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.
Possible chemical utilization of bark requires appropriate knowledge of its composition. Extraction of valuable components before burning is an interesting option for utilization of bark. Here, Norway spruce inner and outer bark were extracted separately with a successive series of solvents of increasing polarity and the extracts, as well as the residues, were analyzed to obtain an overall picture of the bark composition. The lipophilic extractives contained the same major components as found in wood. Inner bark contained over 10% of stilbene glucosides with piceatannol (astringenin) as the main stilbene. Tannins of the proanthocyanidin type were extracted with hot water. Further extraction with pressurized hot water at 140°C or 160°C yielded 11-14% of non-cellulosic polysaccharides, on original bark basis, with pectic polysaccharides built up of arabinose, galacturonic acid and rhamnose dominating. Inner bark contained two times more cellulose than outer bark, but the opposite was true for lignin, determined as Klason “lignin”. Among the potentially valuable components, stilbene glucosides could be extracted with water even at low temperatures, while tannins could be extracted with hot water in a second step. The pectic polysaccharides are also of potential interest and should be studied further. The amount and true chemical character of lignin is also not yet fully elucidated.
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