Search

Rational design and facile preparation of low-cost and efficient catalysts for the selective converting of biomass-derived monosaccharides into high value-added chemicals is highly demanded, yet challenging. Herein, we first demonstrate a N doped defect-rich carbon (NC-800-5) as metal-free catalyst for the selective oxidation of d -xylose into d -xylonic acid in alkaline aqueous solution at 100 °C for 30 min, with 57.4% yield. The doped graphitic N is found to be the active site and hydroxyl ion participating in the oxidation of d -xylose. Hydroxyl ion and d -xylose first adsorb on NC-800-5 surface, and the aldehyde group of d -xylose is catalyzed to form germinal diols ion. Then, C–H bond break to yield carboxylic group. Furthermore, NC-800-5 catalyst shows high stability in recycled test.

Compressible and elastic carbon aerogels with low density, excellent conductivity, high porosity, and chemical stability have attracted much attention in wearable energy storage and sensing devices...

Ultralight and resilient carbon aerogels with high compressibility and fatigue resistance are of great interest in various applications, such as wearable pressure-sensing electronics and flexible energy storage systems. However, owing to the irrational structural design and uncontrollable carbonization process, fabricating carbon aerogels with both high mechanical performances and linear sensitivity from green biopolymers remains a great challenge. Herein, by engineering an ordered lamellar texture and stabilizing the structure during carbonization, an ultralight carbon aerogel (8.16 mg cm−3) with superior mechanical performances and high linear sensitivity is successfully fabricated from graphene oxide and water-soluble cellulose. The ordered, continuous, and waved-shaped lamellar architecture can efficiently transfer stress throughout the microstructure and thus endows the carbon aerogel with exceptionally high compressibility, resilience and structural stability. The as-prepared carbon aerogel maintains high resilience for more than 300 cycles under extremely high compression strain (99%). It also displays an ultrahigh linear sensitivity (15.8 kPa−1) in a wide pressure range (0–18 kPa), which enables it to detect tiny changes in human biosignals, exhibiting promising application in wearable electronics.

The aim of this study is to prepare functional hemicellulose (HC) films with flexibility, thermoplasticity and UV-shielding ability. HC was firstly esterified with vinyl benzoate and then reinforced with poly(vinyl alcohol) (PVA) and nano-zinc oxide (ZnO). After esterification, the solubility of benzoated HC (BH) increased, while the thermal stability decreased. Moreover, esterification could transform HC into crystalline nature and endow HC with tunable transition temperature (Tg). Adding equivalent mass of PVA and 1% ZnO increased the thermal stability of BH/PVA/ZnO films. XRD and DSC analyses showed the new crystalline structure and the decreased Tg of films, probably due to the interactions among BH, PVA and ZnO. From SEM, the cross sections of films were dense, rough, and were connected to form the network structure, promoting the uniform insertion of ZnO into the matrix. The films showed moderate tensile strength and good flexibility with the maximum elongation at break of 87.18%. In addition, the water vapor permeability (WVP) and oxygen permeability (OP) values of BH/PVA/ZnO film were 2.08 × 10−10 g/m s Pa and 0.95 cm3 μm/m2 d kPa, respectively. Moreover, the film with 1% ZnO exhibited excellent UV-shielding properties with the percentage blocking of UV-A and UV-B of 99.34% and 99.99%, respectively.

In surface-enhanced Raman scattering, Ag nanoparticles are broadly employed. However, their lack of oxidation resistance means that their performance diminishes and is difficult to repeat. In this study, with addition of xylan, Au–Ag core–shell and alloy nanoparticles were prepared. Besides functioning as a reducing and stabilizing agent for Au–Ag bimetal nanoparticles, xylan protected them from oxidation and aggregation and created hot spots between interconnected nanoparticles. By seed-mediated methods, Au–Ag hollow alloy and Au@Ag core–shell nanoparticles with different shell thicknesses were prepared. More spherical and larger core–shell nanoparticles were prepared by an optimized dosage of xylan without the generation of excess Ag nanoparticles. Furthermore, the Au@Ag nanoparticles showed enhanced stability against oxidation and corrosion by H2O2 with the packing of xylan. The Raman enhancement performance of xylan-capped Au@Ag nanoparticles with optimized shell thickness to 4-mercaptobenzoic acid wa...

Ancient papers, facing the threat of acidification, aging and microbial corrosion, need to be repaired due to their significance of history, art and culture research. In this work, a new and highly efficient approach was proposed to deacidify and strengthen aging paper by in-situ quaternization for the conservation, in which MgO nanoparticles dispersed in hexamethyldisiloxane was coated on the paper surface and the aqueous alkaline solution and the 2, 3-epoxypropyl trimethyl ammonium chloride/isopropyl alcohol/water mixture were sprayed in a closed reactor. Results showed that properties of ageing papers were improved after MSCE-8/2 treatment. The pH value was in the range of 7.5–9.0 and the maximum amount of alkali storage was 220 mmol/Kg. The tensile strength and folding endurance were increased by 28.05% and 80%, respectively. The fluctuation range of brightness and chromatic aberration was 0.14 and 1.27. Moreover, treated paper also had the great anti-bacteria and anti-aging effects.

Cellulose nanofibers (CNF) are considered to be a potential substrate of energy material for energy storage devices due to the foldable, lightweight, recyclable and environmentally friendly feature. However, the energy materials tend to distribute unevenly or fall off from CNF easily, resulting in the decrease of the devices’ overall performance. Here, for the first time, we used quaternized chitosan (QCS) as stabilizer and adhesive to in situ synthesize and deposite copper sulfide nanocrystals (CuS-NCs) on CNF and further obtained the conductive paper for flexible supercapacitors. In the presence of QCS, CuS-NCs deposited in situ on CNF can be capped and stabilized by the QCS molecular chains for uniform distribution, which is conducive to the capacitive behavior and electrochemical stability of composite paper. The result shows that the specific capacitance of the composite paper was as high as 314.3 F/g at a current density of 1 A/g, a high rate capacitance of 252.6 F/g was achieved even at a high current density of 10 A/g. It reveals that the composite paper exhibited better electrochemical performance than many other CuS-based electrode materials for supercapacitor. More importantly, the composite paper performed well in various folding state without changing much electrochemical performance. Therefore, this work provides a novel strategy to in situ fabricate paper-based electrode for next-generation flexible energy-storage system.

Although hierarchical porous carbons (HPCs) are greatly emphasized in electrochemical energy storage, it is still difficult to develop a facile and cost-effective method for fabricating HPCs. Herei...

There is an increasing demand for developing environment-friendly and cost-effective strategies to synthesize high-performance flexible supercapacitor electrode materials. Biomass-derived carbon materials are very promising and attractive candidates due to their outstanding advantages. Herein, we prepared a foldable composite electrode based on a chitosan-derived N-self-doped carbon sheet (N-CS) and a microfibrillated cellulose fiber (MCF) framework. The N-CS plays a key role in tailoring the electrochemical behavior of electrode, while the MCF framework offers a porous structure with excellent mechanical foldability. In situ PANI improves the conductivity of the MCF framework and provides abundant active redox sites for energy storage. This foldable composite electrode possesses a high specific areal capacitance of 1688.8 mF cm−2 (139.6 F g−1, 84.4 F cm−3) at 1 mA cm−2 and an energy density of 11.75 mW h cm−3 at a power density of 25 mW cm−3. Furthermore, benefitting from the mechanical foldability of the MCF framework, the composite can perform well in the folded state. Besides, as a PANI-containing electrode material, its long-term cycling stability is pretty good (more than 84% retention after 5000 cycles). Therefore, this work provides an environment-friendly, cost-effective and high-performance electrode material for foldable electronic devices.

Compressible carbon materials hold great promise for application in various wearable or flexible electronic devices because of their low density, chemical and thermal stability, and high electrical conductivity. However, it is a great challenge to fabricate a carbon material with excellent mechanical performance and high sensitivity due to the brittleness of carbon. In this work, we fabricate a high-performance and lightweight CNT/rGO–CNF carbon aerogel by two key strategies: (1) forming continuous and ordered wave-shaped rGO layers and (2) reinforcing the carbon layers. It is found that cellulose nanofibers (CNFs) play a very important role in enhancing the interaction of rGO and CNTs, while CNTs give rise to strong yet flexible wave-shape layers. Benefiting from the synergistic effect of CNTs and CNFs, the carbon aerogel exhibits ultrahigh compressibility (up to 95% strain), superior elasticity (94.6% height retention for 50 000 cycles), high sensitivity, and an ultralow detection limit for pressure (0.875 Pa). These advantages make it an excellent candidate for fabricating flexible wearable electronic devices for biosignal detection.

The biomass-based carbon nanofibers (CNFs) have been regarded as promising electrode materials for supercapacitors. However, the preparation of biomass-based hierarchically porous CNFs by electrospinning without any chemical and physical activation is still challenging, especially when using the whole components of lignocellulose. Herein, a feasible way to synthesize a hierarchically porous CNF by electrospinning of the blends of acetylated sugarcane bagasse (ASCB) and polyacrylonitrile (PAN) followed by carbonization is proposed. Degradation of ASCB during carbonization induced multiscale defects that led to the formation of hierarchical pores and introduced flexibility for the CNFs. The specific capacitance and areal capacitance of CNFs respectively were 289.5 F g−1 and 64.2 μF cm−2. The flexible all-solid-state symmetric supercapacitor (ASSC) derived from the CNFs showed high power density (1.26 kW kg−1) and energy density (56.0 W h kg−1), as well as high capacitance retention and great cycling stability. This synthetic strategy provides a practicable way to utilize the whole components of lignocellulosic biomass and explore its application on high-performance flexible electrode materials.

Colloidal lignin nanoparticles (LNPs) from low temperature acid hydrotropic fractionation (AHF) of poplar wood and commercial alkali lignin using p-Toluenesulfonic acid (p-TsOH) were directly mixed with PVA to make PVA/AHF-LNP nanocomposite films. p-TsOH itself acted as a plasticizer for PVA; however the application of p-TsOH alone reduced PVA film tensile strength and therefore toughness. At proper loadings of LNPs and p-TsOH, both the failure strain and tensile strength of PVA/AHF-LNP composites were improved. The formation of hydrogen bonding between the p-TsOH/AHF-LNP aggregates with hydroxyl groups on PVA molecular chains, and the breakage and reforming of p-TsOH/AHF-LNP aggregates, along with the nanophase crazing due to the presence of p-TsOH/AHF-LNP aggregates were identified as the main mechanisms for improving the toughness of PVA/AHF-LNP nanocomposite. The composite also had improved UV shielding performance and biodegradability due to the presence of p-TsOH and LNPs compared with neat PVA. This nanocomposite film could be used as biodegradable anti-ultraviolet packing film.

The efficient production of xylose and arabinose from glucose, is significant but technologically challenging. Herein, the conversion of glucose to pentose (xylose and arabinose) and formic acid was realized using non-toxic artificial zeolite and green solvent of γ-butyrolactone-H2O. The selective conversion of glucose to 5-hydroxymethylfurfural, pentose and furfural could be regulated by controlling Bronsted acid strength. The weak Bronsted acid could promote the formation of pentose, while strong Bronsted acid could lead to the formation of HMF and further degradation of pentose to furfural. The mechanism was investigated spectroscopically to add fundamental insights to the selective C1-C2 bond cleavage. The solvent of γ-butyrolactone-H2O reduced apparent activation energy by promoting the formation of active d -fructofuranose. The favorable yield reached to 54.3 % pentose and 54.7 % formic acid from glucose, while 95.6 % pentose and 96.8 % formic acid from fructose at 453 K for 1.5 h. This strategy offered a new utilization way of glucose in expanding the varieties of platform chemicals.

The use of aqueous ionic liquids as a pretreatment for enhancing enzymatic saccharification of lignocellulosic biomass is well-known, with a focus on lignin and hemicellulose removal. However, in-depth knowledge of changes in cellulose crystallinity during the pretreatment is limited. To this effect, detailed Fourier transform infrared (FT-IR) spectroscopy, cross-polarized magic angle spinning 13C nuclear magnetic resonance (CP/MAS 13C NMR), and X-ray diffraction (XRD) studies on sugar cane bagasse that has been pretreated with aqueous ionic liquids is presented. Secondary derivatives of FT-IR spectra and Gauss deconvolution of XRD patterns were applied to give a detailed understanding of the crystalline changes in sugar cane bagasse cellulose upon pretreatment. The results showed that aqueous ionic liquid pretreatment destroys the semicrystalline region of sugar cane bagasse cellulose, thus disordering the orientation of the cellulose crystallites.

The phthalation of bagasse was comparatively investigated with the isolated three main components in 1-allyl-3-methylidazium chloride (AmimCl) to reveal the reaction behavior of bagasse. In the present study, the reaction behavior of hemicelluloses during the homogeneous phthalation was extensively explored. The phthalation degree of hemicellulosic samples ranged from 16.37% to 52.14%. The reaction priority on the main and side chains of hemicelluloses were revealed by the changes of monosaccharide contents upon phthalation. The results indicated that side-chains of hemicelluloses were more easily phthalated than main-chains, and the phthalation of secondary hydroxyl groups on uronic acids was more difficult than that on neutral sugars. 13C NMR and HSQC analyses suggested the similar reactivity of the secondary hydroxyls at C-2 and C-3 positions in anhydroxylose units. These results provide more detailed understanding of the homogenous modification of lignocellulose.

Homogeneous esterification of lignocellulosic agro-forestry wastes is an efficient approach to transform the biomass into value-added biobased materials. However, the application of fatty acid anhydrides or acyl chlorides as esterified reagents would yield equivalent acids which lead to significant decomposition of lignocellulosic biomass. The present study proposed an alternative chemical approach to prepare bioplastics from lignicellulosic biomass. Sugar cane bagasse esters were prepared by transesterification with vinyl esters using 1-ethyl-3-methylimidazolium acetate as duel solvent and activator. Solution-stated NMR studies suggested that the polysacchirides were highly reactive during the homogeneous transesterification. The chemical mechanism of the transesterification was demonstrated to be a carbene mechanism, which subsequently transferred into the intermediate of 2-alkanoyl-dialkylimidazolium. The as-prepared sugar cane bagasse esters were found to be solvable in common solvents. Bioplastic fil...

In order to obtain new retention and drainage-aid agent, exfoliated xylan-g-QCS/MMT nanocomposites were prepared. Briefly, quaternized chitosan azide (QCS-N3) was intercalated into the layer of montmorillonite (MMT) to enlarge the interplanar gallery; subsequently, QCS-N3/MMT was grafted with xylan by click chemistry, during this process, the interlayer space of MMT was further increased till exfoliated. Subsequently, the exfoliated xylan-g-QCS/MMT was evaluated to act as retention and drainage-aid agent. The initial critical concentration of xylan-g-QCS/MMT was 0.01 mg/g in the adsorption behavior on cellulosic substrate. The maximum flocculation efficiency for CaCO3 was 37.41%. When dosages were about 0.01 mg/g, oSR values were the lowest. All these results show that retention and drainage-aid performance of xylan-g-QCS/MMT was better than only xylan, QCS or MMT. The study combined three kinds of natural resources to prepare organic/inorganic nanocomposites, providing a new method to develop papermaking additive and achieve high-value utilization of natural resources.

Although polysaccharide-based carbon quantum dots (CQDs) are widely used in the field of detection, most of the CQDs-based sensors only take advantage of their optical properties. In this work, considering the selectivity to target substance and reducibility of xylan-based CQDs, a high-sensitive sensor based on greenly synthesized CQDs-based nanocomposite was fabricated for dopamine (DA) detection. First, the CQDs prepared from xylan were used as the reductant and stabilizer to quickly synthesize silver nanoparticles (Ag NPs) and reduced graphene oxide (rGO), and then Ag@CQDs-rGO nanocomposite was obtained and loaded on glassy carbon electrode (GCE) to fabricate electrochemical sensor. The electrochemical sensing of DA is of great significance for studying and treating neurochemical diseases due to its potential feasibility in diagnostics. Under optimal conditions, the linear range for monitoring DA was from 0.1 to 300 μM with a limit of detection of 1.59 nM (S/N = 3). Finally, this sensor was successfully applied to detect DA in dopamine hydrochloride injection and bovine serum solution samples. The proposed strategy may broaden the application of polysaccharide-based CQDs and this sensor may provide a discriminative and sensitive analytical platform for DA clinical diagnostics and drug screening.

The per-O-acylation of xylan-type hemicellulose was firstly carried out in dimethylsulfoxide/N-methylimidazole (DMSO/NMI) at room temperature without additional catalyst. The optimum conditions for esterification of xylan was investigated in terms of the molar ratio of reagents to anhydroxylose units (AXU) in xylan and the kinds of esterification reagents to obtain a high degree of substitution (DS, 1.98) and weight percent gain (WPG, 86.88 %) of xylan esters. In this solvent system, NMI acted as a solvent, a base and an excellent catalyst, therefore, the per-O-acylation of xylan (DS of 1.98) was readily accomplished in DMSO/NMI system at room temperature. Structure elucidation of xylan esters was characterized by FT-IR and NMR (1H-NMR, 13C-NMR and HSQC). FT-IR and NMR analyses provided the direct evidence of per-O-acylation of xylan under the given conditions. Furthermore, HSQC revealed the higher reactivity of hydroxyls at C-2 position than those at C-3 position of xylan. The solubility of xylan in DMSO, DMF and CHCl3 improved after esterification. TGA/DTG indicated that the thermal stability of xylan increased after the esterification with anhydrides, while decreased with acyl chlorides, probably due to degradation and hydrolysis of the acylated xylan at the presence of by-product hydrochloric acid.

Sugarcane bagasse, lignocellulosic residue from the sugar industry, is an abundant and renewable bioresource on the earth. The application of ionic liquids in sugarcane bagasse biorefinery is gaining increasing interest. The homogeneous modification of sugarcane bagasse by free radical initiated graft copolymerization of acrylate monomers using 1-allyl-3-methylimidazolium chloride as solvent was performed. A variety of sugarcane bagasse graft copolymers with different weight percent gain were prepared via adjusting the monomer dosage. FT-IR studies confirmed the success in attaching the poly(acrylate) side chains onto sugarcane bagasse. Oil absorbency studies suggested that the sugarcane bagasse graft copolymers were potential biobased materials for effective treatment of ester-based oils. SEM studies showed that the sugarcane bagasse graft copolymers displayed a dense morphology structure. Thermogravimetric analysis demonstrated that the thermal stability of sugarcane bagasse decreased after the homogeneous modification by the graft copolymerization. The present study provides an alternative strategy to convert sugarcane bagasse into a value-added functional biobased material.

The aim of this study was to investigate the physicochemical properties of chitosan (CS) based composite films with the incorporation of hemicelluloses (HC). Films were obtained via direct immersion method and characterized in terms of structural and morphological properties by FT-IR, XRD, XPS, SEM and EDS. By combining with the increased HC loading efficiency (L) and swelling property (S) of films with the increased HC content to 5%, this study proved the increased hydrogen bond interactions between CS and HC. Films with the tensile strength of 32.81 ± 4.97 MPa and elongation at break of 39.63 ± 4.67% were obtained with 3% HC and 20% glycerol (GC). The water vapor permeability (WVP) of films developed with the increased HC and GC contents, while the oxygen permeability (OP) decreased. Moreover, antibacterial testing indicated that all films exhibited the increased growth inhibition against E. coli and S. aureus as increasing TiO2 content.

An effective and sustainable two-step route including a pre-carbonization and the subsequent pyrolysis/activation to improve pre-carbonization process was developed for synthesizing cornstalk derived hierarchical porous carbons (CHPCs), which showed high porosity (1.498 cm3 g−1 pore volume) and were rich in oxygen groups (15.63 %). The addition of LiCl/ZnCl2 as a green and non-toxic template led to tunable pore structure of carbon materials, which could tailor the pore structure by acting as a pore padding agent and minimizing the collapse of pore channels. Moreover, the subsequent activation further endowed the carbons with enlarged porosity, significantly improving the supercapacitance. The obtained CHPCs exhibited a satisfying specific mass capacity of 375 F g-1 at 0.5 A g−1 in 1 M H2SO4, and the corresponding symmetric supercapacitor set out a superior energy density of 21.6 W h kg−1 while power density is equal to 300 W kg−1, which could make a green light emitting diode (LED) bright for more than 3 min. This salt-template assisted synthesis can effectively enhance the energy storage capacity of HPCs by regulating the pore structure.

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.

An alternative transesterification with vinyl laurate (VL) was applied for chemical modification of hemicelluloses (HC) to prepare functional packaging films. Successful transesterification was confirmed by FT-IR and NMR. Semitransparent laurated HC (LHs) films were prepared by solvent casting method. SEM indicated the ordered honeycomb-patterned surface and the dense cross section of LHs films. The LHs films exhibited excellent hydrophobicity with water contact angle about 120° and the enhanced mechanical properties with tensile strength and elongation at break as 33.94 ± 3.09 MPa and 22.41 ± 2.87%, respectively. The water vapor permeability (WVP) and oxygen permeability (OP) values of LHs films ranged from 1.59 ± 0.07 to 2.23 ± 0.11 (10−10·g/m·s·Pa) and 1.21 ± 0.04 to 4.24 ± 0.30 (cm3·μm/m2·d·kPa), respectively. Moreover, the films had acceptable antioxidant activity. In terms of these properties, the shelf life of green chilies could be largely extended to 15 days after packing with LHs films.

Compressible and elastic carbon materials offer many advantages and have promising applications in various electronic devices. However, fabricating carbon materials with super elasticity, fatigue resistance, and high and wide-range linear sensitivity for pressure or strain remains a great challenge. Herein, a facile and sustainable route is developed to fabricate a carbon aerogel with not only superior mechanical performances but also exceptionally high and wide-range linear sensitivity by using chitosan as a renewable carbon source and cellulose nanocrystal as a nanoreinforcement or support. The as-prepared carbon aerogel with wave-shaped layers shows high compressibility, super elasticity, stable strain–current response, and excellent fatigue resistance (94% height retention after 50 000 cycles). More importantly, it demonstrates both an ultrahigh sensitivity of 103.5 kPa–1 and a very wide linear range of 0–18 kPa. In addition, the carbon aerogel has a very low detection limit (1.0 Pa for pressure and 0...

Esterification is a versatile way to produce the derivatives of lignocellulose with developed properties. However, the traditional heterogeneous esterification of lignocellulose suffered from the drawbacks of low efficiency, additional reaction medium and heating. In the present study, an efficient method was developed to produce the functionalized sugarcane bagasse (SCB) by ball milling without any additional solvents and heating. The effects of pulverization time, rotation speed, the kind of linear chain anhydrides, the ratio of anhydrides to SCB, with or without pyridine catalyst and the dosage of catalyst were investigated on weight percent gain (WPG) of SCB esters. The results indicated that the high efficiency of this mechanocatalystic esterification was probably due to the destroyed crystalline structure and the promoted penetration of the esterifying reagent onto SCB bulk caused by ball milling. The maximum WPG of SCB acetate, propionate and butyrate reached 33.3%, 33.6% and 32.4%, respectively. The physicochemical structure of the esterified SCB was characterized with Fourier transform infrared spectra (FT-IR), solid state cross-polarized magic angle spinning 13C nuclear magnetic resonance (CP/MAS 13C-NMR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The direct evidence of the esterification occurrence was provided with FT-IR and solid-state CP/MAS 13C-NMR. The thermal stability of SCB increased upon the mechanocatalytic esterification. The results implied that the relatively homogeneous modification was achieved with this semi-homogeneous esterification method by ball milling.

The hydrogels obtained from renewable resources have aroused great interests because they are nontoxic, economical, biodegradable, and biocompatible. Hemicellulose is the second most abundant polysaccharides after cellulose in lignocellulosic biomass. In recent years, hemicellulose-based hydrogels as biomaterials have received ever-increasing attention and they have a wide range of the promising applications in drug delivery and release, waste treatment, dye adsorption, and tissue engineering because of their peculiar physicochemical properties. This paper described the structure of hemicellulose in plant and its physical-chemical prosperities, and summarized the type of hemicellulose-based hydrogels and their potential application, which provide useful information for the utilization of hemicellulose polymers.

Recently, IL/cosolvent systems have generated a lot of interest as cellulose-dissolving solvents and reaction media for various kinds of cellulose modification. In the present study, both 1-allyl-3-methylimidazolium chloride (AmimCl)/dimethyl sulfoxide (DMSO) and AmimCl/N,N-dimethylformamide (DMF) systems were employed to synthesize cellulose acetate by transesterification. Microcrystalline cellulose, 1,8-diazabicyclo[5.4.0]undec-7-ene and isopropenyl acetate were chosen as the raw material, catalyst and acetylation reagent, respectively. The results revealed that DMSO was a suitable cosolvent for the transesterification in the homogeneous solution. Moreover, DMSO had a positive effect on the reaction as the cosolvent under the given conditions and the degree of the substitution of cellulose acetate could be significantly enhanced through increasing the molar ratio of DMSO. The synthesized products were characterized by Fourier transform infrared (FT-IR) spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy (1H-NMR and 13C-NMR), correlation spectroscopy (COSY), heteronuclear single quantum correlation (HSQC) spectroscopy, and X-ray diffraction (XRD) to confirm the chemical and physical structure of the cellulose acetate generated. The thermal properties were also evaluated using thermogravimetric analysis (TGA)/derivative thermogravimetry (DTG).

The esterification of bagasse with glutaric anhydride could increase surface adhesion compatibility and the surface of derived polymers has the potential of immobilizing peptides or proteins for biomedical application. Due to its complicated components, the esterification mechanism of bagasse esterified with glutaric anhydride in ionic liquids has not been studied. In this paper, the homogenous esterification of bagasse with glutaric anhydride was comparatively investigated with the isolated cellulose, hemicelluloses, and lignin in 1-allyl-3-methylimidazolium chloride (AmimCl) to reveal the reaction mechanism. Fourier transform infrared (FT-IR) indicated that the three components (cellulose, hemicelluloses, and lignin) were all involved in the esterification. The percentage of substitution (PS) of bagasse was gradually improved with the increased dosage of glutaric anhydride (10–40 mmol/g), which was primarily attributed to the increased esterification of cellulose and hemicelluloses. However, the PS fluctuation of lignin led to a decrease in the PS of bagasse at high glutaric anhydride dosage (50 mmol/g). The esterification reactivity of bagasse components followed the order of lignin > hemicelluloses > cellulose. The esterification mechanism was proposed as a nucleophilic substitution reaction. Nuclear magnetic resonance (NMR) analysis indicated that lignin aliphatic hydroxyls were prior to be esterified, and primary hydroxyls were more reactive than secondary hydroxyls in cellulose and hemicelluloses.

Recently, organic catalysis has become a powerful alternative to the use of more traditional metal-based catalysts. In this study, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were applied to mediate the ring-opening graft polymerization (ROGP) of p-dioxanone (PDO) with xylan-based hemicelluloses in ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). Excellent control of the molar ratio of the catalyst to anhydroxylose units (AXU) in xylan was found for a good tuning of the weight percent gain (WPG) of xylan-graft-poly(p-dioxanone) (xylan-g-PPDO) copolymers. As a result, the maximum WPG of xylan-g-PPDO copolymers was 431.07% (DMAP/AXU of 2/1), 316.72% (DBU/AXU of 0.2/1), and 323.15% (TBD/AXU of 0.2/1), respectively. The structure of xylan-g-PPDO copolymers was characterized with FT-IR and NMR. The thermal properties of copolymers were investigated using thermogravimetric analysis (TGA/DTG) and differential scanning calorimetry (DSC), and a significant difference was observed regarding the transition temperature (Tg), melting temperature (Tm), and crystallization temperature (Tc).

The alcoholic depolymerization and Mannich reaction were conducted to improve the chemical activity of biorefinery technical lignins and introduce amino groups into lignins, respectively. To understand the chemical structural transformations and examine the reaction mechanism, GPC and solution-state NMR techniques were performed. Element analysis was also used to quantify the amount of amine groups. The NMR characterization the depolymerized lignins indicated of the depolymerization, demethoxylation, and bond cleavage of linkages occurred during the depolymerization process. Results showed that the depolymerization temperature instead of the addition of capping reagents was the main factor for improving the reactivity of lignin under the given conditions. The Mannich reaction was very selective, primarily occurred at H3,5 and G5 positions, and the H units present a higher chemical reactivity. It is believed that the understanding of the fundamental chemistry of lignin during depolymerization and Mannich reaction process will contribute to the extension of high value-added applications of biorefinery lignin.

The phthalation of bagasse was investigated comparatively with the three main isolated components in 1-allyl-3-methylidazium chloride (AmimCl) to reveal the reaction behavior of bagasse. In the first two parts, the detailed changes of cellulosic and hemicellulosic components in bagasse were elucidated during phthalation. In Part 3, the phthalation of lignins was performed in AmimCl with various ratios of phthalic anhydride/lignins from 10 to 50 mmol/g. The phthalation degree ranged from 41.1% to 68.8% for the phthalated lignins. The aliphatic hydroxyls of lignins were more easily phthalated than the phenolic hydroxyls as revealed by 31P nuclear magnetic resonance (NMR) analysis. Fourier transform infrared spectroscopy (FT-IR) and two dimensional (2D) heteronuclear single quantum correlation (HSQC) confirmed the attachment of phthaloyl group onto lignins. Severe degradation of lignin macromolecules was found at high ratios of phthalic anhydride/lignins (30 to 50 mmol/g) by gel permeation chromatography (GPC) analysis. These results provide a detailed understanding of reaction behaviors of lignins during bagasse phthalation, which are beneficial to prepare composites based on phthalated lignocellulose with better properties.

Ring-opening graft polymerization (ROGP) of l-Lactide (l-LA) is a practical method of altering the physical and chemical properties of lignocellulose. Previous studies have mainly investigated cellulose and tin-based catalysts, particularly of tin(II) 2-ethylhexanoate (Sn(oct)2), at high temperatures and reported low graft efficiencies. In the present study, ROGP of l-LA was successfully achieved on xylan-type hemicelluloses in ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl) using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an effective organic catalyst. Mild reaction condition (50 °C) was used to limit transesterification, and thus enhance the graft efficiency. The hydroxyl groups on xylan acted as initiators in the polymerization, and DBU, enhanced the nucleophilicity of the initiator and the propagating chain. Xylan-graft-poly(l-Lactide) (xylan-g-PLA) copolymer with a degree of substitution (DS) of 0.58 and a degree of polymerization (DP) of 5.51 was obtained. In addition, the structures of the xylan-g-PLA copolymers were characterized by GPC, FT-IR and NMR, confirming the success of the ROGP reaction. Thermal analysis revealed that the copolymers exhibited a single glass-transition temperature (Tg), which decreased with increasing molar substitution (MS). Thus, modification resulted in the graft copolymers with thermoplastic behavior and tunable Tg.

The preparation of cellulose laurate was investigated through transesterification in 1-allyl-3-methylimidazolium chloride (AmimCl)/dimethyl sulfoxide (DMSO) cosolvent system by using vinyl laurate as an acylation reagent and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an effective catalyst. The effects of reaction temperature, reaction time and the molar ratio of vinyl laurate to anhydride glucose unit (AGU) were investigated. The degree of substitution (DS) ranged from 1.47 to 2.74 under the selected conditions and the reaction order of three hydroxyl groups was C-6 > C-3 > C-2. The chemical structure cellulose laurate were explored by Fourier transform infrared (FT-IR) spectroscopy, 1H-nuclear magnetic resonance (NMR), 13C NMR, heteronuclear single quantum correlation (HSQC) and X-ray diffraction (XRD) to confirm the occurrence of transesterification. The improved thermal stability of cellulose laurate was proved by the thermogravimetric analysis (TGA). The tensile analysis and the contact angle measurement confirmed the ductile behavior and the hydrophobicity of the films made from cellulose laurate.

A feasible approach was developed to produce furfural from the pre-hydrolysis liquor of corncob via biochar catalysts as the solid acid catalyst in a new biphasic system with dichloromethane (DCM) as the organic phase and the concentrated pre-hydrolysis liquor (CPHL) containing NaCl as the aqueous phase. The biochar catalyst possessing many acidity groups (SO3H, COOH and phenolic OH groups) was prepared by the carbonization and sulfonation process of the corncob hydrolyzed residue. The influence of the catalytic condition on furfural yield and selectivity was comparatively studied. It was found that 81.14% furfural yield and 83.0% furfural selectivity were obtained from CPHL containing 5wt% xylose using this biochar catalyst in the CPHL-NaCl/DCM biphasic system at 170°C for 60min. In addition, with the regeneration process, this catalyst displayed the high performance and excellent recyclability.

Xylan-based temperature/pH sensitive hydrogels were prepared by the crosslinking copolymerization of xylan with N-isopropylacrylamide (NIPAm) and acrylic acid (AA) using N,Ń-methylenebis-acrylamide (MBA) as a cross-linker and 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator via ultraviolet irradiation. The influence of the NIPAm, AA and MBA amount on properties of xylan-based hydrogels was discussed. The morphology and interactions of hydrogels were characterized by SEM and FTIR. The lower critical solution temperature (LCST) of hydrogels was investigated by DSC. The results indicated that the LCST of hydrogels emerged at around 34°C and increased with increasing the AA content. The drug encapsulation efficiency of as-prepared hydrogels reached to 97.60% and the cumulative release rate of acetylsalicylic acid was 90.12% and 26.35% in the intestinal and gastric fluid, respectively. Xylan-based hydrogels were proved to be biocompatible with NIH3T3 cell by MTT assay and showed the promising application as drug carriers for the intestinal-targeted oral drug delivery.

Development of high-strength hydrogels has recently attracted ever-increasing attention. In this work, a new design strategy has been proposed to prepare graphene oxide (GO)/polyacrylamide (PAM)/aluminum ion (Al(3+) )-cross-linked carboxymethyl hemicellulose (Al-CMH) nanocomposite hydrogels with very tough and elastic properties. GO/PAM/Al-CMH hydrogels were synthesized by introducing graphene oxide (GO) into PAM/CMH hydrogel, followed by ionic cross-linking of Al(3+) . The nanocomposite hydrogels were characterized by means of FTIR, X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray analysis (SEM-EDX) along with their swelling and mechanical properties. The maximum compressive strength and the Young's modulus of GO3.5 /PAM/Al-CMH0.45 hydrogel achieved values of up to 1.12 and 13.27 MPa, increased by approximately 6488 and 18330 % relative to the PAM hydrogel (0.017 and 0.072 MPa). The as-prepared GO/PAM/Al-CMH nanocomposite hydrogels possess high strength and great elasticity giving them potential in bioengineering and drug-delivery system applications.

The maleation of bagasse could greatly increase the compatibility between bagasse and composite matrixes, and the percentage of substitution (PS) of bagasse maleates could be regulated in the homogeneous system. However, due to the complicated components and the linkages of bagasse, it was difficult to control the reaction behaviors of each component. In this paper, the detailed structural changes of bagasse during the homogeneous maleation in ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) were comparatively investigated with the three main components (cellulose, hemicelluloses, and lignin) from bagasse. The PS of the maleated bagasse was 12.52%, and the PS of the maleated cellulose, hemicelluloses, and lignin were 13.50%, 10.89%, and 14.03%, respectively. Fourier translation infrared (FT-IR) and NMR analyses confirmed that the three main components were all involved in the homogeneous maleation. 1H-13C HSQC analysis indicated that the predominant monoesterification of cellulose, diesterification of hemicelluloses and lignin, and the degradation of the three main components simultaneously occurred. Besides, the quantitative analysis from 1H-13C HSQC revealed the relative PS of reactive sites in each component. 31P NMR results showed that the reactivity of lignin aliphatic hydroxyls was higher than that of phenolic ones, and the reactivity of phenolic hydroxyls followed the order of p-hydroxyphenyl hydroxyls > guaiacyl hydroxyls > syringyl hydroxyls.

Ultralight and compressible carbon materials have promising applications in strain and pressure detection. However, it is still difficult to prepare carbon materials with supercompressibility, elasticity, stable strain-electrical signal response, and ultrasensitive detection limits, due to the challenge in structural regulation. Herein, a new strategy to prepare a reduced graphene oxide (rGO)-based lamellar carbon aerogels with unexpected and integrated performances by designing wave-shape rGO layers and enhancing the interaction among the rGO layers is demonstrated. Addition of cellulose nanocrystalline and low-molecular-weight carbon precursors enhances the interaction among rGO layers and thus produces an ultralight, flexible, and superstable structure. The as-prepared carbon aerogel displays a supercompressibility (undergoing an extreme strain of 99%) and elasticity (100% height retention after 10 000 cycles at a strain of 30%), as well as stable strain-current response (at least 10 000 cycles). Particularly, the carbon aerogel is ultrasensitive for detecting tiny change in strain (0.012%) and pressure (0.25 Pa), which are the lowest detection limits for compressible carbon materials reported in the literature. Moreover, the carbon aerogel exhibits excellent bendable performance and can detect an ultralow bending angle of 0.052°. Additionally, the carbon aerogel also demonstrates its promising application as wearable devices.

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.

A sulphated tin ion-exchanged montmorillonite (SO42−/Sn-MMT) was successfully prepared by the ion exchange method of montmorillonite (MMT) with SnCl4, followed by the sulphation. This catalysis was applied as a solid acid catalyst for the heterogeneous catalytic transformations of xylose and xylan into furfural in the bio-based 2-methyltetrahydrofuran/H2O biphasic system. These prepared catalysts were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), temperature programmed desorption of ammonia (NH3-TPD), pyridine adsorbed Fourier transform infrared spectroscopy (Py-FTIR), element analysis (EA) and Brunauer-Emmett-Teller (BET) method. Their catalytic performance for xylose and xylan into furfural was also investigated. The reaction parameters such as the initial xylose and xylan concentration, the amounts of catalyst, the organic-to-aqueous phase volume ratio, the reaction temperature and time were studied to optimize the reaction conditions. Results displayed that SO42−/Sn-MMT contained both Brønsted acid and Lewis acid sites, and SO42− ions were contributive to the formation of stronger Brønsted acid sites, which could improve the reaction efficiency. Reaction parameters had significant influence on the furfural production. The substitution of water by the saturated NaCl solution in the aqueous phase also had an important effect on the xylose and xylan conversion. The highest furfural yields were achieved up to 79.64% from xylose and 77.35% from xylan under the optimized reaction conditions (160 °C, 120 min; 160 °C, 90 min). Moreover, the prepared catalyst was stable and was reused five times with a slight decrease (10.0%) of the furfural yield.

Lignocellulosic biomass aerogels with relatively high Brunauer–Emmett–Teller (BET) surface area and pore volume were prepared directly from bagasse solutions in the present study. Bagasse was dissolved in DMSO/LiCl, treated with cyclic freezing-thawing processes, and regenerated with water. The resulted bagasse hydrogels were solvent-exchanged to t-butanol and subjected to freeze-drying to obtain the lignocellulosic aerogels. The structure of the aerogels was studied with FTIR, nitrogen absorption, SEM, and XRD. The results showed that the aerogels had sheet-like skeletons interconnected with one another to form three-dimensional networks. The highest BET surface area and total pore volume of the aerogels were 185 m2/g and 0.46 cm3/g, respectively. By adjusting the concentration of bagasse solution in DMSO/LiCl, the structure of the aerogels could be controlled to some extent.