Summary The hydrophilic and lipophilic extractives in the heartwood of knots from 7 Norway spruce trees were analysed by GC, GC-MS and HPSEC. The knots contained extremely large amounts of lignans, 6–24% (w/w), with hydroxymatairesinol comprising 65–85% of the lignans. Even the knots of the young trees contained 4–8% (w/w) of lignans. The variation in the amount of lignans was large among knots, both within a single tree and between trees. In addition to the lignans, knots also contained 2–6% (w/w) of a complex mixture of lignan-like compounds with 3, 4 and even up to 6 phenyl propane units, here called oligolignans. The amounts of lignans in the knots were similar in the radial direction from the pith into the outer branch, but decreased dramatically outwards in the branch, almost disappearing after 10–20 cm. The ratio of the 2 epimers of hydroxymatairesinol differed between different knots and even within the knot. A new spruce lignan, nortrachelogenin, or its enantiomer, wikstromol, was detected in knots from trees in northern Finland as opposed to samples from southern Finland. The amount of lipophilic extractives was small compared to the amount of hydrophilic extractives in the knots. Five of the dead knots contained more resin acids and free diterpenyl alcohols than ordinary stemwood. In the other knots, the amount of lipophilic extractives was on the same level as stem heartwood. The stem sapwood contained larger amounts of esterified fatty acids than the knots.

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.

The phenolic and lipophilic extractives in the heartwood of knots from seven Scots pine trees were analysed by GC, GC-MS and HPSEC. The knots contained large amounts of phenolic stilbenes, 1-7% (w/w), and lignans, 0.4-3% (w/w), while the stemwood contained around 1% (w/w) of stilbenes and no detectable lignans. In young trees without stem heartwood the stilbene content in the knots was up to 200 times that in the stem. Some in-tree and between-tree variation was seen in the content of phenolic compounds in the knots. The ratio of pinosylvin monomethyl ether to pinosylvin was higher in the knots than in the stemwood. The most abundant lignan was nortrachelogenin, but also matairesinol, secoisolariciresinol and liovil were present in small amounts in the knots. The knots also contained a complex mixture of lignan-like compounds, here called oligolignans. The flavonoid pinocembrin was present in both stemwood and knots in amounts below 0.02% (w/w). The stilbene concentration in the radial direction, from the pith to the outer branch, decreased or was on the same level inside the stem, while it decreased markedly in the outer branch. The lignan concentration was on the same level or decreased slightly inside the stem, while it decreased markedly in the branches and became almost non-existent within 10 cm out in the branches. The knots contained large amounts (4.5-32% (w/w)) of lipophilic extractives, mainly resin acids. Some in-tree and between-tree variation was seen for the resin acids. The abietanetype resin acids dominated over the pimarane-type acids and abietic acid was the most abundant resin acid in the knots and in stem heartwood. The amount of resin acids in the radial direction decreased or was on the same level inside the stem, while a clear decrease was detected in the branches. The profile of the distribution of resin acids and phenolic compounds was similar. The knots also contained up to 0.5% (w/w) of diterpenyl aldehydes.

The potential for the extraction of the plant lignan hydroxymatairesinol (HMR) in large scale from Norway spruce (Picea abies) has given us the opportunity to study the metabolism and biological actions of HMR in animals. HMR, the most abundant single component of spruce lignans, was metabolized to enterolactone (ENL) as the major metabolite in rats after oral administration. The amounts of urinary ENL increased with the dose of HMR (from 3 to 50 mg/kg), and only minor amounts of unmetabolized HMR isomers and other lignans were found in urine. HMR (15 mg/kg body wt po) given for 51 days decreased the number of growing tumors and increased the proportion of regressing and stabilized tumors in the rat dimethylbenz[a]anthracene-induced mammary tumor model. HMR (50 mg/kg body wt) did not exert estrogenic or antiestrogenic activity in the uterine growth test in immature rats. HMR also showed no antiandrogenic responses in the growth of accessory sex glands in adult male rats. Neither ENL nor enterodiol showed estrogenic or antiestrogenic activity via a classical alpha- or beta-type estrogen receptor-mediated pathway in vitro at < 1.0 microM. HMR was an effective antioxidant in vitro.

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Galactose oxidase was used as a catalyst to oxidize selectively the C-6 hydroxyls of terminal galactose to carbonyl groups. The polysaccharides studied included spruce galactoglucomannan, guar galactomannan, larch arabinogalactan, corn fiber arabinoxylan, and tamarind seed xyloglucan, with terminal galactose contents varying from 6% to 40%. A multienzyme system was used, with catalase and horseradish peroxidase to enhance the action of galactose oxidase. An analysis technique was developed for the quantification of the reactive aldehydes with GC-MS, utilizing NaBD4 reduction and acidic methanolysis. The best oxidation degrees of terminal galactosyls were obtained with xyloglucan (85% of galactose) and spruce galactoglucomannan (65% of galactose). The highest oxidation degree based on total carbohydrates was achieved with guar gum (28%), which had the highest galactose content. The oxidation resulted in changes in the physicochemical properties of the polysaccharide solutions, and the changes observed varied between the polysaccharides. The clearest change was in tamarind xyloglucan, which formed a gel after the oxidation. After the oxidation, larger particles were present in the solution of spruce galactoglucomannan, but changes in its rheological properties were not observed.

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