lignin fractions that are not accessed by any other lignin isolation procedures.
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"The residual lignin isolated from soda-AQ and k raft pulps cooked to kappa number 15 and 20 of the clone G1xUGL (isolated from the pulps by acidolysis) as well as the lignin precipitated from their respective black liquors were analyzed by two-dimensional nuclear magnetic resonance (2D-NMR). The isolation of MWL and their structural characteristics were compared to those of the milled wood lignin (MWL) isolated from the initial raw material, a lignin preparation that is still considered to be the representative of the native lignin in the plant, despite its limitations (Guerra et al., 2006; Rencoret et al., 2009). The isolation of MWL from wood of the eucalypt clone G1xUGL was previously described by Prinsen et al. (2012). "
[Show abstract][Hide abstract] ABSTRACT: Wood utilization for pulp and paper and biorefinery applications requires some kind of mechanical and/or physical-chemical pretreatment. Among the chemical treatments the alkaline ones are the most used worldwide, although acid and solvent treatments have also being used. This paper deals with eucalypt wood deconstruction with alkaline processes including soda-AQ, soda-AQ-O2, soda-O2, and kraft. The kraft process is largely used by the pulp industry and is evaluated here only to serve as a reference. The behavior of the four eucalypt clones selected in chapter 2 were investigated when submitted to the aforementioned processes regarding their screened yield, chemical demands and pulp quality at different kappa number levels (15, 35, 50, and 70). The two most promising processes (kraft and soda-AQ) were chosen for producing pulps (kappa 15 and 20) which were studied in depth (content of carbohydrates, uronic acid, hexenuronic acid, polysaccharide molecular weight, residual lignin structure, etc.), as well as their respective black liquors (heating value, solid content, elemental analysis, and lignin structure). The main findings of this work were: (1) the wood of the four different hybrid eucalypt clones behave similarly in the various alkaline deconstruction treatments; (2) the soda-AQ and Kraft were considered the most suitable processes for producing pulp on the basis of yield, chemical demands and pulp fiber integrity; (3) the soda-AQ process can potentially replace the kraft for a high degree of wood delignification (kappa number 15); (4) the alkaline processes using oxygen (soda-AQ-O2 and soda-O2) are more suitable for wood deconstruction aimed at biofuels; and (5) the soda-AQ process resulted black liquor of more suitable burning characteristics than the kraft.
Full-text · Article · Mar 2015 · Industrial Crops and Products
". " Isolation of lignin, " BioResources 9(3), 4382-4391. 4383 wood, and this isolation process offers higher yields and purities of lignin than those obtained by MWL and CEL (Guerra et al. 2006; Wu and Argyropoulos 2003). "
[Show abstract][Hide abstract] ABSTRACT: Ball-milled rice straw was dissolved in a lithium chloride/dimethyl sulfoxide (LiCl/DMSO) solvent system, regenerated, and subjected to enzymatic hydrolysis to obtain regenerated cellulolytic enzyme lignin (RCEL). The structure of the isolated lignin was characterized by elemental analysis, gel permeation chromatography (GPC), Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), and proton nuclear magnetic resonance (1 H NMR). Alkaline nitrobenzene oxidation (NBO) was conducted to analyze the structural characteristics of the in-situ lignin. The results showed that the rice straw RCEL was composed of p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) phenylpropane units, with relatively high amounts of H units. The yield of RCEL is about 5% units higher than that of cellulolytic enzyme straw lignin (CEL) on the basis of total lignin in the original rice straw. When compared to the CEL obtained by the traditional method, there were no observed differences versus RCEL in terms of the elemental compositions, NBO product yields, and S/G ratio. The weight-average molecular weight of RCEL was 6835, which was lower than that of CEL, indicating that some rice straw lignin linkages were cleaved during LiCl/DMSO dissolution.
"An EMAL lignin of switchgrass was employed as a control . EMAL has shown to be more representative of the total lignin present in biomass compared to the lignin extracted using other protocols such as milled wood lignin (MWL) or cellulolytic enzyme lignin (CEL) [36,37]. Lignin solutions were prepared in analytical grade N-methyl-2-pyrrolidinone (NMP) and dimethylsulfoxide (DMSO) (1:1, v/v) with sonication for 3 hours at 40°C. "
[Show abstract][Hide abstract] ABSTRACT: Background
The use of Ionic liquids (ILs) as biomass solvents is considered to be an attractive alternative for the pretreatment of lignocellulosic biomass. Acid catalysts have been used previously to hydrolyze polysaccharides into fermentable sugars during IL pretreatment. This could potentially provide a means of liberating fermentable sugars from biomass without the use of costly enzymes. However, the separation of the sugars from the aqueous IL and recovery of IL is challenging and imperative to make this process viable.
Aqueous alkaline solutions are used to induce the formation of a biphasic system to recover sugars produced from the acid catalyzed hydrolysis of switchgrass in imidazolium-based ILs. The amount of sugar produced from this process was proportional to the extent of biomass solubilized. Pretreatment at high temperatures (e.g., 160°C, 1.5 h) was more effective in producing glucose. Sugar extraction into the alkali phase was dependent on both the amount of sugar produced by acidolysis and the alkali concentration in the aqueous extractant phase. Maximum yields of 53% glucose and 88% xylose are recovered in the alkali phase, based on the amounts present in the initial biomass. The partition coefficients of glucose and xylose between the IL and alkali phases can be accurately predicted using molecular dynamics simulations.
This biphasic system may enable the facile recycling of IL and rapid recovery of the sugars, and provides an alternative route to the production of monomeric sugars from biomass that eliminates the need for enzymatic saccharification and also reduces the amount of water required.
Full-text · Article · Mar 2013 · Biotechnology for Biofuels