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The complexation between soy soluble polysaccharide (SSPS) and curcumin at pH 7.0 and 4.0, as well as some physicochemical characteristics of the resultant complexes, was investigated. The encapsulation efficiency and loading amount of curcumin in the complexes at pH 4.0 reached 67.3% and 4.49 μg/mg SSPS, respectively. Ethanol-induced denaturation and structural unfolding of the protein fraction in SSPS was essential for complex formation. The complexation with curcumin resulted in aggregation of SSPS and the subsequent formation of compacted nanoparticles with curcumin as the core. The complexation greatly improved the heat stability and in vitro bioaccessibility of curcumin. In general, the encapsulation efficiency, heat stability, and bioaccessibility of curcumin in the complexes at pH 4.0 were better than those at pH 7.0. The findings are of importance for the development of food grade nanovehicles for enhanced water solubility, stability, and bioaccessibility of hydrophobic bioactives.

Stimulus-responsive hydrogels, which can undergo significant physicochemical changes in response to various physical or chemical stimuli, have drawn wide attention in many fields. In this study, novel photoresponsive hydrogels prepared by free radical copolymerization of xylan-type hemicellulose methacrylate with 4-[(4-acryloyloxyphenyl)azo]benzoic acid (AOPAB) were investigated, which showed multiresponsive behaviors to pH, water/ethanol alternating solutions, and light. The swelling ratios of the prepared hydrogels in distilled water decreased from 9.8 to 2.2 g/g with AOPAB content increase from 2% to 16%. The hydrogel displayed rapid swelling and deswelling performance in water and ethanol alternating solutions. Additionally, under UV irradiation the trans-conformation of azobenzene in the hydrogel would generally convert into the cis-conformation and resulted in the hydrophilic/hydrophobic balance variation of the hydrogel. Therefore, the hydrogel loaded with vitamin B12 (VB12) showed a higher drug cumulative release rate under UV irradiation than that without UV irradiation.

A portion of hemicelluloses and acetic acid can be pre-extracted with dilute sulfuric acid prior to the aspen chemithermomechanical pulp process. The streams collected from the second press-impregnation stage after acid pre-extraction contain a significant amount of acid pre-extracted hemicelluloses. Most of the total sugars obtained from the pressate were xylan, in which xylan was further hydrolyzed to sugar monomers under the acid pre-extraction condition. To fully understand the characteristics of hemicelluloses yielded prior to pulping, the pre-extracted hemicelluloses were separated and characterized by FT-IR, (1)H NMR, and thermogravimetric analysis in this study. Most of the FT-IR bonds from the hemicelluloses agreed well with the other two spectra of birch xylan and CA0050 xylan, except a new absorption at 1734 cm(-1) contributed to acetyl groups. The hemicelluloses obtained from acid pre-extraction began to decompose significantly at about 225 °C, slightly lower in comparison with organosolv and alkaline hemicelluloses reported in the literature.

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.

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.

Lignocellulose materials are potentially valuable resources for transformation into biofuels and bioproducts. However, their complicated structures make it difficult to fractionate them into cellulose, hemicelluloses, and lignin, which limits their utilization and economical conversion into value-added products. This study proposes a novel and feasible fractionation method based on complete dissolution of bagasse in 1-butyl-3-methylimidazolium chloride ([C(4)mim]Cl) followed by precipitation in acetone/water (9:1, v/v) and extraction with 3% NaOH solution. The ionic liquid [C(4)mim]Cl was easily recycled after concentration and treatment with acetonitrile. (1)H NMR analysis confirmed that there was no obvious difference between the recycled [C(4)mim]Cl and fresh material. Bagasse was fractionated with this method to 36.78% cellulose, 26.04% hemicelluloses, and 10.51% lignin, accounting for 47.17 and 33.85% of the original polysaccharides and 54.62% of the original lignin, respectively. The physicochemical properties of the isolated fractions were characterized by chemical analysis, high-performance anion exchange chromatography (HPAEC), gel permeation chromatography (GPC), Fourier transform infrared (FT-IR), and (1)H and 2D (13)C-(1)H correlation (HSQC) nuclear magnetic resonance spectroscopy. The results showed that the acetone-soluble lignin and alkaline lignin fractions had structures similar to those of milled wood lignin (MWL). The easy extraction of the noncellulose components from homogeneous bagasse solution and amorphous regenerated materials resulted in the relatively high purity of cellulosic fraction (>92%). The hemicellulosic fraction was mainly 4-O-methyl-D-glucuronoxylans with some α-L-arabinofuranosyl units substituted at C-2 and C-3.

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.

Starch from bamboo Phyllostachys bambusoides f. shouzhu Yi evaluated by means of solid-state 13C CP/MAS NMR and X-ray diffraction showed a typical B-type pattern with a very low degree of crystallinity (10.9%). In addition to starch, alkali-soluble hemicelluloses were further fractionated by graded precipitation at ethanol concentrations of 0 (HA), 15, 30, 45, 60, and 75% (v/v). Chemical composition and structural features of the six hemicellulosic subfractions were investigated by a combination of sugar analysis, GPC, FT-IR, GC-MS, 1D (1H and 13C) and 2D (HSQC) NMR spectra, and thermal analysis. The results showed that the bamboo hemicelluloses were O-acetylated 4-O-methyl-glucuronoarabinoxylans (GAX) consisting of a linear (1→4)-β-D-xylopyranosyl backbone decorated with branches at O-3 of α-L-arabinofuranosyl (5-12 mol%) or at O-2 of 4-O-methylglucuronic acid units and acetyl groups (0.8-11 mol%). The molecular weights of these polysaccharides ranged between 13400 and 67500 g/mol, and the molar ratios of A/X and G/X increased with ascending ethanol concentrations. Moreover, xylo-oligosaccharides (XOS) with DP 1-6 were produced by enzymatic hydrolysis of hemicelluloses and the total yields of XOS were range of 21.5 to 40.6%. The structure-property relationships were also established in order to improve enzyme accessibility.

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.

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.

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.

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.

Lauroylation of wheat straw hemicelluloses in the N, N-dimethylformamide/lithium chloride system under microwave irradiation was studied. The parameters optimized included lauroyl chloride concentration as the molar ratio of xylose unit in hemicelluloses/lauroyl chloride (1:1-1:4), 4-dimethylaminopyridine concentration (2-10%), reaction time (1-8 min), molar ratio of xylose unit in hemicelluloses/triethylamine (1:2), and reaction temperature (78 degrees C). The reaction efficiency was measured by the yield and degree of substitution (DS). Under an optimum reaction condition (molar ratio of xylose unit in hemicelluloses/lauroyl chloride 1:3, molar ratio of xylose unit in hemicelluloses/triethylamine 1:2, 5% 4-dimethylaminopyridine, 78 degrees C, 5 min), a DS of 1.63 was obtained. Changes in the structure of hemicelluloses were verified by FT-IR and 1H and 13C NMR spectroscopy. The results showed that the lauroylation occurred preferentially at the C-3 position of the xylose unit in hemicelluloses. The behavior of the lauroylated hemicelluloses was monitored by means of thermogravimetric (TG) and differential thermogravimetric (DTG) analysis. It was found that the product with low DS had a lower thermal stability than the native hemicelluloses, whereas the lauroylated polymers with high DS showed a higher thermal stability than the unmodified hemicelluloses.