Comparison of emulsifying capacity of two hemicelluloses from moso bamboo in soy oil-in-water emulsions.

Oil-in-water food emulsions consisting of natural emulsifiers has been an active field of green scientific inquiry. Here, we extract two types of new hemicellulose-based emulsifiers (HH and HL) from holocellulose and dewaxed materials of bamboo (Phyllostachys pubescens), as well as compare their emulsifying soy oil ability, respectively. The main content of HH is arabinoxylan, while the primary composition in HL is glucan. The emulsifying capacity of these two types of hemicellulose-based emulsifiers are evaluated by droplet size distribution, surface charge and optical microscopy. Since HL possesses higher lignin and protein residual contents, the resultant emulsion exhibits smaller droplets and higher emulsion stability. In comparison, HH emulsifier has almost no emulsifying capacity due to the lack of non-polar groups. This study provides insight into the choice of hemicelluloses-based emulsifiers for the formation of stable oil-in-water food emulsions.

MnO2@Corncob Carbon Composite Electrode and All-Solid-State Supercapacitor with Improved Electrochemical Performance.

Two corncob-derived carbon electrode materials mainly composed of micropores (activated carbon, AC) and mesopores/macropores (corncob carbon, CC) were prepared and studied after the anodic electrodeposition of MnO2. The capacity of the MnO2/activated carbon composite (MnO2@AC) electrode did not noticeably increase after MnO2 electrodeposition, while that of the MnO2/corncob carbon composite (MnO2@CC) electrode increased up to 9 times reaching 4475 mF cm-2. An asymmetric all-solid-state supercapacitor (ASC) was fabricated using AC as the anode, MnO2@CC as the cathode, and polyvinyl alcohol (PVA)/LiCl gel as the electrolyte. An ultrahigh specific capacitance of 3455.6 mF cm-2 at 1 mA cm-2, a maximum energy density of 1.56 mW h cm-2, and a long lifetime of 10,000 cycles can be achieved. This work provides insights in understanding the function of MnO2 in biomass-derived electrode materials, and a green path to prepare an ASC from waste biomass with excellent electrochemical performance.

Xylan-Modified-Based Hydrogels with Temperature/pH Dual Sensitivity and Controllable Drug Delivery Behavior.

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.

Synthesis and Characteristic of Xylan-grafted-polyacrylamide and Application for Improving Pulp Properties.

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.

Molecular mechanism of G1 arrest and cellular senescence induced by LEE011, a novel CDK4/CDK6 inhibitor, in leukemia cells.

BACKGROUND: Overexpression of cyclin D1 dependent kinases 4 and 6 (CDK4/6) is a common feature of many human cancers including leukemia. LEE011 is a novel inhibitor of both CDK4 and 6. To date, the molecular function of LEE011 in leukemia remains unclear. METHODS: Leukemia cell growth and apoptosis following LEE011 treatment was assessed through CCK-8 and annexin V/propidium iodide staining assays. Cell senescence was assessed by ß-galactosidase staining and p16INK4a expression analysis. Gene expression profiles of LEE011 treated HL-60 cells were investigated using an Arraystar Human LncRNA array. Gene ontology and KEGG pathway analysis were then used to analyze the differentially expressed genes from the cluster analysis. RESULTS: Our studies demonstrated that LEE011 inhibited proliferation of leukemia cells and could induce apoptosis. Hoechst 33,342 staining analysis showed DNA fragmentation and distortion of nuclear structures following LEE011 treatment. Cell cycle analysis showed LEE011 significantly induced cell cycle G1 arrest in seven of eight acute leukemia cells lines, the exception being THP-1 cells. ß-Galactosidase staining analysis and p16INK4a expression analysis showed that LEE011 treatment can induce cell senescence of leukemia cells. LncRNA microarray analysis showed 2083 differentially expressed mRNAs and 3224 differentially expressed lncRNAs in LEE011-treated HL-60 cells compared with controls. Molecular function analysis showed that LEE011 induced senescence in leukemia cells partially through downregulation of the transcriptional expression of MYBL2. CONCLUSIONS: We demonstrate for the first time that LEE011 treatment results in inhibition of cell proliferation and induction of G1 arrest and cellular senescence in leukemia cells. LncRNA microarray analysis showed differentially expressed mRNAs and lncRNAs in LEE011-treated HL-60 cells and we demonstrated that LEE011 induces cellular senescence partially through downregulation of the expression of MYBL2. These results may open new lines of investigation regarding the molecular mechanism of LEE011 induced cellular senescence.

Inhibiting PLK1 induces autophagy of acute myeloid leukemia cells via mammalian target of rapamycin pathway dephosphorylation.

Decreased autophagy is accompanied by the development of a myeloproliferative state or acute myeloid leukemia (AML). AML cells are often sensitive to autophagy­inducing stimuli, prompting the idea that targeting autophagy can be useful in AML cytotoxic therapy. AML NB4 cells overexpressing microtubule-associated protein 1 light chain 3-green fluorescent protein were screened with 69 inhibitors to analyze autophagy activity. AML cells were treated with the polo-like kinase 1 (PLK1) inhibitors RO3280 and BI2536 before autophagy analysis. Cleaved LC3 (LC3-II) and the phosphorylation of mammalian target of rapamycin (mTOR), adenosine monophosphate-activated protein kinase, and Unc-51-like kinase 1 during autophagy was detected with western blotting. Autophagosomes were detected using transmission electron microscopy. Several inhibitors had promising autophagy inducer effects: BI2536, MLN0905, SK1-I, SBE13 HCL and RO3280. Moreover, these inhibitors all targeted PLK1. Autophagy activity was increased in the NB4 cells treated with RO3280 and BI2536. Inhibition of PLK1 expression in NB4, K562 and HL-60 leukemia cells with RNA interference increased LC3-II and autophagy activity. The phosphorylation of mTOR was reduced significantly in NB4 cells treated with RO3280 and BI2536, and was also reduced significantly when PLK1 expression was downregulated in the NB4, K562 and HL-60 cells. We demonstrate that PLK1 inhibition induces AML cell autophagy and that it results in mTOR dephosphorylation. These results may provide new insights into the molecular mechanism of PLK1 in regulating autophagy.

A novel sphingosine kinase 1 inhibitor (SKI-5C) induces cell death of Wilms' tumor cells in vitro and in vivo.

Sphingosine kinase 1 (SphK1) is over-expressed in many cancers and therefore serves as a biomarker for cancer prognosis. SKI-5C is a new SphK1 inhibitor, and until now its molecular function in Wilms' tumor cells remained unknown. Here, using CCK-8 and nude mice experiments we assessed cell growth in Wilms' tumor cell lines (SK-NEP-1 and G401) in vitro and in vivo. We demonstrated that SphK1 is highly expressed in SK-NEP-1 and G401 cells, and through annexin V/propidium iodide staining and flow cytometry analysis, we detected cell apoptosis. Treatment with SKI-5C inhibited proliferation and induced apoptosis of SK-NEP-1 and G401 cells in a dose-dependent manner. Moreover, SKI-5C treatment inhibited the growth of SK-NEP-1 xenograft tumors in nude mice, with few side effects. Our microarray analysis revealed that SKI-5C-treated SK-NEP-1 cells mostly downregulated PRKACA and significantly inhibited phosphorylation of ERK1/2 and NF-κB p65. These results imply that SKI-5C induces apoptosis of SK-NEP-1 cells through the PRKACA/MAPK/NF-κB pathway. While, further research is required to determine the underlying details, these results provide new clues for the molecular mechanism of cell death induced by SKI-5C and suggest that SKI-5C may act as new candidate drug for Wilms' tumor.

Synthesis of Acylated Xylan-Based Magnetic Fe3O4 Hydrogels and Their Application for H2O2 Detection.

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.

Synthesis and properties of hemicelluloses-based semi-IPN hydrogels.

Hemicelluloses were extracted from holocellulose of bamboo by alkaline treatment. The phosphorylated poly(vinyl alcohol) (P-PVA) samples with various substitution degrees were prepared through the esterification of PVA and phosphoric acid. A series of hydrogels of semi-interpenetrating polymeric networks (semi-IPN) composed of hemicelluloses-g-poly(acrylic acid) (HM-g-PAA) and the phosphorylated poly(vinyl alcohol) (P-PVA) were prepared by radical polymerization using potassium persulphate (KPS) as initiator. The HM-g-PAA networks were crosslinked by N,N-methylenebisacrylamide (MBA) as a crosslinking agent in the presence of linear P-PVA. FT-IR results confirmed that the hydrogels comprised a porous crosslink structure of P-PVA and HM with side chains that carried carboxylate and phosphorylate groups. SEM observations indicated that the incorporation of P-PVA induced highly porous structure, and P-PVA was uniformly dispersed in the polymeric network. The interior network structures of the semi-IPN matrix became more porous with increasing P-PVA. The TGA results showed that the thermo-decomposing temperature and thermal stability were increased effectively for intruding the chain of P-PVA. The maximum equilibrium swelling ratio of hydrogels in distilled water and 0.9 wt% sodium chloride solutions was up to 1085 g g(-1) and 87 g g(-1), respectively. The compressive strength increased with increasing the MBA/HM and P-PVA/HM ratios, and decreased with the increment of AA/HM ratio.

Separation and characterization of acetyl and non-acetyl hemicelluloses of Arundo donax by ammonium sulfate precipitation.

Delignified Arundo donax was sequentially extracted with DMSO, saturated barium hydroxide, and 1.0 M aqueous NaOH solution. The yields of the soluble fractions were 10.2, 6.7, and 10.0% (w/w), respectively, of the dry Arundo donax materials. The DMSO-, Ba(OH)(2)- and NaOH-soluble hemicellulosic fractions were further fractionated into two subfractions by gradient 50% and 80% saturation ammonium sulfate precipitation, respectively. Monosaccharide, molecular weight, FT-IR, and 1D ((1)H and (13)C) and 2D (HSQC) NMR analysis revealed the differences in structural characteristics and physicochemical properties among the subfractions. The subfractions precipitated with 50% saturation ammonium sulfate had lower arabinose/xylose and glucuronic acid/xylose ratios but had higher molecular weight than those of the subfractions precipitated by 80% saturation ammonium sulfate. FT-IR and NMR analysis revealed that the highly acetylated DMSO-soluble hemicellulosic subfraction (H(D50)) could be precipitated with a relatively lower concentration of 50% saturated ammonium sulfate, and thus the gradient ammonium sulfate precipitation technique could discriminate acetyl and non-acetyl hemicelluloses. It was found that the DMSO-soluble subfraction H(D50) precipitated by 50% saturated ammonium sulfate mainly consisted of poorly substituted O-acetyl arabino-4-O-methylglucurono xylan with terminal units of arabinose linked on position 3 of xylose, 4-O-methylglucuronic acid residues linked on position 2 of the xylan bone, and the acetyl groups (degree of acetylation, 37%) linked on position 2 or 3. The DMSO-soluble subfraction H(D80) precipitated by 80% saturated ammonium sulfate was mainly composed of highly substituted arabino-4-O-methylglucurono xylan and ß-d-glucan.

Highly effective adsorption of heavy metal ions from aqueous solutions by macroporous xylan-rich hemicelluloses-based hydrogel.

Xylan-rich hemicelluloses-based hydrogel was developed as a novel porous bioadsorbent by graft co-polymerization of acrylic acid (AA) and xylan-rich hemicelluloses for adsorption of heavy metal ions (Pd(2+), Cd(2+), and Zn(2+)) from aqueous solutions. The chemical structure, the interaction between the hydrogel and metal ions, and the porous structure of xylan-rich hemicelluloses-g-AA hydrogel were revealed by Fourier transform infrared spectroscopy and scanning electron microscopy. The effects of AA and cross-linker dosage, pH value, contacting time, and initial concentration of metal ion on the adsorption capacity were studied. The adsorption equilibrium time was about 60 min from the adsorption kinetics study. The maximum adsorption capacities of Pd(2+), Cd(2+), and Zn(2+) were 859, 495, and 274 mg/g, respectively. Furthermore, xylan-rich hemicelluloses-g-AA hydrogel also exhibited highly efficient regeneration and metal ion recovery efficiency and can be reused without noticeable loss of adsorption capacity for Pd(2+), Cd(2+), and Zn(2+) after quite a number of repeated adsorption/desorption cycles.

Synthesis and characterization of amphoteric xylan-type hemicelluloses by microwave irradiation.

In this study, a novel amphoteric macromolecule was synthesized by sequential incorporation of carboxymethyl and quaternary ammonium groups into the backbone of xylan-type hemicelluloses under microwave irradiation. The reaction parameters such as the molar ratio of reagent (NaOH or 3-epoxypropyltrimethylammonium chloride)/anhydroxylose unit in hemicelluloses, the temperature, and the reaction time were investigated to optimize the reaction condition. The maximum degrees of substitution (DS) of carboxymethyl and quaternary ammonium groups under the optimum reaction condition were 0.90 and 0.52, respectively, exhibiting a higher efficiency as compared to the conventional heating method. Moreover, the thermal stability and weight-average molecular weight of amphoteric hemicellulosic derivatives decreased as compared to the native hemicelluloses. The viscosity, elastic modulus, and loss modulus of the amphoteric biomacromolecules increased with the increasing DS of quaternary ammonium groups in aqueous solution due to stronger electrostatic attraction. This study provides an efficient and rapid method to prepare amphoteric biomacromolecules.

Nanocomposite films based on xylan-rich hemicelluloses and cellulose nanofibers with enhanced mechanical properties.

Interest in xylan-rich hemicelluloses (XH) film is growing, and efforts have been made to prepare XH films with improved mechanical properties. This work described an effective approach to produce nanocomposite films with enhanced mechanical properties by incorporation of cellulose nanofibers (CNFs) into XH. Aqueous dispersions of XH (64-75 wt %), sorbitol (16-25 wt %), and CNF (0-20 wt %) were cast at a temperature of 23 °C and 50% relative humidity. The surface morphology of the films was revealed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The thermal properties and crystal structure of the films were evaluated by thermal analysis (TG) and X-ray diffraction (XRD). The surface of XH films with and without CNF was composed primarily of nanonodules, and CNFs were embedded in the XH matrix. Freeze-dried XH powder was amorphous, whereas the films with and without CNF showed a distinct peak at around 2θ = 18°, which suggested that XH molecules aggregated or reordered in the casting solution or during water evaporation. Furthermore, the nanocomposite films had improved thermal stability. XH film with 25 wt % plasticizer (sorbitol, based on dry XH weight) showed poor mechanical properties, whereas incorporation of CNF (5-20 wt %, based on the total dry mixture) into the film resulted in enhanced mechanical properties due to the high aspect ratio and mechanical strength of CNF and strong interactions between CNF and XH matrix. This effective method makes it possible to produce hemicellulose-based biomaterials of high quality.

Xylan-rich hemicelluloses-graft-acrylic acid ionic hydrogels with rapid responses to pH, salt, and organic solvents.

Exploitation of biomaterials derived from renewable resources is an important approach to address environmental and resource problems in the world today. In this paper, novel ionic hydrogels based on xylan-rich hemicelluloses were prepared by free radical graft copolymerization of acrylic acid (AA) and xylan-rich hemicelluloses (XH) by using N,N-methylene-bis(acrylamide) (MBA) as cross-linker and ammonium persulfate/N,N,N',N'-tetramethylethylenediamine (APS/TMEDA) as redox initiator system. The network characteristics of the ionic hydrogels were investigated by Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM), as well as by determination of mechanical properties, swelling, and stimuli responses to pH, salts, and organic solvents. The results showed that an increase in the MBA/XH or AA/XH ratio resulted in higher cross-linking density of the network and thus decreased the swelling ratio. Expansion of the network hydrogels took place at high pH, whereas shrinkage occurred at low pH or in salt solutions as well as in organic solvents. The ionic hydrogels had high water adsorption capacity and showed rapid and multiple responses to pH, ions, and organic solvents, which may allow their use in several areas such as adsorption, separation, and drug release systems.

Microwave-induced synthesis of carboxymethyl hemicelluloses and their rheological properties.

In this article, a facile, rapid, and efficient method was developed for the preparation of carboxymethyl hemicelluloses using microwave-induced organic reaction enhancement chemistry. The influences of the factors including reaction time, temperature, and the amount of sodium monochloroacetate and sodium hydroxide on the degree of substitution (DS) of the products were investigated. The rheological properties and the chemical structure of the resulting polymers were also studied. It was found that microwave irradiation could significantly promote the chemical reaction efficiency and accelerate the carboxymethylation of hemicelluloses with sodium monochloroacetate. Therefore, carboxymethyl hemicelluloses with higher DS of 1.02 could be obtained in much shorter time scales as compared to the conventional heating method. Results from rheological analysis indicated that carboxymethyl hemicellulose solutions exhibited shear-thinning behavior in the range of shear rates tested and showed lower viscosity and modulus in comparison with those of the native hemicelluloses due to lower molecular weight and the role of carboxymethyl groups in reducing the entanglements between hemicelluloses chains.

Homogeneous esterification of xylan-rich hemicelluloses with maleic anhydride in ionic liquid.

Generation of bioenergy, new functional polymers, or chemicals and biomaterials from hemicelluloses are important uses for biomass. In this paper, a novel functional biopolymer with carbon-carbon double bond and carboxyl groups was prepared by a homogeneous esterification of xylan-rich hemicelluloses (XH) with maleic anhydride in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid using LiOH as catalyst. The biopolymers with degrees of substitution (DS) between 0.095 and 0.75 were accessible in a completely homogeneous system by changing reaction temperature, reaction time, the dosage of catalyst, and the molar ratio of maleic anhydride to anhydroxylose unit in XH. Results obtained from FT-IR and (13)C NMR spectroscopies confirmed the structure of hemicellulosic derivatives with carbon-carbon double bond and carboxyl groups, implying an efficient method to prepare a novel and important functional biopolymer for biomaterials.

Fractionation of alkali-solubilized hemicelluloses from delignified Populus gansuensis: structure and properties.

The dewaxed cell walls of Populus gansuensis were delignified with NaClO(2) and then sequentially extracted with 0.25, 0.5, and 1.0 M KOH under a solid to liquid ratio of 1: 25 (g mL(-1)) at 25 degrees C for 10 h. The successive treatments together resulted in the dissolution of 83.7% of original hemicelluloses. The solubilized hemicellulosic fractions were further fractionated into six hemicellulosic subfractions by an iodine-complex precipitation technique. Their chemical and physical characteristics were determined by HPAEC, GPC, FT-IR, and (1)H and (13)C NMR spectroscopy. Neutral sugar composition and molecular weight analysis showed that, for each extract, the hemicellulosic subfractions that precipitated with aqueous potassium iodide-iodine had lower overall uronic acid/xylose (Uro/Xyl) ratios and higher molecular weights (M(w)) than those remaining in the solution. FT-IR, (1)H, and (13)C NMR spectroscopy analysis indicated that the alkali-soluble hemicelluloses of Populus gansuensis had a structure composed of the (1 --> 4)-linked beta-D-xylopyranosyl backbone with 4-O-methyl-alpha-D-glucuronic acid attached to O-2 of the xylose residues.

Fractional study of alkali-soluble hemicelluloses obtained by graded ethanol precipitation from sugar cane bagasse.

The two hemicellulosic fractions were subsequentially extracted with 5% and 8% NaOH aqueous solution at a solid to liquid ratio of 1:25 (g mL(-1)) at 50 degrees C for 3 h from the water, 1 and 3% NaOH-treated sugar cane bagasse, and subfractionated into six preparations by a graded ethanol precipitation method at concentrations of 15%, 30% and 60% (v/v). Sugar composition and molecular weight analysis showed that, with an increasing concentration of ethanol, hemicellulosic subfractions with both higher Ara/Xyl ratios and higher molecular weights were obtained. In other words, with an increasing ethanol concentration from 15% to 60%, the Ara/Xyl ratios increased from 0.043 in H(1) to 0.088 in H(3) and from 0.040 in H(4) to 0.088 in H(6), and the weight-average molecular weights of hemicellulosic subfractions increased from 42 430 (H(1)) to 85 510 (H(3)) g mol(-1) and from 46 130 (H(4)) to 64 070 (H(6)) g mol(-1), respectively. The results obtained by the analysis of Fourier transform infrared, sugar composition, and (1)H and (13)C nuclear magnetic spectroscopy showed that the alkali-soluble hemicelluloses had a backbone of xylose residues with a beta-(1-->4)-linkage and were branched mainly through arabinofuranosyl units at C-2 and/or C-3 of the main chain, whereas the differences may occur in the distribution of branches along the xylan backbone.

Comparative study of hemicelluloses obtained by graded ethanol precipitation from sugarcane bagasse.

The sequential treatment of dewaxed sugarcane bagasse with H(2)O and 1 and 3% NaOH at a solid to liquid ratio of 1:25 (g mL(-1)) at 50 degrees C for 3 h yielded 74.9% of the original hemicelluloses. Each of the hemicellulosic fractions was successively subfractionated by graded precipitation at ethanol concentrations of 15, 30, and 60% (v/v). Chemical composition, physicochemical properties, and structures of eight precipitated hemicellulosic fractions were elucidated by a combination of sugar analysis, nitrobenzene oxidation of bound lignin, molecular determination, Fourier transform infrared (FT-IR), (1)H and (13)C nuclear magnetic spectroscopies, and thermal analysis. The results showed that the sequential treatments and graded precipitations were very effective on the fractionation of hemicelluloses from bagasse. Comparison of these hemicelluloses indicated that the smaller sized and more branched hemicelluloses were extracted by the hot water treatment; they are rich in glucose, probably originating from alpha-glucan and pectic polysaccharides. The larger molecular size and more linear hemicelluloses were dissolved by the alkali treatment; they are rich in xylose, principally resulting from l-arabino-(4-O-methylglucurono)-d-xylans. In addition, noticeable differences in the chemical composition and molecular weights were observed among the graded hemicellulosic subfractions from the water-soluble and alkali-soluble hemicelluloses. The Ara/Xyl ratio increased with the increment of ethanol concentration from 15 to 60%, and the arabinoxylans with higher Ara/Xyl ratios had higher molecular weights. There were no significant differences in the structural features of the precipitated hemicellulosic subfractions, which are mainly constituted of l-arabino-(4-O-methyl-d-glucurono)xylan, whereas the difference may occur in the distribution of branches along the xylan backbone.

Fractionation of wheat and barley straw to access high-molecular-mass hemicelluloses prior to ethanol production.

The cost efficiency of the biorefining process can be improved by extracting high-molecular-mass hemicelluloses from lignocellulosic biomass prior to ethanol production. These hemicelluloses can be used in several high-value-added applications and are likely to be important raw materials in the future. In this study, steam pretreatment in an alkaline environment was used to pretreat the lignocellulosic biomass for ethanol production and, at the same time, extract arabinoxylan with a high-molecular-mass. It was shown that 30% of the arabinoxylan in barley straw could be extracted with high-molecular-mass, without dissolving the cellulose. The cellulose in the solid fraction could then be hydrolysed with cellulase enzymes giving a cellulose conversion of about 80-90% after 72 h. For wheat straw, more than 40% of the arabinoxylan could be extracted with high-molecular-mass and the cellulose conversion of the solid residue after 72 h was about 70-85%. The high cellulose conversion of the pretreated wheat and barley straw shows that they can be used for ethanol production without further treatment. It is therefore concluded that it is possible to extract high-molecular-mass arabinoxylan simultaneously with the pretreatment of biomass for ethanol production in a single steam pretreatment step.