Isolation and characterisation of water soluble polysaccharides from Norway spruce and Scots pine

Water soluble polysaccharides from Norway spruce, Scots pine, and Siberian larch were compared. For all species the total amount of polysaccharides isolated from the heartwood was higher than that from the sapwood. The heartwood polysaccharides had a high content of galactose and arabinose units, and some glucuronic acid units, suggesting the presence of acidic arabinogalactans. The total amounts of recovered water-soluble arabinogalactans were 1.9 mg/g for spruce heartwood, 5.3 mg/g for pine heartwood, and as much as 106 mg/g for larch heartwood. The other water-soluble polysaccharides were mainly glucomannans. The average ratio of Gal:Ara:GlcA in the water-soluble arabinogalactans of spruce heartwood was about 4.3:1:1, pine heartwood about 4.5:1:0.2, and larch heartwood about 6.7:1:0.1. The corresponding molar ratios then being about 3.6:1:0.8 for spruce, 3.8:1:0.2 for pine, and 5.6:1:0.08 for larch. Thus, the content of glucuronic acid units was especially high in the spruce heartwood arabinogalactans. The content of arabinose was slightly higher in spruce and pine than in larch heartwood arabinogalactans.     

Knotwood and bark extracts: strong antioxidants from waste materials

The antioxidant properties of hydrophilic extracts of knotwood of several industrially important tree species were evaluated by lipid-peroxidation inhibition and peroxyl-trapping capacity tests. The results were compared with the antioxidant properties of hydrophilic extracts of bark, and pure lignans and flavonoids isolated from knotwood extracts. The knot extracts from several tree species were stronger antioxidants than the bark extracts, which can, however, also be classified as strong antioxidants. In addition, the antioxidant properties of most of the knotwood extracts are stronger than the pure compounds. It is concluded that knotwood is a rich source of natural antioxidants.     

Chemical composition of earlywood and latewood in Norway spruce heartwood,sapwood and transition zone wood

This study focused on the distribution of wood components along a cross section of a spruce stem. Thin samples of earlywood and latewood were analysed by special micro-scale analytical techniques. Heartwood contained significantly more lignin and less cellulose than sapwood. The total content of hemicelluloses was the same along the radial direction, but the distribution of sugar units differed. The amounts of arabinoglucuronoxylan and pectins were larger in the heartwood. The transition zone between heartwood and sapwood had a specific composition, with less lignin and lipophilic extractives than heartwood and sapwood. For earlywood and latewood, significant differences were found in the distribution of sugar units in hemicelluloses. Latewood contained clearly more galactoglucomannan than earlywood, and conversely less pectins. The lipophilic extractives were also less concentrated in the latewood.Abbreviations EW or E earlywood - LW or L latewood - HW heartwood - SW sapwood - TZ transition zone wood - A.R. annual ring - AcBr Acetyl bromide - Ara arabinose - Xyl xylose - Gal galactose - Glc glucose - Man mannose - Rha rhamnose - GlcA glucuronic acid - MGlcA 4-O-methyl-glucuronic acid - GalA galacturonic acid - o.d. oven dry     

Characteristic fragment ions from lignin and polysaccharides in ToF–SIMS

Different model compounds for lignin, hemicelluloses and pectins were studied by time-of-flight secondary-ion mass spectrometry (ToF–SIMS). Mass spectra of Klason lignin from normal and compression spruce wood, aspen wood and wheat straw were compared. Spectra of brominated spruce and aspen wood sections showed fragment ions attributed to brominated guaiacyl and syringyl units in lignin at m/z 215, 217, 229 and 231, and m/z 245, 247, 249 and 261, respectively. Spectra of mono-, oligo- and polysaccharides showed fragment ions at m/z 127 and 145 characteristic for hexose units, and ions at m/z 115 and 133 characteristic for pentose units. The same ions were detected in spectra of delignified spruce and aspen wood sections. Labelling of anionic groups by Sr²⁺ ions followed by ToF–SIMS analysis showed that pectins were present at specific locations on the surfaces of spruce and aspen wood sections still after delignification with hydrogen peroxide in acetic acid.     

Structural features of water-soluble arabinogalactans from Norway spruce and Scots pine heartwood

 Isolated water-soluble acidic arabinogalactans from Norway spruce and Scots pine heartwood were analysed and compared to Siberian larch heartwood arabinogalactans. The carbohydrate monomer composition was determined by acid methanolysis and gas chromatography, while structural studies were performed by ¹³C NMR spectroscopy and methylation analysis. The main structural features were found to be the same in the three types of arabinogalactans. However, the structure of the arabinogalactans from spruce and pine were found slightly different from the structure of larch arabinogalactans. The amount of single unit side-chains, consisting of arabinose and glucuronic acid units, was higher in the spruce and pine arabinogalactans than in the larch arabinogalactans. The amount of glucuronic acid was higher in the spruce arabinogalactans than in the pine arabinogalactans. The pine arabinogalactans had a higher amount of side chains with more than two sugar units than the spruce arabinogalactans. Received 30 December 1999     

Polysaccharides in some industrially important softwood species

The content and composition of carbohydrates comprising polysaccharides in sapwood and heartwood of 12 industrially important pulpwood species were analysed. The polysaccharide content was between 60% and 80% (w/w) for all species, with cellulose as the predominant polysaccharide type. The carbohydrate composition suggested that the main non-cellulose polysaccharides were galactoglucomannans, except in Larix heartwood, where arabinogalactans were predominant, while the content of xylans were in the same range as the mannans in Pinus resinosa heartwood and Thuja occidentalis heartwood and sapwood. Pectins, i.e. polygalacturonic acids, were the main acidic polysaccharides in all species. The amount and composition of water-soluble carbohydrates from ground wood samples were also analysed, since these are important in mechanical pulping and as a possible source of bioactive polymers. The main polysaccharides released from the spruce species were mannans, together with starch from sapwood. Especially Abies balsamea stemwood, but also Abies sibirica heartwood, released considerable amounts of pectins, suggesting that fir species may release more troublesome anionic polysaccharides than spruce species. Heartwood of Larix lariciana, Larix decidua, Pinus banksiana, and Pinus resinosa released considerable amounts of acidic arabinogalactans. Thuja occidentalis released mainly arabinogalactans and pectins. Pseudotsuga menziesii heartwood released a large amount of arabinogalactans.     

Antioxidant activity of knotwood extractives and phenolic compounds of selected tree species

The antioxidant potency and the radical scavenging capacity of superoxide and peroxyl radicals were assessed for 13 hydrophilic knotwood extracts of commercially important wood species, or fractions thereof, as well as for five pure wood-derived lignans and the flavonoid taxifolin. The chemical composition of the knotwood extracts was determined by gas chromatography combined with mass spectrometry. Most of the investigated wood species were rich in hydrophilic extractives (10-20% of the dry wood) with one or a few compounds dominating in each extract. All extracts had a high antioxidative potency and/or radical scavenging capacity as compared to the well-known antioxidants Trolox and butylated hydroxyanisole. The pure wood-derived lignans and taxifolin also had a high antioxidative potency and/or radical scavenging capacity. However, the antioxidant potency and/or radical scavenging capacity of several of the hydrophilic knotwood extracts were higher than that of the dominating compounds in pure form.     

Carbohydrate analysis of plant materials with uronic acid-containing polysaccharides–A comparison between different hydrolysis and subsequent chromatographic analytical techniques

Acid hydrolysis, acid methanolysis, and enzymatic hydrolysis were compared for depolymerization of five different plant materials containing uronic acids. The analyzed plant materials were oat spelt, wheat straw, spruce thermomechanical pulp, aspen stemwood, and totally chlorine-free (TCF) bleached hardwood kraft pulp. Furthermore, GC (using both HP-1 and HP-5 capillary columns and FID and MSD detectors), HPAEC-PAD, and HPAEC-Borate techniques were compared for subsequent analysis of the released monosaccharides. It was shown that acid methanolysis combined with GC analysis is a convenient method for obtaining the sugar unit composition and amount of non-crystalline polysaccharides in different plant materials. The methanolysis method was generally superior to the hydrolysis method for xylan- and uronic acid-containing samples. However, acid and enzymatic hydrolysis showed the highest recoveries for bleached chemical pulp samples. Acid hydrolysis is also required for crystalline polysaccharides, but the strong acid conditions evidently lead to degradation of labile sugars. The plant methanolysates were not suitable as such for analysis on an HPAEC-PAD system. For analysis of the total amount of sugar units, hence including cellulose, other non-crystalline hemicelluloses, and pectins, a combination of the methanolysis and hydrolysis methods is recommended.     

Quercus suber and Betula pendula outer barks as renewable sources of oleochemicals: A comparative study

A comparative study on the chemical composition of oak cork (Quercus suber L.) and corresponding industrial residues and birch (Betula pendula L.) outer bark is reported. Cork oak samples have lower extractives contents (6–9%) and higher contents of carbohydrates and lignin (23–27 and 33–38%, respectively) than those found for birch outer bark (40, 6 and 9%, respectively); suberin contents accounted for around 30% of cork, 11% of industrial cork powder and 45% of birch outer bark. Analysis of the suberin monomeric composition revealed that C18 and C22 ω-hydroxyfatty acids (including mid-chain epoxy- and dihydroxy-derivatives), followed by α,ω-dicarboxylic acids, are the main components in both suberins, with 9,10-epoxy-18-hydroxyoctadecanoic, 18-hydroxyoctadec-9-enoic, 9,10,18-trihydroxyoctadecanoic and octadec-9-enoic acids as the major components. The differences in the relative amounts of these acids in the suberin samples and the impact on the potential exploitation of the different industrial by-products are discussed.     

Kinetics of acid hydrolysis of water-soluble spruce O-acetyl galactoglucomannans

Water-soluble O-acetyl galactoglucomannan (GGM) is a softwood-derived polysaccharide, which can be extracted on an industrial scale from wood or mechanical pulping waters and now is available in kilogram scale for research and development of value-added products. To develop applications of GGM, information is needed on its stability in acidic conditions. The kinetics of acid hydrolysis of GGM was studied at temperatures up to 90 degrees C in the pH range of 1-3. Molar mass and molar mass distribution were determined using size exclusion chromatography with multiangle laser light scattering and refractive index detection. The molar mass of GGM decreased considerably with treatment time at temperatures above 70 degrees C and pH below 2. The molar mass distribution broadened with hydrolysis time. A first-order kinetic model was found to match the acid hydrolysis. The reaction rate constants at various pH values and temperatures were calculated on the basis of the first-order kinetic model. Furthermore, the activation energy, E, was obtained from the Arrhenius plot. The activation energy E was 150 kJ mol (-1) for acid hydrolysis of spruce GGM. The apparent rate constant during acid hydrolysis increased by a factor of 10 with a decrease in pH by 1 unit, regardless of temperature. In addition, gas chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry were applied to study the released GGM monomers and oligomers.