Unraveling the Lignin Structural Variation in Different Bamboo Species.

The structure of cellulolytic enzyme lignin (CEL) prepared from three bamboo species (Neosinocalamus affinis, Bambusa lapidea, and Dendrocalamus brandisii) has been characterized by different analytical methods. The chemical composition analysis revealed a higher lignin content, up to 32.6% of B. lapidea as compared to that of N. affinis (20.7%) and D. brandisii (23.8%). The results indicated that bamboo lignin was a p-hydroxyphenyl-guaiacyl-syringyl (H-G-S) lignin associated with p-coumarates and ferulates. Advanced NMR analyses displayed that the isolated CELs were extensively acylated at the γ-carbon of the lignin side chain (with either acetate and/or p-coumarate groups). Moreover, a predominance of S over G lignin moieties was found in CELs of N. affinis and B. lapidea, with the lowest S/G ratio observed in D. brandisii lignin. Catalytic hydrogenolysis of lignin demonstrated that 4-propyl-substituted syringol/guaiacol and propanol guaiacol/syringol derived from ß-O-4' moieties, and methyl coumarate/ferulate derived from hydroxycinnamic units were identified as the six major monomeric products. We anticipate that the insights of this work could shed light on the sufficient understanding of lignin, which could open a new avenue to facilitate the efficient utilization of bamboo.

Structural characterization of poplar lignin based on the microwave-assisted hydrothermal pretreatment.

Increasing application for lignin due to its unique aromatic structures has encouraged the development of pretreatment techniques for lignin separation and recovery. In this work, the integration of microwave-assisted hydrothermal pretreatment (MW-HTP) and alkaline post-treatment was proposed for separating lignin from poplar wood and revealing its structural characteristics. Results showed that the yields of the lignins fractionated via the integrated treatment based on MW-HTP were increased up to 52.6%, and their associated sugars contents were clearly decreased to 0.19-0.09%, as compared to the fractionated lignins without the microwave pretreatment (29.8% and 0.29%). Interestingly, the integrated treatment based on MW-HTP promoted the cracking of ß-O-4 ethers in the lignin macromolecules of poplar wood, resulting in the raise of their phenol OH groups up to 2.36 mmol/g. Overall, the fulfillment of this work will be conducive to improve the fractionation and efficient utilization of lignin in biorefinery industry.

Revealing the structural characteristics of lignin macromolecules from perennial ryegrass during different integrated treatments.

To reveal the structural characteristics and physicochemical properties of perennial ryegrass lignin, sequential alkali extractions or double ball-milling and enzymatic hydrolysis on the basis of ultrasonic and hydrothermal pretreatments were proposed in this study. Results revealed that sequential alkali extractions released 89.4% of original lignin from the ryegrass cell walls and 0.75-4.16% of associated carbohydrates as compared to the double ball-milling and enzymatic hydrolysis (96.0% and 18.39%). It was observed that the two types of lignin prepared were SGH-type and had different amounts of p-coumarates and ferulates, and primarily consisted of ß-O-4' linkages combined with minor amounts of ß-ß' and ß-5' linkages. Besides, alkali-soluble lignins exhibited relatively fewer ß-O-4' linkages, higher S/G ratios and H-type units, and abundant phenolic OH groups as compared to the double enzymatic lignin. Overall, the deeper investigation of the lignin structure of ryegrass will provide useful information for the efficient utilization of lignin macromolecules in biorefineries.

Enzymatic response of ryegrass cellulose and hemicellulose valorization introduced by sequential alkaline extractions.

BACKGROUND: In view of the natural resistance of hemicelluloses in lignocellulosic biomass on bioconversion of cellulose into fermentable sugars, alkali extraction is considered as an effective method for gradually fractionating hemicelluloses and increasing the bioconversion efficiency of cellulose. In the present study, sequential alkaline extractions were performed on the delignified ryegrass material to achieve high bioconversion efficiency of cellulose and comprehensively investigated the structural features of hemicellulosic fractions for further applications. RESULTS: Sequential alkaline extractions removed hemicelluloses from cellulose-rich substrates and degraded part of amorphous cellulose, reducing yields of cellulose-rich substrates from 73.0 to 27.7% and increasing crystallinity indexes from 31.7 to 41.0%. Alkaline extraction enhanced bioconversion of cellulose by removal of hemicelluloses and swelling of cellulose, increasing of enzymatic hydrolysis from 72.3 to 95.3%. In addition, alkaline extraction gradually fractionated hemicelluloses into six fractions, containing arabinoxylans as the main polysaccharides and part of ß-glucans. Simultaneously, increasing of alkaline concentration degraded hemicellulosic polysaccharides, which resulted in a decreasing their molecular weights from 67,510 to 50,720 g/mol. CONCLUSIONS: The present study demonstrated that the sequential alkaline extraction conditions had significant effects on the enzymatic hydrolysis efficiency of cellulose and the investigation of the physicochemical properties of hemicellulose. Overall, the investigation the enzymatic hydrolysis efficiency of cellulose-rich substrates and the structural features of hemicelluloses from ryegrass will provide useful information for the efficient utilization of cellulose and hemicelluloses in biorefineries.

Integrated treatment of perennial ryegrass: Structural characterization of hemicelluloses and improvement of enzymatic hydrolysis of cellulose.

An integrated treatment coupling ultrasonic and hydrothermal pretreatments with sequential alkali post-extractions was performed to isolate and characterize hemicelluloses from perennial ryegrass and improve the enzymatic hydrolysis efficiency of cellulose. The yield, chemical composition, and structure of water-soluble and alkali-soluble hemicelluloses obtained from the hydrothermal supernatant and hydrothermally pretreated ryegrass as well as the enzymatic hydrolysis efficiency of cellulose were comprehensively investigated by gel permeation chromatograph, high-performance anion exchange chromatography, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectra. Results showed that more than 90 % of the original hemicelluloses in ryegrass were released during the integrated treatment and all hemicellulosic fractions obtained were mainly composed of ʟ-arabino-(4-O-methyl-ᴅ-glucurono)-ᴅ-xylans, galactoanrabinoxylans and ß-glucans. In addition, the effective removal of amorphous hemicelluloses and lignin significantly increased the cellulose enzymatic hydrolysis rate of ryegrass from 43.8 to 91.1 %. These results provided new insights into the collaborative utilization of hemicelluloses and cellulose in ryegrass.

Changes of Chemical Composition and Hemicelluloses Structure in Differently Aged Bamboo ( Neosinocalamus affinis) Culms.

To study the differences in chemical composition analysis and spatial distribution of young Neosinocalamus affinis bamboo, we used the methods of standard of National Renewable Energy Laboratory and confocal Raman microscopy, respectively. It was found that the acid-soluble lignin and acid-insoluble lignin content showed an inverse relationship with the increasing bamboo age. Raman analysis revealed that Raman signal intensity of lignin in both the secondary cell wall and the compound middle lamella regions showed a similar increase trend with growth of bamboo. In addition, eight hemicellulosic fractions were obtained by successively treating holocellulose of the 2-, 4-, 8-, and 12-month-old Neosinocalamus affinis bamboo culms with DMSO and alkaline solution. The ratio of arabinose to xylose of hemicelluloses was increased with the growth of bamboo. FT-IR and NMR analyses revealed that DMSO-soluble hemicelluloses of young bamboo culms are mainly composed of highly substituted xylans and ß-d-glucans.

Structural variation of bamboo lignin before and after ethanol organosolv pretreatment.

In order to make better use of lignocellulosic biomass for the production of renewable fuels and chemicals, it is necessary to disrupt its recalcitrant structure through pretreatment. Specifically, organosolv pretreatment is a feasible method. The main advantage of this method compared to other lignocellulosic pretreatment technologies is the extraction of high-quality lignin for the production of value-added products. In this study, bamboo was treated in a batch reactor with 70% ethanol at 180 °C for 2 h. Lignin fractions were isolated from the hydrolysate by centrifugation and then precipitated as ethanol organosolv lignin. Two types of milled wood lignins (MWLs) were isolated from the raw bamboo and the organosolv pretreated residue separately. After the pretreatment, a decrease of lignin (preferentially guaiacyl unit), hemicelluloses and less ordered cellulose was detected in the bamboo material. It was confirmed that the bamboo MWL is of HGS type (p-hydroxyphenyl (H), vanillin (G), syringaldehyde (S)) associated with a considerable amount of p-coumarate and ferulic esters of lignin. The ethanol organosolv treatment was shown to remove significant amounts of lignin and hemicelluloses without strongly affecting lignin primary structure and its lignin functional groups.

Hydrothermal treatment and enzymatic hydrolysis of Tamarix ramosissima: evaluation of the process as a conversion method in a biorefinery concept.

The present work investigated the effects of hydrothermal treatment (HTT) of Tamarix ramosissima by determination of sugar and inhibitor formation in the liquid fraction, and chemical and morphological changes of the pretreated solid material coupled with an evaluation of enzymatic hydrolysis. HTT was carried out in a batch reactor system at a maximal temperature (TMAX 180-240 °C) and evaluated for severities logRo ranging from 2.40 to 4.17. The liquid fractions were analyzed by HPLC, GPC, and GC-MS. The morphology and composition of the solid residues were characterized using an array of techniques, such as SEM, XRD, BET surface area, and CP/MAS (13)C NMR. Using a variety of tools, we have developed a better understanding of how HTT process affects biomass structure and cellulose properties that impact on its digestibility. These results provided new insights into the factors limiting enzymatic digestibility and mechanism of biomass deconstruction during hydrothermal process.

Hydrothermal carbonization of lignocellulosic biomass.

Hydrothermal carbonization (HTC) is a novel thermochemical conversion process to convert lignocellulosic biomass into value-added products. HTC processes were studied using two different biomass feedstocks: corn stalk and Tamarix ramosissima. The treatment brought an increase of the higher heating values up to 29.2 and 28.4 MJ/kg for corn stalk and T. ramosissima, respectively, corresponding to an increase of 66.8% and 58.3% as compared to those for the raw materials. The resulting lignite-like solid products contained mainly lignin with a high degree of aromatization and a large amount of oxygen-containing groups. Liquid products extracted with ethyl acetate were analyzed by gas chromatography-mass spectrometry. The identified degradation products were phenolic compounds and furan derivatives, which may be desirable feedstocks for biodiesel and chemical production. Based on these results, HTC is considered to be a potential treatment in a lignocellulosic biomass refinery.

Structural characterization of lignins isolated from Caragana sinica using FT-IR and NMR spectroscopy.

In order to efficiently explore and use woody biomass, six lignin fractions were isolated from dewaxed Caragana sinica via successive extraction with organic solvents and alkaline solutions. The lignin structures were characterized by Fourier transform infrared spectroscopy (FT-IR) and 1D and 2D Nuclear Magnetic Resonance (NMR). FT-IR spectra revealed that the "core" of the lignin structure did not significantly change during the treatment under the conditions given. The results of 1H and 13C NMR demonstrated that the lignin fraction L2, isolated with 70% ethanol containing 1% NaOH, was mainly composed of beta-O-4 ether bonds together with G and S units and trace p-hydroxyphenyl unit. Based on the 2D HSQC NMR spectrum, the ethanol organosolv lignin fraction L1, extracted with 70% ethanol, presents a predominance of beta-O-4' aryl ether linkages (61% of total side chains), and a low abundance of condensed carbon-carbon linked structures (such as beta-beta', beta-1', and beta-5') and a lower S/G ratio. Furthermore, a small percentage (ca. 9%) of the linkage side chain was found to be acylated at the gamma-carbon.