Abstract
The norlignan (NorL) is a class of secondary metabolites, which occurs in the heartwood (hW) of certain softwood species. Although the NorL is often assumed to be secondarily altered (e.g., oxidized and/or polymerized in the hW over time), the formation and the chemical structure of oxidized/polymerized products remained unclear. In this study, we focused on the question whether an NorL oligomer/polymer exists in the hW of Cryptomeria japonica. First, NorL model polymers were prepared by horseradish peroxidase-catalyzed oxidation and their chemical structures were investigated by size exclusion chromatography-high-performance liquid chromatography (SEC-HPLC), nuclear magnetic resonance (NMR), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Second, methanol (MeOH) extracted from the hW of C. japonica was fractionated, and one of the fractions contained NorL polymers as demonstrated by its chromatographic and spectrometric data in comparison with those of model polymers. Third, five kinds of agatharesinol (AGA) model dimers were synthesized and their chemical structures were determined. 13C-NMR signals corresponding to the model dimer structures were observed in the NMR spectrum of the natural polymer fraction. In summary, an NorL polymer was found in the hW of C. japonica, and its preliminary chemical structure was proposed for the first time.
Acknowledgments
This work was supported by the Grant-in-Aid for Scientific Research (Nos. 20248018 and 25450240) from the Japan Society for the Promotion of Science (JSPS). The authors thank technical personnel Mr. Kazushi Koga for his technical help with NMR analyses as well as Ms. Ruka Takama for her technical support with MS analyses.
References
Bito, N., Nakada, R., Fukatsu, E., Matsushita, Y., Fukushima, K., Imai, T. (2011) Clonal variation in heartwood norlignan of Cryptomeria japonica: evidence for independent control of agatharesinol and sequirin C biosynthesis. Ann. For. Sci. 68:1049–1056.Search in Google Scholar
Chen, X., H., Kim, C., S., Kashiwagi, T., Tebayashi, S., Horie, M. (2001) Antifeedants against Acusta despesta from the Japanese cedar, Cryptomeria japonica. Z. Naturforsch. 56c:249–252.10.1515/znc-2001-3-413Search in Google Scholar
Higuchi, T., Shimada, M., Watanabe, K. (1967) Studies on the mechanism of heartwood formation. VI. On the artificial heartwood of Cryptomeria japonica and Pinus densiflora. Mokuzai Gakkaishi 13:274–279.Search in Google Scholar
Hishiyama, S., Kato, A. (1999) Synthesis of phenolic constituents in sugi heartwood (3). Abstracts of the 49th Annual Meeting of the Japan Wood Research Society: 2P13.Search in Google Scholar
Hishiyama, S., Kato, A. (2006) Dehydrogenative polymerization of norlignan in sugi heartwood. Abstracts of the 56th Annual Meeting of the Japan Wood Research Society: PP012.Search in Google Scholar
Imai, T. (2012) Chemistry of heartwood formation. Mokuzai Gakkaishi 58:11–22.10.2488/jwrs.58.11Search in Google Scholar
Imai, T., Ito, E., Fukushima, K. (2005) Biochemical studies of matured xylem of Cryptomeria japonica. Attempts to detect the enzymes involved in the biosyntheses of the heartwood extractives. Nagoya Univ. For. Sci. 24:1–6.Search in Google Scholar
Imai, T., Asai, K., Takino, M., Fukushima, K. (2009) In vitro hydroxylation of a norlignan: from agatharesinol to sequirin C and metasequirin C with a microsomal preparation from Cryptomeria japonica. Phytochem. Lett. 2:196–200.10.1016/j.phytol.2009.07.002Search in Google Scholar
Kai, Y., Kuroda, H., Teratani, F. (1972) On the phenolic constituents from Cryptomeria japonica D. Don. VI. Hydroxysugiresinol and coloration of heartwood. Mokuzai Gakkaishi 18:315–321.Search in Google Scholar
Kano, H., Shibutani, S., Hayashi, K., Ijima, Y., Doi, S. (2004) Effect of high-temperature drying process on termite resistance of sugi (Cryptomeria japonica) heartwood. Mokuzai Gakkaishi 50:91–98.Search in Google Scholar
Karplus, M., Jeffrey, C., Christopher, M. (1985) Vicinal coupling constants and protein dynamics. Biochemistry 24:3831–3841.10.1021/bi00336a003Search in Google Scholar
Kuroda, H., Shimaji, K. (1983) Distribution of coloring substances in sugi heartwood. Holzforschung 37:225–230.10.1515/hfsg.1983.37.5.225Search in Google Scholar
Lukmandaru, G., Takahashi, K. (2009) Radial distribution of quinones in plantation teak (Tectona grandis L.f.). Ann. For. Sci. 66:605p1–605p5.10.1051/forest/2009051Search in Google Scholar
Matsukuma, N., Kawano, H., Shibata, Y., Kondo, T. (1965) Studies on the intermediate zone of sugi wood. Some physiological activities of the xylem tissue. Mokuzai Gakkaishi 11:227–231.Search in Google Scholar
Muraoka, O., Bao-Zhong, Z., Fujiwara, N., Tanabe, G. (1995) Enantioselective total synthesis of the di-O-methyl ethers of (-)-agatahresinol, (+)-hinokiresinol and (-)-sugiresinol, characteristic norlignans of Coniferae. J. Chem. Soc. Perkin Trans. 1 1995:405–411.Search in Google Scholar
Nagasaki, T., Yasuda, S., Imai, T. (2002) Immunohistochemical localization of agatharesinol, a heartwood norlignan, in Cryptomeria japonica. Phytochemistry 60:461–466.10.1016/S0031-9422(02)00141-3Search in Google Scholar
Nault, J. (1988) Radial distribution of thujaplicins in old growth and second growth western red cedar (Thuja plicata Donn). Wood Sci. Technol. 22:73–80.Search in Google Scholar
Ohashi, H., Imai, T., Yoshida, K., Yasue, M. (1990) Characterization of physiological functions of sapwood fluctuation of extractives in the wethering process of Japanese cedar sapwood. Holzforschung 44:79–86.10.1515/hfsg.1990.44.2.79Search in Google Scholar
Ohtani, Y., Noguchi, T., Ichiura, H. (2009) Relationship between sugi butt-rot disease and norlignans in the heartwood. Mokuzai Gakkaishi 55:92–100.10.2488/jwrs.55.92Search in Google Scholar
Saito, K., Mitsutani, T., Imai, T., Matsushita, Y., Fukushima, K. (2008) Discriminating the indistinguishable sapwood from heartwood in discolored ancient wood by direct molecular mapping of specific extractives using time-of-flight secondary ion mass spectrometry. Anal. Chem. 80:552–557.Search in Google Scholar
Takahashi, K. (1981) Heartwood phenols and their significance to color in Cryptomeria japonica D. Don. Mokuzai Gakkaishi 27:654–657.Search in Google Scholar
Takahashi, K. (1996) Relations between the blacking phenomenon and norlignans of sugi (Cryptomeria japonica D. Don) heartwood I. A case of partially black heartwood. Mokuzai Gakkaishi 42:998–1005.Search in Google Scholar
Takahashi, K., Mori, K. (2006) Relations between blacking phenomenon and norlignans of sugi (Cryptomeria japonica) heartwood III: coloration of norlignans with alkaline treatment. J. Wood. Sci. 52:134–139.Search in Google Scholar
©2015 by De Gruyter
Articles in the same Issue
- Frontmatter
- Original Articles
- Characterization of dissolved lignins from acetic acid Lignofibre (LGF) organosolv pulping and discussion of its delignification mechanisms
- Organic materials in black liquors of soda-AQ pulping of hot-water-extracted birch (Betula pendula) sawdust
- Effects of concentration and temperature on the rheological behavior of concentrated sodium lignosulfonate (NaLS) solutions
- Raman microscopic analysis of wood after treatment with the ionic liquid, 1-ethyl-3-methylimidazolium chloride
- Isolation and structural elucidation of norlignan polymers from the heartwood of Cryptomeria japonica
- Effect of ball milling on lignin polyesterification with ε-caprolactone
- Property enhancement of kenaf fiber composites by means of vacuum-assisted resin transfer molding (VARTM)
- Wood polypropylene composites prepared by thermally modified fibers at two extrusion speeds: mechanical and viscoelastic properties
- Numerical analysis of temperature profiles during thermal modification of wood: chemical reactions and experimental verification
- Fast online NIR technique to predict MOE and moisture content of sawn lumber
- Numerical study of the influence of veneer lathe checks on the elastic mechanical properties of laminated veneer lumber (LVL) made of beech
- Amination of pretreated ayous (Triplochiton scleroxylon) sawdust with two organosilanes: characterization, stability, and permselective property
- Damage evolution in wood – pattern recognition based on acoustic emission (AE) frequency spectra
- Mechanical stability of superhydrophobic epoxy/silica coating for better water resistance of wood
- Short Note
- Urea-formaldehyde resin penetration into Pinus radiata tracheid walls assessed by TEM-EDXS
- Obituary
- Professor Dr. Arnis Treimanis
Articles in the same Issue
- Frontmatter
- Original Articles
- Characterization of dissolved lignins from acetic acid Lignofibre (LGF) organosolv pulping and discussion of its delignification mechanisms
- Organic materials in black liquors of soda-AQ pulping of hot-water-extracted birch (Betula pendula) sawdust
- Effects of concentration and temperature on the rheological behavior of concentrated sodium lignosulfonate (NaLS) solutions
- Raman microscopic analysis of wood after treatment with the ionic liquid, 1-ethyl-3-methylimidazolium chloride
- Isolation and structural elucidation of norlignan polymers from the heartwood of Cryptomeria japonica
- Effect of ball milling on lignin polyesterification with ε-caprolactone
- Property enhancement of kenaf fiber composites by means of vacuum-assisted resin transfer molding (VARTM)
- Wood polypropylene composites prepared by thermally modified fibers at two extrusion speeds: mechanical and viscoelastic properties
- Numerical analysis of temperature profiles during thermal modification of wood: chemical reactions and experimental verification
- Fast online NIR technique to predict MOE and moisture content of sawn lumber
- Numerical study of the influence of veneer lathe checks on the elastic mechanical properties of laminated veneer lumber (LVL) made of beech
- Amination of pretreated ayous (Triplochiton scleroxylon) sawdust with two organosilanes: characterization, stability, and permselective property
- Damage evolution in wood – pattern recognition based on acoustic emission (AE) frequency spectra
- Mechanical stability of superhydrophobic epoxy/silica coating for better water resistance of wood
- Short Note
- Urea-formaldehyde resin penetration into Pinus radiata tracheid walls assessed by TEM-EDXS
- Obituary
- Professor Dr. Arnis Treimanis