Hemicelluloses of oak wood extracted with aqueous-alcoholic media

Hemicellulose fractions were isolated from ethanol extracts (40-90%) of oak wood. To determine the composition of these fractions, they were hydrolyzed, and the hydrolysis products in the form of trimethylsilyl derivatives were analyzed by GLC-MS. Depending on the content of ethanol, hemicelluloses of different composition were extracted from wood. In alcohols stored in a contact with oak wood and intended for manufacturing brandy and whisky, the content of hemicelluloses increased depending on storage duration. It is assumed that this makes drinks more full-bodied and imparts softness to them.     

Mechanical,chemical and X-ray analysis of wood in the two tropical lianas<Emphasis Type="Italic"> Bauhinia guianensis</Emphasis> and<Emphasis Type="Italic"> Condylocarpon guianense</Emphasis>: variations during ontogeny

Mechanical and chemical properties as well as microfibril angles of wood tissues from different ontogenetic stages are determined for the neotropical lianas Bauhinia guianensis and Condylocarpon guianense. The mechanical properties include the elastic moduli under bending and under dynamic torsion. The chemical analyses cover (i) the content of cellulose, lignin and hemicelluloses fractions, (ii) the monomeric composition of the uncondensed lignin, and (iii) the composition of the hemicelluloses with respect to neutral monosaccharides. By comparing the wood properties of these lianas with the corresponding properties of wood from self-supporting deciduous trees, common characteristics and differences are revealed. Additionally, the changes in the lignin and polysaccharides fractions as well as the variations in microfibril orientation that occur during ontogeny of the two liana species are discussed with regard to their implications for the mechanical properties of wood.     

Red oak wood derived inhibitors in the ethanol fermentation of xylose byPichia stipitis CBS 5776

Summary Xylose, the predominant sugar in red oak prehydrolysate, is fermented to ethanol byPichia stipitis CBS 5776. Toxic model compounds derived from red oak hemicelluloses, lignin, and extractives inhibited the fermentation. Treatment of the prehydrolysate with molecular sieve and mixed bed ion resins facilitated the ethanol fermentation giving about 10 g/l ethanol from 32 g/l initial xylose. Fermentation inhibitors derived from red oak lignin and extractives were identified.     

Eucalyptus globulus wood fractionation by autohydrolysis and organosolv delignification

This work provides an assessment on the fractionation of Eucalyptus globulus wood by sequential stages of autohydrolysis (to cause the solubilization of hemicelluloses) and organosolv pulping (to dissolve lignin, leaving solids enriched in cellulose). With this approach, valuable products (hemicellulose-derived saccharides, sulphur-free lignin fragments and cellulosic substrates with low contents of residual hemicelluloses) are obtained in separate streams, according to the biomass refinery approach. Autohydrolysis was carried out under optimized operational conditions, and organosolv pulping was performed using uncatalyzed ethanol-water solutions. The effects of the most influential operational variables (autohydrolysis severity, delignification temperature and ethanol concentration in the organosolv stage) on solid yield, solid composition, cellulose susceptibility and recovery of the various fractions was assessed using statistical methods, which enabled the identification of the most favourable operational conditions.     

Pretreatment and Lignocellulosic Chemistry

Lignocellulosic materials such as wood, grass, and agricultural and forest residues are promising alternative energy resources that can be utilized to produce ethanol. The yield of ethanol production from native lignocellulosic material is relatively low due to its native recalcitrance, which is attributed to, in part, lignin content/structure, hemicelluloses, cellulose crystallinity, and other factors. Pretreatment of lignocellulosic materials is required to overcome this recalcitrance. The goal of pretreatment is to alter the physical features and chemical composition/structure of lignocellulosic materials, thus making cellulose more accessible to enzymatic hydrolysis for sugar conversion. Various pretreatment technologies to reduce recalcitrance and to increase sugar yield have been developed during the past two decades. This review examines the changes in lignocellulosic structure primarily in cellulose and hemicellulose during the most commonly applied pretreatment technologies including dilute acid pretreatment, hydrothermal pretreatment, and alkaline pretreatment.     

Biomechanics and transgenic wood

Wood, or secondary xylem, is composed mostly of three components-cellulose, hemicelluloses, and lignin. Yet this apparent simplicity is deceiving because the sophisticated arrangement of the components on various structural levels, ranging from intricate molecular architecture to defined cellular arrangements to tissue morphology, makes wood a challenging and interesting subject of biomechanical investigation. Recent advances in genetic transformation, providing easier access to wood of specifically altered composition or structure, have opened new opportunities for research on the intricate relation between material structure and composition and mechanical properties. At the same time, investigations into the mechanical properties have provided new information regarding the structural configuration of wood. The present paper reviews the work conducted in this field and outlines future perspectives and prospects for research.     

Xylan-degrading activity in yeasts: Growth on xylose,xylan and hemicelluloses

The ability to grow in liquid media withD-xylose, xylan from deciduous trees, and hemicelluloses from conifers was tested in 95 strains of 35 genera of yeasts and yeast-like organisms. Of 54 strains thriving on xylose, only 13 (generaAureobasidium, Cryptococcus andTrichosporon) utilized xylan and hemicelluloses as growth substrates. The árowth media of these strains were found to contain xylandegrading enzymes splitting the substrate to xylose and a mixture of xylose oligosaccharides. The ability of these yeasts to utilize the wood components (hitherto unknown in the genusCryptococeus) makes them potential producers of microbial proteins from industrial wood wastes containing xylose oligosaccharides, xylan, and hemicelluloses as the major saccharide components without previous saccharification.     

Biodegradation of Lignocellulose by White-Rot Fungi: Structural Characterization of Water-Soluble Hemicelluloses

In the biological pretreatment process, white-rot fungi are mostly used to degrade lignin and carbohydrates in lignocellulosic biomass. In this study, water-soluble hemicelluloses were recovered from birch wood (Betula alnoides) decayed by white-rot fungi (Ganoderma lucidum C7016) for different durations up to 16 weeks. Accordingly, the dimethyl sulfoxide (DMSO)-soluble hemicelluloses were isolated from the untreated birch wood as a comparison. Results showed that the fungal-degraded polysaccharides were acidic hemicelluloses having a high content of uronic acids ranging from 20.6 to 22.5 %. Gel permeation chromatography analysis demonstrated that the recovered water-soluble hemicelluloses had a lower average molecular weight (M _w, 15,990–27,560 g?mol^?1) than that of the DMSO-soluble hemicelluloses (M _w , 33,960 g?mol^?1). Fourier transform infrared spectroscopy, scanning electron microscopy, one- and two-dimensional nuclear magnetic resonance spectroscopy also revealed significantly changes between those of fungal degraded and DMSO-soluble hemicelluloses. It was proposed that the hemicelluloses with low molecular weights were easily removed from wood by fungal degradation. This research revealed the changes of hemicelluloses in fungal degradation in the natural environment, which may enable the exploration of novel methods in bioconversion of lignocellulosic biomass for the production of biofuels and biopolymers, in addition to the development of new and better ways to protect wood from biodegradation by microorganisms.     

Isolation and fractionation of hemicelluloses by graded ethanol precipitation from Caragana korshinskii

Caragana korshinskii hemicelluloses were isolated with 10% KOH at 25 °C for 10 h from the delignified materials. The alkali-extractable hemicelluloses were then successively sub-fractionated by graded precipitation at final ethanol concentrations of 10%, 20%, 30%, 45%, 60%, and 80%, respectively. Neutral sugars and molecular weight analyses of the six hemicellulosic subfractions revealed that the molecular weights and the distribution of branches along the xylan backbone are different among the hemicellulosic fractions obtained in various ethanol concentrations. The less branched hemicelluloses with large molecules were precipitated in lower ethanol percentages, while with the increasing ethanol concentrations, more branched hemicelluloses with low molecular weights were obtained. ¹H and ¹³C NMR studies revealed that the hemicellulosic subfraction precipitated at an ethanol concentration of 45% had a backbone of d-xylose residues and were branched mainly through 4-O-methyl-α-d-glucopyranosyl units.     

Fermentability of hemicelluloses extracted from municipal waste and commercial xylans by Clostridium sp.

The fermentability of commercial xylans and municipal waste hemicelluloses in the presence of Clostridium sp. (C.SAIV; ATCC 700188) has been evaluated. Teak, deal wood, banana stalk and bagasse of the municipal waste contained significant amounts (approx. 12 %–23 %) of hemicellulose. Under optimized growth conditions, the growth rate of C.SAIV was improved as indicated by an increase in the concentration of ethanol in the culture broth. Commercial xylans were utilized fairly efficiently and ethanol formed from larch wood xylan and bagasse hemicellulose was at least 64 mM. The amount of ethanol formed from the bagasse hemicellulose was at least three times higher than any other reported value. The current study also indicated that the source and composition of hemicellulose played an important role in determining the fermentability of the substrate for some microorganisms. Received: 19 June 1996 / Received revision: 22 October 1996 / Accepted: 25 October 1996     

Toxicity of hardwood extractives toward Saccharomyces cerevisiae glucose fermentation

The toxicity of oak and yellow-poplar wood extracts, as well as a first-stage hardwood hydrolyzate liquor prepared from a red oak:white oak:yellow-poplar (1:1:1) sawdust, on Saccharomyces cerevisiae D5A was examined. Acetone/water and hot methanol extracts of solid biomass samples from white oak, red oak, and yellow-poplar gave 88-94% of the ethanol produced with controls. The organism was tolerant to the compounds present in the xylose-rich hydrolyzate, with fermentation efficiency being improved to 97% of that obtained with controls by using an overliming/thermal conditioning protocol.     

Fractional and physico-chemical characterization of hemicelluloses from ultrasonic irradiated sugarcane bagasse

The present study was undertaken to investigate the extractability of the hemicelluloses from bagasse obtained by ultrasound-assisted extraction methods. The results showed that the ultrasonic treatment and sequential extractions with alkali and alkaline peroxide under the conditions given led to a release of over 90% of the original hemicelluloses and lignin. This fact as well as the sugar composition and structural features of the isolated seven hemicellulosic fractions indicated that ultrasonication attacked the integrity of cell walls, cleaved the ether linkages between lignin and hemicelluloses, and increased accessibility and extractability of the hemicelluloses. Increasing alkali concentration from 0.5 to 2M and alkaline peroxide percentage from 0.5% to 3.0% resulted in degradation of hemicellulosic backbone as shown by a decrease in their molecular weights from 43,580 to 14,470 and 30,180 to 18,130gmol(-1), respectively. However, there were no significant differences in the structural features of the seven sequential alkali- or alkaline peroxide-soluble hemicellulosic fractions, which are composed mainly of L-arabino-(4-O-methyl-D-glucurono)-D-xylans. Ferulic and p-coumaric acids were found to be chemically linked with hemicelluloses.     

Characterisation of thermally modified hard- and softwoods by C CPMAS NMR

The changes induced by thermal modification in the chemical structure of spruce [Picea abies (L.) Karst.], birch (Betula pendula), aspen (Populus tremula) and oak (Quercus robur) were studied by ¹³C CPMAS NMR spectroscopy. Spruce, birch and aspen were thermally modified at 195 °C and oak at 160 °C, under steam, according to an industrial-scale heat treatment process. In both hard- and softwood samples, ¹³C CPMAS NMR measurements revealed a degradation of less ordered carbohydrates (i.e. hemicelluloses and amorphous cellulose) in the thermally modified wood, which resulted in an increase in the cellulose crystallinity. Furthermore, thermal modification induced changes in the lignin structure by a cleavage of the β-O-4 linkages. In the softwood lignin, a decrease also occurred in the methoxyl group content leading to a more condensed lignin structure.     

Characterization of water-soluble hemicelluloses from spruce and aspen employing SEC/MALDI mass spectroscopy

Partly depolymerized hemicelluloses isolated from wood chips of spruce and aspen employing microwave treatment were resolved using size-exclusion chromatography (SEC) into oligo- and polysaccharide fractions containing components with a narrow range of sizes, as determined by MALDI mass spectroscopy. The degree of substitution with acetyl moieties (DS) was also calculated on the basis of the MALDI-MS spectra obtained prior to and following deacetylation. For spruce hemicelluloses, the low molecular mass fraction contained small arabino-4-O-methylglucuronoxylan oligosaccharides, with DP values ranging from 4 to approximately 20, separated primarily on the basis of their charge density. The fraction eluted last consisted of an O-acetyl-(galacto)glucomannan polysaccharide of peak-average DP value (DP(p)) 14. The degree of substitution with acetyl groups (DS) decreased with decreasing DP, a value DS of 0.39 being obtained for the fraction with DP(p) 12. For the aspen hemicelluloses, the SEC fractions eluted first contained an acidic O-acetyl-4-O-methylglucuronoxylan polysaccharide with DP ranging from 10 to approximately 28 and an average DS of approximately 0.75. The fractions eluted last consisted of oligosaccharide mixtures composed primarily of small neutral O-acetyl-xylooligosaccharides (DP(p) 6, DS 0.41), together with minor quantities of an O-acetyl-glucomannan.     

Ethanol production from acid hydrolysates based on the construction and demolition wood waste using Pichia stipitis

The feasibility of ethanol production from the construction and demolition (C&D) wood waste acid hydrolysates was investigated. The chemical compositions of the classified C&D wood waste were analyzed. Concentrated sulfuric acid hydrolysis was used to obtain the saccharide hydrolysates and the inhibitors in the hydrolysates were also analyzed. The C&D wood waste composed of lumber, plywood, particleboard, and medium density fiberboard (MDF) had polysaccharide (cellulose, xylan, and glucomannan) fractions of 60.7-67.9%. The sugar composition (glucose, xylose, and mannose) of the C&D wood wastes varied according to the type of wood. The additives used in the wood processing did not appear to be released into the saccharide solution under acid hydrolysis. Although some fermentation inhibitors were detected in the hydrolysates, they did not affect the ethanol production by Pichia stipitis. The hexose sugar-based ethanol yield and ethanol yield efficiency were 0.42-0.46 g ethanol/g substrate and 84.7-90.7%, respectively. Therefore, the C&D wood wastes dumped in landfill sites could be used as a raw material feedstock for the production of bioethanol.     

Bioethanol fermentation by recombinant E. coli FBR5 and its robust mutant FBHW using hot-water wood extract hydrolyzate as substrate

Hemicellulose is a potential by-product currently under-utilized in the papermaking industry. It is a hetero-carbohydrate polymer. For hardwood hemicelluloses, D-xylose is the major component upon depolymerization. At SUNY-ESF, wood extracts were obtained by extracting sugar maple wood chips with hot water at an elevated temperature. The wood extracts were then concentrated and acid hydrolyzed. Ethanologenic bacteria, E. coli FBR5, had a good performance in pure xylose medium for ethanol production. However, FBR5 was strongly inhibited in dilute sulfuric acid hydrolyzate of hot-water wood extract. FBR5 was challenged by hot-water wood extract hydrolyzate in this study. After repeated strain adaptation, an improved strain: E. coli FBHW was obtained. Fermentation experiments indicated that FBHW was resistant to the toxicity of hydrolyzate in the fermentation media of concentrated hydrolyzate, and xylose was completely utilized by the strain to produce ethanol. FBHW was grown in the concentrated hydrolyzate without any detoxification treatment and has yielded 36.8 g/L ethanol.     

Genetic improvement of the chemical composition of Scots pine (Pinus sylvestris L.) juvenile wood for bioenergy production

Chemical composition is one of the key characteristics that determines wood quality and in turn its suitability for different end products and applications. The inclusion of chemical compositional traits in forest tree improvement requires high‐throughput techniques capable of rapid, non‐destructive and cost‐efficient assessment of large‐scale breeding experiments. We tested whether Fourier‐transform infrared (FTIR) spectroscopy, coupled with partial least squares regression, could serve as an alternative to traditional wet chemistry protocols for the determination of the chemical composition of juvenile wood in Scots pine for tree improvement purposes. FTIR spectra were acquired for 1,245 trees selected in two Scots pine (Pinus sylvestris L.) full‐sib progeny tests located in northern Sweden. Predictive models were developed using 70 reference samples with known chemical composition (the proportion of lignin, carbohydrates [cellulose, hemicelluloses and their structural monosaccharides glucose, mannose, xylose, galactose, and arabinose] and extractives). Individual‐tree narrow‐sense heritabilities and additive genetic correlations were estimated for all chemical traits as well as for growth (height and stem diameter) and wood quality traits (density and stiffness). Genetic control of the chemical traits was mostly moderate. Of the major chemical components, highest heritabilities were observed for hemicelluloses (0.43–0.47), intermediate for lignin and extractives (0.30–0.39), and lowest for cellulose (0.20–0.25). Additive genetic correlations among chemical traits were, except for extractives, positive while those between chemical and wood quality traits were negative. In both groups (chemical and wood quality traits), correlations with extractives exhibited opposite signs. Correlations of chemical traits with growth traits were near zero. The best strategy for genetic improvement of Scots pine juvenile wood for bioenergy production is to decrease and stabilize the content of extractives among trees and then focus on increasing the cellulose:lignin ratio.     

Fractional extraction and physico-chemical characterization of hemicelluloses and cellulose from sugar beet pulp

Four hemicelluloses and cellulose fractions were extracted with 10% KOH or 7.5% NaOH at 15°C for 16 h and with 24% KOH or 17.5% NaOH at 15°C for 2 h from defatted, protein and pectin free, lignified or delignified sugar beet pulp (SBP). There was no significant difference in the yield and sugar composition of isolated hemicelluloses and cellulose obtained from four different procedures. 7.5% NaOH extraction at 15°C for 16 h from lignified SBP gave a slightly higher yield of hemicelluloses (10.96%), while 24% KOH extraction at 15°C for 2 h from delignified SBP produced the highest yield of cellulose (18.35%). Molecular-average weights ranged from 88 850 to 91 330 Da for the hemicelluloses obtained from lignified SBP, and 21 620–21 990 Da for the hemicelluloses isolated from delignified SBP. The neutral sugar composition of the hemicelluloses consisted of glucose, arabinose, galactose, xylose, and minor quantities of rhamnose and mannose. The infrared spectra showed an absorption band at 900 cm⁻¹, indicating some amounts of β-linked polysaccharides. Besides ferulic and p-coumaric acids, six other phenolics were also identified in the mixture of alkaline nitrobenzene oxidation of associated lignin in the isolated hemicelluloses and cellulose fractions.     

Ethanol production from alfalfa fiber fractions by saccharification and fermentation

This work describes ethanol production from alfalfa fiber using separate hydrolysis and fermentation (SHF) and simultaneous saccharification and fermentation (SSF) with and without liquid hot water (LHW) pretreatment. Candida shehatae FPL-702 produced 5 and 6.4 g/l ethanol with a yield of 0.25 and 0.16 g ethanol/g sugar respectively by SHF and SSF from alfalfa fiber without pretreatment. With LHW pretreatment using SSF, C. shehatae FPL-702 produced 18.0 g/l ethanol, a yield of 0.45 g ethanol/g sugar from cellulosic solids or ‘raffinate’. Using SHF, it produced 9.6 g/l ethanol, a yield of 0.47 g ethanol/g sugar from raffinate. However, the soluble extract fraction containing hemicelluloses was poorly fermented in both SHF and SSF due to the presence of inhibitors. Addition of dilute acid during LHW pretreatment of alfalfa fiber resulted in fractions that were poorly saccharified and fermented. These results show that unpretreated alfalfa fiber produced a lower ethanol yield. Although LHW pretreatment can increase ethanol production from raffinate fiber fractions, it does not increase production from the hemicellulosic and pectin fractions.     

Comprehensive utilization of waste hemicelluloses during ethanol production to increase lactic acid yield: from pretreatment to fermentation

Background

Reducing the cost of producing cellulosic ethanol is essential for the industrialization of biorefinery. Several processes are currently under investigation, but few of these techniques are entirely satisfactory in terms of competitive cost or environmental impact. In this study, a new ethanol and lactic acid (LA) coproduction is proposed. The technique involved addition of waste alkaline peroxide pretreated hydrolysate (mainly LA and hemicelluloses) to the reaction mixture after ethanol fermentation (mainly LA and xylose) to reduce the ethanol production cost.

Results

The following processes were investigated to optimize LA production: no addition of hemicelluloses or hydrolysate, addition of recycled hemicelluloses, and addition of concentrated hydrolysate. The addition of concentrated hydrolysate at 48 hours, which resulted in a maximum LA concentration of 22.3 g/L, was the most environment-friendly and cost-effective process. After the improved fermentation, 361 mg LA and 132 mg ethanol were produced from 1 g of raw poplar wood. That is, the production of one gallon of ethanol produced $9 worth of LA.

Conclusions

The amount of LA produced from the pretreated hydrolysate and reaction mixture after ethanol fermentation cannot be underestimated. The recovery of hydrolysate rich in LA and hemicelluloses (or xylose) significantly improved LA yield and further reduced the ethanol production cost.