Jarl Hemming

Determination of the strong mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone in chlorinated drinking and humic waters☆

The strong Ames test mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-2-(5H)-furanone (MX) was found to occur in chlorinated drinking and humic waters in sub μg L−1 concentrations. Quantitation by GC/MS using Selective Ion Monitoring in parallel with Ames tests of waters indicated that this furanone accounted for 15 – 30% of the Ames test mutagenicity of both a drinking water and a humic water.

Lignans and lipophilic extractives in Norway spruce knots and stemwood

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.

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.

Knots in trees - A new rich source of lignans

Recent research in our group has revealed that knots, i.e. the branch bases inside tree stems, commonly contain 5–10% (w/w) of lignans. Norway spruce (Picea abies) knots contain as much as 6–24% of lignans, with 7-hydroxymatairesinol (HMR) as the predominant (70–85%) lignan. Some other spruce species also contain HMR as the main lignan, but some spruce species have also other dominating lignans. Most fir (Abies) species contain secoisolariciresinol and lariciresinol as the main lignans. Lignans occur also in knots of pines (Pinus spp.), although in lower amounts than in spruces and firs. Scots pine (Pinus silvestris) knots were found to contain 0.4–3% of lignans with nortrachelogenin as the main lignan. Lignans have been identified also in knots of some hardwoods, although flavonoids are more abundant in hardwoods. Knots are detrimental in the manufacture of pulp and paper and should preferably be removed before pulping. This is possible using a recently developed industrially applicable process called ChipSep. Recent research has also established novel synthetic routes to several lignans, such as matairesinol, secoisolariciresinol, lariciresinol and cyclolariciresinol, starting from hydroxymatairesinol by applying fairly straight-forward chemical transformations. We conclude that wood knots in certain spruce and fir species constitute the richest known source of lignans in nature. The lignans occur in knots in free form and are easily extracted by aqueous ethanol, or even by water. Not only HMR, but also other potentially valuable lignans, could be produced in a scale of hundreds of tons per year by extraction of knots separated from wood chips at pulp and paper mills.

Phenolic and lipophilic extractives in Scots pine knots and stemwood

Summary 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 abietane-type 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.

Scots pine (Pinus sylvestris) bark composition and degradation by fungi: potential substrate for bioremediation.

The composition of Scots pine bark, its degradation, and the production of hydrolytic and ligninolytic enzymes were evaluated during 90 days of incubation with Phanerochaete velutina and Stropharia rugosoannulata. The aim was to evaluate if pine bark can be a suitable fungal substrate for bioremediation applications. The original pine bark contained 45% lignin, 25% cellulose, and 15% hemicellulose. Resin acids were the most predominant lipophilic extractives, followed by sitosterol and unsaturated fatty acids, such as linoleic and oleic acids. Both fungi degraded all main components of bark, specially cellulose (79% loss by P. velutina). During cultivation on pine bark, fungi also degraded sitosterol, produced malic acid, and oxidated unsaturated fatty acids. The most predominant enzymes produced by both fungi were cellulase and manganese peroxidase. The results indicate that Scots pine bark supports enzyme production and provides nutrients to fungi, thus pine bark may be suitable fungal substrate for bioremediation.

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.

Bioactive phenolic substances in industrially important tree species. Part 1: Knots and stemwood of different spruce species

Abstract Knots (i.e., branch bases inside tree stems) in spruce trees contained remarkably higher concentrations of lignans and oligolignans than the adjacent stemwood. The amount of lignans in some knots exceeded 10% (w w−1) and some knots contained hundreds of times more lignans than the heartwood in the same tree. However, there were large variations between different species and even between different knots in the same tree. 7-Hydroxymatairesinol was the predominant lignan in knots of Picea abies, P. glauca, P. koraiensis, P. mariana, and P. omorika, while liovil and secoisolariciresinol dominated in P. sitchensis and P. pungens. The lignans occur in free form in knots and are easily extracted with polar solvents. In addition to the true lignans, especially the knots contained large amounts of lignan-related oligomeric aromatic substances, here called oligolignans, consisting of three or four phenylpropane units. 7-Hydroxymatairesinol, but also other lignans, could be extracted in large scale from spruce knots at pulp and paper mills. Other potentially important lignans could be produced from 7-hydroxymatairesinol by semisynthesis. The ready availability of large amounts of lignans and oligolignans now enables research to assess their bioactivity and provide the basis for applications in medicine and nutrition or as natural antioxidants and antimicrobial agents in a variety of technical products.

Bioactive phenolic substances in industrially important tree species. Part 2: Knots and stemwood of fir species

Abstract Knots, i.e. branch bases inside tree stems, in fir trees contained remarkably higher concentrations of lignans, oligolignans, and juvabiones than the adjacent stemwood. Eight fir species were analysed (Abies sibirica, A. lasiocarpa, A. balsamea, A. alba, A. amabilis, A. veitchii, A. sachalinensis, and A. concolor). The amount of lignans could in some knots exceeds 6% (w/w) and the knots generally contained 20–50 times more lignans than the stemwood. However, there were large variations, not only between species but also even between knots in the same tree. Secoisolariciresinol was the predominant lignan in all knots. The lignans occur in free form in the knots and are easily extracted with polar solvents. In addition to the lignans, oligomeric aromatic substances, mainly sesquineo- and dineolignans, and juvabiones were accumulated in the knotwood. Secoisolariciresinol, but also lariciresinol (Abies alba) and 7-hydroxymatairesinol (A. amabilis), could be extracted in large scale from fir knots at pulp and paper mills. The ready availability of large amounts of lignans and oligolignans now enables research to assess their bioactivity and provide the base for applications in medicine and nutrition, or as natural antioxidants and antimicrobial agents in various technical products.

Phenolic extractives in Salix caprea wood and knots

Salix caprea stemwood and knots were found to contain the phenolic extractives vanillic acid, 3-p-coumaryl alcohol, coniferyl alcohol, sinapylaldehyde, dihydrokaempferol, catechin, naringenin, gallocatechin, dihydromyrcetin and taxifolin. The knots contained larger quantities of flavonoids than did stemwood of the same tree.