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Summary: Epoxy resin is widely used in various fields of the national economy due to its excellent chemical and mechanical properties. Lignin is mainly derived from lignocelluloses as one of the most abundant renewable bioresources. Due to the diversity of lignin sources and the complexity as well as heterogeneity of its structure, the value of lignin has not been fully realized. Herein, we report the utilization of industrial alkali lignin for the preparation of low-carbon and environmentally friendly bio-based epoxy thermosetting materials. Specifically, epoxidized lignin with substituted petroleum-based chemical bisphenol A diglycidyl ether (BADGE) in various proportions was cross-linked to fabricate thermosetting epoxies. The cured thermosetting resin revealed enhanced tensile strength (4.6 MPa) and elongation (315.5%) in comparison with the common BADGE polymers. Overall, this work provides a practicable approach for lignin valorization toward tailored sustainable bioplastics in the context of a circular bioeconomy.

Abstract Rechargeable zinc (Zn) batteries have been regarded as a potential alternative for energy storage instrument, but the poor life‐span of Zn metal anodes restrain their commercial application. In this work, stripy Zn array (ZnSA) with preferential (002) crystal plane was designed and fabricated through the facile treatment with concentrated phosphoric acid. The depth of stripy array and the content of (002) plane were controlled through the optimization of etching time. The synergistic effect of stripy morphology and preferential crystal plane can increase the electroactive surface area, suppress the corrosion and hydrogen evolution of aqueous electrolyte, induce the horizontal growth along with basal (002) plane, and inhibit the formation of Zn dendrites. The as‐synthesized ZnSA electrodes can achieve ultra‐long lifespan of 2500 h at the current density of 2 mA cm−2 with a constant capacity of 2 mAh cm−2 and still maintain stable cycling of 1200 and 1400 h even at the higher current density of 10 mA cm−2 and plating/stripping depth of 5 mAh cm−2, respectively. This work proposes a facile and effective strategy to improve electrochemical performance of metallic Zn anodes and contributes to the commercial application of Zn ion batteries.

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 β-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.

Abstract Background Lignocellulosic biomass, which is composed of cellulose, hemicellulose and lignin, represents the most abundant renewable carbon source with significant potential for the production of sustainable chemicals and fuels. Current biorefineries focus on cellulose and hemicellulose valorization, whereas lignin is treated as a waste product and is burned to supply energy to the biorefineries. The depolymerization of lignin into well-defined mono-aromatic chemicals suitable for downstream processing is recognized increasingly as an important starting point for lignin valorization. In this study, conversion of all three components of Eucalyptus grandis into the corresponding monomeric chemicals was investigated using solid and acidic catalyst in sequence. Results Lignin was depolymerized into well-defined monomeric phenols in the first step using a Pd/C catalyst. The maximum phenolic monomers yield of 49.8 wt% was achieved at 240 °C for 4 h under 30 atm H2. In the monomers, 4-propanol guaiacol (12.9 wt%) and 4-propanol syringol (31.9 wt%) were identified as the two major phenolic products with 90% selectivity. High retention of cellulose and hemicellulose pulp was also obtained, which was treated with FeCl3 catalyst to attain 5-hydroxymethylfurfural, levulinic acid and furfural simultaneously. The optimal reaction condition for the co-conversion of hemicellulose and cellulose was established as 190 °C and 100 min, from which furfural and levulinic acid were obtained in 55.9% and 73.6% yields, respectively. Ultimately, 54% of Eucalyptus sawdust can be converted into well-defined chemicals under such an integrated biorefinery method. Conclusions A two-step process (reductive catalytic fractionation followed by FeCl3 catalysis) allows the fractionation of all the three biopolymers (cellulose, hemicellulose, and lignin) in Eucalyptus biomass, which provides a promising strategy to make high-value chemicals from sustainable biomass.

Abstract The removal of chromium (Cr) from wastewater by various adsorbents has been investigated. As compared with the commercial activated carbon, the biosorbents with inexpensive and high adsorption capacities are developed from lignocellulosic wastes. Lignin, existing in lignocellulosic biomass, is the second most abundant resource in nature. Recently, lignin-based bio-sorbents were served as an advanced novel material for the metal ions and dye adsorption from wastewater. It has showed several advantages in the wastewater treatments because of the low-cost, high adsorption capacity, easy recover, and possibility of metal recovery. In this review, the isolation of lignin from lignocellulosic biomass was summarized, and the structural characteristics of lignin were comparably analyzed. The modification of lignin was performed to obtain a large surface area, strong binding-site, and high and quick adsorption properties of lignin-based adsorption materials. The adsorption efficiency of Cr ions was found to be strongly dependent on the pH of the wastewater. To further illustrate the adsorption process, the structural changes and the interactions between the metal ions and the functional groups of the lignin-based biosorbents in the adsorption process should be further investigated. Once the cost-effective and high-efficiency modification techniques are developed, lignin-based adsorbents can be expected to be the most suitable alternatives for Cr ions removal from wastewater in industry. Graphical abstract Fractionational and structural characterization of lignin and its modification as biosorbents for efficient removal of chromium from wastewater.

Designing non-noble electrocatalysts with low-cost and efficient is crucial to the development of sustainable and clean energy resources. Here, we synthesized a novel S–CoSe2/CoMoO4 and O–CoSe2/CoMoO4hybrid electrocatalysts for the HER and OER, respectively. Possibly due to the synergetic chemical coupling effects between CoSe2/DETA and CoMoO4, and the introduction of S heteroatom and oxygen vacancy, this hybrid could expose enough active edges, and then promoted the constructed hybrid displayed superior hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic performance. The S–CoSe2/CoMoO4 sample afforded a current density of 10 ​mAcm-2 at a small overpotential of 177 ​mV and a small Tafel slope of 54 ​mV dec−1. Moreover, the oxidized CoSe2/CoMoO4 (O–CoSe2/CoMoO4) also displayed a remarkable catalytic property for OER with a small Tafel slope of 43 ​mV dec−1, as well as excellent stability in 1.0 ​M KOH. Therefore, this noble-metal-free and highly efficient catalyst enables prospective applications for electrochemical applications.

Abstract Background To increase the production of bioethanol, a two-step process based on hydrothermal and dilute alkaline treatment was applied to reduce the natural resistance of biomass. However, the process required a large amount of water and a long operation time due to the solid/liquid separation before the alkaline treatment, which led to decrease the pure economic profit for production of bioethanol. Therefore, four one-step processes based on order of hydrothermal and alkaline treatment have been developed to enhance concentration of glucose of wheat straw by enzymatic saccharification. The aim of the present study was to systematically evaluated effect for different one-step processes by analyzing the physicochemical properties (composition, structural change, crystallinity, surface morphology, and BET surface area) and enzymatic saccharification of the treated substrates. Results In this study, hemicelluloses and lignins were removed from wheat straw and the morphologic structures were destroyed to various extents during the four one-step processes, which were favorable for cellulase absorption on cellulose. A positive correlation was also observed between the crystallinity and enzymatic saccharification rate of the substrate under the conditions given. The surface area of the substrate was positively related to the concentration of glucose in this study. As compared to the control (3.0 g/L) and treated substrates (11.2–14.6 g/L) obtained by the other three one-step processes, the substrate treated by one-step process based on successively hydrothermal and alkaline treatment had a maximum glucose concentration of 18.6 g/L, which was due to the high cellulose concentration and surface area for the substrate, accompanying with removal of large amounts of lignins and hemicelluloses. Conclusions The present study demonstrated that the order of hydrothermal and alkaline treatment had significant effects on the physicochemical properties and enzymatic saccharification of wheat straw. The one-step process based on successively hydrothermal and alkaline treatment is a simple operating and economical feasible method for the production of glucose, which will be further converted into bioethanol.

In this study, lignin with fine structures and facile enzymatic saccharifying residue were successively dissociated based on the lignin-first biomass deconstruction strategy. In the lignin-first process, aldehyde-protected lignin fractions were firstly isolated by acid-catalyzed dioxane extraction in the presence of formaldehyde (FA) and acetaldehyde (AA) and then analyzed by advanced nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The optimized hydrogenolysis of the extracted lignin (LFA and LAA) resulted in a high yield (42.57% and 33.00%) of lignin monomers with high product selectivity (mainly 2,6-dimethoxy-4-propylphenol) (39.93% and 46.61%). Moreover, the cellulose-rich residues were saccharified into fermentable glucose for bioethanol production. The glucose yield of the substrate (RAA) reached to 75.12%, which was significantly higher than that (15.4%) of the substrate (RFA). In short, the lignin-first biomass deconstruction by adding AA is a promising and sustainable process for producing value-added products (energy and fine chemicals) from lignocellulosic biomass.

To achieve high value-added utilization of lignin extracted from the biorefinery process in the wood composite industry, binderless particle boards were manufactured by bamboo materials combined with alkaline lignin (AL) in various proportions under various hot-pressing conditions. To elucidate the reactivity and chemical transformations of lignin macromolecules during the hot-pressing process, lignin samples were isolated from the corresponding boards and characterized by high-performance anion-exchange chromatography (HPAEC), gel permeation chromatography (GPC), quantitative 31P-NMR, and 2D-HSQC NMR. The best bonding strength (1.36 MPa) of the binderless particle boards was obtained under the conditions of 180 °C, pressure 5 MPa, and lignin/bamboo mass ratio 0.4. The molecular weight of the lignin samples decreased from 3260 to 1420 g/mol during hot-pressing. The NMR results showed that the contents of β-O-4' and β-β' linkages were reduced and β-5' linkages were increased as the hot-pressing temperature rose. Simultaneously, the percentage of G-type and H-type lignins as well as the content of phenolic OH increased.

Lignin-based polyols were synthesized through microwave-assisted liquefaction under different microwave heating times (5–30 min). The liquefaction reactions were carried out using polyethylene glycol (PEG-400)/glycerol as liquefying solvents and 97 wt% sulfur acid as a catalyst at 140 °C. The polyols obtained were analyzed for their yield, composition and structural characteristics using gel permeation chromatography (GPC), Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectra. FT-IR and NMR spectra showed that the liquefying solvents reacted with the phenol hydroxyl groups of the lignin in the liquefied product. With increasing microwave heating time, the viscosity of polyols was slightly increased and their corresponding molecular weight (MW) was gradually reduced. The optimal condition at the microwave heating time (5 min) ensured a high liquefaction yield (97.47%) and polyol with a suitable hydroxyl number (8.628 mmol/g). Polyurethane (PU) foams were prepared by polyols and methylene diphenylene diisocyanate (MDI) using the one-shot method. With the isocyanate/hydroxyl group ([NCO]/[OH]) ratio increasing from 0.6 to 1.0, their mechanical properties were gradually increased. This study provided some insight into the microwave-assisted liquefied lignin polyols for the production of rigid PU foam.

Hydrogels have been widely studied as tissue engineering scaffolds due to their swelling capabilities in water and other physical properties. In this study, phosphatized PVAs of varying degrees were prepared by esterification of phosphoric acid, and a freeze-thaw technique was introduced to fabricate hydrogels from hemicelluloses, poly(vinyl alcohol phosphate) (P-PVA), and chitin nanowhiskers. The obtained hydrogels were characterized by Fourier transform infrared (FT-IR) spectrometry, scanning electron microscopy (SEM), X-ray diffraction (XRD), and CP/MAS 13C nuclear magnetic resonance; their swelling properties and compressive strength were also determined. The repeated freeze-thaw cycles induced physically crosslinked chain packing among the three polymers by hydrogen bonds. The results showed that the hydrogels possessed higher swelling ratio and mechanical strength when the PVA was phosphatized by phosphoric acid and urea and more hydroxyl groups were introduced into the polymer matrices. This suggested that hydrogels with good mechanical properties were prepared successfully by the freeze-thaw technique.

This study is aimed at achieving the optimum conditions of hydrothermal treatment and acetylation of Populus fiber to improve its oil sorption capacity (OSC) in an oil-water mixture. The characteristics of the hydrolyzed and acetylated fibers were comparatively investigated by FT-IR, CP-MAS 13C-NMR, SEM and TGA. The optimum conditions of the hydrothermal treatment and acetylation were obtained at170 °C for 1 h and 120 °C for 2 h, respectively. The maximum OSC of the hydrolyzed fiber (16.78 g/g) was slightly lower than that of the acetylated fiber (21.57 g/g), but they were both higher than the maximum OSC of the unmodified fiber (3.94 g/g). In addition, acetylation after hydrothermal treatment for the Populus fiber was unnecessary as the increment of the maximum OSC was only 3.53 g/g. The hydrolyzed and the acetylated Populus fibers both displayed a lumen orifice enabling a high oil entrapment. The thermal stability of the modified fibers was shown to be increased in comparison with that of the raw fiber. The hydrothermal treatment offers a new approach to prepare lignocellulosic oil sorbent.

Thermomechanical pulp (TMP) is used for fiber production in binderless boards industries. Milled wood lignin (MWL) and enzymatic mild acidolysis lignin (EMAL) isolated from raw material and from binderless boards (BB) were comparatively analyzed to investigate the effects of chemical changes on the bonding performance in BB. The results showed that acid-insoluble lignin of the BB were increased during the sodium silicate solution pretreatment after hot-pressing. The lignin fractions obtained were characterized by gel permeation chromatography (GPC), Fourier transform infrared (FT-IR) spectroscopy, and 1H-13C correlation heteronuclear single-quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy. Results showed that 31.1% of EMAL (based on Klason lignin) with low molecular weight (Mw=1630 g/mol) was isolated from the BB. The increased total phenolic OH groups (3.97 mmol/g) of EMAL from sodium silicate solution pretreated BB indicated that there was degradation of lignin and cleavage of lignin-carbohydrate linkages during hot-pressing. In addition, the content of β-O-4' aryl ether linkages of EMAL from the BB increased to 69.2%, which was higher than that of the untreated sample (60.1%). It was found that S units (syringyl-like lignin structures) were preferentially condensed by hot pressing over G (guaiacyl-like lignin structures) units, and the S/G ratio increased after the hot-pressing process.

The mechanism of hydrothermal liquefaction of cypress was investigated by examining the effects of temperature and retention time on the characteristics of the solid residues remaining after liquefaction. The solid residues were divided into acid-soluble and acid-insoluble residues. Results showed the polymerization reactions also mainly occurred at low temperatures. The reactive fragments transformed into acid-insoluble solid residue in the form of carbon and oxygen through polymerization reactions. The process of cellulose degradation consists of two steps: an initial hydrolysis of the more solvent- accessible amorphous region and a later hydrolytic attack on the crystalline portion. Hemicelluloses were decomposed into small compounds during the initial stage of the cypress liquefaction process, and then these compounds may rearrange through polymerization to form acid-insoluble solid residues above 240 °C. The higher heating value of the solid residues obtained from liquefaction at 260–300 °C was 23.4–26.3 MJ/kg, indicating that they were suitable for combustion as a solid fuel.

The demand for efficient utilization of biomass induces a detailed analysis of the fundamental chemical structures of biomass, especially the complex structures of lignin polymers, which have long been recognized for their negative impact on biorefinery. Traditionally, it has been attempted to reveal the complicated and heterogeneous structure of lignin by a series of chemical analyses, such as thioacidolysis (TA), nitrobenzene oxidation (NBO), and derivatization followed by reductive cleavage (DFRC). Recent advances in nuclear magnetic resonance (NMR) technology undoubtedly have made solution-state NMR become the most widely used technique in structural characterization of lignin due to its versatility in illustrating structural features and structural transformations of lignin polymers. As one of the most promising diagnostic tools, NMR provides unambiguous evidence for specific structures as well as quantitative structural information. The recent advances in two-dimensional solution-state NMR techniques for structural analysis of lignin in isolated and whole cell wall states (in situ), as well as their applications are reviewed.

In order to elucidate the reaction behavior of cellulose component in bagasse, the homogeneous phthalation of bagasse was investigated comparatively with the isolated cellulose in 1-allyl-3-methylimidazium chloride (AmimCl) with phthalic anhydride (PA) at the dosage of 10–50 mmol/g. The phthalation degrees of bagasse and the isolated cellulose were in the range of 5.66% to 22.71% and 11.61% to 44.11%, respectively. A phthalation degree increase of cellulose was proportional to phthalic anhydride dosage due to its regular macromolecular structure and followed the equation yPDI=0.004x-0.02. FT-IR and 2D HSQC NMR analyses confirmed the attachment of phthaloyl group. The phthalation reactivity of the three hydroxyls in the isolated cellulose followed the order of C-6 > C-2 > C-3, and the more selective phthalation to C-6 position was found in the cellulose component in bagasse. These results provide detailed understanding of the homogenous modification mechanism of lignocellulose.

Crude cellulose prepared from alkali-extracted sugarcane bagasse was subjected to a rapid purification treatment with a mixture of 80% acetic acid-68% nitric acid (10/1, v/v) at 120 °C for 15 min. The yields of the preparations decreased slightly from 57.3%-58.6% in the crude cellulose preparations to 50.3%-51.9% in the purified cellulose samples. The purification treatment removed large amounts of resistant hemicelluloses strongly associated to the cellulose. XRD analysis revealed that the structure of both the crude and purified cellulose was cellulose I. Compared to the crude cellulose, a slight increase in the crystallinity index of the purified cellulose was observed by FTIR, XRD, and CP/MAS 13C NMR analyses. In addition, SEM showed that the macrofibril surface of the crude cellulose was almost free of trenches, but many terraces, steps, and kinks formed in the preparations after the purification.

Six hemicellulosic samples were isolated from cell wall material of dewaxed sweet sorghum (Sorghum bicolor (L.) Moench) leaves by sequential extractions with distilled water, alkali, and organic alkali solvent. The samples were treated with water, 1% NaOH, and 60% ethanol. The organic alkali samples were treated with 1%, 3%, 5%, and 8% NaOH, which yielded 8.3%, 5.4%, 1.0%, 5.6%, 2.5%, and 4.9% hemicelluloses based on the dry initial sweet sorghum leaves, respectively, and resulted in a total release of 81% of all hemicelluloses originally present in the cell wall. The results indicated that water-soluble hemicelluloses contained noticeable amounts of glucose, arabinose, galactose, and xylose, and had a relatively lower molecular weight (17300 g/mol). The four alkali-soluble hemicellulosic fractions, rich in xylose, were more linear, and had higher molecular weights (48500-128000 g/mol) than those of the alkali organic-soluble hemicellulosic fraction. With an increase of NaOH concentration from 1% to 8%, the ratio of arabinose to xylose decreased from 0.29 to 0.01, which implied that the hemicelluloses obtained by the higher concentration of alkali appeared to be more linear. Based on the sugar analysis, Fourier transform infrared (FT-IR), and nuclear magnetic resonance (NMR) results, 4-O-methylglucuronoarabinoxylans were the major constituents of the hemicellulosic polymers.

The effects on both cellulose conversion rate and lactic acid yield were studied by adding inhibitors, including formic acid, acetic acid, furfural, and vanillin into the hydrolysate of steam-pretreated Lespedeza stalks. The results suggest that formic acid has a significant influence on the enzyme activity and poisoned bacterial cells, resulting in the reduction of cellulose conversion rate and lactic acid yield by 21% and 16.4%, respectively. Acetic acid showed a strong inhibition on simultaneous saccharification fermentation (SSF) process, but little effect on enzymatic hydrolysis. Hydrolysis and SSF were less affected by furfural and vanillin compared with weak acids. The lactic acid yield of Lespedeza stalks rinsed with water increased from 64.0% to 89.4%, and the time to reach the maximum concentration was shortened from 96 hours to 48 hours when compared with the unwashed materials.

Bagasse acetate butyrates were prepared homogeneously in 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) ionic liquid from ball-milled sugarcane bagasse by acylation with acetic anhydride and butyric anhydride. The parameters, including reaction temperature, reaction time, feeding method of adding anhydrides, the dosage of total anhydrides to SCB, and the molar ratio of acetic anhydride to butyric anhydride, were considered, and the extent of acylation was measured by weight percent gain (WPG). The results showed the positive effects of reaction duration and total anhydride dosage on WPG and the negative effects of reaction temperature and molar ratio of AA/BA on WPG. The feeding method of acetylation after butyrylation resulted in the increased WPG compared with acetylation before butyrylation. FT-IR and 1H–13C correlation 2D NMR (HSQC) studies provided evidence for acylation. The bagasse acetate butyrates showed increased thermal stability after acylation. This study provides a new way for high value-added utilization of renewable lignocellulosic biomass.

The hydrolytic potential of cellulases produced by Trichoderma viride, Trichoderma pseudokoningii, Trichoderma koningii, and Trichoderma reesei with addition of exogenous β-glucosidase was evaluated on cellulose of steam-pretreated Lespedeza. The T. viride enzyme achieved the highest glucose conversion (90.09%), while T. pseudokoningii cellulase achieved the highest ratio of cellobiose to glucose (4.94%) at the end of hydrolysis. Enzymatic adsorption on the substrate was evaluated on filter paper activity and β-glucosidase activity in the corresponding digest with the obtained T. cellulases. T. viride cellulase possessed an efficient adsorption-desorption on the substrate and reached the highest FPA difference (0.72 U/mL) among enzyme activities, indicating to its excellent hydrolysis capability. However, β-glucosidase in T. viride cellulase system showed close bonding on the substrate, suggesting that efficiencies of adsorption-desorption on the cellulose are different between the entire cellulase system and β-glucosidase. T. viride cellulase, with active endogenous β-glucosidase (1.60 U/mL), has compatible synergism with the additional exogenous β-glucosidase.

Sequential treatments of dewaxed Calamagrostis angustifolia Kom with water (60 ºC and 90 ºC), 70% ethanol, and 70% ethanol containing 0.2%, 1.0%, 2.0%, 4.0%, and 8.0% NaOH at a solid to liquid ratio of 1:25 (g/mL) at 80 ºC for 3 h yielded 36.2% soluble polysaccharides of the dry dewaxed material. The eight polysaccharide fractions obtained were comparatively studied by sugar analysis, GPC, FT-IR, 1H and 13C-NMR, and 2D-NMR (HSQC) spectroscopy. The results showed that the water-soluble polysaccharides might contain noticeable amounts of β-D-glucan, as well as some pectic substances and galactoarabinoxylan. 70% ethanol-soluble polysaccharide was mainly arabinogalactan. The five alkali-soluble hemicelluloses were mainly galactoarabinoxylans. The Ara/Xyl and Ara/Gal values of H5-H8 fractions decreased with the increment of NaOH concentration from 1.0% to 8.0%. Meanwhile, the molecular weights had a declining trend from ~60,000 to ~40,000 g/mol. The smaller sized and more branched polysaccharides tended to be extracted in the early stages under milder conditions, and the larger molecular sized and more linear hemicelluloses tended to be isolated under more highly alkaline conditions.

Cellulose-silica composite fiber samples have been successfully synthesized using cellulose solution, tetraethoxysilane, and NH3•H2O in ethanol/water mixed solvents at room temperature for 24 h. The cellulose solution was previously prepared by the dissolution of microcrystalline cellulose in a solvent mixture of N,N-dimethylacetamide (DMAc)/lithium chloride (LiCl). The effect of the tetraethoxysilane concentration on the product was investigated. The products were characterized by X-ray powder diffraction (XRD), thermogravimetric analysis (TG), differential scanning calorimetric analysis (DSC), scanning electron microscopy (SEM), Fourier transform infrared spectrometry (FT-IR), energy-dispersive X-ray spectrum (EDS), and cross polarization magic angle spinning (CP/MAS) solid state 13C-NMR. The morphology of the cellulose-silica composite fiber was investigated by SEM, while their composition was established from EDS measurements combined with the results of FT-IR spectral analysis and XRD patterns. The XRD, FT-IR and EDS results indicated that the obtained product was cellulose-silica composite fiber. The SEM micrographs showed that the silica particles were homogeneously dispersed in the cellulose fiber. The CP/MAS solid state 13C-NMR results indicated that the silica concentration had an influence on the crystallinity of the cellulose. This method is simple for preparation of cellulose-based composites.

As an initial step in an alternative use of woody biomass to produce bioethanol, this work was aimed at investigating the effect of hot compressed water (HCW) pretreatment within the temperature range 100 to 200 °C in a batch-type reactor on the structural changes of Tamarix ramosissima. The untreated and pretreated solid residues were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), solid-state cross polarization/magic angle spinning (CP/MAS), 13C NMR spectroscopy, and thermogravimetric analysis (TGA), as well as chemical methods. The results showed that HCW pretreatment solubilized mainly hemicelluloses and resulted in enriched cellulose and lignin content in the pretreated solids. It was found that the deposition of lignin droplets on the residual surfaces was produced during pretreatment under the hot water conditions above 140 °C. In addition, the removal of hemicelluloses and lignin re-localisation as a result of condensation reactions under the severe pretreatment condition may lead to an increase in cellulose crystallinity and thermal stability of biomass solid residues, thus consequently influencing the downstream digestibility of biomass for sugars and bioethanol production.

Triploid Populus tomentosa Carr. (Salicaceae) is a good alternative to meet the increasing need of the global pulp and paper industry. Meanwhile, the xylem of this species could be a useful bioresource to develop low molecular extractives with significant bioactive potential. In the present work, a phytochemical investigation on aqueous EtOH extractives of Triploid P. tomentosa xylem, by systematical performance of Sephadex LH-20 open column chromatography and Thin Layer Chromatography (TLC), resulted in the isolation of two phenolic acids (ρ-coumaric acid (I) and caffeic acid (II)), two flavonoids (apigenin (III) and luteolin (IV)), and three phenolic glucosides (salicortin (V), salireposide (VI) and populoside (VII)). The structure elucidation and determination of the isolated extractives were based on their spectroscopical data and physiochemical evidences. This was the first time to report the low molecular weight extractives of Triploid P. tomentosa. Various low molecular weight extractives from Triploid P. tomentosa xylem exhibited significant antioxidative activities by DPPH and hydroxyl radical scavenging assays.

Wood auto-hydrolysates (WAH) are obtained in the pulping process by the hydrothermal extraction, which contains lots of hemicelluloses and slight lignin. WAH and chitosan (CS) were introduced into this study to construct WAH-based films by the casting method. The FT-IR results revealed the crosslinking interaction between WAH and CS due to the Millard reaction. The morphology, transmittance, thermal properties and mechanical properties of composite WAH/CS films were investigated. As the results showed, the tensile strength, light transmittances and thermal stability of the WAH-based composite films increased with the increment of WAH/CS content ratio. In addition, the results of oxygen transfer rate (OTR) and water vapor permeability (WVP) suggested that the OTR and WVP values of the films decreased due to the addition of CS. The maximum value of tensile strengths of the composite films achieved 71.2 MPa and the OTR of the films was low as 0.16 cm3·μm·m−2·24 h−1·kPa−1, these properties are better than those of other hemicelluloses composite films. These results suggested that the barrier composite films based on WAH and CS will become attractive in the food packaging application for great mechanical properties, good transmittance and low oxygen transfer rate.

Ball-milled bamboo (Neosinocalamus affinis) was first treated under ultrasound at 20 oC in 95% ethanol solution for 0 to 50 min, dissolved in sodium hydroxide/urea solution (7% NaOH/12% urea) at –12 oC, and then extracted with ethanol and dioxane to isolate lignin. The structure of the isolated lignin was characterized with a set of wet chemical and spectroscopic methods, including UV, FT-IR, 13C NMR, and HSQC spectroscopies. The results showed that the lignin extracted from bamboo consisted of p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) type lignins with minor cinnamate units. The predominate lignin inter-units were β-O-4´ ether linkages, followed by phenylcoumaran and a lower proportion of resinol and spirodienone. It was also found that the ester groups of lignin were cleaved during the pretreatment process with cold alkaline solution.

Polyvinyl acetate emulsion adhesive has been widely used due to its good bonding performance and environmentally friendly properties. Indeed, the bonding performance can be further improved by copolymerizing with other monomers. In this study, the effect of the adjunction of redox initiator (hydrogen peroxide–tartaric acid, H2O2–TA) on the properties of the poly (vinyl acetate-butyl acrylate) (P (VAc–BA)) emulsion adhesive was investigated. With increasing dosage, the reaction became more complete and the obtained film was more compact, as identified via SEM. The core-shell structure of the emulsion particles was confirmed via TEM. Results indicate that while the initiator content increased from 0.5 to 1.0%, a clearer core-shell structure was obtained and the bonding strength of the plywood improved from 2.34 to 2.97 MPa. With the further incorporation of H2O2–TA (i.e., 1.5%), the bonding performance deteriorated. The optimum wood bonding strength (2.97 MPa) of the prepared P (VAc-BA) emulsion adhesive was even better than that (2.55 MPa) of a commercial PVAc emulsion adhesive, suggesting its potential application for the wood industry.

The lignin-carbohydrate complex (LCC) was isolated from milled wood lignin of 2- and 24-month-old crude bamboo (Neosinocalamus affinis) culms using acetic acid (AcOH) and then characterized. The results have shown that the LCC preparation from 2-month-old bamboo (L2) exhibited a slightly lower molecular weight than the LCC preparation from the 24-month-old bamboo (L24). Further studies using Fourier transform infrared spectroscopy (FT-IR) and heteronuclear single quantum coherence (2D-HSQC) NMR spectra analyses indicate that the LCC preparations included glucuronoarabinoxylan and G-S-H lignin-type with G>S>>H. The content of the S lignin units of LCC in the mature bamboo was always higher than in the young bamboo. Combined with sugar composition analysis, the contents of phenyl glycoside and ether linkages in the L24 preparation were higher than in the L2 preparation; however, there was a reverse relationship of ester LCC bonds in L2 and L24. Lignin–xylan was the main type of LCC linkage in bamboo LCCs. Lignin–lignin linkages in the LCC preparations included β-β, β-5 and β-1 carbon-to-carbon, as well as β-O-4 ether linkages, but β-1 linkages were not present in L2.

In this work an optimization of the solvent-free acetylation of cellulose with acetic anhydride under microwave heating with iodine as a catalyst was performed. The optimized parameters included the microwave irradiation power from 300 W to 800 W, the reaction time between 5 to 40 min, the reaction temperature from 80 to 130 °C, and the amount of iodine from 1 to 15 mol%. The extent of the acetylation was measured by yield and the degree of substitution (DS), which was determined by a back-titration method. Acetylated cellulose was characterized by FT-IR, CP/MAS 13C-NMR, WRXD, and thermogravimetric analysis. The results showed that within the range of catalyst amounts studied, the DS increased as the amount of iodine used increased, however, it was barely affected by microwave output. It was also found that the reaction time and temperature had an active influence on the extent of acetylation, however, this did not mean that at the higher temperature a better acetylation of cellulose would be obtained. The optimal reaction time and temperature found in this work were 30 min and 130 °C.

Lignocellulosic materials such as agricultural residues have been recog-nized as potential sustainable sources of mixed sugars for fermentation to bioethanol. To obtain a high overall ethanol yield and achieve an economically feasible production process, the removal of lignin and hemicelluloses improves the accessibility of cellulosic material to hydro-lytic enzymes and avoids the degradation products that are inhibitory to the yeast used in the subsequent fermentation. Technological advances, e.g., environmentally friendly removal of lignin and hemicelluloses from lignocellulosic biomass prior to fermentation of the librated glucose from cellulose into bioethanol, has the potential to provide for sustainable and cost effective production of biofuel.

Recently, more attentions have been focused on the exploration of hemicelluloses in the paper industry. In this work, xylan-grafted-polyacrylamide (xylan-g-PAM) biopolymers were synthesized by the graft copolymerization of xylan with acrylamide, and their interaction with fibers was also investigated to improve waste newspaper pulp properties with or without cationic fiber fines. The influences of synthesis conditions were studied on the grafting ratio and the grafting efficiency of biopolymers. Prepared biopolymers were characterized by FTIR, 13C NMR, TGA and rheology. It was found that the grafting of PAM on xylan was conductive to improve xylan properties, such as the solubility in water, rheological features, and thermal stability, and the maximum grafting ratio was achieved to 14.7%. Moreover, xylan-g-PAM could obviously enhance the mechanical properties of waste paper pulps. Xylan-g-PAM also played the dominant role in increasing the strength of paper in the combination with prepared cationic fine fibers. When the amounts of xylan-g-PAM and cationic fiber fines were 1.0 wt % and 0.5 wt %, the mechanical properties such as the tensile index was increased by 49.09%, tear index was increased by 36.54%, and the burst index was increased by 20.67%, when compared with the control handsheets. Therefore, xylan-g-PAM as the new biopolymer could be promising in the application of strength agents for the paper industry as well as cationic fiber fines.

Among the natural macromolecules potentially used as the scaffold material in hydrogels, xylan has aroused great interest in many fields because of its biocompatibility, low toxicity, and biodegradability. In this work, new pH and thermoresponsive hydrogels were prepared by the cross-linking polymerization of maleic anhydride-modified xylan (MAHX) with N-isopropylacrylamide (NIPAm) and acrylic acid (AA) under UV irradiation to form MAHX-g-P(NIPAm-co-AA) hydrogels. The pore volume, the mechanical properties, and the release rate for drugs of hydrogels could be controlled by the degree of substitution of MAHX. These hydrogels were characterized by swelling ability, lower critical solution temperature (LCST), Fourier-transform infrared (FTIR), and SEM. Furthermore, the cumulative release rate was investigated for acetylsalicylic acid and theophylline, as well as the cytocompatibility MAHX-based hydrogels. Results showed that MAHX-based hydrogels exhibited excellent swelling–deswelling properties, uniform porous structure, and the temperature/pH dual sensitivity. In vitro, the cumulative release rate of acetylsalicylic acid for MAHX-based hydrogels was higher than that for theophylline, and in the gastrointestinal sustained drug release study, the acetylsalicylic acid release rate was extremely slow during the initial 3 h in the gastric fluid (24.26%), and then the cumulative release rate reached to 90.5% after sustained release for 5 h in simulated intestinal fluid. The cytotoxicity experiment demonstrated that MAHX-based hydrogels could promote cell proliferation and had satisfactory biocompatibility with NIH3T3 cells. These results indicated that MAHX-based hydrogels, as new drug carriers, had favorable behavior for intestinal-targeted drug delivery.

The demand for substitution of fossil-based materials by renewable bio-based materials is increasing with the fossil resources reduction and its negative impacts on the environment. In this study, environmentally friendly regenerated cellulose films were successfully prepared using 1-allyl-3-methylimidazolium chloride (AmimCl), 1-butyl-3-methylimidazolium chloride (BmimCl), 1-ethyl-3-methylimidazolium chloride (EmimCl), and 1-ethyl-3-methylimidazolium acetate (EmimAc) as solvents, respectively. The results of morphology from scanning electron microscopy (SEM) and atomic force microscopy (AFM) showed that all the cellulose films possessed smooth, highly uniform, and dense surface. The solid-state cross-polarization/magic angle spinning (CP/MAS) 13C NMR spectra and X-ray diffraction (XRD) corroborated that the transition from cellulose I to II had occurred after preparation. Moreover, it was shown that the ionic liquid EmimAc possessed much stronger dissolubility for cellulose as compared with other ionic liquids and the cellulose film regenerated from EmimCl exhibited the most excellent tensile strength (119 Mpa). The notable properties of regenerated cellulose films are promising for applications in transparent biodegradable packaging and agricultural purpose as a substitute for PP and PE.

Acylated xylan-based magnetic Fe3O4 nanocomposite hydrogels (ACX-MNP-gels) were prepared by fabricating Fe3O4 nanoctahedra in situ within a hydrogel matrix which was synthesized by the copolymerization of acylated xylan (ACX) with acrylamide and N-isopropylacrylamide under ultraviolet irradiation. The size of the Fe3O4 fabricated within the hydrogel matrix could be adjusted through controlling the crosslinking concentrations (C). The magnetic hydrogels showed desirable magnetic and mechanical properties, which were confirmed by XRD, Raman spectroscopy, physical property measurement system, SEM, TGA, and compression test. Moreover, the catalytic performance of the magnetic hydrogels was explored. The magnetic hydrogels (C = 7.5 wt %) presented excellent catalytic activity and provided a sensitive response to H2O2 detection even at a concentration level of 5 × 10−6 mol·L−1. This approach to preparing magnetic hydrogels loaded with Fe3O4 nanoparticles endows xylan-based hydrogels with new promising applications in biotechnology and environmental chemistry.

Utilization of hemicelluloses from biomass energy is an important approach to explore renewable resources. A convenient, quick, and inexpensive method for the preparation of blended films from quaternized hemicelluloses (QH) and carboxymethyl cellulose (CMC) was introduced into this study. QH and CMC solution were first mixed to form homogeneous suspension, and then were dried under vacuum to fabricate the blended films. The FT-IR and XRD results indicated that the linkage between QH and CMC was due to the hydrogen bonding and electrostatic interaction. From the results of mechanical properties and water vapor permeability (WVP), the tensile strength of the blended films increased with the QH/CMC content ratio increasing in appropriate range, and the WVP of the blended films decreased. The maximum value of tensile strength of blend film achieved was 27.4 MPa. In addition, the transmittances of the blended films increased with the decreasing of QH/CMC content ratio. When the weight ratio (QH: CMC) was 1:1.5, the blend film showed the best light transmittance (45%). All the results suggested that the blended films could be used in areas of application in the coating and packaging fields from the good tensile strength, transmittance, and low WVP.