US20040199032A1 - Method for isolating phenolic substances or javabiones from wood comprising knotwood - Google Patents

Method for isolating phenolic substances or javabiones from wood comprising knotwood Download PDF

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US20040199032A1
US20040199032A1 US10/476,382 US47638203A US2004199032A1 US 20040199032 A1 US20040199032 A1 US 20040199032A1 US 47638203 A US47638203 A US 47638203A US 2004199032 A1 US2004199032 A1 US 2004199032A1
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wood
lignan
fraction
lignans
secoisolariciresinol
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Bjarne Holmbom
Christer Eckerman
Jarl Hemming
Markku Reunanen
Kenneth Sundberg
Stefan Willfor
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G99/00—Subject matter not provided for in other groups of this subclass

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  • This invention relates to a method for isolating chemical substances, i.e. phenolic substances or juvabiones from wood comprising knotwood.
  • Pinosylvin (a stilbene) and flavonoids have been identified in pine wood.
  • the flavonoids aromadendrin and taxifolin have been isolated from larch wood.
  • Both stilbenes and flavonoids have been isolated from hardwoods.
  • Many of these phenolic compounds have been reported to possess valuable therapeutical properties, particularly as antitumour agents and antioxidants. (S Nishibe, 1997, (3)), J D Ford et al 1999 (4) and N M Saarinen et al 2000 (5)).
  • Juvabiones are a group of cyclohexane derivatives and are useful e.g. as insecticides.
  • knots and branches of the trees are particularly rich in flavonoids and stilbenes, compared to other parts of the tree.
  • This invention in based on the idea of combining the isolation of phenolic substances or juvabiones from wood with the utilization of wood in manufacturing of pulp or various mechanical wood products.
  • the aim of this invention is thus to i) provide a practically useful source for these useful chemical substances and ii) improve the economy for the manufacturing processes of pulp or mechanical wood products in that by-products, hitherto used only for energy production, are offered a new use as source for phenolic substances and juvabiones.
  • this invention relates to a method for isolating of phenolic substances or juvabiones from wood comprising knotwood, said method comprising the steps of
  • FIG. 1 shows a vertical cross section of a tree stem with a branch, and a vertical cross section of the branch. The figure shows further sampling of the knots and branches for studying the distribution of lignans.
  • the dashed vertical line along the outermost layer of the bark-free stem wood is defined as zero line (0 cm).
  • FIGS. 2A to 2 E show the distribution of total lignan in opposite wood (diamonds), side wood (filled squares) and compression wood (filled triangles) of five knot and samples and three branch samples, taken at various positions from the zero line shown in FIG. 1.
  • phenolic substances shall be understood to cover lignans, oligolignans, flavonoids, isoflavonoids, stilbenes, tannins and phenolic acids. All these groups are mainly hydrophilic substances that can be extracted with polar, i.e. hydrophilic solvents.
  • notwood shall be understood to include the “knots”, i.e. the part of the branches that is embedded in the stem, and the branches extending outwards from the stem.
  • the “over-sized chip fraction” means the rejected fraction obtained in the screening stage of the chips aimed for the pulping process.
  • This over-sized chip fraction which can constitute about 1 to 5% of the total amount of wood chipped, cannot be forwarded as such to the pulping process.
  • this fraction has been recirculated to the chipping stage or withdrawn to be burnt.
  • This over-sized fraction comprises in addition to knotwood also considerable amounts of “normal wood”, i.e wood usable in the pulping process.
  • the amount of knotwood in the over-sized chip fraction depends on the wood species and wood quality used, and is estimated to about 10-30%.
  • the content of knotwood in the over-sized chip fraction is hereinafter also called “knot-rich fraction”.
  • the over-sized chip fraction as such for extraction of phenolic substances, it may be preferable to first separate the material into a knot-rich fraction and a knot-poor fraction and to use the knot-rich fraction for extraction.
  • the “knot-poor fraction” means the “normal wood” that can be led to the pulping process. This separation can be made directly from the over-sized chip fraction, or the material can first be refined before the screening stage.
  • Knotwood obtained as residue in finishing of mechanical wood products includes, for example, the plywood sheet pieces which include knots and are cut out and replaced by corresponding pieces of normal plywood in the manufacturing stage before the individual plywood sheets are pasted together to form the finished product.
  • Other examples are pieces of planks and boards rich in knots and therefore rejected for various reasons in building and construction, in furniture industry and the like.
  • sawdust is an example of such residues.
  • the useful residues are not restricted to those listed herein.
  • the “polar solvent” is either a single polar agent, or a mixture of two or more polar agents, where said polar agent or agents have a dielectric constant that is greater than 3, determined at 25 Celsius degrees.
  • polar solvents can be mentioned pure water only, and mixtures of water and acetone and water and alcohol, such as water and ethanol.
  • the extraction can be carried out on dried wood or on raw wood material.
  • the extraction can be physically integrated with the utilization of wood in the manufacturing of pulp or mechanical wood products, the extraction can alternatively be carried out as a separate process, because the knotwood, especially the knot-rich fraction of the over-sized chips, can easily be transported and stored for later processing.
  • the amount of phenolic substances in knotwood varies greatly and depends on the phenolic substance in question and the wood species used. Therefore, the extract derived from the extraction stage may contain considerable concentrations of a desired phenolic compound, and may therefore, depending on the purpose, be used as such without further purification.
  • the methods to be used depend i.a. on the substance to be isolated and the desired degree of purity.
  • useful purification methods can be mentioned chromatography or crystallization.
  • lignans to be isolated by the method of this invention can be mentioned hydroxymatairesinol, allohydroxymatairesinol, matairesinol, conidendrin, pinoresinol, oxomatairesinol, lariciresinol, liovil, isolariciresinol, secoisolariciresinol, picearesinol, conidendric acid, and nortrachelogenin.
  • lignans is not restricted to these compounds.
  • “Oligolignans” are compounds having 3 to 6 phenylpropane units that are beta-beta linked instead of normal lignans which have two beta-beta linked phenylpropane units.
  • flavonoids which can be isolated according to the method of this invention can be mentioned pinocembrin, dihydrokaempferol, pinobanksin, naringenin, catechin, 2,4,6-trihydroxychalcone, aromadendrin and taxifolin.
  • stilbenes can be mentioned pinosylvin, pinosylvin monomethyl ether, dihydropinosylvin, methylpinosylvin, methyldihydropinosylvin and reservatrol.
  • juvabiones can be mentioned epijuvabione, dehydrojuvabione, dihydroepijuvabione and epijuvabione acid.
  • This invention thus offers a unique method for deriving the desired phenolic compound or juvabione in high concentrations in the extract.
  • the wood material utilized for the extraction is material that hitherto has been regarded as a wood fraction useful as energy source only.
  • the wood samples were splintered, freeze-dried and ground in a Wiley mill, producing particles passing a 10-mesh screen. A second freeze-drying step after the milling ensured almost complete removal of volatile compounds.
  • the wood samples for the lignan distribution study were freeze-dried, splintered using a scalpel, and freeze-dried again.
  • Lignans, free fatty acids, resin acids and free sterols were, after evaporation of the extract solutions and silylation of the extractives, analysed on a 25 m ⁇ 0.20 mm i.d. crosslinked methyl polysiloxane column (HP-1). Heneicosanic acid and betulinol were used as internal standards. A correction factor of 1.2 for betulinol was used for the quantification of the lignans. All results given as mg/g or % (w/w) are calculated on a freeze-dried wood basis.
  • Oligolignans in the same silylated samples as above, were analysed according to (6) using cholesteryl heptadecanoate as internal standard.
  • the lignans and oligolignans were the main components of the hydrophilic extractives in all samples (Table 2). Small amounts ( ⁇ 1.1 mg/g) of monomeric sugars were also found in most samples. Trace amounts ( ⁇ 0.2 mg/g) of simple phenols, dominated by coniferyl alcohol and vanillic acid, were also present in all samples.
  • HMR was the most abundant lignan in all samples.
  • Lignans Oligolignans Total HMR Trimers Tetramers mg/g % of total mg/g mg/g Tree 1 HW 1.5 1.1 44 0.26 0.18 SW 1.5 0.7 53 0.17 0.08 DK 3.5 118 66 17 13 DK 5.5 123 68 17 10 LK 4.5 119 68 22 10 LK 9-a 124 69 21 9 LK 12 159 73 26 12 LK 13.5 120 73 20 10 LK 15-a 156 77 24 15 LK 15-b 149 80 25 14 Tree 2 HW 1.5 0.5 17 0.11 0.05 SW 1.5 0.2 25 0.07 0.03 DK 4.5 90 76 11 11 DK 6.5 134 75 16 14 DK 7.5 144 73 18 14 DK 13.5 117 76 15 11 LK 8 142 74 18 10 LK 9 129 75 17 10 LK 14.5 154 77 21 9 Tree 3 HW 1.5 2.2 37 0.32 0.13 SW 1.5 0.2 25 0.06 0.02 DK
  • FIGS. 2A to 2 E show the distribution of lignans from near the base of the knot to 10-20 cm out in the branch.
  • the lignans were almost absent 20 cm out in the branches from Tree 2 and 3, while they had decreased strongly in the branch from Tree 1.
  • the amount of lignans in a radial direction, from the pith into the outer branch, was quite even inside the stem.
  • the concentration of lignans decreased in the order opposite wood-side wood-compression wood.
  • knots usually contain smaller amounts of opposite wood than side wood and compression wood, the highest amount of lignans is situated in side wood and compression wood.
  • Trees 1-3 were felled in May, trees 4-5 in January, and trees 6-7 in October. Trees 1-3 and 6-7 were densely grown in sandy soil, while trees 4-5 were planted on former arable land. Trees 1-5 had an average diameter of about 30 cm at 1.5 m height, while the diameters of trees 6-7 were about 25 cm. Trees 4-5 had grown fast.
  • the heartwood from knots at a dead branch (DK), still attached or fallen off, and knots at a living branch (LK) were sampled.
  • the expression knots means knot heartwood.
  • HW Stem heartwood
  • SW stem sapwood
  • the number in each sample code expresses the height in meters above ground while the suffix a or b expresses different knots at the same height.
  • the heartwood of seven additional knots and five branches were split into 1 cm thick discs and further divided into opposite, side, and compression wood, for examining the distribution of lignans (FIG. 1).
  • the lignans and oligolignans were the main components of the hydrophilic extractives (Table 4). In addition, mainly small amounts of monomeric sugars, simple phenols (or monolignols), and dimeric non-lignan aromatic compounds of dilignoltype, such as 1,3-(bis-guaiacyl)-1,2-propandiol, were detected in most samples.
  • the amount of lignans was exceptionally large in the knots compared to the stemwood (Table 4).
  • the knots of the trees from northern Finland contained 14-24% (w w ⁇ 1 ), while the knots from southern Finland contained 6-16% (w w ⁇ 1 ) of lignans. Even the knots from the young trees contained 4-8% (w w ⁇ 1 ) lignans. Lignans were found in small amounts also in the sapwood.
  • the main identified lignans were mainly the same as found earlier in Norway spruce (7).
  • the identified lignans were two epimers of hydroxymatairesinol (HMR), ⁇ -conidendrin, liovil (two isomers), secoisolariciresinol, lariciresinol, pinoresinol, matairesinol, isolariciresinol, ⁇ -conidendric acid and a lignan called lignan A. Seven unknown minor lignans were also detected and quantified.
  • the two epimers of HMR dominated in all knots (Table 4).
  • the epimers are here called HMR 1 and HMR 2 based on their elution order on GC.
  • HMR 2 major lignan
  • HMR 1 or allo-HMR The structure of the major lignan, HMR 2, and its minor epimer, HMR 1 or allo-HMR, has been discussed in the literature (8, 9).
  • the ratio HMR 2/HMR 1 was between 2 and 4 in trees 1-2 and 6-7, while the range was 2-7 in tree 3, 4-5 in tree 4, and 1-3 in tree 5.
  • HMR was the dominating lignan also in the stem sapwood and heartwood samples, even though the contribution of the other lignans was higher.
  • the ratio HMR 2/HMR 1 was between 2 and 5 in heartwood and even up to 11 in sapwood.
  • knots from tree 6 and 7 we found a lignan that has not been identified earlier in spruce trees, in amounts ranging from 2 to 7 mg g ⁇ 1 .
  • the volume of the pith was quite large compared to the total knot volume in most knots. Even though the dry mass of the pith is small compared to the total knot mass, it was of interest to analyse the extractives in the pith.
  • the pith material contained mainly lignans, about 120 mg g ⁇ 1 , with HMR as the most abundant lignan. Small amounts of an NTG-isomer, with the same mass spectrum but different GC retention time, was also identified in the pith material.
  • Pinus banksiana (epijuvabione acid 1.2%, pinosylvin monomethyl ether 1.1%, nortrachelogenin 1.3%)
  • Pinus resinosa pinosylvin 1.4%, pinosylvin monomethyl ether 2.8%, matairesinol 1.2%)
  • Larix decidua (dihydrokaempferol 1.1%, taxifolin 2.8%, isolariciresinol 1.1%, secoisolariciresinol 4.8%, lariciresinol 1.3%)
  • Betula pendula Betula verrucosa
  • Alnus incana severe stilbene glycosides 1-2%)

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  • Organic Chemistry (AREA)
  • Medicines Containing Plant Substances (AREA)
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FI20011194A FI20011194A0 (fi) 2001-06-06 2001-06-06 Menetelmä kemikaalien eristämiseksi puusta
PCT/FI2002/000418 WO2002098830A1 (en) 2001-06-06 2002-05-16 A method for isolating phenolic substances or juvabiones from wood comprising knotwood

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008121021A1 (ru) 2007-03-29 2008-10-09 Nikolay Eduardovich Nifantiev Способ выделения секоизоларицирезинола и дигидрокверцетина из древесины
US20100240104A1 (en) * 2007-12-19 2010-09-23 Xiao Zhang Conversion of knot rejects from chemical pulping
US20110005125A1 (en) * 2008-02-11 2011-01-13 Universita1 Degli Studi Di Milano Procedure for the production of biofuel from organic wastes
US20110160442A1 (en) * 2008-07-01 2011-06-30 Suvi Pietarinen Method for the fractionation of knotwood extract and use of a liquid-liquid extraction for purification of knotwood extract
CZ304352B6 (cs) * 2012-06-25 2014-03-19 Výzkumný ústav potravinářský Praha, v.v.i. Zařízení na získání části využitelného odpadu při zpracování dřeva na řezivo
CZ305794B6 (cs) * 2015-04-20 2016-03-16 Výzkumný ústav potravinářský Praha, v.v.i. Způsob úpravy dřevních suků s přesně regulovanou strukturou drtě pro výrobu lignanů a zařízení k provádění tohoto způsobu, s využitím v potravinářské výrobě
CZ306700B6 (cs) * 2014-12-05 2017-05-17 Výzkumný ústav potravinářský Praha, v.v.i. Způsob výroby lignanů pro potravinářské účely extrakcí ze suků jehličnanů
WO2021023914A1 (en) * 2019-08-02 2021-02-11 Oy Granula Ab Ltd A method and a compound for preventing mammalian cancer cell proliferation and for treating cancer

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2444346A (en) * 1946-01-05 1948-06-29 Univ Recovery of nordihydroguaiaretic acid from plant extracts
US5335790A (en) * 1991-02-08 1994-08-09 Andritz-Pantentverwaltungs-Gesellschaft M.B.H. Method and device for separating pieces of wood

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2444346A (en) * 1946-01-05 1948-06-29 Univ Recovery of nordihydroguaiaretic acid from plant extracts
US5335790A (en) * 1991-02-08 1994-08-09 Andritz-Pantentverwaltungs-Gesellschaft M.B.H. Method and device for separating pieces of wood

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008121021A1 (ru) 2007-03-29 2008-10-09 Nikolay Eduardovich Nifantiev Способ выделения секоизоларицирезинола и дигидрокверцетина из древесины
US20100286255A1 (en) * 2007-03-29 2010-11-11 Nikolay Eduardovich Nifantiev Method for extracting secoisolariciresinol and dihydroquercetin from wood
EA016246B1 (ru) * 2007-03-29 2012-03-30 Николай Эдуардович Нифантьев Способ выделения секоизоларицирезинола и дигидрокверцетина из древесины
US20100240104A1 (en) * 2007-12-19 2010-09-23 Xiao Zhang Conversion of knot rejects from chemical pulping
US8283140B2 (en) * 2007-12-19 2012-10-09 Fpinnovations Conversion of knot rejects from chemical pulping
US20110005125A1 (en) * 2008-02-11 2011-01-13 Universita1 Degli Studi Di Milano Procedure for the production of biofuel from organic wastes
US8754274B2 (en) * 2008-02-11 2014-06-17 Università delgi Studi di Milano Procedure for the production of biofuel from organic wastes
US20110160442A1 (en) * 2008-07-01 2011-06-30 Suvi Pietarinen Method for the fractionation of knotwood extract and use of a liquid-liquid extraction for purification of knotwood extract
CZ304352B6 (cs) * 2012-06-25 2014-03-19 Výzkumný ústav potravinářský Praha, v.v.i. Zařízení na získání části využitelného odpadu při zpracování dřeva na řezivo
CZ306700B6 (cs) * 2014-12-05 2017-05-17 Výzkumný ústav potravinářský Praha, v.v.i. Způsob výroby lignanů pro potravinářské účely extrakcí ze suků jehličnanů
CZ305794B6 (cs) * 2015-04-20 2016-03-16 Výzkumný ústav potravinářský Praha, v.v.i. Způsob úpravy dřevních suků s přesně regulovanou strukturou drtě pro výrobu lignanů a zařízení k provádění tohoto způsobu, s využitím v potravinářské výrobě
WO2021023914A1 (en) * 2019-08-02 2021-02-11 Oy Granula Ab Ltd A method and a compound for preventing mammalian cancer cell proliferation and for treating cancer

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