Inhomogeneities in the chemical structure of sugarcane bagasse lignin

Sequential treatments of dewaxed bagasse with distilled water, 0.5 M NaOH, 0.5, 1.0, 1.5, 2.0, and 3.0% H(2)O(2) at pH 11.5, and 2 M NaOH at 55 degrees C for 2 h solubilized 2.8, 52.5, 14.9, 3.3, 5.5, 5.0, 2.8, and 2.2% of the original lignin, respectively. The eight isolated lignin fractions were subjected to a comprehensive structural characterization by UV, FT-IR, and (1)H and (13)C NMR spectroscopies and thermal analysis. The nitrobenzene oxidation method was also applied to the in situ lignins. The seven lignin fractions, isolated successively with alkali and alkaline peroxide, were all SGH-type lignins, with a small amount of esterified p-coumaric acid and mainly etherified ferulic acid. No significant differences were found in the weight-average molecular weights (1680-2220 g/mol) of the seven alkali and alkaline peroxide dissolved lignins. However, the first four lignin fractions, isolated with 0.5 M NaOH and 0.5, 1.0, and 1.5% H(2)O(2) at pH 11.5, were rich in syringyl units and contained large amounts of noncondensed ether structures, whereas the last three lignin fractions, isolated sequentially with 2.0 and 3.0% H(2)O(2) at pH 11.5 and 2 M NaOH at 55 degrees C for 2 h, had a higher degree on condensation and were rich in guaiacyl lignins.     

Anatomy and cell wall polysaccharides of almond (Prunus dulcis D. A. Webb) seeds

The anatomy of Prunus dulcis was analyzed by applying several differential staining techniques and light microscopy. Prunus dulcis seed has a thin and structurally complex seed coat, with lignified cellulosic tissue. The embryo has two voluminous cotyledons. Cotyledon cells have a high number of protein and lipid bodies, some of which have phytin. The provascular tissue, located in the cotyledons, is oriented in small bundles perpendicular to the transverse embryonic axis. Prunus dulcis cell wall material is very rich in arabinose (45 mol %). Glucose (23%), uronic acids (12%), and xylose (12%) are also major sugar components. The polymers obtained from the imidazole and Na(2)CO(3) extracts contain mainly pectic substances rich in arabinose, but the sugar content of these extracts was very low. The majority of the pectic substances (also rich in arabinose) was recovered with the KOH extracts. These extracts, with high sugar content, yielded also xyloglucans and acidic xylans. The 4 M KOH + H(3)BO(3) extracts yielded polysaccharides rich in uronic acids and xylose and very rich in arabinose, accounting for 27% of the cell wall material.     

Olive fruit cell wall: degradation of cellulosic and hemicellulosic polysaccharides during ripening

Cellulose and hemicelluloses obtained from the cell walls of partially depectinated olives have been studied at three stages of ripening (green, cherry, and black). Hemicelluloses were fractionated into two groups, the amounts of which diminished during ripening: those soluble in 4% KOH diminished between the cherry and black stages, whereas those soluble in 24% KOH did so between the green and cherry stages. Arabinoxylans, xyloglucans, and homo- and/or rhamnogalacturonans to a lesser extent were present in these fractions. After ion exchange and size exclusion chromatographies, decreases in the molecular weights of hemicelluloses, mainly in the neutral fractions, were observed. The amount of cellulose also decreased, but at the second stage of the ripening process. Approximately 2 mg/fruit of glucose was lost from cellulose, and the amount of uronic acids increased (0.23 mg/fruit).     

Fractional and structural characterization of lignins isolated by alkali and alkaline peroxide from barley straw.

A sequential treatment of dewaxed barley straw with sodium hydroxide, different concentrations of hydrogen peroxide, and potassium hydroxide/sodium borate degraded various proportions of the original lignin and solubilized different amounts of the original hemicelluloses. The isolated lignin fractions were subjected to comprehensive structural characterization by UV, FT-IR, and (13)C NMR spectroscopy, and their chemical compositions were analyzed by alkaline nitrobenzene oxidation. All of the lignin fractions were typical of grass lignins and had weight-average molecular weights between 1750 and 2190. It was found that the peroxide treatment at low concentrations (< or =2.0%) resulted in a slight increase in the amount of carboxyl groups, whereas the treatment at a relatively high concentration of alkaline peroxide, such as at 3.0% H(2)O(2), led to a noticeable oxidation of the lignins, as shown by an increase of carboxyl groups. Moreover, the results obtained indicated that the successive treatments with alkali and alkaline peroxide under the conditions used did not significantly affect the beta-O-4 structures of lignins. Substantial amounts of etherified ferulic acids were cleaved by the sequential treatments with alkaline peroxide, as shown in the (13)C NMR spectra. The results underscore the structural differences between alkali- and alkaline peroxide-soluble lignins from barley straw.     

Characterization of dietary fiber lignins from fruits and vegetables using the DFRC method

Insoluble fiber fractions from 11 fruits and vegetables were investigated for their lignin composition using the derivatization followed by reductive cleavage (DFRC) methodology. To enrich lignin contents and to minimize polysaccharide excess that led to nonanalyzable DFRC chromatograms, the insoluble fibers were degraded by a carbohydrolases mixture. The residues that were found to be representative for the insoluble fiber lignins were analyzed. The investigated fibers differ considerably in their lignin contents and also in their lignin compositions. With the exception of radish fiber, only trace amounts (or none) of the products resulting from p-hydroxyphenyl units were detected. Lignins noticeably differed in the ratio of the DFRC products resulting from syringyl units (S) and guaiacyl (G) units (G/S ratios ranged from approximately 39 to 0.2). The insoluble fiber lignins were classified as G-rich lignins (G/S ratio > 3; carrot, spinach, kiwi, curly kale, radish, and asparagus), S-rich lignins (S/G ratio > 3; rhubarb), or balanced lignins (0.3 < G/S ratio < 3; pear, apple, small radish, and kohlrabi). Information about further structural characteristics, for example, cinnamyl endgroups, was obtained from the analysis of DFRC minor products.     

Isolation and characterization of cellulose obtained from ultrasonic irradiated sugarcane bagasse

Cell walls of sugarcane bagasse were first delignified with chlorite followed by ultrasonic irradiation and then by two-step sequential extractions at 23 degrees C with 15 and 18% KOH for 2 h, 15 and 18% NaOH for 2 h, 8 and 10% KOH for 12 h, and 8 and 10% NaOH for 12 h and by a single one-stage isolation with 10% KOH for 16 h and with 10% NaOH for 16 h, which released 79.4, 81.8, 83.6, 85.7, 61.5, and 65.6% of the original hemicelluloses, and subsequently yielded 50.7, 49.5, 48.6, 47.8, 57.2, and 55.4% of the cellulose, respectively. The six cellulosic preparations were free of bound lignin and had a purity of 77.1-90.1% with the intrinsic viscosity (eta), viscosity average degree of polymerization, and molecular weight (M(w)) ranging from 534.1 to 631.6 mL g(-1), from 1858.1 to 2238.2 mL g(-1), and from 301000 to 362600 g mol(-1), respectively. The structural features of the isolated six cellulosic samples were comparatively examined by Fourier transform infrared and cross-polarization/magic angle spinning (13)C NMR spectroscopy and X-ray diffraction, and their thermal stability was investigated by using thermogravimetric analysis. It was found that all of the cellulosic preparations have the typical cellulose I structure but the crystallinity of the SCB cellulose was lower than that of flax, cotton, and kenaf.     

Characterization of residual lignin after SO(2)-catalyzed steam explosion and enzymatic hydrolysis of Eucalyptus viminalis wood chips

The lignin component found in both water insoluble (WI) and water and alkali insoluble (WIA) fractions derived from SO(2)-impregnated steam-exploded eucalyptus chips (SEE) was isolated and characterized. Dioxane lignins with a sugar content lower than 2% (w/w) were obtained after each material was treated with commercial cellulases. The C9 formulas of both SEE-WI and SEE-WIA dioxane lignins were C(9)H(6.83)N(0.04)O(2.24)(OCH(3))(1.21)(OH(aro))(0.56)(OH(ali))(0. 77) and C(9)H(8.65)N(0.29)O(1.97)(OCH(3))(0.90)(OH(aro))(0. 46)(OH(ali))(1.02), respectively. The weight-average molecular weight (M(w)) of the SEE-WI lignin corresponded to 3.85 kDa, whereas the SEE-WIA lignin had an M(w) of 3.66 kDa for the same polydispersity of 2.4. The SEE-WIA lignin was shown to be more thermally stable than the SEE-WI lignin, requiring temperatures in the range of 520 degrees C for complete degradation. FTIR and (1)H NMR analyses of both untreated and peracetylated lignin fractions showed that (a) the alkali insoluble lignin contained a relatively higher degree of substitution in aromatic rings per C9 unit and that (b) alkaline extraction removed lignin fragments containing appreciable amounts of phenolic hydroxyl groups.     

Evolution of Organic Matter Within Sixty Days of Composting of Lignocellulosic Food Industry Waste in Malaysia

Empty fruit bunches (EFB), coffee grounds (CG), and palm oil mill sludge (POMS) were composted in the laboratory for 60 days in order to study the composting process of lignocellulosic food industry wastes. In the first part of the experiment, EFB, CG, and POMS were composted alone (composting of single lignocellulosic material), and in the second part, EFB was composted with CG (1EFB:1CG ratio) and POMS (1EFB:1POMS ratio). The effects of different turning frequencies on the physical and chemical properties of composting were observed and its relation with the degradation process was highlighted. Results showed that oil and grease were first degraded, followed by recalcitrant compounds like alpha-cellulose, hemicellulose, and lignin. Cellulose and hemicellulose were degraded mainly during the 60 days of composting, and the progressive reduction of the cellulose/lignin ratio proved that the main evolution of these wastes took place. It was observed that 3, 6, and 9 days of turning frequency did not affect the physicochemical properties of the compost. Composting EFB alone failed to achieve the required quality of maturity compost within 60 days, while CG and POMS recorded low in biological activity. Better results were shown in composting of EFB mixed with coffee grounds and POMS, the C/N ratio dropped to less than 20 by the 8th week of the composting period. Composting of mixed lignocellulosic materials showed larger changes compared to composting of single lignocellulosic material, reaching a C/N ratio below 20 within 8 weeks.     

Quantitative characterization of a hardwood milled wood lignin by nuclear magnetic resonance spectroscopy

The structure of Eucalyptus grandis milled wood lignin (MWL) was investigated by 2D 1H-13C HSQC, HMQC, and 1H-1H TOCSY correlation NMR techniques and by quantitative 13C NMR as well as by the permanganate oxidation degradation technique. The combination of 2D NMR and quantitative 13C NMR spectroscopy of nonacetylated and acetylated lignin preparations allowed reliable identification and calculation of the amount of different lignin structures. About 85% of side-chain moieties were estimated on the structural level. This information was substantiated by data on the quantity of various functional groups and interunit linkages as a whole. A modified method for calculation of the h:g:s ratio has been suggested and compared with previously suggested approaches. E. grandis MWL has been determined to have an h:g:s ratio of 2:36:62. The amounts of various phenolic/etherified noncondensed/condensed guaiacyl and syringyl moieties were approximately estimated. E. grandis MWL contained approximately 0.60/Ar of beta-O-4 moieties along with small amounts of other structural units such as pino/syringyresinol (0.03/Ar), phenylcoumaran (0.03/Ar), and spirodienone (0.05/Ar). The degree of condensation was estimated at approximately 21%; the main condensed structures are 4-O-5 moieties (approximately 0.09/Ar). The structure of E. grandis MWL was compared with those of other lignin preparations isolated from various hardwoods.     

Mild acetosolv process to fractionate bamboo for the biorefinery: structural and antioxidant properties of the dissolved lignin

Fractionation of lignocellulosic material into its constitutive components is of vital importance for the production of biofuels as well as other value-added chemicals. The conventional acetosolv processes are mainly focused on the production of pulp from woody lignocelluloses. In this study, a mild acetosolv process was developed to fractionate bamboo under atmospheric pressure to obtain cellulosic pulp, water-soluble fraction, and acetic acid lignin. The structural features of the lignins obtained under various conditions were characterized with elemental analysis, sugar analysis, alkaline nitrobenzene oxidation, gel permeation chromatography (GPC), (1)H nuclear magnetic resonance ((1)H NMR), and heteronuclear single-quantum coherence (HSQC) spectroscopy. As compared to milled wood lignin (MWL) of bamboo, acetic acid lignins had low impurities (carbohydrates 2.48-4.56%) mainly due to the cleavage of linkages between lignin and carbohydrates. In addition, acetic acid lignins showed a low proportion of syringyl (S) units. Due to the cleavage of linkages between lignin units, acetic acid lignins had weight-average molecular weights ranging from 4870 to 5210 g/mol, less than half that of MWL (13000 g/mol). In addition, acetic acid lignins showed stronger antioxidant activity mainly due to the significant increase of free phenolic hydroxyls. The lignins obtained with such low impurities, high free phenolic hydroxyls, and medium molecular weights are promising feedstocks to replace petroleum chemicals.     

Apoplastic pH and monolignol addition rate effects on lignin formation and cell wall degradability in maize

Monolignol polymerization rate and apoplastic pH and may influence the formation of lignin and its interactions in cell walls. Primary maize walls were artificially lignified by gradual "end-wise" or rapid "bulk" polymerization of coniferyl alcohol at pH 4 or 5.5. Lignification efficiency was greatest for end-wise polymers at pH 5.5 (90-98%), intermediate for bulk polymers formed at either pH (54-82%), and lowest for end-wise polymers at pH 4 (41-53%). End-wise polymers had about 2.2-fold more ether inter-unit linkages and 70% fewer end-groups than bulk polymers. Low pH enhanced the formation of ether linkages in end-wise but not in bulk polymers. Differences in lignin structure did not influence the enzymatic degradability of cell walls, but lowering apoplastic pH from 5.5 to 4.0 during lignification reduced cell wall degradability by 25%. Further studies indicated this pH-dependent depression in degradability was related to cell wall cross-links formed via lignin quinone methide intermediates.     

Chemical characterization of Klason lignin preparations from plant-based foods

To analyze the accuracy of the Klason lignin method as applied for the determination of lignin contents in plant based-food products, Klason lignin preparations from curly kale, pears, whole wheat grains, and corn bran were chemically characterized. Characterization included routine ash and protein determinations and the extraction of fat/waxes as well as cutin/suberin depolymerization and extraction of the liberated monomers. Fat/wax and cutin/suberin amounts in the Klason lignin preparations were determined gravimetrically, and their compositions were analyzed by using GC-MS. Typical fat, wax, and cutin (and suberin) constituents such as saturated and unsaturated fatty acids, hydroxy and/or epoxy fatty acids, and phenolic acids were identified in all samples, whereas the detection of long-chain hydrocarbons, alcohols, and ketones, sterols, stanols, and dioic acids was dependent on the sample analyzed. Estimation of the contribution of non-lignin compounds to the Klason lignin contents reduced the noncorrected Klason lignin contents of the insoluble fibers from 28.7% (kale), 22.8% (pear), 14.8% (wheat), and 9.9% (corn) to maximum lignin contents of 6.5% (kale), 16.4% (pear), 4.9% (wheat), and 2.3% (corn). These data demonstrate that certain commonly used statements such as "cereal brans are highly lignified" need to be revised.     

Fractionation of bagasse into cellulose, hemicelluloses, and lignin with ionic liquid treatment followed by alkaline extraction

Lignocellulose materials are potentially valuable resources for transformation into biofuels and bioproducts. However, their complicated structures make it difficult to fractionate them into cellulose, hemicelluloses, and lignin, which limits their utilization and economical conversion into value-added products. This study proposes a novel and feasible fractionation method based on complete dissolution of bagasse in 1-butyl-3-methylimidazolium chloride ([C(4)mim]Cl) followed by precipitation in acetone/water (9:1, v/v) and extraction with 3% NaOH solution. The ionic liquid [C(4)mim]Cl was easily recycled after concentration and treatment with acetonitrile. (1)H NMR analysis confirmed that there was no obvious difference between the recycled [C(4)mim]Cl and fresh material. Bagasse was fractionated with this method to 36.78% cellulose, 26.04% hemicelluloses, and 10.51% lignin, accounting for 47.17 and 33.85% of the original polysaccharides and 54.62% of the original lignin, respectively. The physicochemical properties of the isolated fractions were characterized by chemical analysis, high-performance anion exchange chromatography (HPAEC), gel permeation chromatography (GPC), Fourier transform infrared (FT-IR), and (1)H and 2D (13)C-(1)H correlation (HSQC) nuclear magnetic resonance spectroscopy. The results showed that the acetone-soluble lignin and alkaline lignin fractions had structures similar to those of milled wood lignin (MWL). The easy extraction of the noncellulose components from homogeneous bagasse solution and amorphous regenerated materials resulted in the relatively high purity of cellulosic fraction (>92%). The hemicellulosic fraction was mainly 4-O-methyl-D-glucuronoxylans with some α-L-arabinofuranosyl units substituted at C-2 and C-3.     

Chemical characterization of lignin and lipid fractions in kenaf bast fibers used for manufacturing high-quality papers

The chemical composition of lignin and lipids of bast fibers from kenaf (Hibiscus cannabinus) used for high-quality paper pulp production was studied. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of fibers showed a lignin with a high syringyl/guaiacyl ratio (5.4) and minor amounts of p-hydroxyphenyl units. Simultaneously, sinapyl and coniferyl acetates were also identified, indicating that this lignin is partially acetylated. p-Hydroxycinnamic acids were found in only trace amounts. The main lipids identified by GC/MS of extracts from kenaf fibers were series of long-chain n-fatty acids, waxes, n-alkanes, and n-fatty alcohols. Free and esterified sterols and triterpenols, steroid hydrocarbons, and steroid and triterpenoid ketones, as well as steryl glycosides, were also found. Finally, the fate of the main constituents of kenaf fibers in alkaline pulping was also investigated.     

Structural characterization of guaiacyl-rich lignins in flax (Linum usitatissimum) fibers and shives

The structural characteristics of the lignins from flax (Linum usitatissimum) fibers and shives were studied. Significant differences in the content and composition of the lignin from both parts were observed. The lignin contents were 3.8% in the fibers and 29.0% in the shives. Analysis by Py-GC/MS indicated a H:G:S molar ratio of 13:72:15 in the milled wood lignin (MWL) isolated from flax fibers and a molar ratio of 5:87:8 in the MWL isolated from flax shives. In addition, 2D-NMR showed a predominance of β-O-4' aryl ether linkages, followed by β-5' phenylcoumaran and β-β' resinol-type linkages in both MWLs, with a higher content of condensed linkages in flax shives. Thioacidolysis (followed by Raney nickel desulfurization) gave further information on the lignin units involved in the different linkages and confirmed the enrichment of G units. The thioacidolysis dimers released were similar from both lignins, with a predominance of the β-5' followed by β-1' and 5-5' structures.     

Ligno-Cellulose Composting: Case Study on Monitoring Oil Palm Residuals

Oil palm empty fruit bunches (EFB) composting is increasingly being considered by tropical farmers as a worthwhile alternative to direct spreading in the field. EFB are ligno-cellulose residues comprising 46% cellulose and 16.5% lignin with a high C:N ratio ranging from 45 to 70. In hot regions, it is essential to control variations in the water content of the substrate. This case study set out to optimize the EFB composting procedure by monitoring two key factors, namely the nutritional balance of the biomass and its water content. The trial was conducted on a composting platform belonging to the PT SMART Tbk company (Indonesia) in windrows comprising shredded EFB watered weekly with oil mill effluents. The quantity of effluent to be added was calculated so as to systematically top up to 60% humidity. The initial C:N ratio of the EFB was reduced by urea and/or ripe compost applications (seeding). Application times and rates were studied on two windrows, one in an open area, the other in an area sheltered by a roof to prevent over-rapid drying. After ten weeks the compost could be considered ripe for all the treatments; at that stage, composting had reduced the volume and initial weight of the fresh EFB by 85% and 50% respectively. The combined action of a temperature rise and windrow turning led to substantial water losses through evaporation, resulting in a sudden drop in windrow humidity at the start of composting. When rainfall was insufficient, effluent applications became essential. The total amount of effluent to be applied during composting (without rainfall) was around 3 m³ per initial tonne of EFB. This amount approximately corresponded to the standard effluents : EFB ratio in the oil mill. Inoculation of the mass of EFB to be composted with ripe compost had a significant effect on the speed with which the mixture was reduced. A urea application a fortnight after the start of fermentation seemed to be beneficial. The resulting compost had a good agronomic value. However, the mineral balance was considerably affected, as the nutrients provided by the effluents were poorly retained by the substrate, and partially lost in percolation water following the weekly watering operations. For instance, almost 50% of the phosphorus, 70% of the potassium, 45% of the magnesium and between 10% and 20% of the calcium theoretically applied were lost ten weeks into the trial. Better distribution of the effluent applications, combined with a system to recover the leachings, should substantially reduce these losses, while maintaining suitable humidity for microbial degradation.     

Identifying new lignin bioengineering targets: impact of epicatechin, quercetin glycoside, and gallate derivatives on the lignification and fermentation of maize cell walls

Apoplastic targeting of secondary metabolites compatible with monolignol polymerization may provide new avenues for designing lignins that are less inhibitory toward fiber fermentation. To identify suitable monolignol substitutes, primary maize cell walls were artificially lignified with normal monolignols plus various epicatechin, quercetin glycoside, and gallate derivatives added as 0 or 45% by weight of the precursor mixture. The flavonoids and gallates had variable effects on peroxidase activity, but all dropped lignification pH. Epigallocatechin gallate, epicatechin gallate, epicatechin vanillate, epigallocatechin, galloylhyperin, and pentagalloylglucose formed wall-bound lignin at moderate to high concentrations, and their incorporation increased 48 h in vitro ruminal fiber fermentability by 20-33% relative to lignified controls. By contrast, ethyl gallate and corilagin severely depressed lignification and increased 48 h fermentability by about 50%. The results suggest several flavonoid and gallate derivatives are promising lignin bioengineering targets for improving the inherent fermentability of nonpretreated cell walls.     

Chemical composition of abaca (Musa textilis) leaf fibers used for manufacturing of high quality paper pulps

The chemical composition of leaf fibers of abaca (Musa textilis), which are commonly used for high-quality paper pulp production, was thoroughly studied. The results revealed that the lignin content was 13.2% of the total fiber. The analysis of abaca fibers by pyrolysis coupled to gas chromatography-mass spectrometry (Py-GC/MS) released predominantly compounds arising from lignin and p-hydroxycinnamic acids, with high amounts of 4-vinylphenol. The latter compound was demonstrated to arise from p-coumaric acid by pyrolysis of abaca fibers in the presence of tetramethylammonium hydroxide, which released high amounts of p-coumaric acid (as the methyl derivative). Products from p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) propanoid units, with a predominance of the latter (H:G:S molar ratio of 1.5:1:4.9), were also released after Py-GC/MS of abaca fibers. Sinapyl and coniferyl acetates, which are thought to be lignin monomer precursors, were also found in abaca. The extractives content of the abaca fiber (0.4%) was low, and the most predominant compounds were free sterols (24% of total extract) and fatty acids (24% of total extract). Additionally, significant amounts of steroid ketones (10%), triglycerides (6%), omega-hydroxyfatty acids (6%), monoglycerides (4%), fatty alcohols (4%), and a series of p-hydroxycinnamyl (p-coumaric and ferulic acids) esterified with long chain alcohols and omega-hydroxyfatty acids were also found, together with minor amounts of steroid hydrocarbons, diglycerides, alpha-hydroxyfatty acids, sterol esters, and sterol glycosides.     

Potential antioxidant capacity of sulfated polysaccharides from the edible marine brown seaweed Fucus vesiculosus

Fucus vesiculosus was sequentially extracted with water at 22 degrees C (fraction 1 (F1)) and 60 degrees C (F2), and with 0.1 M HCl (F3) and 2 M KOH (F4) at 37 degrees C. Soluble fractions (42.3% yield) were composed of neutral sugars (18.9-48 g/100 g), uronic acids (8.8-52.8 g/100 g), sulfate (2.4-11.5 g/100 g), small amounts of protein (< 1-6.1 g/100 g), and nondialyzable polyphenols (0.1-2.7 g/100 g). The main neutral sugars were fucose, glucose, galactose, and xylose. Infrared (IR) spectra of the fractions showed absorption bands at 820-850 and 1225-1250 cm(-1) for sulfate. F1, F2, and F4 also exhibited an absorption band at 1425 cm(-1), due to uronic acids, and their IR spectra resembled that of alginate. F3 had an IR spectrum similar to that of fucoidan with an average molecular weight of 1.6 x 10(6) Da, calculated by molecular exclusion high-performance liquid chromatography. The presence of fucose in this polysaccharide was confirmed by (1)H NMR spectroscopy. This fraction showed the highest potential to be antioxidant by the ferric reducing antioxidant power (FRAP) assay, followed by the alkali- and water-soluble fractions. Sulfated polysaccharides from edible seaweeds potentially could be used as natural antioxidants by the food industry.     

Structural transformation of Miscanthus × giganteus lignin fractionated under mild formosolv, basic organosolv, and cellulolytic enzyme conditions

Detailed chemical structural elucidation of lignin fractions from Miscanthus × giganteus was performed by several analytical techniques. Mild formosolv, basic organosolv, and cellulolytic enzyme treatments were applied to isolate three lignin fractions (AL, BL, and CL, respectively), and their structural characterization was comparatively evaluated. Both non-destructive techniques [e.g., Fourier transform infrared (FTIR) spectroscopy, size-exclusion chromatography (SEC), and two-dimensional (2D) nuclear magnetic resonance (NMR)] and degradation methods [e.g., acidic hydrolysis, derivatization followed by reductive cleavage (DFRC), and thioacidolysis] were used. The analysis revealed that a certain amount of carbohydrates (12.8%) was associated with CL and partially led to its increased molecular weight determined by SEC before acetylation. β-O-4 linkages were determined to be the predominant interunits (82%), but also, extensively acylated structures were observed. Alkaline organosolv treatment significantly improved the purity of the lignin fraction (carbohydrate content of 1.0%) and basically kept the original structure of the lignin macromolecule. Under acidic conditions, not only the portion of aryl alkyl ether bonds were cleaved but also new carbon-carbon bonds were formed by condensation reactions, resulting in an increment of the lignin molecular weights. Guaiacyl units were more reactive toward condensation than syringyl units, which was evidenced by an increasing S/G ratio from 0.7 (CL) to 1.7 (AL).