Junli Ren

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.

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.

Catalytic hydrothermal pretreatment of corncob into xylose and furfural via solid acid catalyst.

Selectively catalytic hydrothermal pretreatment of corncob into xylose and furfural has been developed in this work using solid acid catalyst (SO4(2-)/TiO2-ZrO2/La(3+)). The effects of corncob-to-water ratio, reaction temperature and residence time on the performance of catalytic hydrothermal pretreatment were investigated. Results showed that the solid residues contained mainly lignin and cellulose, which was indicative of the efficient removal of hemicelluloses from corncob by hydrothermal method. The prepared catalyst with high thermal stability and strong acid sites originated from the acid functional groups was confirmed to contribute to the hydrolysis of polysaccharides into monosaccharides followed by dehydration into furfural. Highest furfural yield (6.18 g/100g) could be obtained at 180°C for 120 min with 6.80 g/100g xylose yield when the corncob/water ratio of was 10:100. Therefore, selectively catalytic hydrothermal pretreatment of lignocellulosic biomass into important platform chemicals by solid acids is considered to be a potential treatment for biodiesel and chemical production.

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.

Production of furfural from xylose, water-insoluble hemicelluloses and water-soluble fraction of corncob via a tin-loaded montmorillonite solid acid catalyst.

The conversion of xylose, water-insoluble hemicelluloses (WIH) and water-soluble fraction (WSF) of corncob to furfural was performed using montmorillonite with tin ions (Sn-MMT) containing double acid sites as a solid acid catalyst. The co-existence of Lewis acids and Brønsted acids in Sn-MMT was shown to improve the furfural yield and selectivity. 76.79% furfural yield and 82.45% furfural selectivity were obtained from xylose using Sn-MMT as a catalyst in a biphasic system with 2-s-butylphenol (SBP) as the organic extracting layer and dimethyl sulfoxide (DMSO) as the co-solvent in contact with an aqueous phase saturated with NaCl (SBP/NaCl-DMSO) at 180°C for 30min. Furthermore, Sn-MMT also demonstrated the excellent catalytic performance in the conversion of pentose-rich materials of corncob and 39.56% and 54.15% furfural yields can be directly obtained from WIH and WSF in the SBP/NaCl-DMSO system, respectively.

Direct transformation of xylan-type hemicelluloses to furfural via SnCl4 catalysts in aqueous and biphasic systems

Direct catalytic transformation of xylan-type hemicelluloses to furfural in the aqueous system and the biphasic system were comparatively investigated under mild conditions. Screening of several promising chlorides for conversion of beech xylan in the aqueous system revealed the Lewis acid SnCl4 was the most effective catalyst. Comparing to the single aqueous system, the bio-based 2-methyltetrahydrofuran (2-MTHF)/H2O biphasic system was more conducive to the synthesis of furfural, in which the highest furfural yield of 78.1% was achieved by using SnCl4 as catalysts under the optimized reaction conditions (150°C, 120 min). Additionally, the influences of xylan-type hemicelluloses with different chemical and structural features from beech, corncob and bagasse on the furfural production were studied. It was found that furfural yield to some extent was determined by the xylose content in hemicelluloses and also had relationships with the molecular weight of hemicelluloses and the degree of crystallization.

Properties of polyvinyl alcohol/xylan composite films with citric acid

Composite films of xylan and polyvinyl alcohol were produced with citric acid as a new plasticizer or a cross-linking agent. The effects of citric acid content and polyvinyl alcohol/xylan weight ratio on the mechanical properties, thermal stability, solubility, degree of swelling and water vapor permeability of the composite films were investigated. The intermolecular interactions and morphology of composite films were characterized by FTIR spectroscopy and SEM. The results indicated that polyvinyl alcohol/xylan composite films had good compatibility. With an increase in citric acid content from 10% to 50%, the tensile strength reduced from 35.1 to 11.6 MPa. However, the elongation at break increased sharply from 15.1% to 249.5%. The values of water vapor permeability ranged from 2.35 to 2.95 × 10(-7)g/(mm(2)h). Interactions between xylan and polyvinyl alcohol in the presence of citric acid become stronger, which were caused by hydrogen bond and ester bond formation among the components during film forming.

The impact of glycerol organosolv pretreatment on the chemistry and enzymatic hydrolyzability of wheat straw.

Given that the glycerol organosolv pretreatment (GOP) can effectively improve the hydrolyzability of various lignocellulosic substrates, physicochemical changes of the substrate before and after the pretreatment was characterized to elucidate what is responsible for it. The effect of GOP on the main components and hydrolyzability of wheat straw was revisited. Results demonstrate that the GOP should be a promising candidate for the current pretreatment. Then the composition and structure of substrates was measured at multi-dimensional scales by using various analytic equipment such as TGA, SEM, AFM, CLSM, FT-IR, XRD and solid-state CP/MAS (13)C NMR. This paper reports some new insights on the mechanism behind that, which can be beneficial for further development, optimization, and scale-up of the GOP process.

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.

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.