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Arsenic and other heavy metal contaminants in water are a significant global health threat. In this study, low-cost, sulfur-free, sustainable, water-insoluble materials with heavy metal remediation properties were produced from renewable resources such as starch, xylan, citric acid, and chitosan. Synthesized starch citrate-chitosan (SCC) foam and xylan citrate-chitosan (XCC) foam were flexible, porous, and elastic. The foams' arsenic uptake in water was significantly greater than five different commercial metal remediating agents. The mercury and lead uptakes with the synthesized foams were similar to the performance of a commercial sulfur-based product, SorbaTech 450 (ST450). However, the cadmium and selenium uptakes were comparatively lower. The complexation of arsenic with oxygen and nitrogen of the SCC foam was shown with time-of-flight secondary ion mass spectrometry (TOF-SIMS). The XCC foam was also shown to adsorb potassium iodide (KI) at a similar rate to sodium chloride. This may be used to remediate water contaminated with radioactive materials, such as iodine 131. [ABSTRACT FROM AUTHOR]

The importance of renewable and environmentally friendly wood pulp fibers as an input material for single-use products has grown significantly. However, discarded single-use materials are found in the environment as litter and are sometimes disposed of in wastewater. It is important that these materials are biodegradable and environmentally benign. Wood pulp is mainly comprised of lignocellulosic material, and its composition and structure can vary depending on raw materials and processing, ultimately impacting the biodegradability. In this research, the aquatic biodegradation of five kinds of wood pulp and six different samples of isolated lignocellulosic components (cellulose, hemicellulose, and lignin) have been explored in a consistent detailed manner for the first time, and the effects of chemical composition on the biodegradation discussed. Several lignocellulosic materials were characterized using compositional analysis and were subjected to aquatic biodegradation with bio-solids from a wastewater treatment plant as an inoculum to indicate the potential to biodegrade in the environment. Cellulose and hemicellulose were readily biodegraded over a course of one month. The lignin samples were not biodegradable under these conditions, and the lignin within fibers decreased the biodegradability of the other components of the lignocellulosic fibers. It was also determined that ash and extractives negatively affect the biodegradability. The aerobic aquatic biodegradation results are useful for product designers to select different lignocellulosic materials for applications and for environmental scientists to understand the fate of these fibers in the environment. [ABSTRACT FROM AUTHOR]

Hemicellulose is a polymer found abundantly in lignocellulosic feedstocks, with many potential market applications. However, there has yet to be a large‐scale commercial process to isolate hemicellulose from lignocellulosic biomass. A techno‐economic assessment for hemicellulose extraction from sugarcane bagasse, switchgrass, and poplar was made. Two isolation processes after alkaline extraction were considered: (1) producing total hemicellulose and (2) producing hemicellulose A (water‐insoluble fraction) only. In a greenfield scenario, a byproduct of the process is sugar, whereas in a co‐location scenario the biomass after hemicellulose extraction is returned to the pulp mill for its fiber value. Operating costs, capital investment, minimum hemicellulose selling price (MHSP), the effect of input material and product prices along with several other process parameters on the MHSP were determined for each scenario. Co‐location scenarios had a dramatically lower capital cost and MHSP relative to greenfield scenarios. This was due to co‐location scenarios utilizing existing biomass processing and utilities equipment and not requiring a sugar‐production process. Among the three biomasses, hemicellulose extraction from sugarcane bagasse had the lowest MHSP for all scenarios, mainly due to a higher hemicellulose extraction yield. Extraction of hemicellulose A from sugarcane bagasse in a co‐location scenario had a low capital cost of 56 million USD and had a reasonable MHSP of 274 USD/t (metric ton). This research indicates that there is reasonable economic potential for hemicellulose extraction from lignocellulosic biomass for applications to replace starch or as a starting material for the production of xylo‐oligomeric prebiotics. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd [ABSTRACT FROM AUTHOR]

Hemicellulose is a highly available polysaccharide but with poor industrial applications attributed mainly to difficulties in processability, owing to extensive intermolecular hydrogen bonds. In the current study, hemicellulose was subjected to a chemical modification by ring-opening graft polymerization of ε-caprolactone (CL) to improve its processability for value-added applications. Hemicellulose- graft -poly-(ε-caprolactone) (HC g PCL) copolymers were synthesized using 1,5,7-triazabicyclodecene [4.4.0] (TBD) as an organic catalyst. The extent and length of grafted PCL sidechains in HC g PCL copolymers were controlled by adjusting the molar ratios of CL monomer to anhydroxylose residues. The various characterization analysis of the physicochemical and mechanical properties of HC g PCL materials revealed a successful grafting. The NMR analyses indicated that the degree of polymerization (DP) of the grafted PCL can range between 1.82 and 4.26 based on the changes in the molar ratio of the reactants. Furthermore, results indicated that the mechanical and the hydrophobic properties of the materials were enhanced by PCL grafting onto hemicellulose. Finally, biodegradability measurements indicated a remarkable (95.3–99.7%) materials biodegradation. We anticipate that the HC g PCL copolymers will have great potential to be an eco-friendly part of the bioplastic industry. [ABSTRACT FROM AUTHOR]

Hemicellulose is an abundant and underutilized carbohydrate polymer in plants. The objective of this study was to understand the effect of delignification on hemicellulose extraction efficiency with different types of lignocellulosic biomass. In the case of pine, with a prior sodium chlorite or peracetic acid delignification, more than 50% of the original hemicellulose in the biomass could be extracted using a 10% sodium hydroxide solution; without delignification, only 3.4% of hemicellulose could be extracted from pine. In contrast, without prior delignification, acceptable hemicellulose extraction efficiencies (55.5% and 50.7%, respectively) were achieved from switchgrass and poplar. In addition, the effect of hemicellulose extraction processes on the enzymatic convertibility of the celluloserich residues after extraction was determined. The cellulose-rich residues from switchgrass after hemicellulose alkali extraction showed high glucose recovery with enzyme hydrolysis with or without prior delignification. For pine and poplar, high glucose recovery with enzyme hydrolysis of the cellulose-rich residues only occurred if the sample had a delignification step prior to hemicellulose extraction. This information on commercially available biomass feedstocks is useful for those considering isolating hemicellulose within a biorefinery concept. [ABSTRACT FROM AUTHOR]

Hemicellulose materials are arguably the second most abundant renewable component of lignocellulosic biomass after cellulose. They are relatively under-utilized hetero-polysaccharides present in lignocellulosic biomass. In this research an alkaline treatment was optimized for extraction of polymeric hemicellulose from fully bleached hardwood pulp (B-HWP) and partially delignified switchgrass (SWG). The hemicellulose extracted from B-HWP was relatively pure with zero percent lignin and 89.5% xylose content whereas the partially delignified SWG hemicellulose contained about 6-3% lignin and 72–82% xylose, depending on the NaOH concentration during extraction (3–17% NaOH solution). A maximum molecular weight of SWG hemicellulose of 64,300 g/mol was achieved for the 10% NaOH solution extraction, whereas the MW of B-HWP hemicellulose at 10% NaOH solution extraction was lower at 49,200 g/mol. We have demonstrated that the residual lignin in SWG hemicellulose lowered the system T g and this might be utilized as a way to increase the applications of hemicellulose in high value biomaterials. Furthermore, the hemicellulose could be crosslinked with zirconium to develop a water resistant gel for coating or adhesive applications. Our results showed that the loading stress required to break an hemicellulose based adhesive connection between two paper surfaces was 0.89, 2.02, 2.75, 3.46, and 3.11 (MPa) for 2, 4, 6, 8 and 10% AZC samples, indicating that up to about 8% AZC crosslinker in the hemicellulose increases the adhesive behavior of the material. [ABSTRACT FROM AUTHOR]

Hemicelluloses, due to their hydrophilic nature, may tend to be overlooked as a component in water-resistant product applications. However, their domains of use can be greatly expanded by chemical derivatization. Research in which hydrophobic derivatives of hemicelluloses or combinations of hemicelluloses with hydrophobic materials are used with to prepare films and composites is considered herein. Isolation methods that have been used to separate hemicellulose from biomass are also reviewed. Finally, the most useful pathways to change the hydrophilic character of hemicelluloses to hydrophobic are reviewed. In this way, the water resistance can be increased and applications of targeted water-resistant hemicellulose developed. Several applications of these materials are discussed. [ABSTRACT FROM AUTHOR]

Hemicellulose material is an abundant and relatively under-utilized hetero-polysaccharide material present in lignocellulosic materials. In this study, an alkaline treatment was applied to sweetgum and Eucalyptus globulus chips to extract hemicelluloses prior to kraft pulping to subsequently evaluate the final product and process. An alkaline extraction (10 and 50% NaOH by weight on wood) for 60 min at 100 °C followed by precipitation in ethanol recovered 4.3% of the biomass as a predominantly xylan material (sweetgum 50% NaOH) with an average degree of polymerization around 250 and functional groups similar to a commercial xylan (sweetgum 10% NaOH). This process in comparison to autohydrolysis (water extraction at 100 °C) produced a much higher molecular weight and more pure hemicellullose. The results obtained indicate a promising combination between the effective extraction of hemicellulose from wood and a distillation process that recovers the ethanol, which may be an attractive alternative to recover liquor and ethanol after hemicellulose precipitation. Hemicellulose from sweetgum showed more thermal stability with high molecular weight compared to the hemicellulose extracted from Eucalyptus globulus. An attractive alternative looks to be to recover liquor and ethanol after hemicellulose precipitation. [ABSTRACT FROM AUTHOR]

Abstract: Hemicellulose material is an abundant and relatively under-utilized hetero-polysaccharides material present in lignocellulosic materials. In this research, an alkaline treatment was applied to switchgrass in order to extract hemicelluloses to subsequently produce an acetylated product. An extraction at 75°C recovered 27% of the biomass as a predominantly hemicellulose material with a number average degree of polymerization of ∼500 determined by gel permeation chromatography. These hemicelluloses were acetylated with acetic anhydride in 1-allyl-3-methylimidazolium chloride ([Amim]+Cl−) ionic liquid in a complete homogeneous procedure without catalyst for the first time. It was determined that the yield and degree of substitution increased with reaction temperature from 30 to 80°C and reaction time from 1 to 20h. The product was characterized by FTIR spectroscopy, NMR, gel permeation chromatography for molecular weight and water contact angle analysis. FTIR spectroscopic analysis showed that the characteristic absorption intensities of acetylated hemicellulose increased and the hydroxyl group decreased with the increase in the degree of substitution. Increased degree of substitution increased the water contact angle and thermal stability in nitrogen. It was possible to cast films of the acetylated hemicellulose although the films were brittle. The results obtained indicate a promising combination between the effective extraction of hemicellulose from grasses and an environmentally friendly process using acetic anhydride in an ionic liquid without a catalyst to generate hemicellulose acetate with high degree of polymerization for use in various industrial applications. [Copyright &y& Elsevier]

Abstract: The applications for hemicellulose are currently very narrow, because of its low molecular weight and varying chemical composition. In this research, novel applications for modified hemicellulose are developed making it a valuable biomaterial for absorbency applications in health care and medical textiles. The incorporation of carboxylic acid groups into hemicellulose via reaction with citric acid followed by cross linking with chitosan greatly improve the properties relative to hemicellulose, chitosan, a cellulose sponge product, and hemicellulose citrate alone. Optimum conditions for the cross linking of the hemicellulose citrate–chitosan include a 2.5h reaction time at 110°C with pH 3.5, a solid to liquid ratio of 1:100 and a hemicellulose citrate to chitosan ratio of 1:1 (w/w). The hemicellulose citrate–chitosan crosslinked foam is elastic, very soft, highly porous and durable. The hemicellulose citrate–chitosan can absorb up to 100g of a saline solution per gram of material and up to 80g of water per gram of material. Analysis of the hemicellulose citrate–chitosan foams with FTIR, DMA, and SEM confirms the crosslinked and hygroscopic behavior of the materials. [Copyright &y& Elsevier]

Abstract: Films of microfibrillated celluloses (MFCs) from pulps of different yields, containing varying amounts of extractives, lignin, and hemicelluloses, were produced by combining refining and high-pressure homogenization techniques. MFC films were produced using a casting-evaporation technique and the physical and mechanical properties (including density, roughness, fold endurance and tensile properties) were determined. Homogenization of bleached and unbleached Kraft pulps gave rise to highly individualized MFCs, but not for thermo-mechanical pulp (TMP). The resulting MFC films had a roughness equivalent to the surface upon which the films were cast. Interestingly, after homogenization, the presence of lignin significantly increased film toughness, tensile index, and elastic modulus. The hornification of fibers through a drying and rewetting cycle prior to refining and homogenization did not produce any significant effect compared to films from never-dried fibers, indicating that MFC films can potentially be made from low-cost recycled cellulosic materials. [Copyright &y& Elsevier]

Coastal Bermuda grass (CBG) has been shown to have potential as a biomass feedstock for sugar production. In this study, the effectiveness of ozone pretreatment for CBG to improve the sugar recovery via enzyme hydrolysis was investigated. Raw CBG and autohydrolysistreated CBG were pretreated with ozone at ozone consumption of 1.8 to 26.4 % (w/w) at room temperature. Lignin degradation and hemicellulose solubilization increased with increased ozone consumption. At 26.4% ozone consumption by weight on CBG the amount of lignin in the CBG was reduced by 34%. Autohydrolysis of CBG increased the reactivity of cellulose, hemicellulose, and lignin with ozone. The maximum total sugar recovery after enzymatic hydrolysis was 32% for a 14.0% consumption of ozone on raw CBG. For CBG samples pretreated with autohydrolysis followed by a 3.1% ozone consumption pretreatment the maximum total sugar recovery after enzyme hydrolysis was 40.1%. Autohydrolysis pretreatment followed by enzyme hydrolysis yielded a 36.4% sugar recovery, indicating that the application and benefits of ozone after autohydrolysis with the conditions studied herein are marginally better than autohydrolysis alone. [ABSTRACT FROM AUTHOR]

Abstract: Coastal Bermuda grass (GBG) was pretreated using an autohydrolysis process with different temperatures and times, and the pretreated materials were enzymatically hydrolyzed using a mixture of cellulase, xylanase and β-glucosidase with different enzyme loadings to evaluate sugar yields. Compared with untreated CBG, autohydrolysis pretreatments at all elevated temperatures and residence times tested enhanced enzymatic digestibility of both cellulose and hemicellulose. Increasing the temperature and residence time also helps to solubilize hemicelluloses, with 83.3% of the hemicelluloses solubilized at 170°C for 60min treatment. However, higher temperatures and longer times resulted in an overall lower sugar recovery when considering monosaccharides in the prehydrolyzate combined with the enzyme hydrolyzate. Autohydrolysis at 150°C for 60min provided the highest overall sugar yield for the entire process. A total of 43.3g of sugars, 70% of the theoretical sugar yield, can be generated from 100g CBG, 15.0g of monosaccharide in the prehydrolyzate and 28.3g in the enzyme hydrolyzate. The conversion efficiency could be further improved by optimizing enzyme dosages and xylanases:cellulases ratio and pretreatment conditions to minimize sugar degradation. [Copyright &y& Elsevier]