Quinone Methides in Lignification

Quinone Methides

Volumn , Issue , 2009, Pages 385-420

  Ralph, John ^a,b   Schatz, Paul F ^b   Lu, Fachuang ^a   Kim, Hoon ^a   Akiyama, Takuya ^b,c   Nelsen, Stephen F ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

^b U S DAIRY FORAGE RESEARCH CENTER   (United States)

^c RIKEN Plant Science Center   (Japan)

Author keywords

Coupling reactions with 9 oxidized analogues of monolignols; Quinone methide reduction during lignification; Quinone methides in lignification

Indexed keywords

EID: 84884445147     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9780470452882.ch12     Document Type: Chapter

References (137)

1. Sarkanen, K. V.; Ludwig, C. H. Lignins, Occurrence, Formation, Structure and Reactions; Wiley-Interscience: New York, 1971.
2. Umezawa, T. Diversity in lignan biosynthesis. Phytochem. Rev. 2004, 2, 371-390.
3. Lewis, N. G.; Davin, L. B. Lignans: biosynthesis and function. In Comprehensive Natural Products Chemistry; Barton, D. H. R.; Nakanishi, K., Eds.; Elsevier: New York, 1999; Vol. 1.
4. Freudenberg, K.; Neish, A. C. Constitution and Biosynthesis of Lignin; Springer-Verlag: Berlin, 1968.
5. Gierer, J.; Opara, A. E. Enzymic degradation of lignin. Action of peroxidase and laccase on monomeric and dimeric model compounds. Acta Chem. Scand. 1973, 27, 2909-2922.
6. Boerjan, W.; Ralph, J.; Baucher, M. Lignin biosynthesis. Annu. Rev. Plant Biol. 2003, 54, 519-549.
7. Ralph, J.; Lundquist, K.; Brunow, G.; Lu, F.; Kim, H.; Schatz, P. F.; Marita, J. M.; Hatfield, R. D.; Ralph, S. A.; Christensen, J. H.; Boerjan, W. Lignins: natural polymers from oxidative coupling of 4-hydroxyphenylpropanoids. Phytochem. Rev. 2004, 3, 29-60.
8. Ralph, J.; Brunow, G.; Boerjan, W.; Encyclopedia of Life Sciences Rose, F.; Osborne, K., Eds.; John Wiley & Sons, Ltd.: Chichester, UK, 2007, pp. 1-10.
9. Ralph, J.; Peng, J.; Lu, F.; Hatfield, R. D. Are lignins optically active? J. Agric. Food Chem. 1999, 47, 2991-2996.
10. Ralph, J.; Brunow, G.; Harris, P. J.; Dixon, R. A.; Schatz, P. F.; Boerjan, W. Lignification: Are lignins biosynthesized via simple combinatorial chemistry or via proteinaceous control and template replication? In Advances in Polyphenols Research; Daayf, F.; El Hadrami, A.; Adam, L.; Ballance, G. M., Eds.; Blackwell Publishing: Oxford, UK, 2008, pp. 36-66.
11. Lloyd, R. V.; Wood, D. E. Free-radicals in an adamantane matrix. 8. EPR and INDO study of benzyl, anilino, and phenoxy radicals and their fluorinated derivatives. J. Am. Chem. Soc. 1974, 96, 659-665.
12. Dewar, M. J. S.; David, D. E. Ultraviolet photoelectron-spectrum of the phenoxy radical. J. Am. Chem. Soc. 1980, 102, 7387-7389.
13. Russell, W. R.; Forrester, A. R.; Chesson, A.; Burkitt, M. J. Oxidative coupling during lignin polymerization is determined by unpaired electron delocalization within parent phenylpropanoid radicals. Arch. Biochem. Biophys. 1996, 332, 357-366.
14. Katayama, Y.; Fukuzumi, T. Enzymic synthesis of three lignin-related dimers by an improved peroxidase-hydrogen peroxide system. Mokuzai Gakkaishi 1978, 24, 664-667.
15. Tanahashi M.; Takeuchi H.; Higuchi T. Dehydrogenative polymerization of 3,5- disubstituted p-coumaryl alcohols. Wood Res. 1976, 61, 44-53.
16. Akiyama, T.; Magara, K.; Matsumoto, Y.; Meshitsuka, G.; Ishizu, A.; Lundquist, K. Proof of the presence of racemic forms of arylglycerol-b-aryl ether structure in lignin: studies on the stereo structure of lignin by ozonation. J. Wood Sci. 2000, 46, 414-415.
17. Brunow, G.; Karlsson, O.; Lundquist, K.; Sipilä, J. On the distribution of the diastereomers of the structural elements in lignins: the steric course of reactions mimicking lignin biosynthesis. Wood Sci. Technol. 1993, 27, 281-286.
18. Bardet, M.; Robert, D.; Lundquist, K.; von Unge, S. Distribution of erythro and threo forms of different types of b-O-4 structures in aspen lignin by carbon-13 NMR using the 2D inadequate experiment. Magn. Reson. Chem. 1998, 36, 597-600.
19. Akiyama, T.; Goto, H.; Nawawi, D. S.; Syafii, W.; Matsumoto, Y.; Meshitsuka, G. Erythro/threo ratio of b-O-4-structures as an important structural characteristic of lignin. Part 4: variation in the erythro/threo ratio in softwood and hardwood lignins and its relation to syringyl/guaiacyl ratio. Holzforschung 2005, 59, 276-281.
20. Akiyama, T.; Magara, K.; Matsumoto, Y.; Ishizu, A.; Meshitsuka, G.; Lundquist, K. Studies on the optical activities of arylglycerol-b-aryl ether structures in lignin. In 11th International Symposium of Wood and Pulping Chemistry, Nice, France, Association Technique de l'Industrie Papetiére (ATIP), Paris; 2001; Vol. III, pp 537-540.
21. Lundquist, K.; Stomberg, R. On the occurrence of structural elements of the lignan type (b-b structures) in lignins. The crystal structures of (+)-pinoresinol and (-)-trans-3,4-divanillyltetrahydrofuran. Holzforschung 1988, 42, 375-384.
22. Ämmälahti, E.; Brunow, G.; Bardet, M.; Robert, D.; Kilpeläinen, I. Identification of side-chain structures in a poplar lignin using three-dimensional HMQC-HOHAHA NMR spectroscopy. J. Agric. Food Chem. 1998, 46, 5113-5117.
23. Zhang, L.; Gellerstedt, G. NMR observation of a new lignin structure, a spiro-dienone. J. Chem. Soc., Chem. Commun. 2001, 2744-2745.
24. Zhang, L.; Gellerstedt, G.; Ralph, J.; Lu, F. NMR studies on the occurrence of spirodienone structures in lignins. J. Wood Chem. Technol. 2006, 26, 65-79.
25. Ralph, J.; Landucci, L. L. NMR of lignins. In Lignins; Heitner, C.; Dimmel, D. R., Eds.; Marcel Dekker: New York, in press.
26. Tobimatsu, Y.; Takano, T.; Kamitakahara, H.; Nakatsubo, F. Azide ion as a quinone methide scavenger in the horseradish peroxidase catalyzed polymerization of sinapyl alcohol. J. Wood Sci. 2008, 54, 87-89.
27. Humphreys, J. M.; Hemm, M. R.; Chapple, C. Ferulate 5-hydroxylase fromArabidopsis is a multifunctional cytochrome P450-dependent monooxygenase catalyzing parallel hydroxylations in phenylpropanoid metabolism. Proc. Natl. Acad Sci. USA 1999, 96, 10045-10050.
28. Osakabe, K.; Tsao, C. C.; Li, L.; Popko, J. L.; Umezawa, T.; Carraway, D. T.; Smeltzer, R. H.; Joshi, C. P.; Chiang, V. L. Coniferyl aldehyde 5-hydroxylation and methylation direct syringyl lignin biosynthesis in angiosperms. Proc. Natl. Acad. Sci. USA 1999, 96, 8955-8960.
29. Li, L.; Popko, J. L.; Umezawa, T.; Chiang, V. L. 5-Hydroxyconiferyl aldehyde modulates enzymatic methylation for syringyl monolignol formation, a new view of monolignol biosynthesis in angiosperms. J. Biol. Chem. 2000, 275, 6537-6545.
30. Van Doorsselaere, J.; Baucher, M.; Chognot, E.; Chabbert, B.; Tollier, M.-T.; Petit-Conil, M.; Leplé, J.-C.; Pilate, G.; Cornu, D.; Monties, B.; Van Montagu, M.; Inzé, D.; Boerjan, W.; Jouanin, L.Anovel lignin in poplar trees with a reduced caffeic acid/5-hydroxyferulic acid O-methyltransferase activity. Plant J. 1995, 8, 855-864.
31. Lapierre, C.; Tollier, M. T.; Monties, B. A new type of constitutive unit in lignins from the corn bm3 mutant. C. R. Biol. 1988, 307, 723-728.
32. Lapierre, C.; Pollet, B.; Petit-Conil, M.; Toval, G.; Romero, J.; Pilate, G.; Leple, J. C.; Boerjan, W.; Ferret, V.; De Nadai, V.; Jouanin, L. Structural alterations of lignins in transgenic poplars with depressed cinnamyl alcohol dehydrogenase or caffeic acid O-methyltransferase activity have an opposite impact on the efficiency of industrial kraft pulping. Plant Physiol. 1999, 119, 153-163.
33. Ralph, J.; Lapierre, C.; Marita, J.; Kim, H.; Lu, F.; Hatfield, R. D.; Ralph, S. A.; Chapple, C.; Franke, R.; Hemm, M. R.; Van Doorsselaere, J.; Sederoff R. R.; O'Malley, D. M.; Scott, J. T.; MacKay, J. J.; Yahiaoui, N.; Boudet, A.-M.; Pean, M.; Pilate, G.; Jouanin, L.; Boerjan, W. Elucidation of new structures in lignins of CAD- and COMT-deficient plants by NMR. Phytochemistry 2001, 57, 993-1003.
34. Marita, J. M.; Ralph, J.; Lapierre, C.; Jouanin, L.; Boerjan, W. NMR characterization of lignins from transgenic poplars with suppressed caffeic acid O-methyltransferase activity. J. Chem. Soc., Perkin Trans. 2001, 1, 2939-2945.
35. Ralph, J.; Lapierre, C.; Lu, F.; Marita, J. M.; Pilate, G.; Van Doorsselaere, J.; Boerjan, W.; Jouanin, L. NMR evidence for benzodioxane structures resulting from incorporation of 5-hydroxyconiferyl alcohol into lignins of O-methyl-transferase-deficient poplars. J. Agric. Food Chem. 2001, 49, 86-91.
36. Marita, J. M.; Ralph, J.; Hatfield, R. D.; Guo, D.; Chen, F.; Dixon, R. A. Structural and compositional modifications in lignin of transgenic alfalfa down-regulated in caffeic acid 3-O-methyltransferase and caffeoyl coenzyme A 3-O-methyltransferase. Phytochemistry 2003, 62, 53-65.
37. Marita, J. M.; Vermerris, W.; Ralph, J.; Hatfield, R. D. Variations in the cell wall composition of maize brown midrib mutants. J. Agric. Food Chem. 2003, 51, 1313-1321.
38. Morreel, K.; Ralph, J.; Lu, F.; Goeminne, G.; Busson, R.; Herdewijn, P.; Goeman, J. L.; Van der Eycken, J.; Boerjan, W.; Messens, E. Phenolic profiling of caffeic acid O-methyltransferase-deficient poplar reveals novel benzodioxane oligolignols. Plant Physiol. 2004, 136, 4023-4036.
39. Jouanin, L.; Gujon, T.; Sibout, R.; Pollet, B.; Mila, I.; Leplé, J. C.; Pilate, G.; Petit-Conil, M.; Ralph, J.; Lapierre, C. Comparison of the consequences on lignin content and structure of COMT and CAD downregulation in poplar and Arabidopsis thaliana. In Plantation Forest Biotechnology in the 21st Century; Walter, C.; Carson, M., Eds.; Research Signpost: Kerala, India, 2004; pp. 219-229.
40. Miksche, G. E. Lignin reactions in alkaline pulping processes (rate processes in soda pulping). In Chemistry of Delignification with Oxygen, Ozone, and Peroxides; Nakano, J.; Singh, R. P., Eds.; Uni Publishers Co: Tokyo, Japan, 1980; pp. 107-120.
41. Ralph, J. Reactions of lignin model quinone methides and NMR studies of lignins. Ph. D. thesis, University ofWisconsin-Madison, University Microfilms #DA 82-26987. 1982.
42. Ralph, J.; Quideau, S.; Grabber, J. H.; Hatfield, R. D. Identification and synthesis of new ferulic acid dehydrodimers present in grass cell walls. J. Chem. Soc., Perkin Trans. 1994, 1, 3485-3498.
43. Kim, H.; Ralph, J.; Yahiaoui, N.; Pean, M.; Boudet, A.-M. Cross-coupling of hydroxycinnamyl aldehydes into lignins. Org. Lett. 2000, 2, 2197-2200.
44. del Rio, J. C.; Marques, G.; Rencoret, J.; Martinez, A. T.; Gutierrez, A. Occurrence of naturally acetylated lignin units. J. Agric. Food Chem. 2007, 55, 5461-5468.
45. Ralph J. An unusual lignin from kenaf. J. Nat. Prod. 1996, 59, 341-342.
46. Ralph, J.; Hatfield, R. D.; Quideau, S.; Helm, R. F.; Grabber, J. H.; Jung, H.-J. G. Pathway of p-coumaric acid incorporation into maize lignin as revealed by NMR. J. Am. Chem. Soc. 1994, 116, 9448-9456.
47. Smith, D. C. C. p-Hydroxybenzoates groups in the lignin of aspen (Populus tremula). J. Chem. Soc. 1955, 2347.
48. Nakano, J.; Ishizu, A.; Migita, N. Studies on lignin. XXXII. Ester groups of lignin. Tappi 1961, 44, 30-32.
49. Landucci, L. L.; Deka, G. C.; Roy, D. N. A 13C NMR study of milled wood lignins from hybrid Salix clones. Holzforschung 1992, 46, 505-511.
50. Sun, R. C.; Fang, J. M.; Tomkinson, J. Fractional isolation and structural characterization of lignins from oil palm trunk and empty fruit bunch fibres. J. Wood Chem. Technol. 1999, 19, 335-356.
51. Meyermans, H.; Morreel, K.; Lapierre, C.; Pollet, B.; De Bruyn, A.; Busson, R.; Herdewijn, P.; Devreese, B.; Van Beeumen, J.; Marita, J. M.; Ralph, J.; Chen, C.; Burggraeve, B.; Van Montagu, M.; Messens, E.; Boerjan, W. Modifications in lignin and accumulation of phenolic glucosides in poplar xylem upon down-regulation of caffeoylcoenzyme A O-methyltransferase, an enzyme involved in lignin biosynthesis. J. Biol. Chem. 2000, 275, 36899-36909.
52. Li, S.; Lundquist, K. Analysis of hydroxyl groups in lignins by 1H NMR spectrometry. Nordic Pulp Pap. Res. J. 2001, 16, 63-67.
53. Lu, F.; Ralph, J. Non-degradative dissolution and acetylation of ball-milled plant cell walls; high-resolution solution-state NMR. Plant J. 2003, 35, 535-544.
54. Lu, F.; Ralph, J. Preliminary evidence for sinapyl acetate as a lignin monomer in kenaf. J. Chem. Soc., Chem. Commun. 2002, 90-91.
55. Lu, F.; Ralph, J.; Morreel, K.; Messens, E.; Boerjan, W. Preparation and relevance of a cross-coupling product between sinapyl alcohol and sinapyl p-hydroxybenzoate. Org. Biomol. Chem. 2004, 2, 2888-2890.
56. Lu, F.; Ralph, J. Novel b-b-structures in natural lignins incorporating acylated monolignols. In Thirteenth International Symposium on Wood, Fiber, and Pulping Chemistry, Auckland, New Zealand, APPITA, Australia; 2005; Vol. 3, pp 233-237.
57. Ralph, J.; Adams, B. R. Determination of the conformation and isomeric composition of lignin model quinone methides by NMR. J. Wood Chem. Technol. 1983, 3, 183-194.
58. Zinke, T.; Hahn, O. Über die Einwirkung von Brom und von Chlor auf Phenole: Substitutionsproducted, Pseudobromide and Pseudochloride; IX. Über die Einwirkung von Brom auf Isoeugenol. Justus Liebigs Ann. Chem. 1903, 329, 1-36.
59. Li, S. M.; Lundquist, K.; Soubbotin, N.; Stomberg, R. 2-Bromo-4-[2-bromo-(E)-propylidene]-6-methoxy-2,5-cyclohexadien-1-one. Acta Crystallogr. 1995, 51, 2366-2369.
60. Ralph, J.; Ede, R. M.; Robinson, N. P.; Main, L. Reactions of b-aryl lignin model quinone methides with anthrahydroquinone and anthranol. J. Wood Chem. Technol. 1987, 7, 133-160.
61. Ralph, J.; Young, R. A. Stereochemical aspects of addition reactions involving lignin model quinone methides. J. Wood Chem. Technol. 1983, 3, 161-181.
62. Johansson, B.; Miksche, G. E.Über die Benzyl-arylätherbindung im Lignin. II. Versuche an Modellen. Acta Chem. Scand. 1972, 26, 289-308.
63. Lu, F.; Ralph, J. Facile synthesis of 4-hydroxycinnamyl p-coumarates. J. Agric. Food Chem. 1998, 46, 2911-2913.
64. Landucci, L. L.; Ralph, J. Adducts of anthrahydroquinone and anthranol with lignin model quinone methides. 1. Synthesis and characterization. J. Org. Chem. 1982, 47, 3486-3495.
65. Landucci, L. L. Formation of carbon-linked anthrone-lignin and anthrahydroquinonelignin adducts. J. Wood Chem. Technol. 1981, 1, 61-74.
66. Ralph J.; Landucci, L. L. Adducts of anthrahydroquinone and anthranol with lignin model quinone methides. 9,10-13C labeled anthranol-lignin adducts; examination of adduct formation and stereochemistry in the polymer. J. Wood Chem. Technol. 1986, 6, 73-88.
67. Zanarotti, A. Synthesis and reactivity of lignin model quinone methides. J. Org. Chem. 1983, 50, 941-945.
68. Quideau, S.; Ralph, J. A biomimetic route to lignin model compounds via silver(I) oxide oxidation. 1. Synthesis of dilignols and non-cyclic benzyl aryl ethers. Holzforschung 1994, 48, 12-22.
69. Zanarotti, A. Synthesis and reactivity of vinyl quinone methides. J. Org. Chem. 1985, 50, 941-945.
70. Zanarotti, A. Synthesis and reactivity of lignin model quinone methides. Biomimetic synthesis of 8.0.40 neolignans. J. Chem. Res., Synop. 1983, 306-307.
71. Zanarotti, A. Preparation and reactivity of 2,6-dimethoxy-4-allylidene-2,5-cyclohexadien-1-one (vinyl quinone methide). A novel synthesis of sinapyl alcohol. Tetrahedron Lett, 1982, 23, 3815-3818.
72. Marita, J.; Ralph, J.; Hatfield, R. D.; Chapple, C. NMR characterization of lignins in Arabidopsis altered in the activity of ferulate-5-hydroxylase. Proc. Natl. Acad. Sci. USA 1999, 96, 12328-12332.
73. Hu, W.-J.; Lung, J.; Harding, S. A.; Popko, J. L.; Ralph, J.; Stokke, D. D.; Tsai, C.-J.; Chiang, V. L. Repression of lignin biosynthesis in transgenic trees promotes cellulose accumulation and growth. Nat. Biotechnol. 1999, 17, 808-812.
74. Karhunen, P.; Rummakko, P.; Pajunen, A.; Brunow, G. Synthesis and crystal structure determination of model compounds for the dibenzodioxocine structure occurring in wood lignins. J. Chem. Soc., Perkin Trans. 1996, 1, 2303-2308.
75. Karhunen, P.; Rummakko, P.; Sipilä, J.; Brunow, G.; Kilpeläinen, I. Dibenzo- dioxocins; a novel type of linkage in softwood lignins. Tetrahedron Lett. 1995, 36, 169-170.
76. Karhunen, P.; Rummakko, P.; Sipilä, J.; Brunow, G.; Kilpeläinen, I. The formation of dibenzodioxocin structures by oxidative coupling. A model reaction for lignin biosynthesis. Tetrahedron Lett. 1995, 36, 4501-4504.
77. Quideau, S. Incorporation of p-hydroxycinnamic acids into lignins via oxidative coupling. Ph.D. Thesis, University of Wisconsin-Madison, USA, University Microfilms International #9428350, 1994. 1994.
78. Ralph, S. A.; Landucci, L. L.; Ralph, J. Available at http://ars.usda.gov/Services/docs.htm?docid1/410429(previouslyhttp://www.dfrc.ars.usda.gov/software.html), updated at least annually since 1993, 2005.
79. Nakatsubo, F.; Higuchi, T. Enzymic dehydrogenation of p-coumaryl alcohol. III. Analysis of dilignols by gas chromatography and NMR spectrometry. Wood Res. 1975, 58, 12-19.
80. Akiyama, T.; Kim, H.; Dixon, R. A.; Ralph, J. Dibenzodioxocin structures involving p-hydroxyphenyl units inC3Hdown-regulated lignins. In 10th International Congress on Biotechnology in the Pulp and Paper Industry, Madison, WI, USA, ICBPPI, University of Wisconsin Press. 2007, pp 71; Poster PS PGMB 1.4.
81. Ede, R. M.; Main, L.; Ralph, J. Evidence for increased steric compression in anti compared to syn lignin model quinone methides. J. Wood Chem. Technol. 1990, 10, 101-110.
82. Ralph, J.; Elder, T. J.; Ede, R. M. The stereochemistry of guaiacyl lignin model quinonemethides. Holzforschung 1991, 45, 199-204.
83. Ralph, J.; Ede, R. M.NMR of lignin model quinone methides. Corrected carbon-13 NMR assignments via carbon-proton correlation experiments.Holzforschung1988,42, 337-338.
84. Miksche, G. E. Über das Verhalten des Lignins bei der Alkalikochung. VIII. Isoeugenolglykol-b-(2-methoxyphenyl)-äther €uber ein Chinonmethid. (Behavior of lignins during alkaline pulping. VIII. Isomerization of the phenolate anions of erythro- and threo-isoeugenolglycol-b-(2-methoxyphenyl) ether via a quinone methide.) Acta Chem. Scand. 1972, 26, 4137-4142.
85. Ralph, J. Lignin model quinone methides-facts and fallacies. In Proceedings of the Third International Symposium of Wood and Pulping Chemistry, Vancouver, BC, Canada, Chemical Institute of Canada (CIC), and Canadian Pulp and Paper Association (CPPA), Canada. 1985.
86. Cook, C. D.; Norcross, B. E. Oxidation of hindered phenols. V. The 2,6-di-t-butyl-4-isopropyl and -4-sec-butylphenoxy radicals. J. Am. Chem. Soc. 1956, 78, 3797-3799.
87. Leary, G.; Miller, I. J.; Thomas, W.; Woolbouse, A. D. The chemistry of reactive lignin intermediates. Part 5. Rates of reactions of quinone methides with water, alcohols, and carboxylic acids. J. Chem. Soc., Perkin Trans. 1977, 2, 1737-1739.
88. Hemmingson, J. A.; Leary, G. The chemistry of reactive lignin intermediates. Part II. Addition reactions of vinyl-substituted quinone methides in aqueous solution. J. Chem. Soc., Perkin Trans. 1975, 2, 1584-1587.
89. Ralph, J.; Helm, R. F. Rapid proton NMR method for determination of threo:erythro ratios in lignin model compounds and examination of reduction stereochemistry. J. Agric. Food Chem. 1991, 39, 705-709.
90. Ralph, J.; Marita, J. M.; Ralph, S. A.; Hatfield, R. D.; Lu, F.; Ede, R. M.; Peng, J.; Quideau, S.; Helm, R. F.; Grabber, J. H.; Kim, H.; Jimenez-Monteon, G.; Zhang, Y.; Jung, H.-J. G.; Landucci, L. L.; MacKay, J. J.; Sederoff, R. R.; Chapple, C.; Boudet, A. M. Solution-state NMR of lignins. In Advances in Lignocellulosics Characterization; Argyropoulos, D. S. Ed.; TAPPI Press: Atlanta, GA, 1999; pp. 55-108.
91. Nakatsubo, F.; Higuchi, T. Synthesis of 1,2-diarylpropane-1,3-diols and determination of their configurations. Holzforschung 1975, 29, 193-198.
92. Akiyama, T.; Sugimoto, T.; Matsumoto, Y.; Meshitsuka, G. Erythro/threo ratio of b-O-4 structures as an important structural characteristic of lignin. I: improvement of ozonation method for the quantitative analysis of lignin side-chain structure. J. Wood Sci. 2002, 48, 210-215.
93. Matsumoto, Y.; Ishizu, A.; Nakano, J. Studies on chemical structure of lignin by ozonation. Holzforschung 1986, 40, 81-85.
94. Landucci, L. L. Quinones in alkaline pulping. Characterization of an anthrahydroquinone- quinone methide intermediate. Tappi 1980, 63, 95-99.
95. Ralph, J.; Landucci, L. L.; Nicholson, B. K.; Wilkins, A. L. Adducts of anthrahydroquinone and anthranol with lignin model quinone methides. 4. Proton NMR hindered rotation studies. Correlation between solution conformations and X-ray crystal structure. J. Org. Chem. 1984, 49, 3337-3340.
96. Ralph, J.; Landucci, L. L. Adducts of anthrahydroquinone and anthranol with lignin model quinone methides. 2. Dehydration derivatives. Proof of threo configuration. J. Org. Chem. 1983, 48, 372-376.
97. Ralph, J.; Landucci, L. L. Adducts of anthrahydroquinone and anthranol with lignin model quinone methides. 3. Independent synthesis of threo and erythro isomers. J. Org. Chem. 1983, 48, 3884-3889.
98. Gierer, J.; Ljunggren, S. The reactions of lignin during sulfate pulping. Part 17. Kinetic treatment of the formation and competing reactions of quinone methide intermediates. Sven. Papperstidn. 1979, 82, 503-512.
99. Ralph, J.; Grabber, J. H. Dimeric b-ether thioacidolysis products resulting from incomplete ether cleavage. Holzforschung 1996, 50, 425-428.
100. Ralph, J.; MacKay, J. J.; Hatfield, R. D.; O'Malley, D. M.; Whetten, R.W.; Sederoff, R. R. Abnormal lignin in a loblolly pine mutant. Science 1997, 277, 235-239.
101. Savidge, R. A.; Forster, H. Coniferyl alcohol metabolism in conifers-II. Coniferyl alcohol and dihydroconiferyl alcohol biosynthesis. Phytochemistry 2001, 57, 1095-1103.
102. Lapierre, C.; Pollet, B.; MacKay, J. J.; Sederoff, R. R. Lignin structure in a mutant pine deficient in cinnamyl alcohol dehydrogenase. J. Agric. Food Chem. 2000, 48, 2326-2331.
103. Sederoff, R. R.; MacKay, J. J.; Ralph, J.; Hatfield, R. D. Unexpected variation in lignin. Curr. Opin. Plant Biol. 1999, 2, 145-152.
104. Ralph, J.; Kim, H.; Peng, J.; Lu, F. Arylpropane-1,3-diols in lignins from normal and CAD-deficient pines. Org. Lett. 1999, 1, 323-326.
105. Savidge, R. A. Dihydroconiferyl alcohol in developing xylem of Pinus contorta. Phytochemistry 1987, 26, 93-94.
106. Gang, D.R.; Fujita, M.; Davin, L.D.; Lewis, N.G.Theábnormallignins':mappingheartwood formation through the lignan biosynthetic pathway. In Lignin and Lignan Biosynthesis; Lewis, N. G.; Sarkanen, S., Eds.; American Chemical Society:Washington, DC, Vol. 697, American Chemical Society Symposium Series; 1998, pp 389-421.
107. MacKay, J. J.; Dimmel, D. R.; Boon, J. J. Pyrolysis MS characterization of wood from CAD-deficient pine. J. Wood Chem. Technol. 2001, 21, 19-29.
108. Holmgren, A.; Brunow, G.; Henriksson, G.; Zhang, L.; Ralph, J. Non-enzymatic reduction of quinone methides during oxidative coupling of monolignols: implications for the origin of benzyl structures in lignins. Org. Biomol. Chem. 2006, 4, 3456-3461.
109. Brunow, G.; Ronnberg, M. The peroxidatic oxidation of some phenolic lignin model compounds. Acta Chem. Scand., Ser. B 1979, 33, 22-26.
110. Aoyama, W.; Sasaki, S.; Matsumura, S.; Mitsunaga, T.; Hirai, H.; Tsutsumi, Y.; Nishida, T. Sinapyl alcohol-specific peroxidase isoenzyme catalyzes the formation of the dehydrogenative polymer from sinapyl alcohol. J. Wood Sci. 2002, 48, 497-504.
111. RosBarceló, A.; Pomar, F. Oxidation of cinnamyl alcohols and aldehydes by a basic peroxidase from lignifying Zinnia elegans hypocotyls. Phytochemistry 2001, 57, 1105-1113.
112. Kobayashi, T.; Taguchi, H.; Shigematsu, M.; Tanahashi, M. Substituent effects of 3,5-disubstituted p-coumaryl alcohols on their oxidation using horseradish peroxidase-H2O2 as the oxidant. J. Wood Sci. 2005, 51, 607-614.
113. Önnerud, H.; Zhang, L.; Gellerstedt, G.; Henriksson, G. Polymerization of monolignols by redox shuttle-mediated enzymatic oxidation: a new model in lignin biosynthesis I. Plant Cell 2002, 14, 1953-1962.
114. Hatfield, R. D.; Vermerris, W. Lignin formation in plants. The dilemma of linkage specificity. Plant Physiol. 2001, 126, 1351-1357.
115. Takahama, U.; Oniki T.; Shimokawa H. A possible mechanism for the oxidation of sinapyl alcohol by peroxidase-dependent reactions in the apoplast: enhancement of the oxidation by hydroxycinnamic acids and components of the apoplast. Plant Cell Physiol. 1996, 37, 499-504.
116. Takahama, U.; Oniki, T. Enhancement of peroxidase-dependent oxidation of sinapyl alcohol by esters of 4-coumaric and ferulic acid. In Plant Peroxidases, Biochemistry and Physiology; Obinger, C.; Burner, U.; Ebermann, R.; Penel, C.; Greppin, H., Eds.; Université de Genéve, Genéve: Switzerland, 1996; pp. 118-123.
117. Takahama, U.; Oniki, T. A peroxidase/phenolics/ascorbate system can scavenge hydrogen peroxide in plant cells. Physiol. Plantarum 1997, 101, 845-852.
118. Christensen, J. H.; Baucher, M.; O'Connell, A. P.; Van Montagu, M.; Boerjan, W. Control of lignin biosynthesis. In Molecular Biology of Woody Plants; Jain, S. M.; Minocha; S. C., Eds.; Kluwer Academic Publishers: Dordrecht, 2000; Vol. 1 (Forestry Sciences, Vol. 64); pp. 227-237.
119. Ralph, J.; Bunzel, M.; Marita, J. M.; Hatfield, R. D.; Lu, F.; Kim, H.; Schatz, P. F.; Grabber, J. H.; Steinhart, H. Peroxidase-dependent cross-linking reactions of p-hydroxycinnamates in plant cell walls. Phytochem. Rev. 2004, 3, 79-96.
120. Fournand, D.; Cathala, B.; Lapierre, C. Initial steps of the peroxidase-catalyzed polymerization of coniferyl alcohol and/or sinapyl aldehyde: capillary zone electrophoresis study of pH effect. Phytochemistry 2003, 62, 139-146.
121. Sasaki, S.; Nishida, T.; Tsutsumi, Y.; Kondo, R. Lignin dehydrogenative polymerization mechanism: a poplar cell wall peroxidase directly oxidizes polymer lignin and produces in vitro dehydrogenative polymer rich in b-O-4 linkage. FEBS Lett. 2004, 562, 197-201.
122. Takahama, U. Oxidation of hydroxycinnamic acid and hydroxycinnamyl alcohol derivatives by laccase and peroxidase-interactions among p-hydroxyphenyl, guaiacyl and syringyl groups during the oxidation reactions. Physiol. Plantarum 1995, 93, 61-68.
123. Takahama, U.; Oniki, T. Effects of ascorbate on the oxidation of derivatives of hydroxycinnamic acid and the mechanism of oxidation of sinapic acid by cell wallbound peroxidases. Plant Cell Physiol. 1994, 35, 593-600.
124. Hatfield, R. D.; Ralph, J.; Grabber, J. H. A potential role of sinapyl p-coumarate as a radical transfer mechanism in grass lignin formation. Planta 2008, 228, 919-928.
125. Dunford, H. B. Heme enzymes. In Comprehensive Biological Catalysis; Sinnott, M. Ed.; Academic press: San Diego, CA, 1998, Vol. 3, pp. 196-237.
126. Dunford, H. B. Peroxidases. Adv. Inorg. Biochem. 1982, 4, 41-68.
127. Kim, H.; Ralph, J.; Lu, F.; Ralph, S. A.; Boudet, A.-M.; MacKay, J. J.; Sederoff, R. R.; Ito, T.; Kawai, S.; Ohashi, H.; Higuchi, T. NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins. Org. Biomol. Chem. 2003, 1, 268-281.
128. Ralph, J. What makes a good monolignol substitute? In The Science and Lore of the Plant Cell Wall Biosynthesis, Structure and Function; Hayashi, T., Ed.; Universal Publishers (BrownWalker Press): Boca Raton, FL, 2006; pp. 285-293.
129. Schatz, P. F.; Ralph, J.; Lu, F.; Guzei, I. A.; Bunzel, M. Synthesis and identification of 2,5-bis-(4-hydroxy-3-methoxyphenyl)-tetrahydrofuran-3,4-dicarboxylic acid, an unanticipated ferulate 8-8-coupling product acylating cereal plant cell walls. Org. Biomol. Chem. 2006, 4, 2801-2806.
130. Ralph, J.; Kim, H.; Lu, F.; Grabber, J. H.; Boerjan, W.; Leplé, J.-C.; Berrio Sierra, J.; Mir Derikvand, M.; Jouanin, L.; Lapierre, C. Identification of the structure and origin of a thioacidolysis marker compound for ferulic acid incorporation into angiosperm lignins (and an indicator for cinnamoyl-CoA reductase deficiency). Plant J. 2008, 53, 368-379.
131. Leplé, J.-C.; Dauwe, R.; ]Morreel, K.; Storme, V.; Lapierre, C.; Pollet, B.; Naumann, A.; Kang K.-Y.; Kim, H.; Ruel, K.; Lefébvre, A.; Josseleau, J.-P.; Grima-Pettenati, J.; De Rycke, R.; Andersson-Gunneras, S.; Erban, A.; Fehrle, I.; Petit-Conil, M.; Kopka, J.; Polle, A.; Messens, E.; Sundberg, B.; Mansfield, S. D.; Ralph, J.; Pilate, G.; Boerjan, W. Downregulation of cinnamoyl coenzyme A reductase in poplar; multiple-level phenotyping reveals effects on cell wall polymer metabolism and structure. Plant Cell 2007, 19, 3669-3691.
132. Laskar, D. D.; Jourdes, M.; Patten, A. M.; Helms, G. L.; Davin, L. B.; Lewis, N. G. The Arabidopsis cinnamoyl CoA reductase irx4 mutant has a delayed but coherent (normal) program of lignification. Plant J. 2006, 48, 674-686.
133. Jung, H. G.; Buxton, D. R.; Hatfield, R. D.; Ralph, J., Eds.; Forage Cell Wall Structure and Digestibility; American Society of Agronomy, Crop Science Society of America, Soil Society of America: Madison, 1993; pp 794.
134. Jung, H.; Buxton, D.; Hatfield, R.; Mertens, D.; Ralph, J.; Weimer, P. Improving forage fiber digestibility. Feed Mix 1996, 4, 30-31, 33-34.
135. Pan, X. J.; Arato, C.; Gilkes, N.; Gregg, D.; Mabee, W.; Pye, K.; Xiao, Z. Z.; Zhang, X.; Saddler, J. Biorefining of softwoods using ethanol organosolv pulping: preliminary evaluation of process streams for manufacture of fuel-grade ethanol and co-products. Biotechnol. Bioeng. 2005, 90, 473-481.
136. Chapple, C.; Ladisch, M.; Meilan, R. Loosening lignin's grip on biofuel production. Nat. Biotechnol. 2007, 25, 746-748.
137. Toikka, M.; Sipilä, J.; Teleman, A.; Brunow, G. Lignin-carbohydrate model compounds. Formation of lignin-methyl arabinoside and lignin-methyl galactoside benzyl ethers via quinone methide intermediates. J. Chem. Soc., Perkin Trans. 1998, 1, 3813-3818.